Forensic Tattoo

Forensic

Analysis of Tattoos and Tattoo Inks

Forensic

Analysis of Tattoos and Tattoo Inks Michelle D. Miranda

State University of New York at Farmingdale, USA

Boca Raton London New York

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To my brothers, Brian and D.J.

Contents

Preface xiii Author xv Introduction xvii

Section I TATTOOING HISTORY

1 2

3

Tattoos and Tattooing

3

Terminology and Technique Tattoo Prevalence and Interpretation

4 20

Tattoos and Tattooing in Criminology and Criminal Investigations

25

Tattoos and Criminological Theories Tattoos and Forensic Investigations Identification and Individualization Tattoos and Criminal Investigations Tattoos in the Courtroom Tattoos and Scientific Inquiry

25 29 33 44 46 53

Tattoo Modification, Removal, and Detection

55

The Anatomy of Human Skin Tattoo Pigments and Human Tissue Detection of Pigments in Tattooed Skin Visualization of Tattoos Tattoo Removal Methods Thermal Cautery and Laser Tattoo Removal

55 59 61 62 67 73

vii

viii

Contents

Section II TATTOO INKS AND PIGMENTS: HISTORY AND CHEMISTRY

4

5

6

General Components of Tattoo Inks

83

Liquid Composition of Tattoo Inks Pigment Composition of Tattoo Inks Homemade Tattoo Inks Professional Tattoo Inks

84 85 85 87

The Chemistry of Tattoo Inks from Ancient to Modern Times

97

Black Tattooing Pigments Red Tattooing Pigments Orange Tattooing Pigments Yellow Tattooing Pigments Green Tattooing Pigments Blue Tattooing Pigments Purple Tattooing Pigments White Tattooing Pigments Brown Tattooing Pigments Modern Tattooing Pigments The Transition from Natural to Synthetic Pigments in Tattoo Inks Additional Studies and Reports on Tattoo Ink Composition The Liquid Composition of Modern Tattoo Inks Additional Studies of Modern Tattoo Inks and Pigments

116 124 127

Alternate Sources of Tattoos and Tattoo Inks

131

Pigments for Medicinal Purposes Pigments for Cosmetic Purposes Pigments Used in Art and Manufacturing Writing Inks

98 101 104 105 106 106 108 108 108 109 112

131 133 134 136

Section III MODERN TATTOO INKS

7

Modern Organic Pigments

149

Contents

8

The Chemical Analysis of Modern Tattoo Inks: Microscopy 161 Iron Works Brasil Tattoo Inks Skin Candy Tattoo Inks Flying Tigers Tattoo Inks

9

ix

Part 1—The Chemical Analysis of Modern Tattoo Inks: Spectroscopy

167 173 182

203

X-Ray Fluorescence: Theory and Practice 203 UV–Vis Spectrometry: Theory and Practice 203 Infrared Spectrometry: Theory and Practice 206 Raman Spectroscopy: Theory and Practice 209 SERS: Theory and Practice 214 Instrument Calibration, Method Development, and Standard Practices 217 Spectroscopic Analysis of Tattoo Inks 226 Instrumental Analysis: Molecular SpectroscopyRaman and Infrared Spectroscopy 226 Chemistry and UV–Vis Spectroscopy 228 Tattoos in Tissue 233

10

Part 2—The Chemical Analysis of Modern Tattoo Inks: Spectroscopy

237

Results: Pigment Standards 237 Pigment Red 122 237 Pigment Red 146 238 Pigment Red 170 239 Pigment Red 255 239 Pigment Orange 16 241 Pigment Orange 34 243 Pigment Orange 62 244 Pigment Yellow 3 245 Pigment Yellow 73 246 Pigment Yellow 83 247 Pigment Yellow 151 248 Pigment Green 7 250 Pigment Blue 15, 15:1, 15:2, 15:3 251 Pigment Violet 23α 254 Pigment Violet 23β 255 Results: Tattoo Inks 257

x

Contents

Skin Candy 257 Candy Apple Red 258 Red Hot 258 Marz 258 Dolemite 261 Blisterine 264 Sassygrass 266 Tastywaves 268 Bellbottom Blue 269 SRV Teal 2 269 Muddy Water Blue 270 Ripple 270 Razberry Creem 274 Black Cherry Roan 2 275 San Brownadino 275 Whitegirl 276 Tokyo Pink 277 Iron Works Brasil 281 Vermelho 281 Pink 281 Citrus 282 Amarelo Canario 283 Amarelo Fluor 285 Verde Claro 286 Azul Royal 288 Magenta 288 Lilas Claro 288 Flying Tigers 290 Salmon Pink 290 Pink Red 290 Reds 291 Orange Red and Orange 291 Yellows 293 Greens 294 Blues 294 Purple and Violet 294 Dark Brown and Light Chocolate 294 Skin Tone 296 White 296 Results: Pigskin 296

Contents

xi

Section IV FURTHER STUDIES AND CONCLUSIONS

11

Current Status and Future Work Scientific Inquiries Manufacture and Distribution Legislation and Regulation Concerning Tattooing

305 305 309 314

References 317 Index 353

Preface

A few years ago, I engaged in the scientific inquiry regarding the chemical composition of modern tattoo inks. This study, the focus of my doctoral research, led me beyond experimentation into an attempt to trace the evolutionary history of tattoo inks and pigments over time. The study also led to tracing the role of tattoos and tattooing in the criminal justice system, specifically with regard to medico-legal and forensic investigations. It became apparent that there is a need for a body of literature that should adequately cover the subject of tattooing and its role in criminal investigations completely, and in one volume. While literature on tattoos and tattooing is somewhat vast, references to the chemical compositions and preparations of tattoo ink and the resultant tattoos within these works is sparse. Most texts are either picture books of tattoos from a variety of tattooists while others ponder the social and cultural significance of the meaning and semiotics of tattoos. As such, it seemed that a more comprehensive approach was needed to bring together the hard-to-find texts, random papers in scientific journals, and the sporadic sentences lost within historical, anthropological, criminological, and scientific treatises. It should be noted that this work may not be exhaustive and that many historical records have no references other than the observations and experiences of the author, especially in those instances of nonscientific endeavors. In many instances, the mention of tattoo ink composition is a vague sentence in a text spanning several hundred pages. However, during the review of the literature, consistency in reporting along with cross-referencing the reports and their dates with those of pigment availability and production helped to form a clearer and more reliable evolutionary path. This book is not meant solely for forensic scientists and medicolegal investigators; it is intended to reach a wider audience, including scientists, medical professionals, anthropologists, historians, criminologists, tattoo artists, and tattoo aficionados as well as the layperson having a general interest in tattooing and/or forensic endeavors. Section I focuses on the historical perspective—the introduction and evolution of technique, the modification and removal methods, and the role of tattoos in criminology and criminal investigation. Section II focuses on the chemistry and science of tattoo inks— the general composition, the evolution of chemical composition from ancient to modern times, and the variety of pigmented materials that were used for xiii

xiv

Preface

tattooing. Section III consists of the analysis and results of the chemical analysis of modern tattoo inks, which is based on microscopic and spectroscopic examinations. Section IV evaluates the current status of tattoos and tattooing and proposes future work in the discipline. I have been lucky enough to have the support of many individuals from the initial development of this as a research endeavor to what it has become presently. I would like to acknowledge my research mentors Thomas A. Kubic, Marco Leona, and John Lombardi. I would also like to acknowledge my family, friends, and colleagues, specifically Larry Sullivan and MarieHelen Maras—thank you.

Author

Michelle D. Miranda earned a PhD in criminal justice, forensic science concentration, from the Graduate Center of the City University of New York; an MS in forensic science from John Jay College of Criminal Justice (the City University of New York); an MPhil in criminal justice from the Graduate Center of the City University of New York; and a BS in biology from Manhattan College. Dr. Miranda is a diplomate with the American Board of Criminalistics and a member of the American Academy of Forensic Sciences. Dr. Miranda worked as a criminalist in the Trace Evidence Analysis Unit of the New York City Police Department Crime Lab, and as both a medical photographer and a death investigator for regional Medical Examiner’s Offices in New York State. She is an adjunct assistant professor at John Jay College of Criminal Justice and is currently employed as an assistant professor in the Department of Security Systems and Law Enforcement Technology at Farmingdale State College of the State University of New York.

xv

Introduction

The interest in and the study of tattoos and tattooing has existed for centuries. Although the interest has waxed and waned over time, it has spanned multiple disciplines from anthropology and archeology to criminology and forensic science to cultural heritage and medical sciences. The focus of the historical literature has varied over time, with research addressing such topics as symbolism and semiotics, social stratification, criminal behavior and punishment methods, religious and medical trends, and meaning and perception. Tattoos and tattooing are perhaps best described as enigmatic, where many disciplines have weighed in on the history, meaning, and perception, yet no interpretation has captured an all-encompassing, universally accepted understanding of the tattoo. Perhaps this task is futile; there will always be a subjective element to the tattoo which will always open to interpretation by the wearer, the observer, and the researcher. It is proposed that the focus of the study of tattoos and tattooing should undergo another paradigm shift toward science, specifically, forensic science. Although this shift is by no means novel, it will provide an objective way to understand tattooing as it relates to identification (as opposed to the more standard behavioral and psychological approaches, which seek to understand identity in a more subjective manner). In order to understand tattooing and to demonstrate the need for the objective, scientific analysis to form the standard for evaluating tattooing, it is essential to track the history of tattooing with a focus on the scientific aspect of the process; namely, the composition and chemistry of tattoo ink throughout history. In addition, tracking history is essential to demonstrate the rise and fall of the subjective interpretations that have spanned many disciplines. Although each discipline’s approach has been paramount in understanding tattooing, it will be demonstrated that the most reliable interpretations stem from the medico-legal and forensic sciences in which objective analysis through experimentation has been applied. The process of tattooing has a vast and varying history, mostly passed on orally. These traditions were not always reported based on personal experience, but on observation, speculation, and stories that had been passed down over time; generally, reports on tattooing were described as more anecdotal than scientific. While this oral tradition has enabled the process to remain secretive, which at times was the desired effect of the storyteller, the oral tradition has resulted in broken links, embellishments, inaccurate accounts xvii

xviii

Introduction

of the process and methodology of tattooing, as well as the misappropriation of credit for skill and the development of the techniques and tools that improved upon the tattooing process. Stonehouse said it best, “(a)s is so often the case with traditions that evolve on the periphery of mainstream culture, tattooing in America has suffered from the vagaries of oral history. Stories traded between tattooists and the cloudy reminiscences of customers and family are typically laced with hyperbole, misinformation and legend” (Reiter, 2011, p. 1). Although the historical literature specifically addressing tattoos and tattooing has provided a backbone of knowledge on the subject, it is apparent that the history of tattoos and tattooing is incomplete. Whenever researchers found tattoos to be relevant to their discipline, there would be a proliferation in the literature. Interest would ebb and flow over time and could be correlated with the frequency of publications relating to tattoos and tattooing. Tattoos would be forgotten until there was renewed interest, usually with researchers of alternate disciplines. For example, the “discovery” of tattoos at the time of exploration produced a variety of interpretation and description followed by a decrease in interest beyond reporting the findings of various cultures encountered during seafaring expeditions. Superimposed on this bell curve was interest of the criminologists, who used tattoos to shape their ideas of social theory and criminal behavior. Current literature has been aimed at studying the dermatological and medical concerns of tattooing; namely, the harmful effects of synthetic pigments embedded in the skin and reliable methods of tattoo removal. One facet remains clear; of all interpretations including tradition, status, and deviance, the concept of identification has remained consistent since the first reporting of tattoos to the present day. It is this concept of identification that draws interest in tattoos, and within the forensic science framework, identification can lead to individualization, or a uniqueness that is characteristic of forensic science endeavors. Scientific inquiry can be applied in an effort to add an objective component to the interpretation, identification, and individualization of tattoos and tattoo inks. Accordingly, with increased understanding of the science and chemistry of tattooing, tattoos can become a more reliable tool in forensic investigations and other matters of legal significance.

Tattooing History

I

Tattoos and Tattooing

1

From 1768 to 1771, the H.M.S. Bark Endeavour traveled on its first voyage. On the ship was explorer Captain James Cook and naturalist and historian Joseph Banks. This voyage took the crew to the South Sea Islands in the Pacific, which included Polynesia, Micronesia, and Melanesia; islands within the triangle of Australia, New Zealand, and Hawaii. During the voyage, Cook maintained journals, logs, maps, charts, books, and portraits docu­ menting his explorations, observations, and discoveries. Banks observed and collected plants and animals as well as investigated and documented the cus­ toms and languages of the natives. It was during this voyage that Cook docu­ mented the tattoo, giving him the credit for introducing the word “tattoo” into the English language. While in the Tahitian Islands in 1769, Cook wrote, “[b]oth sexes paint their bodys Tattow as it is called in their language; this is done by inlaying the colour of black under their skins in such a manner to be indelible…” (Price, 1958, p. 37). While traveling through the South Sea Islands, Banks wrote, “… I shall now mention their methods of painting their bodies, or tattow as it is called in their language…” He echoed Cook’s comments and added, “[t]he colour they use is a lamp black prepared from the smoke of a kind of oily nut used by them instead of candles. This is kept in coconut shells and occasion­ ally mixed with water for use” (Hooker, 1896, p. 128). The exact origin or “discovery” of tattooing cannot be pinpointed; whether accidental or purposeful, at some point it became apparent that by placing certain pigments underneath the skin and at a certain depth, the ­pigment would remain within the tissue leaving a permanent or semiper­ manent mark. An accident raised as an art, developed and perfected through centuries of use… Whatever scientists may say or deny about the origin of tattooing, the practitioner believes that its discovery was made when a wounded savage, rolling on the ground, happened to come in contact with some burned coal. This coal, getting into the fresh cut in the body, left a blue-black mark when the wound was healed. The savage thereupon adopted the method of filling a burned or cut outline with color to make a design … (Rich, 1930, p. 118).

3

4

Forensic Analysis of Tattoos and Tattoo Inks

Terminology and Technique The process of skin pigmentation, or “cutaneous embellishment” as coined by Bowers (1915, p. 361), was subject to a variety of terminology based on cultural and reporters’ interpretation. It was not uncommon for those reporting on the process to alternate terms throughout their documentation. Some common terms used for documenting tattoos and the process of tattooing included painting, staining, tinting, branding, carving, stigmata, inscription (inscrib­ ing), marking, and others, in which the most interchanged words appear to be painting (staining), tattooing (tinting), cicatrization (or scarification), and branding (which incorporated heat and burning). In addition to these key terms, Fleming adds, “‘[l]isting’, ‘rasing’, ‘pricking’, ‘pinking’, and ‘pouncing’ are the interlinked English terms for tattooing before the middle of the eigh­ teenth century”* (Fleming, 2000, p. 69). In some historical literature, no clear distinction could be drawn between introduction of pigment onto the skin and introduction of the pigment into the skin, in which the former would be temporary and the latter would be permanent or semipermanent (meaning that the effect was intended to be permanent, but the type of pigment used or depth of insertion of the pigment would often result in degradation of the tat­ too over time). In instances where there was a distinction between temporary or permanent, there was often ambiguity between the methods by which these permanent marks were made, and terms such as tattooing and scarification being used interchangeably. In Hambly’s 1925 book, The History of Tattooing, which is believed to be one of the most comprehensive texts on the subject, he acknowledges that “the connection between painting, scarification, and puncture tattoo is difficult to unravel” (Hambly, 1925, p. 121). Bulwer also uses different terminology throughout his seventeenth century text, such as burn (stigmatize), brand, mark[e], paint, spot, stain, dye, color, illustrate, cut, gash, pinck, and deform. In addition to the notes of painting and marking, Bulwer also comments on piercing, cutting (“wound,” “tear[e]s,” and “incisions”), and branding, but routinely distinguishes between the intended temporary and permanent nature of these various techniques. Interestingly, he often uses the term deform when describing the techniques women use painting their faces for vanity and cosmetic purposes. Temporary decorations to the skin were often referred to as painting. In these instances, the introduction of pigment was on the surface of the skin *

Fleming adds, “to pounce may be to bruise, puncture, emboss or engrave … pinking is the cutting out of holes … a list or race is a slit or scratch, a cut that marks … to rase is also to remove by scraping or rasping, to erase.” (Fleming, 2000, p. 69). It is clear that these terms can be used interchangeably with the methods of tattooing, scarification, cicatrization, and branding, adding to the confusion when interpreting and documenting the actual resultant mark. This is especially apparent prior to Cook coining the term tattoo in the late 1700s.

Tattoos and Tattooing

5

with the intention of removal. This is likely to be the first form of marking the body that was employed by many, if not all, cultures that practiced tattooing. Evidence of body painting was reported in the forms of ritual body paint­ ing, cosmetics, and teeth blackening. Reports of body painting ranged from the use of woad (Isatis tinctoria) to accounts of natives rubbing earth, plant material, and other natural pigments onto their bodies and faces. Permanent decorations included scarification and tattooing. Scarification is characterized by deep wounding of the skin that may be fol­ lowed by the introduction of pigments within the skin, resulting in char­ acteristic, raised scars with a three-dimensional appearance. The term scarification was broad in that it included any instances of cutting, carving, or burning the skin to produce a scar. Branding and burning were used to describe those scars that resulted from the application of heat or fire. It has been reported that designs would be placed on the skin using gunpow­ der, which was subsequently lit when the design was finished. This method would open up the tissue by the burning action, and the deposited burned gunpowder would remain in the tissue as it healed. According to a report in 1887, a decoration was made by placing little piles of touch wood on the skin in circular heaps which were ignited (Hambly, 1925, p. 200). This, much like the gunpowder tattoo would serve to expose the deeper layers of skin to enable the resultant soot to embed itself within these layers. Subsequent healing would result in permanent, pigmented scars. Cicatrization is the cutting of the flesh followed by the insertion of pigments. The tissue would be cut or burned to produce an opening and pigments would be rubbed into the wound to facilitate the healing process. In some instances, purposeful irritation, as during punishment or rituals, would be the reason for rub­ bing in pigments; this was done to prevent healing and enhance scar tissue. Substances that were placed into the wound included charcoal, woodash, gunpowder (Hambly, 1925, p.  182), and earth (Van Dinter, 2005, p. 249). The resultant pigmented, raised scar is commonly referred to as a keloid. Whether by accident or through experimentation, it was discovered that by placing pigment into the skin, one could create an indelible mark that would preclude the need to constantly reapply pigments that were routinely applied for ceremony or cosmetic purposes. It is from here that we derive the concept of the tattoo and the method of tattooing. Tattooing is the process of puncturing the skin and introducing pig­ ments within the skin such that the pigment appears within or under the skin. The ink is often a mixture of colored, powdered pigmented material, and a liquid vehicle for facilitating the transfer of the pigment from the nee­ dle into the tissue. The tattoo itself is the indelible design that remains in the skin after completion of the tattooing process. The process of tattooing is characterized by placing the pigment deep into the dermis. By understand­ ing the mechanism of deposition of tattoo pigments within the tissue and

6

Forensic Analysis of Tattoos and Tattoo Inks

the subsequent retention, much can be understood about the nature of the tattoo. The human skin is described as having two major layers, the collagencontaining dermis, or inner layer, which is between 1 and 4 mm thick, and the keratin-rich epidermis, or outer layer, which is typically ~40 µm thick but thicker in areas like the palms of the hands and soles of the feet. Tattoo pigment particles are embedded within the dermal layer of the human skin. In his article in 1991, Sperry provided a detailed account of the tattooing process with regard to ink deposition and retention into the tissue. The needle penetrates through the epidermis and just into the papillary and reticular dermis, but no deeper; this depth is between 1 and 2 millimeters. During the tattoo process, the pigment is deposited along the length of the needle track throughout the epidermis and any superficial dermal layers, but only the pigment left within the dermis will permanently remain, making the final tattoo. As the tissue heals, the superficial epidermal layers peel away, leaving behind the deeper, regenerative basal epidermal layers. Eventually, by sloughing cellular layers during healing, all the pigmented layers of the epidermis are removed with the exception of the dermis. Over time, the epi­ dermis regenerates, and the epidermal layers grow back to their usual thick­ ness over the pigmented dermal layer. Consequently, the body will react to the foreign pigment particles that have been introduced; the pigment particles are assimilated by dermal macrophages, which slowly carry them into the regional lymphatics and thus to the corresponding draining lymph nodes. The macrophages also engulf pigment granules and then migrate short distances within the dermis … in which the majority of pigments will be assimilated by the macrophages, with unassimilated pigment granules remaining within dermal loose fibrous connective tissue between collagen bundles. The effects of healing exhibited by the diffusion of light by the reformed epidermal layers and subsequent pigment migration result in a tattoo that appears smooth, diffuse, and hazy. As such, an individual examining a tattoo that has healed and aged will often describe the tattoo as appearing faded (Sperry, 1991, p. 7).

Methods of inserting the pigment into the skin include sewing and pricking. The sewing technique was done by dipping thread into the pigment or ink and, using a needle to perforate the skin, pulling the thread through the skin so that the pigment is deposited as the thread is pulled through. This method would leave lined patterns within the skin. From a tattoo session observed by Otto Geist during his travels to Alaska from 1927 to 1934, “[o]ne inserts a thread through the eye of a bone or steel needle, and lets the thread soak itself with ink. Ink consists of soot, urine and graphite… [b]y pierc­ ing the needle through the upper layers of the skin, identical to embroider­ ing, one pulls the pigmented thread through the skin” (Schiffmacher, 2010, p. 140). Pricking methods included puncturing the skin and introducing the pigment into the punctured area. The pricking techniques varied based upon how the pigment was introduced into the skin. The pigment could be placed

Tattoos and Tattooing

7

directly onto a sharpened tool that was then pressed into the skin by hand or with a mallet; the ink could be placed onto the skin and then a sharpened tool was pressed into the skin; the skin could be punctured or cut first and then the pigment rubbed into the wounds; or the skin could be punctured or cut first and then the pigment could be placed into the skin by a “fumigation” method. In the latter technique, upon puncturing the skin, a carbon-based material was burned so that the smoke would leave carbonaceous residues deposited on the skin’s surface and within the punctures. In instances where the ink was placed on the skin first prior to the puncturing with a sharpened tool, the tattooer was able to trace out the design first. Woodblocks and carv­ ings of images were created to “stamp” the design onto the skin. These wood­ blocks could also be made to have sharpened projections in order to puncture the design into the skin first so that the ink could simply be rubbed into the resultant wounds. In some instances, the method of tattooing was recorded by the researcher when the tattooed individual was able to be interviewed about the nature and origin of the designs on his skin. The classification of the operative methods of tattooing employed by Lacassagne during his extensive research included the categories of: puncture tattoo, scarification, cicatrization/scarring, ulcer­ ation/burning/budding, sub-epidermal, and methods that were a combina­ tion of the aforementioned methods (Lacassagne and Magitot, 1886, p. 103). The tools employed for puncturing the skin have varied over time. The earliest forms of puncture tattoo included the use of a single sharpened needle pressed forcefully into the skin or with the assistance of a tool that could be used to insert the needle into the skin, such as a stone or a mallet (sometimes referred to as “tapping”). Over time, these tools evolved from having a single point to having several finer points oriented in different shapes, depending on the desired effect. For example, more teeth created a thicker outline, and even more teeth could make shading or coloring a larger area quicker. The tools were made of sharpened animal, fish or bird bones, antlers, teeth, wood, or shells. As tattooing spread from isolated regions and through exchange with explorers, the use of knitting, darning, and sewing needles, which could be made of ivory or steel, became more common. Finally, the introduction of the tattoo machine changed the process of tattooing significantly. While technology has advanced, it is not uncommon to find tattooers still using the original, primitive tools to apply tattoos. Renewed interest in tattooing has resulted in the use of the older, traditional methods that were more common in places such as Japan and the South Sea Islands, specifically inserting the pigment into the skin without the use of a tattoo machine, but instead with a sharpened object which was forcibly inserted into the skin by manual pres­ sure (Figure 1.1) with the use of a mallet-like tool. Modern intradermal tattoo types include amateur tattoos (also called street tattoos or prison tattoos), which are usually homemade inks that are

8

Forensic Analysis of Tattoos and Tattoo Inks

Figure 1.1  Tattoo artist incorporating ancient techniques into his tattooing

practice. The artist is inserting pigment into the skin using a long wooden stick with needle-like projections at one end. By applying substantial force, the artist is manually inserting the tattoo ink into the skin.

tattooed by a nonprofessional. These tattoos are often described as lacking in artistic detail and are usually monochromatic, uneven in color distribution, and are not deep within the layers of the skin. A wide variety of materials may be used to make the ink and the tattooing implements commonly used in amateur tattooing. In contrast, professional tattoos are generated using higher quality inks and pigments, and are done with either a tattoo machine (modern) or tattooing implements according to cultural traditions. Two additional tattoo types are medical tattoos and cosmetic tattoos, the latter used for permanent makeup, tattoo cover-ups, and instances of plastic and reconstructive efforts. Medical and cosmetic tattoo inks are usually neutral and represent skin tones, typically ranging in shades of whites, beiges, pinks, browns, and blacks. In instances of permanent makeup, cosmetic tattoo col­ ors include a wider range of options in order to be used for lip liner, lipstick, eyeliner, and blush. A fifth type of tattoo is described as the traumatic tattoo, pigmentation under the skin that generally results from the embedding of dirt and rocks, gunpowder, fireworks and explosives, or other debris beneath the skin and are usually the result of some type of accident or unintentional method of insertion. These types of tattooing are not typically characterized by the introduction and retention of colored pigments into the skin. A com­ mon example of a simple traumatic tattoo is the accidental embedding of graphite from a pencil into an individual.

Tattoos and Tattooing

9

Professional tattoos, while considered to be of higher quality when compared to amateur tattoos, have experienced an evolution of tools and techniques within their own class. The primary components incorporated into professional tattoos can be broken into three main categories: tattoo machines (noting that some professional tattooers employed needles prior to the introduction of the tattoo machine and some still do today to maintain the traditional method), designs, and pigments. Perhaps the most substantial development in tattooing was the intro­ duction of the tattoo machine. Credit for the first patented tattoo machine is given to Samuel O’Reilly, who patented it in 1891. This Tattooing Machine was based on the 1877 Stencil Pen patent by Thomas Edison. Edison’s improvement on the Stencil Pen was to make the pen actuated by the intro­ duction of an electromagnet and use of electricity in order to cause the pen to vibrate rapidly in succession. This improvement was intended to speed up the printing process by increasing the rate of perforating paper (US Patent No. 196,747). O’Reilly’s patent modified the perforating instrument in both structure and design for the purpose of introducing ink into the perforations made into the skin. The design incorporated a tubular ink res­ ervoir, perforating needles that could be interchanged to vary the number of needles constituting the perforating instrument, a gauge to regulate the depth at which the needles penetrate into the skin and an electromotor (US Patent No. 464,801). The introduction of the tattoo machine enabled tattoo artists to work faster, cleaner, and more efficiently. The increased speed and depth control also reduced the pain experienced by the individual being tattooed. Several variants of the tattoo machine were developed after its introduction (Figure 1.2). Sutherland MacDonald is credited with develop­ ing and patenting the first tattoo machine in Great Britain, which he called the Electric Pen for Tattooing (sic.). This design was more consistent with a spring actuated pen with the pigment placed in the tip of the needle (GB Patent No. 189403035). Charles Wagner patented his improved Tattooing Device in 1904 in which he “produced an electrically operated device which embodies certain features of novel and advantageous construction…” (Wagner, 1904, p. 1). Wagner’s design was intended to increase stability when tattooing as well as make the device more user-friendly and easier for the operator to adjust (US Patent No. 768,413). Percy Waters patented the Electronic Tattooing Device in 1929 in which he describes his improvement as “peculiar and novel construction” (Waters, 1929, p. 1). Waters focused his design around an L-shaped metallic frame with secured electromagnets (US Patent No. 1,724,812). An additional noteworthy patent is the Electrical Marking Device, patented in 1979 by Carol Nightingale, which once again improved on the original tattoo machine in an effort to increase precision, operator modification, and functionality of the instrument (US Patent No. 4,159,659).

10

Forensic Analysis of Tattoos and Tattoo Inks

Edison, 1877

Wagner, 1904

O’Reilly, 1891

Waters, 1929

MacDonald, 1894

Nightingale, 1979

Figure 1.2  Early tattoo machine designs.

Since then, various machine designs and modifications have been devel­ oped and manufactured, with many of the same features of earlier models being the template for these modifications (Figure 1.3). Table 1.1 lists various tattoo machines as well as devices that were the basis for later tattoo machine designs, including writing instruments and surgical tools. The needles employed with a tattoo machine can be an individual or grouped, and sit within the tubes of the machine. The perforating tool, or needle portion of the machine, can be interchanged so that the tattoo artist can use one single needle or multiple needles (Figure 1.4). The single needle is often used for fine details and outlining while multiple needles are used for filling, shading, and coloring the design. Modern liner needles consist of one, three, or more needles where shaders are five or more needles. Configurations vary with regard to needle orientation as well as individual needle shape.

Tattoos and Tattooing

11

Front standoff assembly Clip cord attaches to machine Nylon screw

Front spring

Armature bar RCA or unicord adapter

O-ring Back spring

Front coil Back coil

Rear standoff

Chuck screw Wingnut

Recessed plastic washer behind screws insulates frame Nipple/grommet Needle bar Rubber bands Chuck

Plastic washer Frame insulates frame

Nylon washer insulator Solder lug bent to hold rubber bands

Contact screw

Capacitor

Tube Grip

O-ring Back spring

Front spring

Figure 1.3  Modern tattoo machine, assembly diagram. (Courtesy of Westley Wood, President, Unimax Supply Company. Unimax Supply Company 2013 Catalog, p. 41.)

Needles can be oriented straight (flat tip), alternating (magnum), triangular, polygonal, or circular and the tips of multiple needle setups can be straight or curved (bugpin). Tattoo designs can be generated in various ways; the designs are usually predrawn and simply applied to the skin, or the design is drawn on the cus­ tomers freehand. Flash is the premade design sheets that are usually found on the walls of the tattoo parlor. These designs can be hand drawn and colored by the tattoo artist or are often mass produced and distributed to various tat­ too parlors for display (Figure 1.5). The purpose is to provide the customer with a selection of designs for their consideration. In the past, it was also a way that tattoo artists could control their offerings and limit their selec­ tions, which enabled them to work quickly and robotically—a limited series of designs could be applied in rapid succession without much detail or devia­ tion from the original design. While this could limit the artistic freedom of the tattooer, it enabled him to work with more clients thereby increasing his profits. Standard tattoo flash was often composed of sailor-themed designs such as anchors, ships, hearts, roses, daggers, skulls, military insignias, pinup girls, panthers, eagles, and so on (Figure 1.6). In a short time, a sailor at port could come into the shop, point out the design he desired, pay for the tattoo, and the tattooer could transfer the design to his skin and commence tattooing. The limited selection of ink colors would also limit the time it took to complete the overall tattoo. While these were efficient means of tattooing a large number of customers in a short period and generating revenue, it also

12

Forensic Analysis of Tattoos and Tattoo Inks

Table 1.1  Various Tattoo Machine Designs and Modifications, Including Patent Numbers and Year of Patent Year

U.S. Pat No.

Inventor

Title

1860 1877 1878 1878 1879 1884

28,697 196,747 203,329 205,370 216,086 304,613

Stauch Edison Edison Edison Gunning and Weiland Carey

1891 1892 1892 1894 1900 1904 1905 1907 1909 1929 1930 1930 1932 1932 1938 1938 1939 1941 1943 1950

464,801 473,207 485,767 516,212 11,849 768,413 792,836 839,888 917,146 1,724,812 1,767,469 1,781,362 1,851,672 1,865,610 2,126,777 2,140,409 2,151,274 2,239,761 2,307,424 2,524,636

O’Reilly Carey Lewis Lewis Gibson Wagner Loveless Pryor Ramsay and Brown Waters Metzner Brigida Ker Blair Holt Sterling Hindman Stone Savage Preis et al.

1952

2,588,623

Eliscu et al.

1952 1956 1957 1957 1958

2,593,110 2,754,818 2,805,475 2,807,236 2,840,076

Crane et al. Scherer Adams Wolf Robbins

1958

2,858,703

Willcox

1959 1967

3,026,847 3,297,003

Anderson, Jr. Benson

Scarificator Stencil pen Perforating pen Pneumatic stencil pen Pulsating stencil pen Apparatus for producing manuscript matter in multiple Tattooing machine Manifolding pen Electric perforating pen Electric perforating pen Branding composition Tattooing device Dental obtunder Stencil perforating device Perforating machine Electric tattooing device Manifolding device Electrolysis device Animal marking tool Art and apparatus for indelible marking Tattoo marker Vaccinator Rotary tool Branding tool Paper cutting device Cutter for pantograph engraving machines Surgical instrument for intradermal injection of fluids Nose tattooing device for cattle Hypo jet injector Fine line engraving tool for map making Drawing device for aerial photographs Surgical instruments for intradermal injection of fluids Power-driven hand unit for rotary and reciprocating tools Rotary electric pencil and rack Pencil or pen with a moving point (Continued)

Tattoos and Tattooing

13

Table 1.1 (Continued)  Various Tattoo Machine Designs and Modifications, Including Patent Numbers and Year of Patent Year

U.S. Pat No.

Inventor

1968

3,379,176

Propst

1970 1972

3,509,786 3,633,584

Buttner Farrell

1972 1975

3,688,764 3,905,371

Reed Stickl et al.

1976

3,997,972

Jaunarajs

1977 1977 1979 1979

4,031,783 4,037,283 4,159,659 4,170,234

Paul et al. Moisiuk Nightingale Graham

1980 1980

4,204,438 4,214,490

Binaris et al. Chizek

1980

4,230,001

Noll et al.

1981 1981 1983 1983 1984 1984

4,286,599 4,299,506 4,392,493 4,421,508 4,437,361 4,488,550

Hahn et al. Hashimoto Niemeijer Cohen Steckel et al. Niemeijer

1985

4,508,106

Angres

1985 1986

4,538,612 4,582,060

Patrick, Jr. Bailey

1987 1987 1987

4,644,952 4,665,912 4,671,277

Patipa et al. Burton Beuchat

1987 1988 1988 1988

4,715,853 4,719,825 4,771,660 4,719,825

Prindle LaHaye et al. Yacowitz LaHaye et al.

Title Livestock identification method and apparatus Writing instrument Method and means for marking animals for identification Intracutaneous injection system Inoculating tools for cutaneous vaccination using a dry vaccine Writing device employing writing tip mounted on flexible rotating shaft Tattoo etching machine Electric stippling device Electrical marking device System for use with electrosurgical pencil Tattooing device Method and means for placing an identification mark on a hog Tattooing pincers for marking ears of animals Marking device Mechanical pencil Tattooing apparatus Vacuum compression injector Tattooing gun Tattooing device and program carrier therefore Microsurgical method for applying permanent eyelid liner Skin preparation method and product Tattooing tool and needle assembly for use therein Surgical operating instrument Skin marking device Pigment dispenser and reservoir for a pigmentation system Back fill syringe Metering needle assembly Needle holder Metering needle assembly (Continued)

14

Forensic Analysis of Tattoos and Tattoo Inks

Table 1.1 (Continued)  Various Tattoo Machine Designs and Modifications, Including Patent Numbers and Year of Patent Year

U.S. Pat No.

Inventor

1989 1989 1989

4,796,624 4,798,582 4,862,772

Trott et al. Sarath et al. Piperato

1990 1991 1995

4,914,988 5,054,339 5,401,242

Chang Yacowitz Yacowitz

1995

5,472,449

Chou

1996 1998

5,551,319 5,776,158

Spaulding et al. Chou

2000 2004

6,033,421 6,689,095

Thiess et al. Garitano et al.

2004

2004/0158196

Garitano et al.

2005

2005/0028647

Sloan

2005 2012

2005/0277973 2012/0179134

Huang et al. Garitano et al.

Title Lashliner Needle cartridge Tamperproof, single use, disposable tattoo equipment Eyebrow tattoo machine Tattooing assembly Apparatus for injecting a substance into the skin Permanent pigment applicator having a detachable needle coupler Device for marking and article with ink Permanent pigment applicator having a detachable needle coupler Tattoo machine Needleless permanent makeup and tattoo device Needleless permanent makeup and tattoo device Method and apparatus for applying permanent ink Ultrasonic pigment device Needleless permanent makeup and tattoo device

Note: A review of tattoo patents indicates that modifications have continued from the 1800s to the present day. In addition, devices have varied in application, including writing imple­ ments, medical use (vaccinations) and marking animals.

meant that it was common to find tattooers with little to no artistic ability and limited knowledge of the art of tattooing. A 1930 New York Times article entitled Tattooing Enters on Machine Age describes the perils of the tattoo machine introduction; the availability of predrawn flash; and the concept of novice, unskilled tattooers, termed jag­ gers. According to the article, A jagger is one who does not work out his own designs. He does not even do free hand tattooing. He uses designs prepared by others and copied on cel­ luloid or tracing paper. He places the pattern on the skin of his client and by moving the tattooing needle along the edges of the pattern produces the desired outline. This he fills the spaces with the prescribed pigments. The jag­ ger is ignorant of color, form, proportion or perspective… (Rich, 1930, p. 118).

Transfer sheets consist of hand drawn designs that are applied to the skin in order to transfer the outline to the skin, that serves as a guide for the

Tattoos and Tattooing

15

CHEYENNE NEEDLE CARTRIDGES

Needles size

Diagram

Price

Needles size

Diagram

Price

1-liner

$28.63

5-flat

$29.93

3-liner

$29.28

9-flat

$31.24

5-liner

$29.92

13-flat

$31.88

5-liner BUGPIN

$29.92

5-magnum

$29.93

7-liner

$30.58

7-magnum

$30.58

7-liner BUGPIN

$30.58

7-magnum Soft-edge

$30.58

7-power

$30.58

9-magnum

$31.24

7-shader

$30.58

9-magnum Soft-edge BUGPIN

$31.24

9-liner

$31.24

9-magnum Soft-edge

$31.24

9-power

$31.24

13-magnum

$31.88

9-shader

$31.24

$31.88

11-liner

$31.88

13-magnum Soft-edge 13-magnum Soft-edge BUGPIN

11-shader

$31.88

15-magnum

$32.54

13-liner

$31.88

15-magnum Soft-edge

$32.54

13-shader

$31.88

17-magnum

$32.54

15-liner

$31.88

17-magnum Soft-edge

$32.54

15-shader

$31.88

23-magnum

$33.19

23-magnum Soft-edge

$33.19

27-magnum

$33.84

27-magnum Soft-edge

$33.84

$31.88

Figure 1.4  Needle cartridges. (Courtesy of Konrad Lackner, Cheyenne Tattoo Supply. Unimax Supply Company 2013 Catalog, p. 10.)

16

Forensic Analysis of Tattoos and Tattoo Inks

Figure 1.5  An example of a sheet of Zeis flash. This would typically be hung on

the wall so that shop patrons could easily see and choose a design. Some tattooers would color in the flash sheets prior to hanging them up.

Figure 1.6  Examples of tattoos obtained in New York City c. 1950. Designs

with military insignia, as well as pierced hearts and playing cards were common designs that were exhibited in tattoo flash hanging on parlor walls.

Tattoos and Tattooing

17

tattoo artist to trace. These designs can either be premade designs from flash or sketches prepared by the tattoo artist. The transfer sheets can be tracing paper, carbon paper, or clear acetate or plastic sheets. The transfer pigment can be placed on the outline and then the sheet containing the outline could be pressed into the skin, leaving an impression of the design behind. Cohen lists the pigments that were used for transferring the designs to the skin, both by stencil and freehand; these include fine carbon or lampblack, hectograph pencils which were carbon ink stencil pencils, black tattoo ink, mechanical drawing pencils which were made of graphite or methylene blue stain pow­ der dissolved in 10% or less alcohol (Cohen, 1994, p. 273). Modern tattooists employ transfer techniques of their artwork or draw the design on the skin freehand, but their stencils are often generated with stencil machines or ther­ mal copiers (Figures 1.7 through 1.9). Thermal copiers provide a rapid means of reproducing a drawing or design from paper to an inked sheet that can be easily transferred to the skin. The temporary design affords an opportunity for the tattoo artist and the patron to review the design and its placement and allows for modification, relocation, or removal. The tattoo artist also has the ability to copy designs and enlarge or shrink a design to meet the needs of the client.

Figure 1.7  Transfer of tattoo design to the skin followed by outlining and shad-

ing with a tattoo machine. The design was drafted by the tattoo artist, scanned to thermal copier paper, and pressed against the skin to transfer the outline.

18

Forensic Analysis of Tattoos and Tattoo Inks

Figure 1.8  ​Tattoo design drawn freehand without the use of stencils. The tattoo was drawn with red and black Sharpie® markers.

The following “Thermal Machine Stencil Paper Instructions” describe the layers of the stencil paper for thermal machine use (2013 Unimax Supply Company Catalog, p. 81). Four layers including one protective onionskin layer: 1. The top layer is white. This is the layer that gets the image (on the underside of the layer). It feeds through the stencil machine with this side up. 2. Next layer is a thin brown sheet, loose (not bound in) to protect the purple coated layer during shipping and storage. Most users throw this layer away. 3. The “purple” layer (this is not carbon but the crystalline violet and caruba wax, nontoxic and safe for the skin). The purple coating is transferred to the back of the upper sheet (which when applied, comes out the right side up). 4. The bottom yellow sheet holds the original artwork in place when sending it through the machine. The artwork should be face up. Modern extradermal tattoos include henna tattoos (Figure 1.10) and “temporary” tattoos, premade design sheets that are commonly applied to

Tattoos and Tattooing

19

Figure 1.9 ​Basic stages of tattooing; design transfer (top right), outline and

black shading (bottom left), and color shading (bottom right). Notice the design transfer (top right) is characterized by the purple outline (tattoo template) from the crystalline violet/caruba wax layer of the thermal copier stencil paper.

Figure 1.10  Temporary henna tattoo. Note the color difference between the

henna (reddish brown) and the permanent tattoo of a heart on the ring finger (black).

20

Forensic Analysis of Tattoos and Tattoo Inks

the skin with water. These tattoos lie on the epidermal, superficial layer of skin, which makes them easily removed over time due to washing, abrasion, and photodecomposition.

Tattoo Prevalence and Interpretation Evidence of tattoos can be found in archaeological excavations as well as anthropological investigations and cultural heritage discoveries. Some dis­ coveries include structural drawings such as those found in houses, caves, and burial chambers; artwork such as figurines, statuettes, and sketches; and tools such as pigment bowls and needles. In some instances, designs found etched in pottery are similar to the designs portrayed on tattooed individu­ als. The best evidence of tattoos is found directly on mummified remains and preserved skin specimens. The most common examples of this include Ötzi, “the Iceman” (3350–3100 bc), and the buried remains of the Pazyryk. Ötzi, the Tyrolean Iceman, was discovered in 1991 in the Italian region of the Austrian–Italian Alps and believed to be aged approximately 5300 years. The tattoos visible on Ötzi were located on his lower back, his wrist, the rear lower portion of his legs, knees, and ankles. The designs were groups of tat­ tooed lines and crosses and are believed to be therapeutic in nature. While the various Pazyryk burial sites have been dated as far back as 500 bc, using radiocarbon dating methods, the burial sites containing tattooed remains are reported by Van Noten and Polosmak as dating from the fifth to the third century bc. A series of Pazyryk burial mounds were uncovered in the Altai Mountains; a region incorporating Russia, China, and Mongolia. Within these various burial grounds were well-preserved human remains with tat­ toos. The tattoos found on the Pazyryk remains were much more complex than those found on Ötzi; the blue designs are described as being totemic, mythological animals and likely indicative of social status. While extensive evidence exists concerning the presence of tattooing before the Common Era, Lobell and Powell assert that there is no evidence of tattooing 7000 years ago (Lobell and Powell, 2013, p. 41). Scientific studies of the tattoos found on mummified remains have been focused on dating the remains, genetics and deoxyribonucleic acid (DNA) analysis, surgical and therapeutic treatments, and cause and manner of death, while the anthropological aspect of the tattoos has focused on cultural meaning such as societal status, occupation, totemism, as well as ritual. Few scientific studies have reported on a detailed, comprehensive investigation into the chemical composition of the tattooed sites in an effort to determine the inks and pigments used to mark the individual. Since the introduction of the tattoo to the world, much time has been spent evaluating the meaning behind the tattoo—including the process, the

Tattoos and Tattooing

21

design selection, as well as the motivation to obtain an indelible mark within the skin. Generally speaking, the meanings are classified as being ornamen­ tation, disfigurement, or other. In the past, ornamentation included tattoos received before battle or hunting; for ritual, religious, or magical purposes such as protection or devotion; to define social status or totemism; or for identification within a group, such as members of the military, convicts or ancestry and familial relations. Disfigurement included instances of slav­ ery, punishment, or marks of criminal involvement. These tattoos ranged from lettering to emblems, proverbs, and phrases corresponding to owner­ ship or criminal act, and could often be found on faces, hands, and arms. Other meanings include a combination of ornamentation and disfigurement, behavioral or psychological motivations, medical purposes (i.e., cosmetic reconstructions), or for exhibition and entertainment purposes. In much of the historical literature, the focus was on documenting the tattoos characteristic to a particular region, culture, and/or class of people. In many instances, the documentation was sketches or tracings, sometimes accompanied by the textual description to note colors and physical charac­ teristics. It would not be uncommon during times of academic interest in tattooing to see literature documenting the physical features of tattoos with little to no interpretation of meaning or symbolism. On some occasions, the

Figure 1.11  Images from Bulwer’s 1653 text demonstrating the various markings found on different individuals from different regions.

22

Forensic Analysis of Tattoos and Tattoo Inks

tattooed individual would be asked about the meaning of or catalyst for his tattoo, which was noted in the description. John Bulwer published an account of tattooing practices in various regions in his 1653 text, Anthropometamorphasis: Man transform’d: or, the Artificiall Changling … (Figure 1.11). He writes of tattooing, The Virginian women pounce and rase their faces and whole bodies with a sharp iron, which makes a stamp[e] in curious knots, and draw[e]s the pro­ portions of fowl[e]s, fishes, or beasts; then with painting of sundry lively colors they rub into the stamp, which will never be taken away, because it is dried into the flesh. The Egyptian Moores … distaine their chins into knots, and flowers of blew, made by the pricking of the skin with needles, and rub­ bing it over with ink[e] and the juyce of a herb (p. 252) … They in the golden region of Coiba-Dites … they spare their own flesh, and mark[e] their slaves in the flesh after a strange manner, making holes in their faces, and sprinkling a powder thereon; they moisten the pounced place with a certain black, or red juyce, whose substance is in such tenacity … that it will never wear[e] away (p. 254)… In the Province of Cardandam … the men about their arm[e]s make lifts, pricking the places with needles, and putting therein a black indeleable (sic.) tincture … (p. 286)… The inhabitants of Mangi, in the East Indies … paint and embroider their skins with iron pens, putting indeliable (sic.) tinc­ ture thereinto… They of the Cape of Lopo Gonsalves … pincke their bodies … wherein they put certain grease mixed with colour red, made of red wood, much lighter than Brasil wood (p. 456).

Bulwer also makes references to what would likely be considered consis­ tent with the methods of scarification and cicatrization. The tattoo has undergone its largest interpretation with regard to mean­ ing, symbolism, and semiotics. Interpretations include cultural and religious meanings, including magic, mysticism, the supernatural, and devotion. The tattoo has been contextualized to the military, the penal system, and exhibitions such as the circus, sideshows, and museums. Tattoos have been linked to social status, with progressive shifts from the lower class, described as uncivilized, barbaric, and criminal, to the in-vogue trends of the upper classes. In philosophical and literary accounts, the tattoo has been concerned with the body and soul—the “self”—and has been linked to the perceptions and attitudes of both the tattooed and the observer. In the medical commu­ nity, tattoos have been explored with regard to disease and infection, allergic reactions, and removal methods. Tattoos have been evaluated with respect to their therapeutic uses (such as acupuncture) and have been employed in plastic and cosmetic surgical procedures. Perhaps one of the most wellknown explorations of the tattoo has been concerned with criminal, sexual, and psychiatric behavior and with the tattoo not as an ornament, but as a

Tattoos and Tattooing

23

pictograph in which tattooed individuals express their personality, affilia­ tions, and thoughts through the drawings and images within their skin. With regard to identification, the tattoo has played a substantial role throughout history for both individual identity, group identity, and cultural identity. Tattooing has been used as a form of punishment and as a method of identifying the criminal, the slave, and the soldier (Jones reports on the Greeks practice of tattooing almost exclusively in its punitive and degrad­ ing aspects, [Jones, 2000, p. 9]). As an identification tool, tattooing has also been used in cultural anthropology to associate members with their particu­ lar tribes and worshippers with their particular religious sect. Identification can be described as direct or indirect; the direct associations are those in which identification is intended, such as penal, military, religious, and gang affiliations. The indirect associations are those in which the identification is not the primary intention of the tattoo, such as the forensic identification of human remains. While it could be argued that the majority of individuals do not decide to get tattooed for the purpose of ensuring correct identifica­ tion of their remains in the event of a tragic accident, this was essentially the thought of many soldiers and sailors and the impetus for some of their tat­ toos. Presently, this is a trend among individuals in war zones and regions at high risk for terrorist activities. Tattooing has also found use among criminologists attempting to inter­ pret the behavior and psyche of man, specifically with regard to understand­ ing the criminal mind. In addition, the presence and interpretation of the tattoo have been applied to criminal investigations and has been the subject of the early literature in the discipline of police science. Tattoos eventually found a place as a tool for identification of individuals for forensic purposes, making their way into the courtroom as a substantial type of evidence.

Tattoos and Tattooing in Criminology and Criminal Investigations

2

Early criminological as well as anthropological research on tattoos and tattooing focused largely on the origins, meanings, and semiotics of the designs as well as what the designs could tell the researcher about the wearer. In the eighteenth and nineteenth centuries, tattoos were routinely examined, recorded, and cataloged by many medicolegal doctors, military, and prison physicians as well as law enforcement personnel. This lead to classifications and theories pertaining to the origin, methods, and prevalence of tattoos and tattooing, as well as the behavioral, social, and psychological traits of tattooed individuals, some of which were drafted by individuals with little to no scientific rigor; after all, many were simply tracing or freehand drawing the tattoo designs and providing tallies of which designs were more common than others. Many medical professionals weighed in on tattoos, from physicians to dermatologists, with a large portion of the literature being attributed to the physicians in either military or prison settings. While this was helpful in detailing and cataloging the tattoos found on individuals, most studies were limited to men that were either incarcerated, institutionalized, or serving in a branch of the military. Medical reports focused on transmission of disease (i.e., syphilis) and adverse skin reactions (allergies) as well as focusing on the lack of hygiene and unsanitary conditions employed in the procedure (e.g., the use of saliva to moisten needles or the use of urine to cleanse the area post-procedure). From a psychological perspective, Parry, echoed by other researchers, described the phenomenon as “subconscious sadism” and “forced idleness” (Parry, 1933b, p. 80).

Tattoos and Criminological Theories Tattooing has a place in early forms of law enforcement and punishment. Slaves, runaways, prisoners, captives, and criminals were among those individuals that would be marked, scarred, or branded to convey ownership or display evidence of their crimes. Gustafson describes, “those in power were well aware that the body can function as a permanently running advertisement of one’s guilt and subjugation.” (Gustafson, 2000, p. 24). In the Middle Ages, tattooing and branding with a hot iron were used for marking criminals, procedures also practiced in the British Army on Deserters and 25

26

Forensic Analysis of Tattoos and Tattoo Inks Bad Characters. Branding was abolished in the Army about 1720, but tattooing was retained with considerable ceremony … the disgraced soldier raised his left arm, the drum major jabbed the left side of his chest with an instrument consisting of a row of spikes forming a ‘D’ or a ‘B C.’ The drummer boy then handed him the gunpowder, which was rubbed into the wound. When it healed, the marks were indelible and assured their carrier heavy punishment for any future misdemeanor. Gunpowder was later replaced by a mixture of indigo and lamp black. Tattooing was abolished in the Army in 1869. (Bell, 1934, p. 256)

Tattoos and tattooing were topics discussed in the disciplines of criminology, science, and social theory, with many experts weighing in on the value of tattoos to their particular field of study. Caplan writes of “existing police sciences of investigation and a criminological science of identities” (Caplan, 2006, p. 338), and “the use of tattoos in criminal identification and individual identification” (Caplan, 2006, p. 339). The most well-known researcher of criminology and the criminal man and the correlation of tattoos and deviant behavior was Cesare Lombroso (1836–1909), a military physician in Italy who began his work by studying Italian soldiers and criminals. Lombroso believed in criminal atavism; the idea of man reverting to primitive savage behavior, which was exhibited in tattoos (Figure 2.1). According to Lombroso, “the most important reason for tattooing is atavism, and that other form of atavism called the traditionalism, both of which characterize primitive men and men living in a state of nature…” (Gibson and Rafter, 2006, p. 61). Lombroso established the idea that these pictographs were means of expression relating to religion, imitation, laziness, vanity, camaraderie and belonging, human passions and memories, and love and eroticism (Figure 2.2). He notes that the phenomenon of tattooing “occurs only among the lower classes—peasants, sailors, workers, shepherds, soldiers, and even more frequently among criminals” (Gibson and Rafter, 2006, p. 58). Lombroso wrote, “[g]reat care must be taken to ascertain whether the subject is tattooed, and if so, on what parts of his body. Tattooing often reveals obscenity, vindictiveness, cupidity, and other characteristics of the patient, besides furnishing his name or initials, that of his native town or village, and the symbol of the trade he refuses to reveal … sometimes such indications have been blurred or effaced…” (Lombroso, 2012, p. 112). With regard to the use of tattoos as a form of identification, he adds, “[t]he study of tattoos sometimes helps us track individuals to criminal organizations” (Gibson and Rafter, 2006, p. 59). “Even tattoos that do not seem to have anything criminal about them and resemble those of farmers, shepherds, and sailors from the same region can be useful to the legal system and forensic medicine: they may reveal an individual’s identity, his origins, and the important events in his life” (Gibson and Rafter, 2006, p. 60).

Tattoos and Tattooing in Criminology and Criminal Investigations Figure 2.1  Tattoo diagrams from Lombroso’s book, The Criminal Man (Special Collections, Lloyd Sealy Library, John Jay College 27

of Criminal Justice).

28

Forensic Analysis of Tattoos and Tattoo Inks

Figure 2.2  Diagrams from Lombroso’s text depicting tattoos of the Camorra (top) and tattoos of prostitutes (bottom) (Special Collections, Lloyd Sealy Library, John Jay College of Criminal Justice).

Tattoos and Tattooing in Criminology and Criminal Investigations

29

Havelock Ellis (1859–1939) doubted Lombroso’s theory of atavism and in 1901, he wrote, “[tattooing] is better described as survival” (Ellis, 1901, p. 196). According to Ellis, the greater numbers of tattooed criminals are naturally found among recidivists and instinctive criminals, especially, “those that have committed crimes against the person” (Ellis, 1901, p. 194). Regarding identification, Ellis adds, “[t]here is evidence that criminals frequently refrain from tattooing themselves because they know these marks form an easy method of recognition in the hands of the police” (Ellis, 1901, p. 194). Charles Goring (1870–1919) published a statistical study of physical features of convicts, which challenged Lombroso’s theories of a criminal type (which Lombroso described as “the born criminal”). Goring argued that, with regard to physical abnormalities, Lombroso’s conclusions were oversimplified, rushed, and based on generalizations of incomplete data; “…it is clear that the practice of tattooing cannot be such a peculiarly criminal characteristic as has been alleged” (Goring, 1913, p. 102)… furthermore, “…the statistical evidence before us is sufficient for an interim conclusion that although criminals, like the law abiding public, differ considerably in the extent to which they are tattooed, these differences have no special relation to criminal proclivity” (Goring, 1913, p. 104). Over time, Lombroso’s theories about the criminal man, in general, and with specific regard to tattoos, were considered invalid and unsubstantiated, although his theories remain an integral part of criminological studies. The study of tattoos and tattooing also extended deep into the psychological aspects of criminology. In his 1936 publication on criminological research trends, Monachesi wrote extensively of his interviews with Ottolenghi, as well as on Ottolenghi’s lectures and publications. Monachesi wrote that Ottolenghi believed that a criminal is a result of biological and social selection and that physical characteristics are indicative of psychological characteristics (Monachesi, 1936, p. 401). “According to Ottolenghi, it is possible to understand in part the psychological characteristics of an individual by noting the nature of the scars and tattoo marks on his body. He attaches special significance to tattoo marks because he believes that they have great value in giving knowledge about the morality, sensibility, and attitudes of the tattooed” (Monachesi, 1936, p. 402).

Tattoos and Forensic Investigations Sherlock Holmes’s quick eye took in my occupation, and he shook his head with a smile as he noticed my questioning glances. “Beyond the obvious facts that he has at some time done manual labor, that he takes snuff, that he is a Freemason, that he has been to China, and that he has done considerable amount of writing lately, I can deduce nothing else”

30

Forensic Analysis of Tattoos and Tattoo Inks Mr. Jabez Wilson started up in his chair, with his forefinger upon the paper, but his eyes upon his companion. “How in the name of good-fortune, did you know all that, Mr. Holmes?” he asked… “Well, but China?” “The fish that you have tattooed immediately above your right wrist could only have been done in China. I have made a small study of tattoo marks and have even contributed to the literature of the subject. That trick of staining the fish’s scales of a delicate pink is quite peculiar to China…” A. Conan Doyle The Red-Headed League

In the scientific disciplines of legal medicine, forensic science, and police science and criminal investigation, tattoo research focused on the identification of both living and deceased; identification of criminals as well as their associations and trades; and pigment retention, stability, and tattoo indelibility. “Medical and forensic interest in the anatomy of tattooing (from a medical, dermatological perspective) overlapped in the question of the tattoo’s permanence” (Caplan, 2006, p. 341). Ambrose Tardieu (1818–1879) stated that it is possible to determine identity based on the character of the pattern as well as determine the social status of the deceased since social classes had separate and distinct types of pictures marked on their skin. It was not uncommon for medical practitioners who had studied tattoos to be called upon to establish tattoos as relevant to an investigation or to resolve disputes pertaining to a tattoo’s persistence within human tissue, especially in a forensic context. In 1849 in Berlin, the headless body of a man was found on a riverbank. According to the report, “the head had been so much disfigured by the assassins that recognition was impossible” (Eve, 1857, p. 49). The subsequent report by the two physicians indicated that there were no cicatrices or tattoo marks present on the body. It was suspected that the body belonged to a tattooed cattle merchant named Gottlieb Ebermann, but the lack of tattoos on the remains challenged this assertion. As such, a physician by the name of Caspar, who had observed and interviewed tattooed soldiers, was called upon to address whether or not the tattoo marks could have been diminished over time. According to Casper’s observations, some tattoos were subjected to fading, others were partially effaced, and in some instances, completely obliterated. Perhaps more interesting than the expert report of Casper regarding tattoo persistence and the resultant death sentence of the suspect named Schall, is the subsequent challenge to the scientific rigor of the study as well as the weight of the evidence at trial that occurred in 1852. Dr. Chereau justly observes, respecting Caspar’s report, that it is not one which should influence a judicial decision, for it is not stated at what age, with what substance, and in what manner, the marks were produced … in the instances where there was complete obliteration. Are the men to be trusted? How many

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years elapsed before the marks became effaced? The question cannot be considered in any way satisfactorily settled as it now stands; indeed, Caspar’s assertions tend to raise doubts, which heretofore did not exist, upon a point that might be most important in a prisoner’s favor, viz. the persistence of these stains. There is evidence that the absorbent glands in the neighborhood of a tattoo mark become filled with pigment … We have no hesitation in expressing our opinion that Caspar’s report does not tend in any way to invalidate the statement that has heretofore been received in the courts of law—namely, that tattoo marks and cicatrices are indelible (Eve, 1857, p. 770).

Another well-known researcher that weighed in heavily on tattoos and tattooing was Alexander Lacassagne (1843–1924). Lacassagne was a French army surgeon and professor of medical jurisprudence of the Faculty of Medicine, Lyons. He believed that the phenomenon of tattooing was due to idleness and degeneration (Caplan, 2006, p. 347). In 1886, Lacassagne made several references to the pigments employed in tattooing based on his research [a]bout the coloring materials applied to tattoos, their number is infinite. Ancient writers speak of some black materials, certain juices of herbs, woad… Quite often, the coloring matter is united to an oily liquid (p. 104) … Pine charcoal, gunpowder, coal smoke produced by burning pine, mixed with fish oil or coconut, or sugar cane juice (p. 105) … [b]lack smoke produced by a fire in which we burn nuts … (p. 108) … [b]lue tattoos usually result from the use of carmine … (p. 105) … [i]n Europe, we find the largest varieties of substances. We note China ink, black smoke, indigo carmine, alkanet, vermilion, minium, turmeric, cinnabar, red ocher, black juice of gardenia (Ibid.) … In our country, that tattooers make use of China ink and vermilion, coal wood diluted in water, sometimes blue ink and Prussian blue and laundry blue rarely (p. 133).

Lacassagne kept meticulous records of his studies; research collections were obtained by tracing the tattoo designs of individuals and recording the following information on the back: reference number, first and last name, birthplace, profession and education, dates of tattoos (age), tattooing method used, number of (tattoo) sessions, duration of (tattoo) sessions, information about the tattooist, description of that tattoo, location of the tattoo, color(s), changes in coloration, inflammation, healing time, current state of the tattoo, fading, voluntary removal, covered up (tattooed over), morality of the tattooed individual, as well as any other relevant details (Lacassagne and Magitot, 1886, p. 133). He divided the tattoos into different categories: patriotic and religious, professional (occupational), inscriptions, military, metaphorical (pierced hearts, stars, anchors, intertwined hands, daggers, etc.), love and erotic, fancy, and historical (Lacassagne and Magitot, 1886, p. 134). In addition to recording the information from the military personnel he encountered, he also described the tattoos of the insane and criminals.

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With regard to personal identification, one of the first systems developed was anthropometry, a systematic process of measuring specific features of an individual in an effort to identify and classify criminals. This methodology, developed in the late 1800s by Alphonse Bertillon, kept records of the physical characteristics of the individual (eye color, hair color, ear and nose characteristics, scars and tattoos, etc.) as well as measurements of the head, fingers, foot, arms, and trunk along with a photograph of the individual. Although this system was used extensively by police agencies and law enforcement, measurement errors and variations, the subjective nature of evaluation of some physical features, and the ability of the criminal to modify some physical features decreased the discriminating power of the technique and eventually lead to a decline in its use. Morgan and Rushton note that, “[t]he need for … careful descriptions was partly because people were not what they seemed. On too many occasions, the person facing the authorities was not how they appeared at first glance, particularly with regard to gender…” (Morgan and Rushton, 2005, p. 39). As such, Bertillon was a bit more cautious with the indelibility of tattoos. In 1889, he noted, “[a] tattoo mark may always be worked over, and to a certain extent be obliterated” (Bertillon, 1893, p. 72)… “the consideration which ought to take precedence of all others in picking out the scars and marks to be noted is that of their duration and permanency; the worst mistake an observer can make is to note down as indelible an identifying mark which may disappear or be defaced” (Bertillon, 1893, p. 73). Shortly after that, the system of personal identification that gained a foothold in law enforcement was that of fingerprinting. Several individuals were involved in demonstrating the usefulness of fingerprints as a means of personal identification, including William Herschel, Henry Faulds, Edward Henry, and Francis Galton. In 1892, during his monumental study of fingerprints, Sir Francis Galton (1822–1911) compared prints to tattoos and concluded, “[t]here appear to be no external bodily characteristics, other than deep scars and tattoo marks, comparable in their persistence to these markings, whether they be on the finger, on other parts of the palmar surface of the hands or the sole of the foot” (Galton, 1892, p. 97). In his 1924 text, Criminal Investigation: A Practical Textbook for Magistrates, Police Officers and Lawyers, Hans Gross references tattoos as an investigative tool, discussing the determination of the age of a tattoo mark, determining if a tattoo was once present but has since disappeared based on skin surface features and examination of the lymph nodes, and evaluating the correlation between the tattoo design and trade of the tattooed individual (sailor, soldier, butcher, etc.). He notes, “tattooing that exists or which have existed in the bodies of living or dead persons may be very important in determining identity; they must, therefore, be examined and described in detail” (Gross, 1924, p. 112), as well as “let it also

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be stated that attention must be paid to tattooings which are no longer visible…”(Gross, 1924, p. 112).

Identification and Individualization The use of the tattoo to describe one’s identity in the psychological realm was commonplace, with the tattoo explaining delinquency, prostitution, criminal behavior, perversion, psychoses, and retardation. In some instances, the tattoos found themselves lending insight into physical identity. According to Edgerton and Dingman Let us conceive a set of self-identifications that tattooing may accomplish: It may demonstrate a relationship to a group or a category of people; It may indicate a relationship with another person; It may describe or name the self; It may communicate something about the self to the self in some private or magical fashion … So defined, these four categories are reasonably exhaustive although they are not mutually exclusive (Edgerton and Dingman, 1963, p. 145).

Over time, the reliability of tattoos as an identification technique subsided, especially in the shadow of newer forensic methods of identification and individualization. “As police techniques moved from observation to measurement, so the tattoo was left marooned, the ironic relic of a former state of surveillance and detection” (Caplan, 2006, p. 340). The increased reliability of scientific evidence such as fingerprints and biological fluids rendered identification by tattoos obsolete. Fingerprinting has been accepted as a reliable means of identification since the late 1800s and has only recently been scrutinized regarding its ability to be used as a true form of individualization. Forensic serology was another system of personal identification that became routinely employed in forensic laboratories and police investigations. Blood contains inherited factors, mostly proteins, which can be determined by blood grouping (also referred to as blood typing). The more factors identified the more serology approaches individualization, although individualization is considered not possible through blood typing. Theoretically, the more blood proteins identified in a sample, the smaller the pool of contributors. Forensic science disciplines benefit from the ability to rule out a possible contributor, so, although not individualizing, blood typing could be used as an exclusion tool. The most common blood group system is the ABO system, which is typically defined as an individual’s blood type. Additional systems include the Rh (this accounts for the “positive” or “negative” associated with an individual’s ABO blood type), MNS, Kell, Kidd, Lewis, and Duffy systems, among others.

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Forensic Analysis of Tattoos and Tattoo Inks

The technique credited with being the greatest advancement in the forensic sciences with regard to personal identification and the ability to individualize is forensic DNA (deoxyribonucleic acid; the primary hereditary material in living organisms) analysis, which has evolved since the technology to isolate and identify one’s “DNA fingerprint” was developed in the 1980s. Other methods of personal identification that have been either described as “approaching individualization” or as possessing the potential to individualize (one primary criticism is that these other methods often lack the necessary data sets and statistical support) and include palm prints, sole prints, voice prints, ear prints, lip prints, eye patterns (retina, iris), and vein patterns. One method of personal identification that was described as being individualizing but that has come under increasing scrutiny is that of bitemark analysis. Other methods that have been used for identification include radiological comparisons (dental x-rays, surgical x-rays, frontal sinuses, etc.) and identification and correlation of implants with serial numbers. Physical features (such as those used in anthropometry) are still of critical importance in the identification of individuals and human remains, especially in instances where identification of remains is still possible by visual means. It is standard practice for the medical examiner offices to conduct routine identification of a deceased individual by having family members either view the body directly (usually limited to the face) or view a photograph of the decedent. In many death investigations, an affirmative identification based on visual or photographic examination of the face and/or body, usually documented, is sufficient for identification (and thus individualization). Tattoos have recently shown a resurgence as an identification tool in both criminal investigations and death investigations. In addition, tattoos have been recently applied to advanced biometric technologies, with the development of databases to classify and archive tattoos and their links to possible gangs and terrorist groups (identification) as well as correlating the tattoos to a specific person (individualization). Historical practices indicate that tattoos have long been used as a tool to identify and individualize. Group association, social status, ranking, and affiliation with a particular sect were apparent in cultural groups through the amount, types, and locations of tattoos on an individual’s body. The presence of tattoos, or lack thereof, would indicate the rank of the individual, their role in the community, their age, accomplishments, prowess, marital status, and many other cultural facets of the tribe or group in question. An example of this can be seen in the Moko, or facial markings of the Maori. Tattoos are traditionally seen as a form of general ornamentation, which in some instances can provide individualization. The Moko pattern on the face of a Maori is considered unique to its wearer. Since the Maori could not sign legal documents, they would sketch their facial pattern (often from memory) onto a legal document, which would be considered as unique as a signature. During his

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travels, Banks reports on Amoca facial patterns, “… for of a hundred which at first sight would be judged to be exactly the same, no two on close examination prove alike, nor do I remember ever to have seen any two alike” (Banks, 1896, p. 232). Tattoos have also been a way to identify individuals who had been punished or incarcerated. The latter, sometimes referred to as prison tattoos, were not only made apparent by their traditional monotone (black) style lacking detail and artistic skill. Historically, the design, location, and symbolism depicted in these prison tattoos would also indicate rank, social status, sexual preference, racial, religious or gang affiliations, political beliefs, trade or skill, and so on. These types of tattoos were especially prevalent in Russian Gulags and were the focus of extensive study by prison wardens, guards, and medical personnel. Presently, prison tattoos are used by law enforcement to identify gang affiliation and criminal histories of convicts. In addition to tattoos identifying criminals and convicts as well as gang members and individuals affiliated with organized crime groups, they also identify members of the military and their specific branches of service (e.g., in the case of sailors, Naval tattoos), as well as religious affiliations (some individuals had religious tattoos that were specific for a pilgrimage to a religious location, place of worship, or a holy land). Other forms of identification tattoos were proposed and never implemented while others were adopted but did not endure over an extended period, falling out of favor and use for a variety of reasons. One proposal was made to have all married individuals tattooed so that their marital status can be made apparent visually and easily. Another proposal was to tattoo newborn babies in order to prevent loss, kidnapping, the switching of babies in the hospital, and to identify runaways. Other applications included the tattooing of animals in an effort to prevent kidnapping of farm animals, such as livestock and poultry and domesticated pets (i.e., canines). Zeis reports the use of animal tattooing among dogs, hens, alligators and reptiles, zoo animals, and fish. In a 1946 report in the Science News Letter, “The legendary monopoly of tattoos by sailors may be broken by sheep and horses with the report of successful experiments with colored tattooing to mark the animals” (n.a., 1946, p. 72). Accordingly, a chemist believing that successful identification in animal husbandry practices can be achieved by using color tattoo inks on the lip of the animals reported that blue and green ink can be used for permanent identification after use of black inks resulted in markings becoming illegible over time (n.a., 1946, p. 72). Tattoo inscriptions can be highly individualistic and can be used to facilitate identification in the case of emergencies or mass disasters. The design, color, and placement of tattoos lend themselves to uniqueness, and the presence of more than one tattoo on a body can increase the ability to individualize. In the military, many individuals tattoo their name, blood type (A, B,

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Forensic Analysis of Tattoos and Tattoo Inks

Girl (left) points to spot where TATTOO, designating blood type, might be placed. Chicago Civilian Defense Authorities have recommended identification system to aid in treatment of casualties in case of bombing attack. We have heard that Texas, New York, and other states are planning on adopting this method for walking blood banks.

Figure 2.3  Advertisement for tattooing of blood types, c. 1950s. (Zeis, 1968, p. 14).

O system, and Rh factor), social security number and religious affiliation on their bodies (Figure 2.3). At one time, it was proposed that all individuals, not just military personnel, should have their blood types tattooed on their body in case of a mass disaster. Although considered an older concept, it is common to find individuals currently serving in the military possessing a tattoo that serves to identify the service member in case of death or imprisonment while serving overseas; presently, this technique is seen increasingly more in war-torn countries and regions of conflict. A 2006 news article focused on the increasing prevalence of tattoos on Iraqis; specifically, the name, address, and phone number of the wearer placed in a region of the body in which torture is less likely to occur, thus reducing the chance of damaging or complete obliteration of the tattoo. The purpose of the tattoo is solely to serve as a way for friends and family

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members to identify the body, should the remains be discarded and subsequently discovered. That some Muslims are getting tattoos is an intimate reflection of national chaos, and an outward symbol of the inner turmoil the chaos has created. There’s nothing artful about these tattoos. The branding has the efficient look of a business card, written in clear, bland type. Officials at Baghdad’s morgue say they’ve used tattoos to identify bodies, but never one with a name and address. Police officers … [report] that they’ve encountered bodies with names and phone numbers tattooed on them … Whatever the extent of its use, the decision to tattoo reflects the country’s level of violence. It seems that anyone can be kidnapped and killed for any reason (Youssef, n.p.).

The article chronicles the possibility of individuals being kidnapped, tortured, killed, and subsequently dumped in another neighborhood, buried in a mass grave, or somehow otherwise ending up at the morgue. The possibilities of being the victim of a shooting or a detonated bomb are also contributors to the impetus to get a tattoo. In addition to civilians, the practice has become popular among police officers and national guardsmen in the region. An alternate option to tattooing individualizing marks using visible pigments is using materials that are not visible to the naked eye, but that are photoluminescent. In a 1944 article entitled Fluorochemistry in Military Science, De Ment reports [t]attooing has been employed as a tool for marking persons with serum sensitivity or diseases such as diabetes or epilepsy. For noting blood group and for placing a warning code that an individual may respond unfavorable to certain therapeutic agents, tattooing is of limited applicability. Fluorochemistry, however, has given rise to an invisible form of tattooing which, though yet in the experimental stages, may solve many of the problems in the development of a permanent marking technique. It depends on the use of inert and insoluble phosphors that respond to x-rays or other radiation. A method has already been perfected in the laboratory of the writer whereby special phosphors can be impregnated in the skin by the tattooing needle, remaining invisible to the naked eye, but being easily brought out with x-rays. This invisible tattooing is now being developed so that an ordinary ultraviolet lamp can be employed for rendering the marking visible (De Ment, 1944, p. 122).

The author further goes on to comment on the use of invisible tattoo marks to aid in the identification of soldiers killed in war, to identify habitual criminals or sex offenders, or to mark surgical scars to enable a physician to determine a patient’s medical history (De Ment, 1944). According to a report in the Science News Letter regarding De Ment and Dake’s research “Phosphors such as cadmium borate, which glows red, and zinc orthosilicate, which gives off bright green light under x-rays, are said to be especially

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Forensic Analysis of Tattoos and Tattoo Inks

effective…” furthermore, “ordinary methods of removing tattoo marks, by injecting zinc chloride … are not effective for these” (De Ment, 1944, p. 345). Another feature of the tattoo is the potential to identify the artist based on the work or for the artist to be able to identify his or her own work. According to Gordon, “[t]he men appear to follow regiments from town to town, and I found I was able to identify one man’s handiwork in far distant towns … The girls can be traced by their marks if they rob or infect their clients” (Gordon, 1922, p. 42). According to Steward, it was possible for tattoo artists to identify each other’s artwork “if we’re in the same part of the country and see enough of the kind of work the other fellow does” (Steward, 1990, p. 127). Tracing tattoo a­ rtists based on their work has been reported as a useful tool in the identification of human remains. “…his work is so individual that it is instantly recognizable to other practitioners—so much so that—Irezumi work is occasionally used by Japanese police in the identification of unknown corpses” (Cohen, 1994, p. 101). Recently, prosecutors released a statement looking to speak with any tattoo artists who were responsible for tattooing Aaron Hernandez, a former NFL football player accused of murder. It is apparent that the prosecutors were looking to trace the movement of Hernandez as he was likely to have been tattooed in some of the regions to which he traveled and may have committed crimes in some of these locations. The prosecutors believe that the tattoo artists may also have observed or overheard something of evidentiary value that could assist in their investigation. This apparent attempt to establish a timeline and communicate with witnesses by way of trailing a suspect’s tattooing encounters is novel and provides an interesting application of tattoos and tattooing to criminal investigations. Speculations that Hernandez memorialized the crimes by obtaining tattoos as well as the presence of tattoos that are associated with gang membership have also been proposed by the media, and thus may lend themselves to the interpretation of any resultant tattoos. The presence of a tattoo on a decedent has long served as an identifying characteristic of forensic medicine and pathology. If an individual is not able to be identified by facial recognition then death investigators and forensic pathologists may use confirmation of a tattoo to serve as a tentative means of identification, because it is faster than fingerprint, dental, radiological, and serological methods of identification (Figure 2.4). These tattoos were especially useful in identifying deceased mobsters and gangsters characteristic of Parry’s days. “In Lafayette, Indiana, in a strawberry patch the body of “Orlando Jack” Horton, a Chicago gangster, is found … Identification is made possible by a necklace of playing cards tattooed around his neck” (Parry, 1993b, p. 110). This method of tattoo recognition and documentation is faster than fingerprint recovery followed by comparison and subsequent identification, dental recovery with comparison and

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Figure 2.4  Tattoos can aid in identification based on design, color, and location

on the body. More importantly, due to the uniqueness of the individual designs as well as the locations of the individual tattoos relative to one another, tattoos can be used to individualize. (Photo courtesy of Ian Grushka.)

subsequent identification, and DNA analysis (the latter of which includes several analytical steps including extraction and isolation, quantitation, amplification, separation, and interpretation, which can be time consuming). Furthermore, dentition and fingerprints may not be available, as in cases of decomposition, mummification, charring, or dismemberment. When fingerprints, dentition, and DNA are available, investigators are limited to the availability of standards for comparison, such as a fingerprint card on file with an employer or in an arrest record, dental records, or a DNA profile on file (in addition, the investigators must have some idea of the identity of the decedent in order to begin the acquisition of medical records and related documents). In other words, even after finding a fingerprint or DNA sample of good enough quality for further comparison and identification, there may not be a “hit” if a fingerprint or a DNA profile was never entered into a database. Databases exist for fingerprints and DNA

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Forensic Analysis of Tattoos and Tattoo Inks

profiles, but the lack of a universal dental database further limits the ability of dental records to be useful in a tentative identification. In some regions of the world, lack of comprehensive medical records and databases prevents the use of such identification methods altogether. Ambade et  al. demonstrate an example of this, “[i]dentification is one of the main concerns of investigating agencies (with regard to) decomposed or skeletonised bodies … Dental comparison is not practicable in India and hence not done … In India, police usually established the identity of a dead body, with the help of relatives and acquaintances. The clothes of the deceased and belongings help in the identity of the decomposed bodies along with tattoos, scars and other peculiar features” (Ambade et al., 2011, p. 105, emphasis in original). Tattoos can be characterized based on physical characteristics, such as design and color, as well as the location on the decedent’s body, “…after death, a woman would be recognized by the nature of the tattoo mark and the pigment used” (Hambly, 1937, p. 57). These techniques of describing and photographically documenting tattoos are also done on living persons, typically criminals in a police precinct, jail, or prison setting. Currently, coupling the identification of tattoos with another form of identification, such as fingerprints or DNA results, is considered to be a suitable form of individualization; “In these modern days of gangsters and sawed-off guns, the police find, on a grassy Bronx lot, the body of Frederick Titus … He is identified not only through his fingerprints, but also through the picture of a Red Cross girl on his left arm, inscribed “Rose of No Man’s Land,” a dull, conventional design…” (Parry, 1933b, p. 100) (Figure 2.5). Identification-based tattoos were not limited to the deceased, but also were useful in cases of mistaken identity and fraud. One such case is the Tichborne case. In 1854, Roger Tichborne was believed to have died at sea. In the 1860s, a man claimed to be Tichborne and thus the heir to the Tichborne family fortune. The civil case, beginning in 1871 and lasting approximately 10 months, quickly became a case of establishing the identity of the man now claiming to be Roger Tichborne. The central evidence at the trial was that of

Figure 2.5  Historical tissue samples demonstrating a variety of tattoo designs.

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tattoo marks, specifically their presence, absence, removal, and disappearance over time. Roger was known to have various tattoos on his person while the imposter admitted to having no tattoo marks. Many witnesses came forward to testify that they had seen blue tattoo marks on Roger’s body over a period of several years. “Evidence regarding the durability of the tattooing was of the strongest possible kind” (Taylor, 1874, p. 460). One witness testified that after he had tattooed Roger with Indian ink, Roger tattooed the witness, “in the same hour … done with the same ink and needles.” He then demonstrated to the court that his tattoo was still visible, thereby disputing the claim by the imposter that his tattoos had faded over time. Medical examination of the imposter failed to disclose any evidence (tattoo marks, scars, or otherwise) indicating that he was tattooed or had one time been tattooed or had tattoos removed. The presence of tattooed or colored marks on the skin of a person, verified by a competent observer, may become the strongest possible proof of identity, and their proved absence, if not accounted for or reasonably explained, may furnish the most convincing evidence of non-identity … a medical expert may still be able to demonstrate that there have been such marks and that traces of them still exist … medical evidence must be derived from a comparison of the colour, form and situation of the marks of the two … The operation would require time and an accurate imitation of the colour and design, and the imposter must take care to select precisely the same part of the body for the purpose of tattooing … The presence of tattoo-marks, and their correspondence in situ colour and design with those which could be proved to have existed in a missing person, would furnish the possible evidence of identity. (Taylor, 1874, p. 441).

As a result of the witness statements, it was determined that the individual claiming to be Tichborne and heir to his estate was an imposter. In his account of the trial, Taylor provides some insight into the science behind the process and the pigments used to tattoo, noting [w]hen the colouring matter is quite insoluble, as the charcoal of gunpowder or  vermilion, the most effectual way of introducing it would be by rubbing in the colour mixed with a little water; The designs in vermilion have been observed at this early time to be much more intense than those produced by China ink. When the local symptoms have subsided, the latter marks are fixed permanently, and it is impossible to assign a date to them, as they undergo no further change. The colors commonly employed in tattooing are charcoal (gunpowder), China ink, vermilion and indigo (Taylor, 1874, p. 442).

Another historical case in which the lack of a tattoo played an important role was the Guldensuppe case. In 1897, parts of a man’s body were recovered

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Forensic Analysis of Tattoos and Tattoo Inks

in various locations throughout New York. During the investigation, it was determined that a large section of skin containing a tattoo had been cut and removed from the center of the chest of the decedent in an effort to impede identification of the remains. Identification became an important matter in the case since the head was never recovered. Many individuals came forward claiming to know the identity of the body, but these identifications were repeatedly falsified. The false identifications were reported in the news on a regular basis, which made the correct identification a difficult and timely process. The body seems to be like that of Edwards, both in height and weight. He had once had a felon on his left forefinger, and the nail had thickened and was stronger than his other nails, besides having been kept long for use in picking up negatives. His toes were like those of the corpse. He had a tattoo mark, partially obliterated, and a scar on the part of his left arm which are marked in the corpse by bruises, which might have been made in an effort to conceal his identity. Edwards was a blonde though he dyed his hair and whiskers, and Ring thinks that his hand was exactly like that of the dead man (New York Times, 1897).

Eventually, the investigation led to the body being that of Guldensuppe. Witnesses that knew him were able to verify that he had a large tattoo in the center of his chest. Presently, a search of news articles and media reports concerning the use of tattoos to aid in the identification of human remains produces a wide array of cases, some solved and some seemingly unsolved. It is common for law enforcement agencies to release images of the tattoos found on unidentified human remains. These remains are in various conditions and states of decomposition or mummification and may be found in streets and in alleys, in dumpsters, recovered from bodies of water, stuffed in garbage bags or containers, in clandestine burial sites, and elsewhere. A 2010 article by Gallucci focused on Long Island’s unidentified murder victims, with some of the decedents bearing tattoo marks. The author highlighted a series of cases, including • A 1997 case in which a woman’s torso was found inside a garbage bag in a Rubbermaid container. According to the report, the head, arms, and legs were never recovered, and the only identifying mark was a heart-shaped peach tattoo on the left breast. • A 2003 case in which a dismembered body was found dumped in an isolated region of Long Island. The head and hands were never recovered, but a partially destroyed angel tattoo was present on the right hip region. The tattoo had been partially gouged, likely in an effort to prevent identification upon discovery. According to

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Gallucci, “[a] Washington detective took notice and remembered a woman he had arrested for prostitution in Washington State. Suffolk police located her estranged family and obtained DNA samples to compare.” In this case, dissemination of the tattoo design aided in a tentative identification, which subsequently allowed for individualization through DNA analysis. Of note is the fact that the body was recovered on the East coast (New York), and the identification was made on the West Coast (Washington). Furthermore, efforts to obliterate the tattoo were not enough to render the design unusable for identification. • A 2007 case in which a stabbed torso was found in a suitcase on a beach in Westchester and the legs were found at separate locations of the Long Island shore. The tattoo is a pair of green and red cherries located on the right breast. Retention and preservation of the inks and their pattern of distribution (design) within the tissue allows for visualization even when superficial layers of tissue have been burned, desiccated, or subjected to various environmental, mechanical, and chemical factors. As such, tattoos can be used to identify charred, decomposed, mummified, or otherwise unidentifiable remains. This is especially useful in death investigations, which can be noncriminal motivated (accident, suicide, or natural) or the result of criminal activity (homicide). An example demonstrating the effective use of a tattoo to aid in identification is apparent in the case of a female who was found burned and dumped in a remote region in New York in 2010. The woman’s body was marked with a colorful rose tattoo and a name, which was used to aid in her identification and subsequently aid in the identification and arrest of the perpetrator (Burd, 2010). Tattoo recognition and identification can also be employed in instances of mass fatality and casualty incidents such as accidents and crashes (i.e., a building collapse, a plane or train crash), natural disasters (i.e., a tsunami or a hurricane), war, and terrorist attacks. This identification of tattoos for investigatory purposes is also useful in searching for missing and kidnapped individuals or for the rapid identification of individuals who may be involved in a structural or vehicular fire, or some other noncriminally motivated death (Figure 2.6). The specific tattoos located on an individual (either living or deceased) may provide information about gang or group affiliation, profession, ancestry, religious or ethnic background, and so on. In 2008, a man and admitted gang member was charged with a 2004 shooting death at a liquor store in California (Kahn, n.p.; Laufik, 2013). Law enforcement officials stopped the man for driving with a suspended license in 2008, at which time his mug shot

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Forensic Analysis of Tattoos and Tattoo Inks

Figure 2.6 Tattoo designs visible under charring. Using photographic techniques or by removing the superficial layers of charred skin, it may be possible to resolve the entire design to facilitate identification.

and photos of his tattoos were obtained. According to the separate reports by Kahn and Laufik, while searching the police catalog of tattoo photos for another case, a detective recognized the crime scene depicted in the chest tattoo of the man—a 2004 liquor store shooting—“the details were so accurate down to the trajectory of the bullets” that it was basically “a crime scene sketch and a confession … The inked piece features the store’s Christmas lights, a bent light post in the parking lot and the convalescent home next door. It also shows a chopper (the gang nickname for the shooter) spraying bullets on the victim, who was depicted as a member of a rival gang” (Laufik, 2013). Furthermore, the tattoo was photographed at different times (2005, 2006, 2008), and each instance saw the addition of new elements of the scene (Laufik, 2013). In 2014, a convicted drug smuggler tattooed his criminal case on his back post conviction and while in prison (Golgowski, 2014). The tattoo included the names of the attorneys, investigators, and the judge as well as his sentence.

Tattoos and Criminal Investigations Tattoo equipment may be suspected of being used to facilitate a criminal act. In particular, a tattoo machine and its needles may be used to generate

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puncture marks in the stabbing of skin or fabric. The use of a tattoo machine to assault or murder an individual is possible, as is the use of a tattoo machine to cut out a section of fabric from a garment. In a New York City case, a man claimed to have been sexually assaulted by a police officer, specifically asserting that the officer used his retractable baton to perforate the man’s underwear and penetrate his rectum (Fahim, 2010). At trial, the shape of the damage to the boxer shorts of the individual became key forensic evidence in determining how the hole in the boxers could have been made and what could have made such damage (Figure 2.7). Additionally, microscopic examination of the damaged fibers at the periphery of the hole was shown to be useful in establishing the presence of organic compounds that are found in tattoo ink. Once isolated, components consistent with ink were identified by spectroscopic analysis and subsequent comparison to a chemical database. Interestingly, in an episode of the popular television series CSI: New York, the investigator suspected the tattoo machines of a potential suspect (a tattoo artist) as being a potential murder weapon of a young female victim; in one scene, the investigator systematically stabs a pig cadaver with the confiscated tattoo machines and compares the resultant “wounds” to those found on the victim in an effort to identify the murder weapon through comparison of wound patterns (Norberto, 2010). Other incidents that involve tattooing and criminal activity can include underage tattooing; tattooing without a license; the placement of unwanted tattoos on an individual (as a “prank”); and tattooing while incarcerated. In a 2010 New Hampshire case, a teenager was arrested for allegedly operating an illegal tattoo parlor, tattooing without a license, and endangering the welfare of a child for tattooing minors (Cote, 2010). In a 2011 Pennsylvania case, a tattoo artist was charged with sex crimes for exchanging sex acts for tattoos on minors (Alfano, 2011). Several cases have been reported of individuals, many

Figure 2.7  On left, boxer shorts exhibiting damage (hole) and on right, micro-

scopic examination of the damaged region demonstrating blackened discoloration (Note: distance between black lines equals 1 mm). (Courtesy of Thomas A Kubic, TAKA.)

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Forensic Analysis of Tattoos and Tattoo Inks

not tattoo artists, tattooing minors, including children as young as a year old. In the case of the one-year-old girl, she was tattooed with the letter A on her backside by a relative (Hatch, 2010). Other cases include a three-year-old boy tattooed with the letters DB (for Daddy’s Boy) on his shoulder by his father (Caulfield, n.p.), a four-year-old tattooed with a Batman symbol on his arm by a tattoo artist (Cassidy, 2009), and a seven-year-old boy tattooed with a gang symbol (a dog’s paw) on his stomach by his father’s friend and fellow gang member (Cone, 2009). In 2010, a couple in Georgia was arrested for tattooing six of their underage children, aged 10, 11, 12, 15, and 17 (Smith, n.p.). According to the report, they used a homemade tattoo machine with a guitar string as a needle. In many jurisdictions, it is illegal to tattoo minors (individuals under the age of 18), and it is illegal to tattoo without a license. In 2010, a man requested a tattoo from his friend and amateur tattoo artist (Hartenstein, 2010). Instead of the design requested, the friend tattooed a 16 inch penis along with an obscene slogan on his back as a prank. The tattoo artist was subsequently charged with assault.

Tattoos in the Courtroom Shelverton discusses the history behind the prohibition of tattooing and the eventual determination that the right to tattoo is protected by the First Amendment to the U.S. Constitution,* specifically that tattooing is an exercise of free speech. The author lists a series of cases in which tattooing was prohibited or determined not to be protected by the First Amendment, including People versus O’Sullivan (96 Misc.2d 52, 1978), Yurkew versus Sinclair (495 F.Supp. 1248, 1980), State versus White (560 S.E.2d 420, 2002, et  al.), and Holdfast Tattoo versus City of N. Chicago (U.S. Dist., N.D. Ill., 2008); as well as the case of Lamphear versus Massachusetts (unpublished opinion, 2000), in which providing tattoos cannot be limited to physicians; and a case in which tattooing was viewed as artistic expression and thus protected by the First Amendment, Anderson versus City of Hermosa Beach (21 F.3d 1051, 2010)† (423). Additional First Amendment cases addressed by Frederick include Grossman versus Baumgartner (17 N.Y.2d 345, 1966), Golden versus McCarty (337 So.2d 388, 1976), and State versus Brady (492 N.E.2d 34, 1986). Bible addresses court cases that have impacted employers due to tattooed employees, specifically, Riggs versus City of Fort Worth (229

* The First Amendment states: Congress shall make no law respecting an establishment of religion, or prohibiting the free exercise thereof; or abridging the freedom of speech, or of the press; or the right of the people peaceably to assemble, and to petition the government for a redress of grievances (The Bill of Rights, U.S. Constitution). † As defined in Texas versus Johnson (491 U.S. 397, 1989).

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F. Supp.2d 572, 2002), Montoya versus Giusto (unpublished opinion, 2004), Inturri versus City of Hartford (365 F.Supp.2d 240, 2005), Swartzentruber versus Gunite Corp. (99 F.Supp.2d 976, 2000), and EEOC versus Red Robin Gourmet Burgers, Inc. (unpublished opinion, 2005). In 2012, Lozar posted online a document entitled Tattoos as Evidence, in which he summarized various cases in which tattoos played a role in criminal proceedings.* Lozar documented cases that were based on covering tattoos in the courtroom, specifically those tattoos that could be prejudicial in the eyes of the jury; and cases in which the introduction of defendant’s tattoos as ­evidence of identification was assessed. In addition to the presence or absence of a tattoo and its potential to identify, exculpate, or incriminate an individual, the content of the tattoo may provide information that could be used during the trial. Lozar describes that, information rich tattoos, such as those denoting gang affiliation, past criminal acts, and so on, can effectively reveal the defendant’s affiliations and activities. Realizing the prejudicial effect of visible gang and prison tattoos on the jury, some defendants are choosing to cover up and/or remove tattoos, especially those in prominent locations such as the face, neck, and hands prior to their trials. While some tattoos can be covered with clothing or the growth of facial hair, others cannot be completely masked. According to Lozar, “Lawyers arguing tattoo coverage petitions frequently invoke Estelle versus Williams (425 U.S. 501, 1976), which held that forcing defendants to wear prison garb when they appear before a jury undermines the constitutional presumption of innocence” (Lozar, 2012). In United States versus Quintero (933 F.2d 1017, 1991), defense counsel asked the district court to permit Quintero to change into a long-sleeved shirt to cover the tattoos on his forearms because Quintero believed that tattoos would prejudice the jury against him. After his request was denied, and he was convicted, Quintero raised on appeal the issue that he was denied a fair trial because he was unable to conceal his tattoos. The appeals court affirmed his conviction, stating, “While it is conceivable that a particular tattoo could create prejudice under certain circumstances, the record before us does not reflect what Quintero’s tattoos depicted. We do not believe that all tattoos, as a general matter, create juror prejudice sufficient to violate a defendant’s right to a fair trial. The district court did not err when it concluded that prejudice was unlikely, in this case.” Conversely, other cases have allowed the defendant to cover their tattoos. In 2009, John Ditullio Jr. was given access to a $125-aday cosmetologist to conceal his face and neck tattoos with makeup, which included Nazi symbols. Ditullio’s lawyer argued that that tattoos would prejudice the jury, especially since the case was the stabbing death of a teenager * http://www.callawyer.com/Clstory.cfm?eid=919809

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in an attack prosecutors were describing as a hate crime motivated by racism and homophobia (Rodriguez, 2012). In United States versus Chandler (U.S. District Court; Case No. 2:10-cr-00482-GMN PAL), in which the defense made a motion in Limine seeking an order allowing the defendant to conceal a teardrop tattoo on his face during the trial. According to the opinion, the defendant believed that the tattoo could cause jurors to believe that he was a member of a gang or a murderer. Accordingly, the Court granted the defendant permission to conceal his tattoo during the course of the trial. Recently in 2014, a Kansas man charged with first-degree murder requested a professional artist remove or cover up his “MURDER” tattoo across his neck for fear that it would prejudice a jury (n.a., The Associated Press, April 22, 2014). Lozar adds that no widely accepted standard has been developed to govern this area of the law. In the trial of Gonzales versus Quarterman (458 F.3d 384, 2006), a detective testified that the two teardrops on Gonzales’ face represented the number of people he had killed.* The issue presented was the interpretation of the teardrop tattoos, which were seen as a silent admission of guilt as presented by the prosecution. Accordingly In his state habeas application, Gonzales raised three claims with respect to Robertson’s testimony about the teardrop tattoos: (1) the prosecution violated Brady† (Brady v. Maryland, 373 U.S. 83, 1963) by failing to reveal that teardrop tattoos on the face of a gang member have many possible meanings, as opposed to the false testimony at trial that they mean that the person bearing such marks murdered someone; (2) the prosecution allowed Detective Robertson to present false testimony concerning the teardrop tattoos; and (3) trial counsel rendered ineffective assistance by failing to investigate (including by consulting with a gang expert or Gonzales) the meaning of the teardrop tattoos and failing to use the fact that such tattoos can have many different meanings, and by failing to object to Robertson’s testimony as evidence of an extraneous offense.

The district court reasoned that the tattoos’ significance concerning the murders was open to interpretation … therefore concluding … there is not a reasonable probability that the result would have changed with expert testimony or argument challenging the meaning of the tattoos and when Gonzales acquired them. Citing the totality of the evidence, the appeals court agreed with the district court.

* Gonzales, a member of a gang, was on trial for the capital murder of two individuals. † Brady versus Maryland, 373 U.S. 83, 1963; To establish a Brady violation, a defendant must show: The evidence at issue must be favorable to the accused, either because it is exculpatory, or because it is impeaching; that evidence must have been suppressed by the State, either willfully or inadvertently; and prejudice must have ensued.

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Cases concerning the introduction of a defendant’s tattoos as evidence have varied with regard to the general presence or absence of the tattoo and eye witness statements; the overall content of the tattoo; and any relevance or prejudice that can be correlated to introducing the tattoo evidence at trial. Lozar states, “Defendants sometimes object that being forced to expose their tattoos to a jury violates the Fifth Amendment’s* prohibition against compelling a criminal defendant to be a witness against himself. The objection fails, however, under Schmerber versus California, (384 U.S. 757, 1966), which held that the privilege against self-incrimination implicates testimony or communication, not physical evidence” (n.p.). In United States versus Bay (762 F.2d 1314, 1984), the lack of tattoos on the defendant became relevant; the defendant wished to exhibit tattoos on the back of his hands without testifying (and thus avoiding taking the stand and being subjected to cross-­examination), specifically because the eyewitnesses failed to note “anything unusual” about his hands during the commission of the crime, casting reasonable doubt on their abilities to identify Bay. Bay argued, and the government conceded, that a display of hands is nontestimonial; “Physical characteristics relevant to most eyewitness identifications (such as size, gender, skin and hair color, special deformities, and facial features) are apparent, and can be referred to in argument, without a defendant having to take the stand and subject himself to cross-examination and impeachment. Courtroom geography, which apparently prevented the jury from seeing Bay’s hands, should not determine whether Bay had to take the stand to present potentially exculpatory physical evidence.” In Bay, the matter of establishing a proper foundation was addressed.† In the matter of People versus Perez (216 Cal.App.3d 1346, 1989), Perez’s appeal centered on the issue of whether it was an error for the trial court to refuse to allow Perez to exhibit two tattoos (one on the hand and one on the arm) to the jury without being sworn in or giving testimony (and thus not subject to cross-examination). The appeals court determined that since the defendant was wearing long-sleeves during the commission of the crime, the tattoos were irrelevant and would have been unobservable. The Court explains * The Fifth Amendment states: No person shall be held to answer for a capital, or otherwise infamous crime, unless on a presentment or indictment of a grand jury, except in cases arising in the land or naval forces, or in the militia, when in actual service in time of war or public danger; nor shall any person be subject for the same offense to be twice put in jeopardy of life or limb; nor shall be compelled in any criminal case to be a witness against himself, nor be deprived of life, liberty, or property, without due process of law; nor shall private property be taken for public use, without just compensation (The Bill of Rights, U.S. Constitution). † According to Brown versus United States (356 F.2d 230, 1966), regarding the matter of the defendant exhibiting a scar on his body to the jury, the court stated, “[s]uch physical exhibits are proper only where it is shown that they are relevant to the case.” The appellate court determined that since no proper foundation was laid for showing the scar, the request to exhibit the scar was properly denied.

50

Forensic Analysis of Tattoos and Tattoo Inks The trial court finally ruled that exhibition of the tattoo (presumably only the “relevant tattoo” on Perez’s left hand) would be “testimonial” if offered to impeach [the eyewitness’s] testimony that she observed no tattoo on the hand of the vendor of the marijuana. This would have needs raised the question of whether Perez would be subject to cross-examination about this information. If viewed as “demonstrative” evidence, the tattoo would be irrelevant because there would have been no foundation first laid in accordance with the Court’s earlier expressed concerns.

Another matter addressed in the case with regard to foundation was the length of time the defendant had been tattooed. The basis, on which the trial court did rule, however, was that some foundation would have to be first established as to the length of time Perez had been tattooed. Defense counsel proposed and the court properly rejected the notion of an Evidence Code Section 402* hearing outside of the jury’s presence to have Perez testify to the age of and manner of acquiring the tattoos. In United States versus Greer (631 F.3d 608, 2011), Greer argued that the government violated his Fifth Amendment right against self-incrimination by using a name tattooed on his arm to link him to a car in which ammunition was found.† The appeals court determined that while the tattoo’s content made it testimonial, the tattoo was not the product of compulsion, and thus Greer’s Fifth Amendment rights were not violated. Citing case law, the court stated [b]ecause the exhibition of physical traits is not a “communication by a witness that relates either express or implied assertions of fact or belief,” it does not enjoy constitutional protection … [C]ompulsion which makes a suspect or accused the source of ‘real or physical evidence’ does not violate [the Fifth Amendment]… For that reason, the Fifth Amendment is not offended where a witness relies on a tattoo to identify a defendant. Here, the tattoo was used to a very different end. [The] Detective did not describe Greer’s tattoo to identify Greer… The government relied on the tattoo not as an “identifying physical characteristic” but for * According to California Evidence code §402: (a) When the existence of a preliminary fact is disputed, its existence or nonexistence shall be determined as provided in this article. (b) The court may hear and determine the question of the admissibility of evidence out of the presence or hearing of the jury; but in a criminal action, the court shall hear and determine the question of the admissibility of a confession or admission of the defendant out of the presence and hearing of the jury if any party so requests. (c) A ruling on the admissibility of evidence implies whatever finding of fact is prerequisite thereto; a separate or formal finding is unnecessary unless required by statute. † Greer had a name “Tangela” tattooed on his arm and “Tangela” was name on the car rental agreement found in the abandoned vehicle believed to be driven by Greer. Furthermore, Greer was a felon and charged with possession of a firearm and ammunition. This information, in combination with other evidence, allowed jurors to infer that Greer had constructive possession of the ammunition found in the vehicle rented by a Tangela Hudson.

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the “content of what [was] written.” The tattoo was therefore testimonial and, because it linked Greer to the ammunition, incriminating… The voluntary tattooing of an incriminating word to Greer’s arm was, like the voluntary preparation of documents, not the product of government compulsion…

In United States versus McCarthy * (473 F.2d 300, 1972), which was cited in U.S. versus Greer, McCarthy claimed his Fifth Amendment privilege against self-incrimination was violated when the prosecutor commented on McCarthy’s failure to bear his arms to the jury so they could determine whether tattoo marks were present. The appeals court determined that this action was harmless beyond a reasonable doubt. In an end note, the Court, citing case law, adds, “If the government had considered the presence of tatoo (sic.) marks on McCarthy’s arms to be critical on the issue of identification, it undoubtedly could have obtained an order, upon timely application, requiring him to submit his arms for inspection. The cases are legion that an accused can be required, without violating his privilege against self-incrimination, to submit his bodily or other identifying features for inspection.” Lozar presents cases in which the relevance of tattoos may come into question. In Dawson versus Delaware (503 U.S. 159, 1992), Dawson argued that evidence of his affiliation with the Aryan Brotherhood, including his tattoos, was inflammatory and irrelevant and that its admission into trial would violate his First and Fourteenth Amendments.† The court concluded that Dawson’s First Amendment rights were violated by the admission of the Aryan Brotherhood evidence, in this case, because the evidence proved nothing more than Dawson’s abstract beliefs … [and they] could not find the evidence was properly admitted as relevant character evidence. In United States versus Thomas (321 F.3d 627, 2003), the Court of Appeals found that the district court abused its discretion‡ when it admitted as evidence a photograph of one of the defendant’s tattoos … because the appeals court believed that admission of this evidence unfairly prejudiced his trial… Thomas, who was in possession of a firearm, had a tattoo that contained, in part, two crossed revolvers. The issue of whether the design depicted in the tattoo was * It is noted that throughout this document, the word “tatoo” is used instead of the correct spelling, “tattoo.” † The Fourteenth Amendment states, in part: All persons born or naturalized in the United States and subject to the jurisdiction thereof, are citizens of the United States and of the State wherein they reside. No State shall make or enforce any law that shall abridge the privileges or immunities of citizens of the United States; nor shall any State deprive any person of life, liberty, or property, without due process of law; nor deny to any person within its jurisdiction the equal protection of the laws (Section1; U.S. Constitution). ‡ Rule 403 of the Federal Rules of Evidence, Exclusion of Relevant Evidence on Grounds of Prejudice, Confusion, or Waste of Time states, Although relevant, evidence may be excluded if its probative value is substantially outweighed by the danger of unfair prejudice, confusion of the issues, or misleading the jury, or by considerations of undue delay, waste of time, or needless presentation of cumulative evidence.

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synonymous with tangible ownership of the tattoo’s content became apparent. The appeals court stated The district court first stated that it found the tattoo relevant because it showed Thomas’s knowledge about the existence of guns… While Thomas’s tattoo may indicate that he knows that guns exist, we think that this revelation is of little, if any, probative value, especially when balanced against the prejudicial effect the photo may have had on the jury… The district court’s last reason for admitting the photo of the tattoo, and the government’s primary justification for its admission, is that the tattoo shows that Thomas had a high opinion of guns. We think this only goes to propensity … and is of no other probative value… The tattoo on Thomas’s arm just shows that he wanted a gun tattoo. If a tattoo indicates ownership of an object, the mind reels at the legal and evidentiary consequences of the unicorns, dragons, mermaids, and other flights of fancy that decorate people’s bodies.

As such, having a tattoo of a firearm did not equate to possession of a firearm and be known beyond a reasonable doubt. Again, the length of time the defendant had been tattooed was raised by the Court, “without knowing when Thomas got the tattoo, it is impossible to say that it was drawn after he was convicted of a felony, or if it was a relic of earlier days when it would have been legal for Thomas to pursue his supposed affinity for guns.” In the case of United States versus Irvin [and Pastor] (87 F.3d 860, 1996), the defendants appealed their convictions, claiming that certain motorcycle evidence, including tattoos, should be excluded under Rule 403; specifically that the limited probative value of the evidence was substantially outweighed by its prejudicial effect, and therefore, should have been excluded. The Court of Appeals determined that the potential for prejudice was heightened because the gang evidence presented consisted of tattoos and clothing containing devil’s heads and demonic insignia, with the satanic imagery being inflammatory. The cases of United States versus Butler * (71F.3d 243, 1995) and United States versus Lewis (910 F.2d 1367, 1990) were cited in the case of U.S. versus Irvin. In U.S. versus Butler, Butler argued that the probative value of the evidence concerning his gang membership and activities, which included a gang tattoo, was substantially outweighed by its unduly prejudicial nature. The Court of Appeals indicated that the evidence, including the tattoo, was relevant† to establish his employment and affiliation with a known gang leader. As such, the Court determined, “the evidence was not * It is noted that throughout this document, the word “tatoo” is used instead of the correct spelling, “tattoo.” † According to Rule 401 of the Federal Rules of Evidence, Definition of “Relevant Evidence,” Relevant evidence means evidence having any tendency to make the existence of any fact that is of consequence to the determination of the action more probable or less probable than it would be without the evidence.

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irrelevant, but was probative of the elements of the crime he was charged with.” In U.S. versus Lewis, evidence was admitted regarding gang tattoos on two defendants and was used to establish a joint venture between the two individuals. The Court of Appeals determined that the district court did not abuse its discretion by admitting evidence of Lewis’ gang membership. Finally, Lozar considers matters concerning an individual’s Fourth Amendment rights* in Schmidt versus City of Bella Villa [and Locke] (2007 U.S. Dist. LEXIS 97488). Schmidt alleged that a tattoo, photographed incidental to her arrest, violated her Fourth and Fourteenth Amendment rights. Upon providing false information about her identity, the Chief requested information regarding her true identity, specifically information concerning scars/marks/tattoos/deformities. While several matters arose in the case, such as the photographing of tattoos for identification purposes as a matter of department policy, whether or not a photograph taken at a later date was a fair and accurate representation of the photograph taken on the day of the incident, as well as whether or not the photograph was a violation of the provisions regarding strip searches,† the court determined there was no evidence demonstrating that action violated the plaintiff’s rights. In some instances, the use of tattoos as a method of identification is straightforward. In United States versus Galati (230 F.3d 254, 2000), photos of a tattooed suspect obtained from the surveillance tape of robberies were compared to those tattoos of the defendant and found to match and were, along with additional evidence, sufficient to identify Galati and be presented at trial.

Tattoos and Scientific Inquiry Research on tattoos and tattooing was vast and varied and largely focused on the collection, description, and classification of tattoos. Practitioners, as well as academics and medical professionals, entered the research arena, likely because they found the collection of data and the reporting of statistics easy and rapid. Many “studies” and publications were simply catalogs of the tattoo designs encountered on any given day with little to no contextual information noted. In addition, reporting of physical characteristics varied, making the reliability of sketch details questionable (it is not unreasonable to * The Fourth Amendment states that: [it is] The right of the people to be secure in their persons, houses, papers, and effects, against unreasonable searches and seizures, shall not be violated, and no warrants shall issue, but upon probable cause, supported by oath or affirmation, and particularly describing the place to be searched, and the persons or things to be seized. † The case refers to Bell versus Wolfish (441 U.S. 520, 1979) regarding the scope and justification of searches.

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hypothesize that while some researchers added detail or color where there was none or filled in their own interpretation or embellishments, other researchers recorded the overall design and avoided the time consuming artistic need to record the finer details of the design). Often, information was given to the researcher by the tattooed individual, where details concerning the age of the tattoo, the artist, and the pigment employed could be incorrectly reported or not reported at all. As with the history of tattoos in general, it is likely this lack of attention to scientific rigor contributed to the misidentification or lack of identification altogether with regard to the types of tattoo inks that were in use at a give time or in a given location. According to Caplan, “…very few authors offered anything original in the way of interpretation” (Caplan, 2006, p. 350). As such, notes or scientific studies pertaining to pigments were noticeably absent; in fact, most accounts refer back to a paltry selection of original studies or were based on the bearer’s account or the imagination of the researcher. Little information is available from the actual tattooers for several reasons, most notably the fact that a substantial amount of time was likely to have elapsed between the tattooing event and the interaction with the physician or researcher, as well as the transient nature of both the tattooer and the tattooee, making it virtually impossible to track down or keep tabs on the tattooer and who they tattooed. Other factors, such as the marginalization and lower status of the individuals involved in the trade, the use of drugs or alcohol during tattooing as well as the potential for fines or arrest were certainly instrumental in limiting the communication between researchers and the tattooers. In order to adequately understand the tattoo, it was necessary to understand the manner of deposition and retention of the pigments within the skin, as well as the chemistry of the pigments that were being placed in the tissue. It is apparent that this was not a trivial task; one must understand the nature of the skin, the behavior of radiation as it interacts with the skin and the deposited pigments, the interaction of the pigments with the tissue, and the long-term effects on both the pigment and the skin. All these variables play a role in the overall appearance of the tattoo, the changes to the tattoo over time, and the persistence (permanence) of the tattoo design.

Tattoo Modification, Removal, and Detection

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The Anatomy of Human Skin The human skin is a complex, layered organ characterized by its two primary layers, the epidermis and the dermis. The epidermis is made up of a series of layers, each distinguished by its cellular structure. The layers of the epidermis include the stratum corneum (the outermost layer of skin), stratum lucidum, stratum granulosum, stratum spinosum, and the stratum basale; the presence and thickness of each of these layers depending on the type and region of the skin (Figure 3.1). The stratum corneum is the cornified layer of dead, flattened cells found at the skin’s outermost surface of the epidermis with a thickness of 10–15 µm on most areas of the body (Caspers et al., 2000, p. 572). In most histological texts, the types of skin are divided into thin skin (the general body surface) and thick skin (i.e., the palms of the hands and soles of the feet). The dermal layer consists of connective tissue and contains many of the skin appendages, such as hair follicles, sweat and sebaceous glands, and blood vessels (that carry hemoglobin-containing blood). The layers of the dermis include the papillary layer and the reticular layer. Most human tissues are highly scattering in the visible and near-infrared regions of the electromagnetic spectrum and the various structures (including their relative thickness) that compose human tissue have differing optical properties, contributing to the penetration, absorption, scattering, and remittance of light at its various wavelengths (Kienle et al., 1996, p. 1151). In addition to color perception based on the optical properties of human tissue, Kienle et al. point out that the color observed is a function of the observer and the physiology of the observer’s eye (Kienle et al., 1996, p. 1153). Anderson and Parrish address the optical properties of human skin (Figure 3.2), reporting that numerous substances in the epidermis contribute to absorption of radiation and that the degrees of absorption are dependent upon the wavelength of the incident radiation (Anderson and Parrish, 1981, p. 18). In addition, optical scattering of the dermis is an inverse function of wavelength that defines the depth of optical penetration (Anderson and Parrish, 1981, p. 18). Based on their studies to assess color perception of veins within tissue, Kienle et al. indicate that some minimum depth below the skin surface is necessary for a vein to display its characteristic blue color (Kienle et al., 1996, p. 1158). The authors report that without a scattering medium, deoxygenated 55

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Forensic Analysis of Tattoos and Tattoo Inks Anatomy of the epidermis

Dead cells flaking off at the skin surface

Stratum corneum Stratum lucidum Stratum granulosum

Keratinocytes move up as they age

Stratum spinosum

Stratum basale Dermis

Figure 3.1  Layers of human skin.

blood has a deep red color and oxygenated blood has a light cherry red color (Kienle et al., 1996, p. 1155). As they increased the depth of a simulated vein with 50% oxygenated blood, the vein appeared blue. The authors also report that in addition to the depth requirement, a minimum vessel diameter is needed for the vein to appear blue (Kienle et al., 1996, p. 1158). A summary of their results is displayed in Table 3.1. Kienle et al. conclude that the reason for the blue color of a vein is not greater attenuation of the blue light relative to the red light, but it is the greater attenuation of the red light above the vessel while traversing the tissue. This is in part due to the decreased depth of penetration of the blue radiation within the tissue (Anderson and Parrish, 1981, p. 1159). Light scattering is the basis for skin color, which is based on the presence of melanins,* the natural pigments in human skin that can be found in the epidermal layers of the skin. It is this concept of light interacting with skin * Eumelanin, pheomelanin, neuromelanin; the eumelanins accounting for black and brown colors and the pheomelanins accounting for the lighter ones, with a wide range from yellow to reddish brown (Prota, 1980, p. 123).

Tattoo Modification, Removal, and Detection Incident radiation

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Reflection (remittance) Dermal remittance

Epidermal remittance

Air (nd = 1.0) Stratum corneum (nd ~ 1.55) ~10 μm

Scattering

Epidermis ~100 μm

Absorption

Dermis ~3 mm

Figure 3.2 Optical pathways in skin. (Adapted from Anderson, R. and J. Parrish. 1981. The Journal of Investigative Dermatology, 77(1), 14.)

that enables us to perceive a variety of skin colors and tattoos placed into the layers of skin. Considering that the purpose of the tattoo is for it to be viewable, the tattoo ink would have to be located at a depth such that visible radiation can penetrate and traverse the skin and be reflected back in order for the viewer to perceive the colors of the design; since a major characteristic of the tattoo is its permanence, the pigment has to be deposited deep enough to remain in the tissue over time and not be sloughed off as a result of natural Table 3.1  Assessment of Color Perception of Veins within Tissue Simulation Number 0 1 2 3 4 5 6 7

Depth (mm) ~0.5 0.50 0.50 0.35 0.20 0.04 0.04 0.04

Diameter (mm) ~0.5 0.50 0.50 0.80 0.50 0.50 0.50 0.24

Color (Reflectance Measurements, CCD Detector) Blue Turquoise → Blue Turquoise Turquoise → Blue Turquoise → Red Turquoise → Red Violet, dark red Violet, dark red

Source: Adapted from Kienle, A. et al. 1996. Applied Optics. 35(7), 1151–1160.

700

600

10–8

10–10 10–12 10–14 10–16

500

Cosmic radiation

λ 780

10–6

γ rays

10–4

X-rays

100

UV radiation

102

Visible light

10–2

IR radiation

104

Micro waves

106 Technical alternative current

λ (m)

Forensic Analysis of Tattoos and Tattoo Inks

Radio waves

58

380 nm

Figure 3.3  The electromagnetic spectrum, which includes the visible region (~380–780 nm), that is important for color perception, and the ultraviolet (780 nm) regions, which are important for tattoo visualization within the skin.

epidermal regeneration. By interacting with visible radiation (represented in the electromagnetic spectrum in Figure 3.3), the pigments that make up the tattoo can be detected by the human eye. This principle of the interaction of light with the skin and the tattoo pigments is important from a historical perspective; as occasionally pointed out in the literature, although many of the early pigments were black, carbon-based inks and pigments, the resultant tattoos did not appear black, but actually appeared blue. It is the scattering and absorption of the various wavelengths of light within the skin that affect visual perception of the tattoo color. Light and color perception are key factors to the process of tattooing as well as the visualization of the resultant tattoos. This importance of color, and therefore, pigment chemistry, plays a role in the overall tattoo design and how it is viewed by others, as well as understanding the mechanisms and success of modification or removal of the tattoo. From a forensic perspective, understanding the chemistry of the pigments as well as how light interacts with the tattoo can enable an investigator to locate tattoo designs or residual pigmentation to aid in identifications, even in cases where the tattoo has been modified, removed, or obliterated. Cohen provides a list of factors that are important in judging and evaluating a tattoo (Cohen, 1994, p. 275–77). It is important to note that half of the factors incorporate color, pigments, or perception into the evaluation (emphasis added). 1. Quality of the line 2. Use of value (the intensity of light) 3. Use of chroma (the brightness or intensity of color and its dilution with dark pigment)

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4. Use of hue (the actual range of distinct colors, distinguished by a specific wavelength as determined from reflected or incident light) 5. Monochromatic or polychromatic (use of one chroma or many chromas) 6. Changes in level of the skin 7. Topographic changes in the skin upon movement 8. Harmony of design placement or arrangement 9. Use of realism (demanded knowledge of light, form color and perspective; achievement of three-dimensionality) 10. Use of abstractionism, surrealism, impressionism, and so on 11. Stylism 12. Choice of subject matter 13. Ratio of area tattooed to untattooed skin 14. Shading gradations (gradients of chroma, hue, and value) 15. Use of chiaroscuro (a dark background in which designs appear by contrast) 16. Permanency of design 17. The pain involved 18. The length of time required to render a design 19. The canvas (color, texture, and firmness of the skin) 20. Limitations imposed on different techniques (methodology, skill; pigment availability)

Tattoo Pigments and Human Tissue In the late 1800s, Variot and Morau conducted a histological study of blue and red tattoos. They reported that microscopic examination of the blue tattoos disclosed the presence of coloring particles of absolute black of varying shape in the middle of the dermis (Variot and Morau, 1888, p. 9). The study also disclosed information concerning the migration of the pigments based on the locations of the pigments in the layers of the skin (Figure 3.4). They expanded their study by tattooing an animal and removing sections for microscopic examinations. Variot and Morau reported that the topography of the tattoo pigment particles within the layers of the dermis differs for old tattoos and more recent tattoos (Variot and Morau, 1888, p. 10). In addition to the location of the pigment particles in the skin as well as their migration patterns over time, many scientists were concerned with the permanence of the tattoo design. Mathieu Felix Hutin investigated the retention of pigments; reporting that tattoos made with Indian ink or powdered charcoal remain visible, while those made with gunpowder, washing blue, or ink generally fade, but never become wholly effaced (observations included no change, faded, partially effaced, and completely effaced). Hutin

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Forensic Analysis of Tattoos and Tattoo Inks

Figure 3.4 Example of an eagle tattoo (c. 1950), exhibiting pigment migra-

tion, which has resulted in a loss of detail to the majority of the design (wings, feathers, etc.). This effect can likely be attributed to several causes, including time and healing in addition to the pigments and techniques employed. Careful examination of the tattoo discloses the presence of three colors, red (flower), green (leaves), and blue-black, and possibly a fourth color, yellow (beak).

concluded that the disappearance of the tattoo, in all probability, is related to the depth of penetration of the pigment, the nature of the coloring material employed, and the amount of friction subjected to the tattooed region (Lacassagne and Magitot, 1886, p. 144). Tardieu reported a similar study. He investigated the retention of pigments; reporting that cinnabar and blue ink produce far less indelible marks than Indian ink, soot, and washing blue; (The pigments) “[d]isappear in the following order: cinnabar, gunpowder, washing blue, ink, chalk mixed with lampblack” (Gross, 1924, p. 113). Johann Ludwig Casper (1796–1864) also investigated the retention of pigments (cinnabar, gunpowder, Indian ink, charcoal, ink, and Prussian [washing] blue) and saw similar results as those reported by Hutin. According to Casper’s study, cinnabar disappeared over time. Casper also identified tattoo pigments (i.e., cinnabar) in axillary glands (others report finding pigment in lymphatic glands). In 1861, Casper concluded, “tattoo marks may become perfectly effaced during life; that in not a few cases they disappear, so that they are no longer visible on that body when dead, on which during life witnesses had often seen them, and that their existence at a former period may

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possibly be ascertained by an examination of the axillary glands” (Casper, 1861, p. 109). Ernest Berchon, a naval surgeon in France, conducted studies of vermillion and China ink, and referenced in this work the earlier findings of Hutin, Tardieu, and Casper. In discussing the indelibility and persistence of the tattoo inks, Lacassagne discusses the earlier studies of Casper, Hutin, and Berchon. Lacassagne, along with Magitot, also reported on the detection of residual pigment particles in the lymphatic ganglion, which was later disputed by Virchow. Their methodology was to grind the lymph ganglion, add water and quicklime, and heat. They collected the resultant vapor and examined the condensate for the presence of mercury, which, if present, would be indicative of cinnabar (Lacassagne and Magitot, 1886, p. 155). According to Virchow, the pigment particles would not be transported to the lymph system; the filtration by the vessels would prevent the pigments from entering the ganglions. As such, the only way one would see pigment particles in the lymph would be if they were tattooed directly into the system (Lacassagne and Magitot, 1886).

Detection of Pigments in Tattooed Skin Several studies have been conducted to evaluate the location of tattoo pigments within human skin to assess penetration depth, retention, and migration (Figure 3.5). In 1927, Guillaume demonstrated the migration and aggregation of tattoo pigments within the skin as well as the settling within the dermis. In 1987, Lea et  al. examined biopsy specimens taken from 24 h, 1 month, and 1, 3, and 40 years post-tattooing using scanning electron microscopy (SEM). The tattoo inks employed varied in pigment type and included charcoal ash (amateur tattoos containing a mixture of soot and fat), India ink (black), mercuric sulfide (red), and chromium oxide (green), the latter three made by a professional tattoo artist. The authors reported that the tattoo ink particles remained in the dermal

Figure 3.5  Tattooed skin, ~40×.

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fibroblasts for the lifetime of the tattoo. In 1991, Taylor et al. reported finding membrane-bound pigment granules predominantly within fibroblasts and occasionally in macrophages and mast cells of the biopsy specimens they examined. The tattoos were described as dark blue or black, with some having small areas of red, green, yellow, and turquoise. The authors describe that although polymorphous, the majority of pigment granules were round or oval with diameters ranging from 0.5 to 4.0 μm (Taylor et al., 1991, p. 133). In the professional tattoos, the pigment granules were deposited regularly at the junction of the papillary and reticular dermis, often reaching mid-dermis while in amateur tattoos, the pigment granules were more randomly arranged, extending from the papillary dermis to subcutaneous fat (Taylor et  al., 1991). In addition, Taylor et  al. reported more heterogeneity of size and shape of the pigment granules in the amateur tattoos relative to the professional tattoos. Upon higher magnification, Taylor et al. observed that the pigment granules were composed of loosely packed pigment particles (ranging in diameter from 2–400 nm), which they classified into three categories based on size, shape, density, occurrence, and structure. Using confocal scanning laser microscopy (λ = 830 nm, with a reported depth of imaging of 200–400 μm), O’Goshi et al. reported that their studies demonstrated that different pigments may show different particle sizes, densities, and organizations within the tissue, the latter classified as either clustered or as diffused pigmentation (O’Goshi et al., 2006, p. 96). Conceptually, the latter two points would be explained by the technique of the tattoo artist with regard to shading in an effort to obtain a desired visual effect.

Visualization of Tattoos Several methods have found use in the visualization of tattoos on human remains in various stages of decomposition, including manual techniques such as scraping away the superficial layers of skin, chemical methods such as the application of hydrogen peroxide and lighting techniques employing the visible, and ultraviolet and infrared regions of the electromagnetic spectrum. The latter are often employed with photography equipment and techniques in order to preserve the images produced by the interaction of the tattoo with the electromagnetic radiation. In addition, medical practitioners would remove and dissect tissues from the body, usually the lymphatic tissue adjacent to the tattoo or suspected tattoo and prepare histological sections in order to look for pigment particles that had migrated into the lymph or the adjacent tissue. A method that has been reported as being useful for the visualization of tattoos is the use of hydrogen peroxide (H2O2). Haglund and Sperry

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reported that rubbing 3% H2O2 on tissue would resolve tattoos otherwise obscured by the stages of decomposition that result during the postmortem interval (PMI). According to the authors, “during decomposition … accumulated hydrogen sulfide (produced by bacteria) reacts with hemoglobin to produce sulfmethemoglobin and iron sulfide, which creates colors that vary from … dirty crimson or light green to dark green, brown or black” (Haglund and Sperry, 1993, p. 147). The ferric iron is available to bind with many of the products of decomposition leading to the color production of greens, browns, and blacks. The stages of decomposition produce a variety of colors; for example, when the hemoglobin loses oxygen, deoxyhemoglobin forms resulting in a purple color. Bilirubin, a bile pigment produced by the breakdown of hemoglobin, and its by-products produce shades of reds and greens. All these colors, along with other factors that occur during the PMI can obscure tattoos or contribute to the breakdown of the pigments in the skin. Haglund and Sperry hypothesize that the peroxide reduces the bonds within the chemical structures of the decomposition products causing the colors to fade and thus render the tattoo pigments visible against a light background. The sequence of decomposition products and corresponding color changes are described in Figure 3.6. Spitz describes a more destructive method: “Tattoos are frequently important for identification of an unknown victim … Removal of the superficial layers of the skin has proven to be advantageous in enhancing the tattooed image and enable superior documentation photographically. This is best done by producing a second-degree burn of the area and then wiping the detached epidermis. Placement of a hot light bulb 2–3 inches over the tattooed area will produce the desired effect in several minutes” (Spitz, 1993, p. 789). The use of reflected infrared photography to resolve tattoos that are barely discernible is common and has been reported in forensic and applied photographic literature. Due to the longer wavelengths of infrared radiation, infrared light penetrates deeper into the skin than visible and ultraviolet radiation (Figure 3.7). Photography coupled with the use of filters and forensic alternate light sources has been used for quite some time in forensic work successfully to document latent, superficial bruising of the epidermal and upper dermal layers of human skin with ultraviolet radiation (shorter wavelengths, less penetration) and deeper-set tattoos with infrared radiation

Urobilin (brown)

–H2

Urobilinogen (colorless)

+4H2

Bilirubin (red)

+H2

Biliverdin (green)

–H2

(blue, yellow, etc.)

Figure 3.6  Bile pigments produced by oxidation and reduction reactions of bili-

verdin, the initial product of hemoglobin breakdown. (Adapted from Gill-King, H. 1996. In Haglund & Sorg (Eds.), Forensic Taphonomy: The Postmortem Fate of Human Remains. Boca Raton, FL: CRC Press, 93–108.) These pigments are present in the later stages of decomposition and may mask tattoos.

64

Forensic Analysis of Tattoos and Tattoo Inks Ultraviolet Visible radiation radiation (700 nm)

Dermis (~3 mm)

Figure 3.7  Cross section of skin, demonstrating the relative penetration depths

of different wavelengths. Tattoo particles are generally embedded below the ­epidermal–dermal junction and will remain in the dermis.

(longer wavelengths and deeper penetration). As such, with respect to visible radiation, the depth of penetration will decrease as the wavelengths decrease from 700 nm (red) to 400 nm (blue/violet). De Donno et al. reported the success of infrared photography in resolving tattoos in tissues exposed to various conditions. They report three cases in which they resolved tattoos from a body immersed in water for 20–25 days, from charred remains, and from a mummified, partially skeletonized body. In all instances, infrared photography of the cadavers and subsequent resolution of their tattoos through this technique led to the identification of each individual. McKechnie et  al. were able to photograph and detect tattoos that had been removed by laser tattoo removal procedures using reflected infrared photography, demonstrating that it is possible to detect tattoos that have been “erased” by laser surgery. According to Wright and Golden, the shorter wavelengths of light interact with the surface of the skin whereas the longer wavelengths of light (approximately 700–900 nm) can penetrate the skin up to 3 mm (Wright and Golden, 2010, p. 60). This technique of tattoo visualization with the assistance of an alternate light source has been reported by Bennett and Rockhold, specifically the use of a 450 nm bandpass filter to produce fluorescence and an amber-colored barrier filter to pass the emission as well as absorbance characteristics of inks to resolve the tattoo. The authors studied tattoos in human cadavers as the tissue went through the various stages of decomposition, and they documented the visible characteristics of the tattooed area as these degenerative changes were

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Table 3.2  Resultant Observations of Tattoos through the Stages of Decomposition Stage of Decomposition (Proposed by Reed, [1958]) 1 (“Fresh”) 2 (“Bloating”)

3 (“Decay”)

4 (“Dry”)

Marked Changes to Tissue None reported Slight darkening of the skin Sloughage of epidermal layer followed by formation of waxy layer Increase in skin discoloration Dehydration (leathering) Increasing discoloration Further decomposition

Appearance of Tattoo No change Enhanced tattoo visibility (brighter colors, defined lines) Decreased tattoo visibility Decreased tattoo visibility Leathery appearance, muted colors Decreased tattoo visibility Continued obliteration of the tattoo design

Source: Adapted from Bennett, J. and L. Rockhold. 1999. Journal of Forensic Sciences, 44(1), 183.

taking place. Table 3.2 summarizes their observations. The authors add that in several instances, recognition during the fourth stage of decomposition was only possible due to prior knowledge of tattoo location (Bennett and Rockhold, 1999, p.  183). Since tattoos may be obscured by the effects of decomposition, bodies that come into the morgue should be subjected to a screening process with an alternate light source to determine whether any tattoos may be present, especially in cases where there is no indication of identity. In addition to the work that has been conducted on the living and recently deceased, studies have been conducted using the techniques of infrared photography on mummified tissues, ranging from recent, shortterm mummification to ancient mummified remains. Oliver and Leone used both ultraviolet and infrared photography to visualize a tattoo on the mummified remains of a missing person (approximately 2 months time had elapsed between the missing persons report and discovery of the mummified remains) and Alvrus et al. used infrared reflectography/ photography to visualize tattoos on mummified remains dating from 350 bc to ad 350. Cover-ups are tattoos that have been covered or modified to either render the original tattoo invisible or different from the original design. The most drastic cover-up is blackening or blacking out the tattoo design by covering it completely with black ink. The result is often a boxy black tattoo in which no evidence of the previous tattoo design can be visually

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Forensic Analysis of Tattoos and Tattoo Inks

detected. Skin-colored cover-ups are meant to cover the tattoo design using flesh-toned pigments matched to the skin of the tattooed individual. “The tattoo is indelible, nevertheless, it seems that you can hide it with a new tattoo with a substance having the color of the skin, such as a mixture of white lead and vermilion” (Dechambre et al., 1895, p. 1593). The technique of using flesh-colored tattoo inks is currently considered cosmetic or medical and often used to treat birthmarks, skin grafts, or skin pigmentation abnormalities and diseases. Successful treatment requires understanding of the layering of skin, the presence and relative amount of melanin in the tissue, the depth of the tattoo pigment, light scattering and optical properties of the skin, as well as resultant color rendition. Experimentation with flesh-colored pigments, as well as multiple sessions, are often necessary to achieve the corresponding skin tone. According to Shimada et  al., with regard to predicting the color of the tattooed skin for matching; “The scattering and absorption coefficients of both skin and tattoo dyes were measured using an integrating sphere and an inverse Monte Carlo simulation. The Monte Carlo simulation was preformed to predict the reflectance spectra of the tattoo dye under the skin from the scattering and absorption coefficient … [This was done] to assess the agreement between the calculated reflectance spectra and the measured color” (Shimada et  al., 2002, p. 219). The authors further describe the “blanket method” of tattooing in which they describe peeling the epidermis layer by razor and injecting a sheet of tattoo (Shimada et al., 2002). Skin grafting is another alternative that has been used to cover up unwanted tattoos. Redesigning that tattoo is another common form of covering up an unwanted tattoo. Design modification consists of retaining the original design, but incorporating new details to enhance or improve that tattoo. Examples may include recoloring the original design or adding “touchups” in regions where the color has faded or adding tattoo designs around the existing design to make the design appear larger and in some cases more detailed. A common example of design modification in is the addition of clothing, such as a bikini, to a nude pin-up girl. This modification was often necessary for military personnel in order to maintain active duty in their branch of service, as the nude pin-up was considered obscene and not suitable for servicemen. Design changes consist of covering up a tattoo in its entirety in order to completely mask the original design or to have the new design blend in such that the old design cannot be detected. These complete design changes are often done in instances where a tattooed individual has a name tattooed on their body which they would like completely obscured at a later date. Detection of original tattoo designs that have been covered up or obliterated can often be conducted using infrared photography techniques (Figure 3.8).

Tattoo Modification, Removal, and Detection (a)

(c)

67

(b)

(d)

Figure 3.8  Examples of tattoo cover-ups in which the original design was cov-

ered with a larger design. (a) and (c) are of the existing tattoo, and (b) and (d) are infrared images of the tattoos. Based on the infrared images, the original designs can be resolved. In the photo at the lower right, the name “Jen” becomes apparent.

Tattoo Removal Methods Tattoos as punishment were effective measures to disgrace and humiliate, as well as permanently draw attention to those slaves, deserters, and prisoners who were so marked. It is reasonable to assert that with the application of these tattoos, so arose the need for methods of removal. Gustafson states, “Given the heavy yoke of the tattoo, those released from their sentences are allowed to return home … could never completely resume normal life.

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Unless, of course, they could get rid of those ‘indelible’ marks” (Gustafson, 2000, p. 24). As such, the development and evolution of removal techniques are as numerous as the processes of tattooing; with methods varying in harshness as well as success. Tattoo removal is the method of removing the tattoo from the skin by various methods. Depending on the technique employed, removal success can vary, as well as the number of treatments necessary and the amount of pain experienced by the tattooed individual. In general, removal is affected by several factors, including pigmentation and characteristics of the skin, pigment color, depth of tattoo pigment within the tissue, and pigment chemistry. Early methods of tattoo removal included mechanical methods, chemical cauterization and chemical peels, and thermal methods. Due to the invention and application of lasers to dermatological studies, more advanced thermal methods are routinely employed presently. Mechanical methods vary in their degree of severity and resultant disfigurement (Figure 3.9). Early methods were crude and painful, and the success of removal was questionable. Dermabrasion, or scraping/abrading the skin, was conducted using sandpaper, a wire brush, or any abrasive material that could remove the layers of the skin to expose the pigmented layer. This layer could then subsequently be removed with additional mechanical means or

Figure 3.9  Example of mechanical removal of portions of a tattoo, including an attempt by the tattooed individual to cross out the name TONI using a knife.

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any of the various chemical methods described later. More recent dermabrasion methods may incorporate a diamond fraise.* Other mechanical methods include cutting or excision of the tattooed area that may or may not be followed by skin grafting to replace the excised tissue. Skin grafting was more likely to be found in settings where the tattoo was removed medically under a surgeon’s supervision. “Some tattoos can be treated by cutting a moderately thick Thiersch graft from the area. Often the pigments extend through the full thickness of the skin, and nothing less than total excision of the design and filling the defect with a split-skin graft from elsewhere is satisfactory” (Bell, 1962, p. 259). As expected, these methods, both abrasion and excision, would leave extensive scarring in place of the tattoo. For forensic identification purposes, this resultant scar could be just as important as the tattoo itself. Perhaps the most drastic of all methods to remove a tattoo mechanically would be amputation. Parry reports such an instance, “In 1923, a man named Scanlon had lain down beside a track … with his left arm extended over the rail until a passing locomotive amputated it” (Parry, 1933b, p. 142). Veith describes a technique of removing gunpowder tattooing; the skin with the powder tattoo is raised by puncturing underneath the embedded particles with a needle. Once elevated, a scalpel blade is used to shave off layers of skin until the particle is removed (Veith, 1962, p. 45). In 2014, it was reported that a man used a steel wire brush to grind off his prison tattoos. According to the article, the tattoos were self-made in prison from a combination of melted checkers, grease, toothpaste, and pencil lead (sic.) and were subsequently removed using a wire brush followed by rubbing alcohol and peroxide and then smoothed with steel wool (Kuruvilla, n.p.). The chemicals used for cauterization and peels have varied substantially over time, with some exhibiting a high degree of success while others were debunked rapidly. The chemical treatments could either be applied to the surface of the skin or injected into the tissue similar to the methods used to tattoo. In some instances, chemical treatments were supplemented by mechanical means, such as salabrasion, which used sodium chloride to abrade the skin and facilitate the removal of the pigment once exposed by the action of the chemical. In the 1st century, Largus reported the use of an “ointment containing the heads of white garlic, ground up with cantharides from Alexandria and a concoction of sulfur, bronze coins, beeswax and oil” (Scutt and Gotch, 1974a and b, p. 136), Archigene (first century) and d’Egine (seventh century) report the use of urinary deposits, specifically the “scum on the inside surface of the chamber pot” mixed with strong vinegar (Scutt and Gotch, 1974a and b, p. 138); Marcellus (second century) reports pigeon feces ground up with vinegar (Ibid.); Oribase (fourth century) reports * A stainless steel wheel with diamond chips of varying coarseness.

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Forensic Analysis of Tattoos and Tattoo Inks

buttercups and caper leaves (Ibid.); Aetius (sixth century) reports Egyptian pine wood (acacia), corroded bronze, gall, vitriol, vinegar, water leek juice (Gordon, 1922, p. 15; Berchon, 1869, p. 93) and pepper, rue, orpiment, nitre and turpentine resin, followed by addition of salt (Scutt and Gotch, 1974a and b, p. 138). In their 1886 publication, Lacassagne and Magitot list a variety of methods of removal that they had encountered, including turpentine and potassium nitrate; brushing the tattooed area with indigo in sulfuric acid; retattooing with breast milk; placing a red hot spoon on the area followed by a solution of copper sulfate; scraping the tattooed area with wool followed by the application of hydrochloric acid and water; and retattooing over the design with a caustic liquid (Lacassagne and Magitot, 1886, p. 146). The technique of “tattooing the pigmented surface with glycerol of papoid” was advocated by Dr. Ohmann-Dumesnil in the 1890s (Shoemaker, 1909, p. 567; Steward, 1990, p. 85). Schiffmacher reports on a letter written in the 1950s by “Tattoo Jack” in which he used papain to remove tattoos. According to Tattoo Jack (A.W. Harvey), components required for removal included, cotton wool, healing ointment, local anesthetic, 80% ether or methylated ether plus 20% iodine, sticks of chloride of zinc, one ounce of papian in powder, and a tattoo machine with four or five needles in it (Schiffmacher, 2010, p. 372). In his letter, Tattoo Jack adds, “I don a surgeon’s white coat when tattooing. Little things make big impressions. I use the ether because … the smell resembling chloroform impresses the client with your scientific skill. Operational patients love hospital stinks…” (Schiffmacher, 2010, p. 372). In 1855, Tardieu rubbed in a salve composed of pure acetic acid and axunge, followed by a solution of potash, and finally weak muriatic acid. An acetic acid ointment was spread on and remained for 24 hours. The next day a solution of potash was rubbed into the area. The 1888 method reported by Variot, which used a concentrated solution of tannin (tannic acid) followed by rubbing in silver nitrate, was a technique employed frequently for tattoo removal. Variot’s technique required puncturing that tattooed region with a needle impregnated with the tannin removal solution. Bailliot reported the successful use of potassium bioxalate as a method of tattoo removal using a puncture technique similar to that of Variot (LeBlond, 1899, p. 86). According to the 1892 Western Druggist, “tattoo marks being due to insoluble matter deposited in the tissues, it is difficult to conceive how they could be removed otherwise than by the well-known process of vesication” (West, 1892, p. 471). With regard to the removal of gunpowder stains, the 1893 Western Druggist states, “…gunpowder stains may be removed by painting the skin with a solution of mercuric iodide in an equal weight of water, following this up with dilute hydrochloric acid, to reach the tissues more deeply affected. Just what the effect of this is on the skin, or how it would serve in the cases of [I]ndia ink marks, we are not prepared to say” (West, 1893, p. 70).

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Shoemaker reports, “Tattoo marks may be removed by electrolysis or by the action of some cauterant … Nitric acid and ethylate of sodium have also been used for their cauterizing action, applied by means of a pointed wood or glass rod, allowed to remain upon the surface for a minute or two and then washed off with water … Stains due to gunpowder may be removed by washing the skin with equal parts of biniodide of ammonium and distilled water, which causes the spots to grow gradually red. The red stains are made to disappear by the application of dilute hydrochloric acid” (Shoemaker, 1909, p. 567). Lacassagne and Rousset reported the use of potassium permanganate crystals for removal of tattoos (Scutt and Gotch, 1974a and b, p. 138). In his Famous Zeis Tattoo Artist Course, Zeis devotes a whole lesson to “The Truth About Tattoo Removing.” He laments, There is a great deal of mis-information on the subject of removing tattoo marks … [tattoo artists] will forward such misinformation as goats milk, human breast milk, salt or anything else that comes to mind … Now let us analyze the problem in a rational manner. What is to be removed? It is a color in the lower dermal or skin. What kind of coloring is this? Is it a dye that can be dissolved, or can it be drawn out. Emphatically no. Tattooing colors are insoluble pigment that have been pushed into the skin causing them to be anchored there, intermingled solidly and are inseparable with the skin … And old tattoo appearing faint has not faded, but has grown below and between much new skin. If you can visualize this, then you must come to the conclusion that to remove a tattoo means removing the skin. It now narrows down to the question of how to remove the skin without causing ugly scars (n.p.; emphasis in original).

Zeis then goes on to report a formula and method for which he has received success. It is the formula that required the use of powdered tannic acid, listerine, pure glycerine, and peroxide (Zeis, 1960, n.p.). According to Scutt and Gotch, “The Zeis studio has a salve made of Chinese white, concentrated tannin, glycerine, phenol and peroxide that will remove large surfaces with the smallest amount of scar tissue” (Scutt and Gotch, 1974a and b, p. 141). Goldstein reports salicylic acid, chloroacetic acids, phenol, sulfuric acid, nitric acid, and zinc chloride (Goldstein et al., 1979, p. 901); Solis et al. report imiquimod and tretinoin; and other reports include acetic acid, trichloroacetic acid, sulfuric acid, and a white substance that was believed to be powdered magnesia. Gross reports the use of indigotin disulphonic acid (Gross, 1924, p. 112) as well as reporting on other earlier methods with modifications. Parry reports on tattoo removal methods used by San Francisco tattooer Louis Morgan. Writing in 1912, he described a Chinese white paint in powder form as a good removing agent if mixed with a very weak carbolic acid … Other removal methods recommended in Morgan’s curious manual are; 1) four parts of slacked

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Forensic Analysis of Tattoos and Tattoo Inks lime to one part sulphur, mixed together dry and supplemented with a small percentage of powdered phosphorous, wetted with water…; 2) nitric acid, to be applied to the skin for periods of two to three minutes, and then washed off with clear cold water; 3) three parts of chloride of zinc to four parts of sterilized water; 4) zinc mixed with salt (Parry, 1933b, p. 145).

A variety of “folk” remedies were reported, which met with varied success, including human breast milk (sometimes with honey and oil), urine (stale, decomposed), vinegar, garlic, pepper, lime, pigeon excrement, cow’s milk (attributed to the bacteria), heavy cream, and Spanish fly (cantharides). According to Parry, Samuel O’Reilly “frowned upon the belief that mother’s milk shot through a needle would remove tattooing or that urine would do the job even better” (Parry, 1933b, p. 45). As such, Parry compiled a list of “methods of tattoo removal scientifically tested and approved by chemists, physicians, and surgeons” (Parry, 1933b, p. 145):

1. French Process—tannic acid and silver nitrate 2. Salicylic acid 3. Monochloroacetic or Trichloroacetic acid 4. Carbolic acid (phenol) 5. Sulfuric acid (15 grains to 1 oz of water) 6. Nitric acid (concentrated) 7. Zinc chloride 8. Mercuric chloride 9. Cantharides plaster (Spanish fly). Add vinegar to increase its action or open the blister formed by Spanish fly and add a weak zinc chloride solution 10. Glycerol of papoid (or glycerol of cariod). A powerful organic digestant; it digests the tissue in question 11. Zonite, a solution of sodium hypochlorite, approximately twice as strong as Dakin’s solution 12. Electrolysis—similar to hair-removal by electricity; feasible only on small tattoo designs 13. Surgery: cut mechanically, raise the flap of the cut skin, scrape off the pigment from the bottom of the skin 14. Surgery: use a grattage (a little steel scrubbing brush), apply hydrogen peroxide 15. Use cutaneous trephine (a surgical instrument resembling a hollow carpenter’s tool) 16. When a design is superficial, use dry ice (CO2 snow). It will freeze the skin, turning it gray; then the skin may be removed with tweezers 17. For long thin designs: simple excision 18. For larger designs: excision with skin grafting

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Parry adds, “These methods are not to be used by the tattooed themselves or by tattoo masters but by physicians or surgeons only. The list is compiled on the basis of chemical and medical literature dealing with tattooing and its removal” (Parry, 1933b, p. 146). In their 2010 review, Choudhary et al. describe Tri-Luma and Imiquimod as being “what’s new in laser tattoo removal” (Choudhary et al., 2010, p. 623). They describe Tri-Luma as a commercially available bleaching cream that combines tretinoin, hydroquinone, and fluocinolone acetonide (Choudhary et  al., 2010). Although described as new in the article, both tretinoin and imiquimod were explored as treatment methods by Solis et  al. in 2002, and, in general, topical methods for tattoo removal such as these have been explored prior to this publication.

Thermal Cautery and Laser Tattoo Removal Thermal cautery was another method incorporated for the removal of tattoos. Initially, burning and branding were the primary techniques employed, but the advent of lasers revolutionized tattoo removal. According to Verhaeghe, hot coals, fire, and cigarettes have been used for centuries in an attempt to remove unwanted tattoos (De Cuyper and Perez-Cotapos, 2010, p.  93). In addition, electrocoagulation and infrared coagulation were used to remove tattoos (De Cuyper and Perez-Cotapos, 2010). A variety of lasers have found success in photothermolysis, including argon (Ar; 488 nm and 514 nm wavelength), carbon dioxide (CO2; 10,600 nm wavelength), and Q-switched lasers such as neodymium yttrium aluminum garnet (Nd: YAG; 532, 1064 nm), ruby (694 nm), and alexandrite (755 nm). The use of lasers in removing tattoos advanced the studies of pigment decomposition, which has led to reports about the decomposition products that result from tattoo removal via laser-induced breakdown. Evaluation of tattoo removal by the use of thermal decomposition has seen an extensive evolution since its first applications. The first use of lasers to observe the effects on tattoos was reported in the 1960s. According to a short report published in 1965, Goldman et al. studied the beam impact of various lasers on a dark blue flower tattoo. The authors report, “the dye used was not identified although many tattoo artists use indigo and Campeachywood for blue tints” (Goldman et  al., 1965, p.  69). This report was subsequently followed by the use of lasers to remove tattoos. Since that time, use of lasers has increased and evolved from being an experimental technique to common, routine practice. In addition, the use of various wavelengths to remove tattoos has been explored and has broadened the applicability of the method. The theory of laser removal is based on the optical properties of the skin as well as the selective absorption of different wavelengths of radiation of the

74

Forensic Analysis of Tattoos and Tattoo Inks OH

O O HO

N H

HO

N H O

(COOH)

H2N HOOC

(COOH)

H N

CH2 N

S

HOOC

CH3

O OH

S N

N

(COOH)

H3C

N

N FeII

OH

N

N CH3

H3C

S

CH2

(COOH)

O OH

N H

Eumelanin

H2N

COOH

Pheomelanin

O

OH

O

OH

Hemoglobin

Figure 3.10  Chromophores found within the skin.

various chromophores within the skin and the duration of the pulse of radiation at a given wavelength. Absorption of the radiation by the chromophores generates heat, which can effectively destroy the chromophore, as well as any structures in the vicinity of the chromophore (selective photothermolysis). The characteristics of the chromophore (molecular structure, particle size, volume within the tissue) as well as the substrate (skin pigmentation) should be considered when selecting the laser type (wavelength, pulse duration, spot size, etc.), although this can be challenging when the chemical composition of the tattoo ink is unknown, which is more likely than not. Equally as challenging is the chemistry of the skin, specifically the presence of chromophores inherent in the epidermal and dermal layers (Figure 3.10). A “parameter necessary for selective destruction of tattoo ink is the appropriate wavelength to achieve selective absorption of the light energy to avoid nonspecific thermal effects. The primary tissue chromophores competing for laser absorption are … hemoglobin and melanin” (Goldman and Fitzpatrick, 1994, p.161). While the exact mechanism of tattoo removal is not known, the treatment leads to alteration of the optical properties of the tattoo pigments by destruction and thermal, photochemical, or photoacoustic means (Choudhary et al., 2010, p. 621). Goldman and Fitzpatrick note that, in general, results are better for colored tattoos when the laser wavelength is well absorbed by the particular ink (Goldman and Fitzpatrick, 1994, p. 16). The authors add “[s]ignificant details of wavelength dependent effects are unknown. The chemical identity of most tattoo inks and how they are affected by high intensity laser pulses are unknown” (Goldman and Fitzpatrick, 1994). Lasers routinely employed in tattoo removal include the Q-switched ruby laser (λ = 694 nm), Q-switched Nd:YAG (λ = 1064 nm; the frequency doubled Nd: YAG laser has a wavelength of 532 nm), and the Q-switched Alexandrite laser (λ = 755 nm). Based on the theory of photothermolysis, by choosing the appropriate optical radiation, one can selectively target and

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damage the desired chromophore while minimizing any surrounding collateral damage (Parlette et al., 2008, p. 18). Using the Q-switched ruby laser, Taylor et al. (1991) reported There is clear evidence of mechanical changes in both the tattoo pigment granules and the cells containing them. The reduction in pigment particle size and fragmentation of pigment-containing cells probably results from rapid thermal expansion, shock waves, and potentially localized cavitation. In addition, localized thermal denaturation of cellular proteins, such as enzymes, and extracellular proteins, such as collagen, may play some role in the damage and initiation of its repair … It is also clear that there is also limited fluencedependent thermal damage to collagen immediately surrounding pigmentcontaining cells (Taylor et al., 1991, 136).

Interestingly, the authors add, a redistribution of pigment particles without their removal may also be implicated in the lightening of tattoos (Taylor et al., 1991, p. 136). This potential redistribution, or presence of deeper pigment particles that are not targeted by lasers may explain why it is still possible to resolve tattoo designs using infrared imaging methods. Taylor et al. intuitively note that the task of analyzing Q-switched ruby laser-treated tattoos may be facilitated by knowledge of the specific ingredients used in the making of tattoos (Taylor et al., 1991). Generally speaking, with regard to some of the studies concerning laser removal of tattoo inks, specifically the dermatological and histological studies in which tattoo inks are applied to tissue and then tested for the robustness of tattoo removal with different excitation wavelengths, no specific information regarding the ingredients of the tattoo inks employed is provided, whether from labels or from any confirmatory testing such as microscopy or instrumentation. In many studies, the tattoo inks are simply referred to by their perceived color; black (as well as the derivatives blueblack and green-black; whether these color differences are attributed to actual pigment composition/ink source or due to the effects of light interaction with the pigment particles in the skin is not clearly distinguished, nor does it appear to have been an impetus for any qualitative analysis), yellow, green, red, and so on, and no information concerning chemical composition of the inks is noted. These studies tend to focus on the success of a given laser of known wavelength with given parameters (spot size, pulse duration, passes, etc.) on the removal of an ink based on its color, with success being measured based on the visual fading and disappearance of the tattoo over time. Typically, the “results” will be summarized in a table in which each laser is compared to its ability to successfully remove a particular tattoo ink color (Tables 3.3 and 3.4).

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Forensic Analysis of Tattoos and Tattoo Inks Table 3.3  Lasers and Their Use in Tattoo Removal for Different Color Pigments Pigment →  Laser ↓ Alexandrite (755 nm) Ruby (694 nm) Nd: YAG (1064 nm) Nd: YAG (532 nm)

Black

Blue

Green

X X X

X X X

XX X

Red

X

Source: Adapted from Choudhary, S. et al. 2010. Lasers in Medical Science, 25, 624. Note: The authors do not assign any specific provenance to the table provided or any specific information regarding the relative weight of the X’s.

In their review of laser use for tattoo removal, Choudhary et  al. state, “Tattoos can be classified on the basis of the color of pigment used to create them. The most common color is black, but over the years … multiple colors such as red, blue, green, brown, etc. have become increasingly common and popular. Often, two or more colors may be mixed to develop shades of a particular color or a new color…” (Choudhary et al., 2010, p. 619). Dozier et al. tattooed human skin with red, yellow, blue and green tattoo pigments; their only reference to provenance was the note that the inks were “obtained from a professional tattoo house” (Dozier et al., 1995, p. 238). Furthermore, when some references refer to the chemical compositions of tattoo inks, they refer to older reports, which refer to older chemistries. Taylor et al. refer to Slater and Durrant’s 1984 study* (Taylor et al., 1991, p. 136) and, in Kent and Garber’s 2012 article, the following table (Table 3.5) pertaining to “Pigments found in common tattoo colors” is provided and the author’s note the adaptation of this table from Parlette et al. (2008, p. 5). Pfirrmann et al. note in their 2007 review of tattoo removal the transition from metal salts to industrially manufactured organic pigments (Pfirrmann et al., 2007, p. 891). It would appear that a better way to conduct the aforementioned studies would be to obtain tattoo inks, determine their chemical composition as well as light absorption properties via UV-Visible spectrophotometric methods, and then use those inks to tattoo human skin; which could be subsequently exposed to different types of laser removal treatments. In this way, studies could, potentially, more accurately determine the ideal removal techniques for a given tattoo ink based on the pigment composition, which could affect the absorption characteristics relative to specific laser excitation wavelengths during the removal phase. In addition, these studies may help researchers determine whether or not tattoo pigment composition plays a major role in * See Chapter 5 for details regarding Slater & Durrant’s study.

Pigment →  Laser ↓

Black, Gray Black, Gray

Ruby (694 nm) Nd: YAG (1064 nm) Nd: YAG (532 nm) Alexandrite (755 nm) Dye (510 nm)

+ –+ + + + –+ + + (+) + –+ + + (+)

Blue (+)– + + (+)– + + (+) + –+ +  (+)

Violet/Purple + –+ + + Ø–(+)– + + (+) (+)– + + (+)

Green

Red

Orange

Yellow

Skin Colored, White

Brown

(+)– + + (+)– + + Ø–(+) (+)– +  Ø–(+)

Ø– +  Ø–(+) + –+ + + Ø–(+) + –+ + +

Ø Ø Ø Ø Ø

Ø– + + Ø– + + Ø– + + Ø– +  Ø– + +

Ø– +  Ø– +  Ø– +  Ø– +  Ø– + 

(+)– + + (+)– + + (+) (+) (+)

Source: Adapted from Pfirrmann, G. et al. 2007. Journal der Deutschen Dermatologischen, 10(5), 892. Note: The Ruby, Alexandrite, and both Nd:YAG lasers were quality switched. The authors reference four studies as being the source of the table, although no specific information regarding the system of reporting is provided.

Tattoo Modification, Removal, and Detection

Table 3.4  Suitability of Different Lasers for Different Tattoo Colors

77

78

Forensic Analysis of Tattoos and Tattoo Inks Table 3.5  Pigments Found in Common Tattoo Colors Color

Pigment

Black

Carbon Iron oxide Logwood (extract from logwood tree) Cobaltic aluminate (azure blue) Chrome oxide (Casalis green) Hydrated chromium sesquioxide (Guignet’s green) Malachite green Lead chromate Ferro-ferric cyanide Curcumin green Phthalocyanine dyes (copper salts with yellow coal tar dyes) Mercury sulfide (cinnabar) Cadmium selenide (cadmium red) Sienna (ochre-ferric hydrate and ferric sulfate) Cadmium sulfide (cadmium yellow) Ochre Manganese violet Titanium dioxide Zinc oxide Iron oxides (a variant of color)

Blue Green

Red Yellow Violet White Flesh

Source: Reported by Kent, K. and E. Graber. 2012. Dermatologic Surgery, 38, 1–13.

the success of tattoo removal, relative to other factors such as pigment depth of deposition and encapsulation, characteristics of the skin and characteristics of the laser. In their study focused on laser tattoo removal, Hu et al. reported the following “Properties of tattoo pigments used in [their] study,” of which the chemical compositions were obtained from the pigment bottle labels (Hu et al., 2002, p. 156) (Table 3.6). While the information reported on the bottle labels may not be the most accurate and reliable data, it is certainly information that should be documented and considered when interpreting the strengths and weaknesses of lasers and their removal efficiencies. Correlation to specific pigments may increase the efficiency of laser tattoo removal. In addition, studies of the breakdown products of tattoo pigments as a result of initial laser treatments may help determine the best follow-up methods for complete removal of the tattoo upon subsequent treatments. In what seems to be a more recent phenomenon, semi-permanent, easily removable tattoo inks have been marketed. These tattoo inks are described as being easily broken down by the photodecomposition over time, which can be expedited with the use of laser removal techniques. Interestingly, this concept is not as novel as it may appear; in 1933, Parry indicates “Charlie Wagner now mysteriously hints that he has begun negotiations with a

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certain manufacturer of chemicals. The manufacturer has a new pigment that can be needled into the skin in the old way but for a limited term, at the expiration of which the design will begin to fade and soon will disappear” (Parry, 1933b, p. 12). Currently, an ink developed by the company Freedom2, Infinitink, is described as being a tattoo ink that can easily be removed by laser irradiation. According to the company, the ink is based on a particle encapsulation delivery system (PEDS). Choudhary et  al. describe the ink as, “…microsphere encapsulated bioresorbable pigments. The microspheres contain discrete pigment that can be targeted by a specific laser wavelength. The laser treatment during the tattoo removal would cause the capsule to break, exposing the pigment. The pigment is then resorbed by the body. The tattoos made by using such a solution can be removed using a single treatment” (Choudhary et al., 2010, p. 623). According to Klitzman and Koger’s Tattoo Ink patent, it is to, “present [an] invention to produce a tattoo ink which can produce tattoos that can remain indefinitely or which can be removed on demand, [that is], erasable Table 3.6  Tattoo Pigments Reported in Hu et al.’s (2002) Study Pigment Blue (navy liner) Black Red (red lip liner 3) Green (green 2) a

Chemical Composition (from Bottle Label) Iron oxide, ultramarine blue and violet, glycerin, isopropyl alcohol, titanium dioxide Iron oxide, glycerin, isopropyl alcohol, titanium dioxide (Organic) iron oxide, D&C red no. 30a, D&C red no. 7b, glycerin, isopropyl alcohol Chromium hydroxide green, glycerin, isopropyl alcohol, titanium dioxide

Vat Red 1. O S

S

CI

CI

O b

Pigment Red 57. O

Na+ O– S O

N

N HO –O

O Na+

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Forensic Analysis of Tattoos and Tattoo Inks

tattoos” … “present [an] invention to produce a tattoo ink which yields semipermanent tattoos, [that is], tattoos that disappear after a predetermined period of time” … “provide a method for producing a tattoo that disappears upon imposition of exogenous energy”… “for producing a tattoo with pigments or dyes that were previously considered unsuitable for producing a tattoo” (Klitzman and Koger, 2000, p. 2). With regard to the latter, the authors describe that by “entrapping, encasing, incorporating, complexing or encapsulating or otherwise associating the p ­ igments” … it is possible to increase the variety of pigment colors that can be used for tattooing to include “pigments … that, because of their physical characteristics, would otherwise be readily eliminated from the dermis,” such as water-soluble pigments, as well as expand the effects that can be obtained from tattooing; for example, by the addition of fluorescent or phosphorescent “glow-in-the-dark” pigments to produce tattoo inks which exhibit photoluminescence (Klitzman and Koger, 2000, p. 4). Currently, over 50 different colors and shades of pigment are used in tattooing, ranging from metallic salts, such as iron oxide and titanium dioxide, to synthetic organic dyes. Additionally, colorants obtained from natural sources, such as annatto extract, beta-carotene, B-Apo-8’ carotenal, beet powder, canthazanthin, caramel color, carrot oil, cochineal extract, ferrous gluconate, grape color extract, grape skin extract, paprika, riboflavin, saffron, turmeric, and vegetable juice, can be used in the inks according to the present invention. Additional coloring agents that may be used in preparing inks according to the present invention include color additives for use in the U.S. for foods, drugs, cosmetics, and medical devices … (Klitzman and Koger, 2000, p. 12).

It is evident that having an understanding of pigment composition and the overall chemistry of tattoo inks is critical whether evaluating dermatological methods of removal, the overall retention and detection of tattoos over time, or the reliability of tattoos in forensic investigations. What follows is a detailed report and study of the chemistry of tattoo inks.

Tattoo Inks and Pigments: History and Chemistry

II

General Components of Tattoo Inks

4

Tattoo inks are generally composed of a colorant and auxiliary ingredients. Colorants are generally pigments or dyes. A pigment is a finely divided colored substance that imparts color effects when mixed with another material. When a pigment is mixed or ground in a liquid vehicle, it does not dissolve but remains dispersed or suspended in the liquid (Mayer, 1991, p. 29). Pigment classifications include inorganic or mineral pigments, and organic pigments, which include vegetable, animal, and synthetic pigments. In general, pigments derived from natural sources are less permanent than the average synthetic color while synthetic organic pigments are characterized by great brilliance and intensity. Many of them are permanent but others, particularly the older ones, are fugitive and tend to fade or disappear over time (Mayer, 1991, p. 31). The chemical purity of pigments varies greatly. Some are simple, almost pure compounds while others of equally high quality contain minor components either as natural impurities or as the result of ingredients added during manufacture to modify the color or pigment properties (Mayer, 1991, p. 33). Permanence treatment is defined as resistance to fading. This fading usually occurs through exposure to ultraviolet radiation or sunlight which contributes to the photodecomposition of the pigment. A dye is a colored substance that dissolves in liquid and imparts its color effects to materials by staining or being absorbed (Mayer, 1991, p. 29). An ink is generally defined as a liquid that contains pigment or dye. Often it is in solution in which the solute and solvent are uniformly distributed, producing a homogeneous mixture. A tattoo ink is a suspension of pigment particles in a solution. Although considered a solution, the purpose of the liquid is most often to act as a vehicle to facilitate introduction of the pigment particles into the skin. As such, the liquid portion of the tattoo ink is meant to evaporate or dissipate into the tissue when deposited on and into the skin (Figure 4.1). Tattoo inks contain a variety of auxiliary ingredients, which include the vehicle, the solvent, and additives. Additives may be wetting agents, preservatives, stabilizers, thickeners, and pH regulators. In addition to tattoo inks, which are premixed liquids, powder solids are also encountered. These require the addition of liquid component which is often done by the tattooist.

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Forensic Analysis of Tattoos and Tattoo Inks

Figure 4.1  Green tattoo ink spot on white paper, demonstrating the separation of the pigment and a portion of the liquid component.

Liquid Composition of Tattoo Inks Liquid components of tattoo inks have varied throughout time. According to Parry, in the modern electric method, the dry coloring pigment was mixed with water, alcohol, cocoa oil, or saliva; only the black color came as a readymade ink (Parry, 1933b, p. 46). Current professional inks vary with regard to their ingredients. Vehicles, or carriers, may be composed of one or more of the following: water, alcohol (ethanol, isopropanol), glycerin, glycerol, hamamelis (witch hazel), and propylene glycol. The additives may vary as well: wetting agents include glycerin and ethylene glycol; preservatives include benzoic acid; stabilizers include barium sulfate; and thickeners include glycerin. In addition, there may be substances present that facilitate the adhesion of the pigment particles to the needle. Other materials that may be encountered in the liquid composition of the tattoo inks include methanol, glutaraldehyde, detergents, and benzoates. Homemade tattoo inks, in which a liquid is added to the powder pigment to create an ink, may incorporate the use of Listerine (which can be used as a thinning agent), vodka, propylene glycol, glycerin, or witch hazel. According to Cohen, “… Listerine was used by tattooists to suspend the pigments used to tattoo. Before the recent reformulation of Listerine, it contained a small amount phenol, or carbolic acid, which is a potent bacteriostatic agent. Other components of Listerine acted as wetting agents … The wetting agent’s primary function was to keep insoluble pigment particles suspended in a vehicle which was innocuous to the skin … Glycerine (just a few drops) could be used prevent drying out of the colour jars and as an emulsifying agent” (Cohen, 1994, p. 272). Cohen goes on to discuss the formulation of colors,

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85

“Dry D&C approved color pigments are mixed with pure were 70% isopropyl alcohol (easily obtainable rubbing alcohol without any additive ingredients such as methyl salicylate or methanol). Several drops of pure glycerine are added by some artists at this point (others use rosewater and glycerine in equal parts). Sterile distilled water may be added later for thinning” (Cohen, 1994). Norman “Sailor Jerry” Collins reports that the dry powder pigments are mixed with an antiseptic solution of alcohol and water with zephiran chloride. Some have used liquefied phenol as an additive (Collins, 2004, p. 6). More amateur tattoo inks, such as those that are made in prison, may use saliva, shampoo, water, or urine as a liquid component.

Pigment Composition of Tattoo Inks The ideal pigments for tattoo inks are those that exhibit selective absorption and scattering of light, are chemically stable as well as light and heat stable. The historical evolution of pigments has seen a shift from natural to synthetic and inorganic to organic. Most of this evolution has been due to experimentation by tattooists.

Homemade Tattoo Inks Amateur tattoo inks, characterized as those that are homemade and prisonmade, have incorporated ballpoint pen inks, ink recovered from a print shop or hobby class, such as India ink, as well as the soot collected from burned utensils and plastic materials. “Criminal tattoos are usually blue; multicolored tattoos have only recently appeared. Originally the ink was homemade a mixture of soot, sugar, ashes, and urine. The most common way of applying a tattoo was to bind three or four sewing, or syringe, needles to a match with a thread. Sometimes, Staples or shortened paperclips were used. Another method involved a plank with needles arranged to form the desired design … Today ink from a ballpoint pen is used instead. An electric shaver can easily be fashioned into a tattoo machine” (A. Sidorov in Baldev, 2012c, p. 379). “For the ink, (the prisoners) burn a candle against the cement ceiling and scrape off the soot, or they burn toilet paper and crumble the ashes in water. Either way they get pure carbon, which is after all the basis for the professional tattooist’s black ink. Neither this pure carbon, however, or ordinary “India” ink is stabilized with the addition of iron oxide, and consequently turns blue after a little while” (Steward, 1990, p.  72). The use of drawing and writing inks such as Indian ink, Pelican ink, and printer inks have also been reported (De Cuyper, 2008, p. 18). “In Danish prisons, tattoo colors and instruments

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Forensic Analysis of Tattoos and Tattoo Inks

are forbidden. However, some prisoners constructed tattooing instruments by mounting steel needles on electric shavers. Owing to the lack of standard pigments, the prisoners improvised, viz, they used a paint that is used for posters, for hobby crafts and for decoration” (Schmidt and Christensen, 1978, p. 965). The poster paints used for hobby work in this prison were scarlet and dark green. According to Schmidt and Christensen, the scarlet paint contained Pigment Reds 3, 4, and 95 and the dark green paint contained Pigment Yellow 1, Pigment Green 7, and Pigment Blue 15. Furthermore, they report that both paints contained chalk, dolomite, and casein as binders and the preservative chlormetacresol (Schmidt and Christensen, 1978). Additional ingredients found in homemade tattoo inks may include residue from burning an object such as paper, a StyrofoamTM cup, plastic cutlery, a toothbrush, a plastic chess piece, or any plastic object that could be melted to generate black sooty material (Figure 4.2). Also reported was the use of ash from a cigarette. Ink from a writing implement such as a pen or Sharpie marker, shoe polish or shoe soles, or powdered pigment have also been used. The solution, or liquid portion of the homemade ink, may be made up of a combination of water, saliva, shampoo, witch hazel, vodka, Listerine mouthwash which, according to the MSDS sheet contains ethanol, eucalyptol, thymol, menthol, methyl salicylate, benzoic acid, sodium hydroxide, hydrochloric acid, and water. Glycerin, propylene glycol(s), rubbing alcohol, and nail polish remover (acetone) can also be commonly employed in homemade tattoo inks. The inks are typically introduced into the skin by crude methods using glass, pins, razor blades, paper clips, staples, metal coils, or light bulb filaments. The basic process is to burn the plastic/paper-based material and collect the smoke in or on a material held above it (such as a bottle cap or foil). The resultant sooty residue is collected and mixed with the suspending liquid (soap, water, alcohol, etc.) and then applied into the skin using the injection tool.

Wick (can be made from a dry mop strand)

Object to collect smoke (metal; material that will not melt)

Vaseline Cup

The smoke that will collect on the surface (black soot)

Figure 4.2  A drawing made by a tattooist being held in a detention facility; here he is demonstrating the process of obtaining the soot used as the pigment portion of tattoo ink made while incarcerated. After scraping off the residue, it is combined with hot water and shampoo (C.P., personal communication).

General Components of Tattoo Inks

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Professional Tattoo Inks Professional inks, or those that are used by “official” tattoo artists, have undergone quite an extensive evolution from natural plant-based materials to mineral pigments and more recently to synthetic organic pigments. In Bolton’s 1897 article, the reader gains some insight into the status of colors and types of inks being employed in tattooing at the end of the nineteenth century. Of the Japanese tattooist Hori Chyo, Bolton describes his greatest discovery as the use of the third color brown in addition to the regulation blue-black and vermilion (n.p.). He also describes the practices of sailors, who, for the purpose of identification in case of death by drowning, pricked gunpowder into their arms and the back of their hands, then touched it with a lighted match to produce a scar (n.p.). According to Parry, by the 1930s, the pigments used by the original tattooist were vermilion, gunpowder, India ink, and indigo (Parry, 1933b, p. 147). Ebensten reports, that by the 1950s, Colours in use are chiefly blue-black and red. The blue-black, actually perfectly black but appearing with the bluish tint when under the skin, is by far the most commonly used and may be made of a large variety of ingredients: lamp black, indigo, Chinese ink, gunpowder, animal or vegetable ash, soot, coal dust, and even the deposit scraped from the insides of pipes … Red is made of carmine, iron oxide, brick dust or other materials … Other colours are usually made out of a mixture of inks. Viridian green and brown are fairly common; yellow is considered the most difficult colour as it may cause a blister under the skin when exposed to the sun … Most tattooists work in a blueblack, red and one or two other colors. It is rare to find a tattooist who employs up to ten shades, all of which may be made out of five basic colours. In Japan, thirty two shades are known and in use. Colours are mostly dry and mixed with water, alcohol, special oils or saliva. The blue-black is often supplied in liquid form, ready for use, but more generally each tattooist will mix his own colours according to his own secret and closely guarded formula (Ebensten, 1954, p. 94).

In another note regarding tattoo pigments and the tattooist, Reiter states, Other important progressions in tattooing came with the development of pigments … the stability and longevity of these pigments in the skin in turn played a role in the reputation of the tattooer. A brilliant tattoo kept customers coming back. [Amund] Deitzel and a few others understood the importance of this and strived to find the best available pigments. These findings were also some of the most coveted … With only a basic understanding of these compounds, results could only be had by trial and error. Like-minded tattooers sometimes traded pigment manufacturer and code. And within these transactions was also a code of ethics. When handed privileged information, you kept

88

Forensic Analysis of Tattoos and Tattoo Inks it to yourself and only passed it on with permission of the originator. Those who did not follow this were quickly excluded (Reiter, 2011, p. 181).

Samuel O’Reilly settled in New York in 1875 and became a tattoo artist at 11 Chatham Square in the Bowery (Figure 4.3). He described himself as a “professor,” as many tattoo artists later did as well, and referred to tattoos as tattaugraphs. In the late 1800s, O’Reilly “expanded the choice of materials till it included such old and new stuff as powdered charcoal, finely powdered brick-dust, coal-dust, lamp black, Prussian blue, washing blue, gunpowder, cinnabar, ordinary writing ink, China ink, India ink and other vegetable inks” (Parry, 1933b, p. 45). In the early 1900s, it was reported that tattooists Amund Dietzel and William Grimshaw were tattooing with carbon black, China red, Casali’s green, and Prussian blue (Reiter, 2011, p. 8). It was also reported that Dietzel was using a yellow color of which the chemical composition is unknown. In a letter from Dietzel to Paul Rogers dated 1962, Dietzel writes I am sending you a jar of a new yellow. It’s very pure. Mix very easy, don’t raise, non-toxic. This is a straight yellow, too light alone, as you just add a pinch of red to it and it makes a nice yellow shade and not expensive. I find it better than any yellow I ever used. It will mix in plain water. My chemist friend got it for me … I make mine a deep yellow now and it looks good in the skin (Morse, 1977, p. 22).*

Figure 4.3  The Bowery neighborhood of New York City was considered a primary location for tattooing in the late nineteenth century.

* The color could have been an arylide yellow (“Hansa Yellow”), which was synthesized in the early 1900s.

General Components of Tattoo Inks

89

Milton Zeis (1901–1972) developed a business in tattooing, which included providing tattooing supplies and flash to tattoo artists. Zeis was well-known for his School of Tattooing (Figure 4.4), more specifically, his Tattoo Artist Course, which consisted of a series of lessons that was meant to prepare an individual for becoming a professional tattoo artist. The course provided a “How To” guide to drawing, shading, using a tattoo machine, and setting up a shop according to health department regulations. Zeis also covered matching colors to cover birthmarks and scars, tattooing animals, and hypnotism and tattooing. In Lesson 7 of the Zeis course, a section on How to Make Black Tattoo Ink provides recipes for two black inks. The first used Chinese stick ink (“some call it India ink”) dissolved in hot water, which was combined with a mixture of liquid camphor and “rectified spirits” (180 proof grain alcohol). The second called for lump camphor, rectified spirits, and black waterproof ink (n.p.). Zeis adds, “The best blacks come from Germany which are Chin-Chin concentrated water proof black ink, or Pelican concentrated water proof black ink manufactured by Wagner Gunther, Germany. A suitable black ink made in the United States is Schmincke Black Ink manufactured by the Grumbacker

Figure 4.4  Pamphlet for the Zeis School of Tattooing, c. 1953.

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Forensic Analysis of Tattoos and Tattoo Inks Table 4.1  Colors Used in Tattooing Reported by Zeis Different Colors

Chemical Names

Light and dark red Light and dark green Light yellow Deep yellow Light and dark brown and flesh Ivory black Mineral black White

Mercury sulfide Chrome oxides Iron oxide Cadmium sulfide Oxides of iron Carbon Oxide Zinc oxide

(sic.) Co., New York City” (n.p.). Additionally, a section on The Colors Used in the Tattoo Art provides a table (Table 4.1) of common colors and their chemical names (n.p.). Zeis follows the list of chemicals with a section concerned with How to Mix Dry Tattoo Color. He recommends the addition of zinc oxide (white) to all colors in order to get a variety of shades and to facilitate the tattooing process. To the powders, the addition of an ethyl alcohol and mercury preparation (“Phe-mer-nite 1:1000”) is directed. Pure glycerin and lump camphor can be added to prevent drying and souring, respectively. In addition, Listerine can be added as a thinning agent. Zeis also published pamphlets to educate the tattoo community (Figure 4.5). (a)

(b)

Figure 4.5  ​Zeis Publications, c. 1940s–1950s.

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Norman “Sailor Jerry” Collins (1911–1973) was a tattoo artist in Hawaii who pioneered tattooing and focused on bringing large, Japanese-style tattoos to the United States. He also worked to improve the art and method of tattooing by developing new techniques, tools, and tattoo inks. Don Ed Hardy describes a relationship between Sailor Jerry and Bob Palm, a tattooist in California; “Palm had attended Columbia University and majored in chemistry under the G.I. Bill. His understanding of science fitted well with Jerry’s keen interest and lay research into the composition and compatibility of various pigments for use in tattooing” (Hardy, 2007, p. 14). This reference is one indication that composing tattoo inks was a scientific endeavor for a tattoo artist. In his book, Hardy provides a series of letters exchanged between him and Sailor Jerry. In these letters, there are some notations of Jerry’s experimentation with different pigments as well as indications of the secrecy and competitive nature of their line of work. In a letter dated 1971, Jerry writes, “I was the first dirty bastard to start using purple, white, yellow and blue—now they are all trying to do it. Color is here to stay—good color that is!” (Hardy, 2007, p. 48; emphasis in original). Later in 1971 Jerry writes, “Phthalo green & white was my discovery…and now everybody uses it as standard procedure. I brought out purple, and so far, damn few have it, and that’s the way it should be. Anybody can get good color but damn few can get it in and that’s where we hold the edge and have to keep it” (Hardy, 2007, p.  66). Later, in his book Wear Your Dreams, Hardy comments that “Jerry was the only tattooer in the world with purple. It was a striking, true purple, a majestic, royal color and Jerry used it like secret weapon” (Hardy, 2013, p. 83). Cohen remarks on how Sailor Jerry Collins introduced some new and stronger tattooing pigments, “One was a pigment used in the paint industry (which) produced an intense [color?] which did not deposit unevenly in the skin. It was composed of 87% azo pigment (yellow), 7% calcium resinate and 5% barium sulfate*” (Cohen, 1994, p. 268). Jerry also remarks that he obtained a “really black” pigment by burning gum camphor and collecting the smoke on cheesecloth screens (Hardy, 2007, p. 88). Regarding his experimentation to develop better inks, “… none of these things should ever be tried out on anybody but yourself. I had a patch of violet on my leg that raised hell for 3 years … I got a sample of a hot booster with bright chroma that should beat anything we’ve hit yet. Will stick it in my leg and give you a report on the reaction … Damn these dark reds, they just die in the skin … it don’t have the chroma to stand against light, but I think I’ve got onto a good one” (Hardy, 2007, p. 94). He follows up “Red spot on my leg healing clean, no irritation, so if it stays in and holds its chroma I think it will be better than our present booster…” (Hardy, 2007, p. 95). * This statement is not clear in the text and it is noted that the total does not equal 100%.

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Forensic Analysis of Tattoos and Tattoo Inks

It is apparent that Sailor Jerry had an extensive understanding of pigments and pigment chemistry whether of his own accord or due to his consultation with Bob Palm. According to Collins, “The truth is that all colors used in tattooing are the same basically, some being more chemically pure than others and devoid of adulterating substances or inert materials that may have been added to give more bulk at a lower price. The only guide in this is to buy from a reputable firm that will reveal the contents of the colors they sell, and to buy only the best and purest color available. The rest lies in the way the color is put into the skin” (Collins, 2004, p.  64). Scutt and Gotch report the views of a practicing tattoo artist: My own experience is that … reds, yellows and browns from the U.S.A. are not to be trusted, as, although they are very bright and easy to put into the skin, they often produce a nasty reaction as when the tattoo is exposed to heat or sunlight red and yellow parts of the tattoo will swell … Viridian is difficult to put into the skin, even when mixed with a white base … Windsor green is a very satisfactory bright green … Scarlet lake is about the best and safest red available anywhere … Cadmium-base reds and yellows, viridian green and zinc white may be used satisfactorily in some cases … All the colours … I have mentioned up to now apply mainly to professional tattoo artists. [Amateurs] will use almost any old thing and most of their colours come from doubtful suppliers who advertise in newspapers … It is anyone’s guess what type of colours they supply but I have seen some grisly results from their use … (Scutt and Gotch, 1974a and b, p. 134).

Contradictory information has been recorded in the literature regarding which country possessed superior colors in quality and quantity. Some of the literature attributes the superior abundance of color to Japan, while others report that the better colors were developed in the United States. According to Collins, “A few of the Japanese artists are beginning to recognize the practicability of machine work over the old style of hand work and the superiority of American color as opposed to their own limited color supply” (Collins, 2004, p. 9). It is difficult, even from a comprehensive review of the historical literature, to ascertain which country actually possessed the more superior colors and to determine where the improved colors were first applied to tattooing. Cohen adds that in Japan, the main pigments used in pre-World War II days were brown, vermilion, and sumi (black carbon ink block) … new, less toxic pigments were imported from Australia and the traditional black and white Chinese painting approach to tattooing declined (Cohen, 1994, p. 271). It is likely that the development of novel colors for use in tattooing was occurring concurrently in different regions of the world (such as Japan, Europe, and the United States), as was alluded to by Bolton in 1897. With regard to Sutherland Macdonald of London, Bolton states,

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In addition to using (Hori) Chyo’s three colors (red, blue and black), [Macdonald] has, after much patient investigation, discovered a permanent ultramarine blue and a very beautiful green, both perfectly harmless to the human skin, and he is now diligently practising on his own body for a yellow and a lavender. The two chief difficulties to be overcome is that many skins will not stand any known yellow, throwing it out very soon after it is worked in, or else, as it heals, it will turn to a very different and unpleasant color; and this applies also to all of the lavenders at a present known to science. But it is only a question of time and money with him, and before long he will be using no fewer [than] seven different colours; and, by mixing one [or] two of these, he will have nearly as many to choose from as the oil or water colour artist (n.p.).

Samuel Steward, also known in the tattoo world as Phil Sparrow (1909– 1993), was an academician and college professor that began tattooing in the 1950s and continued into the 1960s (Figure 4.6). According to Steward, “The actual pigments used in tattooing were all metallic rather than organic base. (a)

(b)

Figure 4.6  (a) Cover-up tattoo by Phil Sparrow; the original tattoo was a flower

(right of center) and a banner with a name, which was later covered with the addition of the bouquet and the scroll reading “MOM” (Chicago, c. 1958). Note the two darkened, black lines in the middle of the bouquet to the left of the main flower; this is likely the banner from the original tattoo design. (b) The top portion of the tattoo (a bird with the name LARRY in the banner) was done by Phil Sparrow while the lower portion, the rose and two birds, was added later by Tatts Thomas (Chicago, c. 1959). In both tattoos, use of black and green is apparent. It is possible that there was some yellow applied to the original Sparrow tattoo on the right as well. Upon examination of the tattoos, it is evident that pigment migration and time has resulted in some fading and loss of fine detail.

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They arrived as dry colors … The colors were moistened with 190 (proof) grain alcohol [grain neutral spirits] until they became a thick paste. Too thick will not work; too thin will not leave enough residual color behind. Each pigment and color has its own consistency, a thing that tattooists have to learn by trial. Less thick is the black: a concentrated black India ink, imported from Germany, which contained certain additives that seemed to keep the outlines from early spreading” (Steward, 1990, p. 162). Throughout his text, Steward reports the use of black, green, blue, red, yellow, and white (Steward, 1990, p. 163). Bell reports on the popularity of tattooing with various groups in the British populace, specifically sailors, soldiers, pitmen, and steelworkers. He also comments on the increase in tattooing among teenagers of both sexes, including within gangs and girls, who “may be tattooed by a professional out of bravado, or by their boy-friends as a mark of ownership” (Bell, 1962, p. 256). He adds, that popular pigments are self-propelling pen ink and stovegrate blacking (Bell, 1962). Additional reports on tattoo ink compositions, with regard to both the liquid component and pigments can be found throughout the literature. Gordon reports “The vehicle for tattooing is usually Indian ink or vermilion, but ink, coal dust, blacking, and the tar-bubbles from burning coals are sometimes used” (Gordon, 1922, p.  140). In his 1971 article, Roenigk reported, in addition to India ink, the colors and pigments most commonly used in tattooing (Roenigk, 1971, p. 180). These are listed in Table 4.2. In their 1974 texts, Skin Deep, (printed and published in the UK) and Art Sex and Symbol (printed and published in the United States), Scutt and Gotch provide a table (Table 4.3) entitled Composition of Modern Tattoo Pigments (Scutt and Gotch, 1974a,b, p. 135). In their 1986, second edition of Art, Sex and Symbol, Scutt and Gotch provide an alternate table (Scutt and Gotch, 1974a and b, p. 135) (Table 4.4). Table 4.2  ​Colors and Pigments in Tattooing Reported by Roenigk (1971) Colors Blue-black Red Light blue Green Yellow Brown Flesh Violet White (ranging from chalk to ivory)

Pigments Carbon Cinnabar (mercuric sulfide) Cadmium selenide Sienna Cobaltous aluminate Chromic oxide or chromium sesquioxide Cadmium sulfide and ochre Ochre (iron oxide) Iron oxide plus impurities of ochre Manganese Titanium dioxide

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Table 4.3  Colors and Pigments in Tattooing Reported by Scutt and Gotch (1974) Color Black

Common (and Probably Harmless)

Brown Yellow

Carbon (charcoal suspended in ammoniacal solution containing phenol) for example, black waterproof drawing ink Scarlet Lake (organic pigment) Carmine (dried insect bodies) Cochinilla Venetian red (hydrate of ferric oxide) Yellow ochre (hydrate of ferric oxide)

Green

Chloronated copper phthalocyanine

Blue White

Copper phthalocyanine Titanium white (titanium oxide)

Red

Rare (and Potentially Sensitizing) Logwood (containing chrome) Cinnabar = Vermilion Mercuric sulfide Cadmium red (selenide) Cadmium salts Cadmium sulfide, chrome zinc, and lemon yellow (chrome salts) Viridian (emerald green) (chromium sesquioxide) Cobalt aluminate Flake white (lead carbonate)

Table 4.4  Colors and Pigments in Tattooing Reported by Scutt and Gotch (1986) Color

Probably Harmless

Black

Black India ink (preferably concentrated by boiling). May be diluted with distilled water for shading PR 37 PR 122 PR 48 Naphthanil red PO 13 Brilliant orange Venetian red (hydrate of ferric oxide) Other iron oxides (e.g., Sienna) (Dalamar) Yellow 74 (better mixed with white) (Zulu) Green 7 (chlorinated copper phthalocyanine) Pigment Blue 15 (copper phthalocyanine) (very bright; best diluted with white 1:25) Pigment Violet 23 (sunfast violet: carbazole dioxazine) Mix black and white Titanium oxide (titanium white)

Red

Orange Brown Yellow Green Blue Violet Grey White

Possibly Harmful Logwood (contains inorganic chrome salts) Cinnabar, vermilion Mercuric sulfide Cadmium red (cadmium selenide) Salts containing lead, cadmium, chrome, and mercury Cadmium salts Cadmium and chrome salts Viridian (emerald) (chrome salts) Cobalt aluminate or other cobalt containing blues for example, Blue 29 Mixtures containing mercury red or cobalt blue Flake white (lead carbonate)

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Forensic Analysis of Tattoos and Tattoo Inks

Several New York-based tattoo artists provided information concerning pigments and tattoo inks that were being used in the 1950s. Brooklyn Blackie states, “Pigments I got from Fezandi and Sperrle* on Fulton Street” (McCabe, 2013, p.  46). In the same time period, Tony D’Anessa says “Basically you used blue, green, red and yellow; and blue actually was a rare color. It was the hardest color to put in, you very rarely saw blue” (McCabe, 2013, p. 102). Lou Rubino adds, “We didn’t have many colors. When I started tattooing we only had black, red and green. Then years later we started getting yellows … Yellows didn’t work. Then we would mix, try to make orange (McCabe, 2013, p. 127). Hardy sums up the concept that the composition and chemistry of pigments used to tattoo could vary greatly, as would the final product to be used for tattooing; “Eight colors were considered a full palette—only a few shops in the world offered that … You had to sleuth around to get the pigments. The tattoo suppliers had some okay stuff, but you really had to contact pigment manufacturers. But if you said you were using it to tattoo, they wouldn’t sell it to you, so you had to lie to them … You would buy dry pigments mix them with various ingredients in a blender and cook them on a stove” (Hardy, 2013, p. 83). While accounts from the tattoo artists were important in evaluating pigment use over time, these reports were subject to secrecy (and possibly deception), constant modification and loss of integrity as time passed, and memories faded as stories and recipes were passed to newer generations, and artists came and went. In addition, formulations could change based on availability of supplies, experimentation by the tattoo artists and of course, the manufacturer of the materials being used by the artists. As such, without any reliable scientific data, accounts of pigment composition as reported by tattoo artists, historians, and even the researchers and information seekers such as those conducted by physicians, were limited in their ability to reliably ascertain pigment compositions available during any given time. A review of the scientific literature, in which studies of tattoo ink composition was conducted based on experimentation using chemical and instrumental methods provides a much more solid account of pigments used in tattoo inks for select time periods.

* Fezandie and Sperrle Division of Benbow Chemical Packaging Co. of Syracuse, NY is described as a firm that has a complete line of nearly every available pigment used by artists, selected and assembled from worldwide sources. In addition, these are sold in small or large amounts from a mail order list only (Mayer, 1991, p. 656).

The Chemistry of Tattoo Inks from Ancient to Modern Times

5

In general, the pigments used in tattooing throughout history can be classified into three major categories: Carbon-based black pigments, natural (mineral [inorganic], vegetable/plant and animal [organic]), color pigments, and synthetic (organic) color pigments. This chapter presents an indepth review of the pigments encountered in the historical literature, some of which is based on reported observations and others based on scientific research. Aetius (sixth century) is credited with recording one of the earliest ­tattoo ink recipes.* The ink is described as being made from Egyptian pine wood bark (acacia), corroded/burned bronze/brass, gall, and vitriol; once mixed and ground into a powder, it is mixed with water and leek juice (D’Amide, 1549, p.  449; translated into French in Berchon, 1869, p.  93). Ötzi, the Tyrolean Ice Man, is believed to be the bearer of the oldest tattoos. Discovered in 1991, Ötzi was determined by the scientists to be the oldest complete, mummified body, and approximately 5200–5300 years old. Upon examination of Ötzi, tattoos were found on different areas of his body. Pabst et al. (2009) prepared unstained histological sections of the tattooed skin and examined the prepared sections using optical microscopy, bright field transmission electron microscopy, energy dispersive x-ray spectroscopy, electron energy loss spectrometry, energy filtering transmission electron microscopy, and electron diffraction, in an effort to study the tattoos and their chemical and structural compositions. The authors identified black colored particles that mainly consisted of carbon; more specifically, they identified double-bonded carbon atoms that are typically found in soot (Pabst et al., 2009, p. 2336). They also identified ash particles that consisted of carbon, oxygen, nitrogen, and calcium (Pabst et al., 2009). In their conclusions, Pabst et  al. noted that the quartz and “probable almandine” (Fe+23Al2Si3O12) crystals they identified between the soot particles in the tattooed regions of the skin may have come from stones in a fireplace from which the soot was taken (Pabst et al., 2009).

* Book Four, Second Sermon, Chapter XII, De stigmatis… (Marks inflicted by blows).

97

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Forensic Analysis of Tattoos and Tattoo Inks

Black Tattooing Pigments Much of the literature regarding tattooing in native cultures has reported the burning of various vegetative and plant-based material to acquire a carbonaceous residue suitable for the tattooing process. Examples include Kauri pine, pitch pine, and brazilwood. Many anthropological studies refer to the burning of kukui nut and candlenut (Aleurites moluccana, Aleurites triloba), To make the tattoo ink, the Samoans gather lama nuts (Aleurites moluccana) in coconut baskets and bake them in an underground oven for two days. They then crack the nuts with stones and thread them together as they do when they make a torch. They light the torch inside a special stone hearth. The torch emits a black, oily smoke, which settles as soot on the stone. The Samoans scrape the soot onto a banana leaf and then store it in a coconut shell (Balick and Cox, 1996, p. 121).

When ready for use, the pigment is ground into a fine powder with a mortar and pestle. Also reported in the literature are charcoal, wood ash, vegetable caterpillar, ivory black, lamp black, as well as India and Chinese inks. Black colors are generally carbon black (80%–99% carbon with traces of sulfur and organic material; produced by burning a variety of materials and collecting the resultant sooty residues), graphite; 40%–90% carbon with mineral ash, Parry describes graphite as “almost pure carbon” (Parry, 1902, p. 173), or an iron oxide. “Carbon-based blacks” is the general class of those black and brown pigments that are composed primarily of carbon and includes lamp black, bone black (ivory black), charcoal black, vine black, and graphite. General distinction is made by the manufacturing process, source material, or method of preparation. Examples of sources for carbon-based pigments may include minerals, soots and smokes, and vegetable materials and animal materials (e.g., bone). Variations in color and particle size and degree of crystallinity, when viewed microscopically, can be used to distinguish the different types of black pigments. According to Gettens and Stout, “The organic black pigments, although they all contain carbon as their essential constituent, vary considerably in shade and strength according to the amount and particle size of the amorphous carbon in them” (Gettens and Stout, 1966, p. 103). According to Perrott and Thiessen Carbon black is the fluffy velvety black pigment produced by burning natural gas with a smoky flame against a metal surface. It is entirely different in physical characteristics from lampblack, which is made by burning oil or other carbonaceous material with insufficient air for complete combustion and collecting the smoke in settling chambers. Lampblack is often gray in contrast to the deep black of carbon black, often contains considerable quantities of

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empyreumatic* matter, and when used in printing ink gives a product with very different properties from an ink of similar composition made from carbon black (Perrott and Thiessen, 1920, p. 325).

The authors add that lampblack was used as a pigment for printer’s ink almost exclusively up to 1864 after which its use diminished due to the advent of carbon black (Perrott and Thiessen, 1920, p. 326). Lamp black is generally described as having a slightly bluish color, being an older pigment than carbon black and having been used for thousands of years by ancient cultures such as the Chinese and the Egyptians. According to Parry, ivory/bone black is produced by the ignition of ivory or bone in a covered vessel. The organic matter (ossein and traces of fat) is charred to carbon, and a mixture of this with phosphate or carbonate of lime left behind as either ivory or bone black (Parry, 1902, p. 174) while lamp black is produced when organic matters rich in carbon are burnt, a great deal of unburnt carbon escapes as smoke and condenses, or rather settles out as soot on the cooler parts of the chimney or other draught arrangement (Parry, 1902, p. 175). Bone black has been described as having a brownish color relative to other carbon blacks. Logwood, Haematoxylum campechianum, is a tree whose yellowish bark takes on a dark reddish-brown color. The principle coloring materials of logwood are haematoxylin and haematein (Figure 5.1). References to the use of black powder have also been found, with the literature varying in its reference to a black powder versus blackpowder, the latter being used interchangeably with gunpowder. Gunpowder, in the black powder form, is a propellant and explosive mixture containing saltpeter (potassium nitrate), charcoal (the preferred was obtained from the burning of willow trees), and brimstone (sulfur), with optimum performance obtained with ratios of approximately 75:15:10 as reported by Styers (1987, p. 443) and Dillon (1991, p. 690). Wide variations in the composition OH

OH OH

HO HO

O HO

O

O OH Haematoxylin

HO

OH Haemetein

Figure 5.1  The principle colorants found in logwood. * Decomposition products from animal or vegetable sources; likely the authors are referring to the presence of impurities.

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Forensic Analysis of Tattoos and Tattoo Inks

were present and based upon manufacturing methods, region of manufacture, and time period, with variation existing in homogeneity, purity and degree of refinement of individual constituents, hygroscopic qualities, powder grain size, and both exposure to the atmosphere and handling (Dillon, 1991, p. 690). During the mixing of the three main components, moisture was added to reduce the risk of accidental explosions caused by the resultant friction. Wetting agents included water (likely unpurified), alcohol, or urine (Styers, 1987, p. 444). In addition, graphite may have been added to coat the powder grains. The transition from ancient to more modernized methods of black powder manufacture resulted in the ability to obtain a product with fewer contaminants and increased uniformity in size and chemical composition. For example, magnets were added to draw out contaminants. In a 2008 tattoo ink research project by Poon, the tattoo pigments of interest were ancient and traditional pigments typically found in ancient mummified remains. The purpose of his research was to examine the chemical composition of pigments believed to be found in ancient tattoo inks and to design an experimental method for analyzing the pigments in mummified remains in situ. This was evaluated using an animal model to simulate mummification of tissues tattooed with ancient pigments as reported in early literature. The pigment standards that were the focus of this study included flame carbon/soot, bone black, vine charcoal, magnetite (Fe3O4), lapis lazuli (Na,Ca)8[(Al,Si)12O24](S,SO4); lazurite, the dominant constituent), and indigo. These pigments were evaluated using micro-Raman spectroscopy, scanning electron microscopy/energy dispersive spectroscopy (SEM-EDS), Fourier transform infrared spectroscopy (FT-IR), powder x-ray diffraction (XRD), and laser ablation inductively coupled plasma mass spectrometry (ICP-MS). With respect to the Raman portion, Poon used a 632.8 nm He/Ne laser at 1.8 mW as the only means of excitation. According to Poon’s research, despite the ability of Raman spectroscopy to provide positive identification of carbonaceous materials, the technique failed to discriminate between the particular forms which made it necessary to use SEM-EDS for determination of morphology and elemental composition. Current research on black tattoo inks by Lehner has focused on the identification of phenol and various polycyclic aromatic hydrocarbons (PAHs). In his research, Lehner studied 14 black tattoo inks and analyzed them using gas chromatography-mass spectrometry (GC-MS) and high-pressure liquid chromatography (HPLC). In addition to carbon black, GC-MS revealed the presence of dibutyl phthalate (DBP), hexachloro-1, 3-butadiene (HCBD), methene amine, dibenzofuran (DBF), benzophenone (BP), 9-fluoronone (9F), hexamethylenetetramine (HET), as well as additional materials. HPLC revealed the presence of PAHs; naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo[a]anthracene, chrysene, 5-methylchrysene, benzo[b]fluoranthene, benzo[j]fluoranthene,

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benzo[k]fluoranthene, benzo[a]pyrene, dibenzo[a,h]anthracene, benzo[ghi] perylene, indeno[1,2,3-cd]pyrene, dibenzo[a,e]pyrene, and dibenzo[a,l] pyrene. Lehner identified additional ingredients by using the National Institute of Standards and Technology (NIST) database for mass spectral data (MSD) to identify compounds such as 3,6-dimethyl-1-heptyn-3-ol, 1,6-hexandiole, oleamide ([Z]-9-octadecenamide), 7-hexyl-2-oxepanone, propylene glycol, 1,1′oxybis-2-propanol, 2,2′oxybis-1-propanol, carbitol cellosolve (2-[2-ethoxyethoxy] ethanol), and 1,2,3,4-tetrahydro-1-phenyl-naphthalene. Lehner added that among the quantitatively and qualitatively detected ingredients in the chromatograms, there were some peaks that could not clearly be identified with the NIST database (Lehner 2012, p. 234). In a similar study, Regensburger et al. (2010) conducted a study to identify the extracted PAHs found in nineteen black tattoo inks using HPLC and mass spectrometry.

Red Tattooing Pigments Natural color pigments derived from plant, mineral, and insect sources have been reported extensively in the literature much like the carbon-based black pigments. Over time, the natural pigments were prepared from coal-tar coloring materials, making them synthetic in origin. One general characteristic of the natural pigments is their lightfastness and their tendency to be subject to photodecomposition over time. Natural red colors have included Brazilin (Brazilwood), Santalin/Santalic acid (Sandalwood), Alizarin (Madder plant), and Carmine/Carminic acid (Cochineal insect; also referred to as scarlet lake). Mineral red colors have included cinnabar/vermilion/mercury (II) sulfide (also referred to as brick dust), red lead (Pb2O4), red ochre/hematite /iron (III) oxide/ferric oxide/sienna (these are also reported for yellows and flesh colors), lead chromates/China red (Pb2CrO5), manganese oxide (MnO), and cadmium selenide (CdS). The most commonly reported red color pigments were cinnabar and vermilion. Cinnabar (mercury [II] sulfide, HgS) is a natural mineral that is reported to have been first discovered around 315 bc. According to the Pigment Compendium, cinnabar is the trigonal form of HgS and two other polymorphs are known to exist: metacinnabar, α′-HgS (black in color) and hypercinnabar, β′-HgS (red in color) (Eastaugh et al., 2008, p. 111). Vermilion, the synthetic form of cinnabar, is reported to have been manufactured as early as 27 bc. Gettens et al. describe three distinct kinds of mercuric sulfide pigment, namely, the natural pigment, which is a finely ground cinnabar; the synthetic pigment made by a dry process and referred to as vermilion; and the synthetic pigment made by a wet process and also referred to as vermilion (Gettens et al., 1972, p. 45). Due to cinnabar being a natural mineral, chemical impurities are often present. Adulterants and substitutions have resulted

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Forensic Analysis of Tattoos and Tattoo Inks

COO– Br O–

O Br

Br

Eosin Y (yellowish hue)

COO– Br

O2N

O

–O

NO2 O

O Br

Br

Eosin B (bluish hue)

Figure 5.2  Adulterants that may be found in cinnabar, which would affect the perceived color of the pigment.

in the extensive variants reported throughout the literature. For example, Parry reports red lead and scarlet antimony sulphide (more likely antimony oxide sulfide; 2Sb2S3 ⋅ Sb2O3) as being adulterants as well as eosin (Parry, 1902, p. 108). The presence of these adulterants could impart color effects on the red depending on their color properties (Figure 5.2). Furthermore, lack of regulation, chemical testing, and analytical instrumentation throughout tattooing history makes it difficult, almost impossible, to ascertain the qualitative (the presence or absence of cinnabar, vermilion, or any impurities) and quantitative (relative ratios of pigments and any impurities) properties of any given sample at any given time. Parry reports, “Dr. Marvin Shie, of the New York State Government Service, states that as early as 1835, here as well as abroad, a mixture of cinnabar and red lead was used to bring the natural color to the cheek in certain cases of superficial birth marks. After the birth marks were eliminated by surgery, the middle of the cheek was tattooed a delicate pink” (Parry, 1933b, p. 10). Parry goes on to add that much of the mole and blush tattooing of his day was ascribed by the tattooers to the World War experiences and experiments (Parry, 1933b, p. 10). Gettens et al. report that when used by artists, vermilion was mixed with lead white to achieve flesh tints (Gettens et al., 1972, p. 53). It is highly likely that mixtures of vermilion with white pigments such as seen with artist’s pigments were also used by the tattooer in order to achieve a flesh tone that could be used for cosmetic purposes. Of the other red pigments, Brazilin (C16H14O5; 3,4′,5′,7-tetrahydroxy-2, 3′-methelen-neoflavan) is the dye precursor found in Brazilwood (genus Caesalpinia), which develops into the red dye brazilein, C16H12O5 (Figure 5.3). The exact shade of the lakes formed from the extract of Brazilwood, in the form the color is usually found, depends on the relative quantities of brazilin and brazilein (Parry, 1902, p. 233). Santalin (santaline) is a red dye from wood of Pterocarpus santalinus (Figure 5.4). Alizarin (C14H6O2(OH)2; 1,2-dihydroxy-9,10-­anthracenedione, or 1,2-dihydroxyanthraquinone) is a

The Chemistry of Tattoo Inks from Ancient to Modern Times HO

O

OH

103

OH

HO O

HO OH

O

HO Brazilin (Brazilwood)

Brazilein (Brazilwood)

Figure 5.3  The principle colorants found in Brazilwood. O

OH

O

OH

OH

O OH

O

O

Santalin

Alizarin

Figure 5.4  Natural red pigments.

principle component of madder dyes and is used as a dye in the preparation of lake pigments (Eastaugh et al., 2008, p. 10). It is also produced synthetically from the coal tar dye anthracene. Carmine/carminic acid (C22H22O13; 7-a-d-glucopyranosyl-9,10-dihydro-3,5,6,8-tetraahydroxy-1-methyl-9,10dioxo-2-anthracenecarboxylic acid) is the primary dyestuff in cochineal (Figure 5.5) that is obtained by extraction from insects of the Porphyrophora and Dactylopius species (Eastaugh et al., 2008, p. 92). The iron oxides and hydroxides are an important class of pigments that can exist as various shades of red, orange, yellow, purple, and brown. They are both naturally occurring and synthetically produced. The iron oxides can range in composition from pure ferric oxide (Fe2O3) to containing an extensive amount of adulterants such as barium sulfate (BaSO4), manganese oxide (MnO), and various salts (Parry, 1933a,b, 1934, p. 128). The iron oxides and hydroxides occur as secondary pigments referred to as ochres, umbers, and siennas. The ochres are composed of hydrated iron oxide (yellow and brown) OH

O

HO HO

OH

O OH OH

HO OH

Figure 5.5  Carminic acid.

OH

O

O

104

Forensic Analysis of Tattoos and Tattoo Inks

and anhydrous oxide (reds) and can also contain adulterants. The variations of oxides and hydroxides along with the various adulterants contribute to the ranges of colors possible.

Orange Tattooing Pigments Orange colors have included lead, cadmium, chrome, and mercury salts. Cadmium oranges are often cadmium selenide (CdSe), cadmium sulfide (CdS), and cadmium mercury sulfide (CdHg)S. Cadmium oranges are described as impure forms of cadmium selenide (usually red), with the color variation (yellow to red) depending on secondary factors relating to the structure of the colloidal aggregates and the coagulating anion in precipitation reactions (Eastaugh et al., 2008, p. 75). As such, mixing the pigment having any degree of impurities with any number of liquids (each with its own chemistry, pH, etc.) and under varying conditions (e.g., reaction temperature) could produce myriad color variations. This could impact the stability of the resultant pigment used for tattooing, and, therefore, its persistence within human tissue. With regard to impurities, compounds typically found in cadmium sulfide pigments include zinc oxide (ZnO), zinc carbonate (ZnCO3), zinc sulfide (ZnS), zinc chromate (variations of hydrates and hydroxides), arsenic yellow (lead arsenic oxide), lead chromate (PbCrO4, PbCrO4 ⋅ Pb[OH]2), gypsum (CaSO4 ⋅ H2O), cadmium carbonate (CdCO3), cadmium oxalate (Cd[C2O4]), cadmium oxide (CdO), cadmium phosphate, Indian yellow (a mixture of calcium and magnesium salts of euxanthic acid; magnesium euxanthate; C19H16O11Mg ⋅ 5H2O; Figure 5.6), tin sulfide (SnS2), free sulfur (S), antimony, mercury and bismuth compounds, lead iodide (PbI2), barium sulfate (BaSO4), as well as titanium and strontium compounds (Eastaugh et al., 2008, p. 78). The chrome pigments could be composed of chromate (CrO4) or dichromate (Cr2O7) and can vary in color from red, orange, and yellow to greens, purples, and browns (Eastaugh et al., 2008, p. 102). Adulterants present in the chrome oranges included lead sulfate (various forms of PbSO4), China clay (kaolin/kaolinite; Al4[Si4O10]OH8), gypsum (CaSO4 ⋅ H2O) or baryte (natural O OH O OH

O

O HO

OH OH

Figure 5.6  Euxanthic acid (Indian yellow).

O

The Chemistry of Tattoo Inks from Ancient to Modern Times

105

barium sulfate; BaSO4), and red lead (2PbO ⋅ PbO2 or Pb3O4) (Eastaugh et al., 2008, p. 104). The Pigment Compendium lists synonyms for chrome orange and chrome red, some of which have been reported in the tattoo literature. The synonyms include American vermilion, Australian cinnabar, Austrian red, Austrian cinnabar, Chinese red, chrome cinnabar, chrome scarlet, Derby red, garnet chrome, golden orange yellow, orange paste, Persian red, ruby red chrome, Victoria red, and Vienna red (Eastaugh et al., 2008, p. 104).

Yellow Tattooing Pigments Natural yellow colors have included curcumin (turmeric), saffron, American oak, and aloe. Turmeric is a yellow pigment primarily derived from a herbaceous plant from the ginger family, Curcuma longa, in which the principle yellow dye is curcumin (Eastaugh et al., 2008, p. 377; Figure 5.7). Saffron is a yellow pigment derived from the plant Crocus sativus in which the main dyestuff produced is crocetin (Eastaugh et al., 2008, p. 337; Figure 5.8). American oak (Figure 5.9), or black oak is characterized by the yellow dye quercitron extracted from the bark of the oak, in which the principle coloring matter is quercetin (Eastaugh et al., 2008, p. 322). The color of quercetin varies depending on the presence of metal compounds such as aluminum, tin, chromium, and iron. Aloe is a genus of succulent plants, with some species yielding a yellow pigment-containing colored juice in which the major constituent is the yellow-brown pigment barbaloin or aloin (Eastaugh et al., 2008, p. 11). Mineral yellow colors have included iron oxide/yellow ochre, lead chromate, zinc chromate, and cadmium sulfide/cadmium yellow (CdS).

O

O

HO

OH OCH3

H3CO

Figure 5.7  Circumin (turmeric).

O HO

OH O

Figure 5.8  Crocetin (saffron).

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Forensic Analysis of Tattoos and Tattoo Inks OH

O

OH

OH OH O

HO

OH HO OH

OH OH

O

Quercetin (American oak)

O

OH

OH Barbaloin (aloe)

Figure 5.9  Natural yellow pigments.

As described above, the various salt forms of many minerals were subject to color variation based on factors such as hydration states, photodegradation, contaminants, and adulterants.

Green Tattooing Pigments Mineral green colors have included chromium, chromium oxide, chrome hydroxide, and chromium sesquioxide (Chromium [III] oxide, Cr2O3). Viridian is described as a hydrated chromium oxide (chromium [III] oxide dihydrate) characterized by its green color (Eastaugh et al., 2008, p. 397). Other names used for viridian include Giugnet’s green and Casali’s green, which have been listed in the historical literature as being encountered as tattoo pigments.

Blue Tattooing Pigments With regard to blue pigments, indigo (indigotin, Indigofera tinctoria; also used interchangeably with woad [vitrum and glastum] which is actually derived from Isatis tinctoria), Prussian blue, Campeachy wood, and cobalt aluminate have been reported. Indigo (C16H10N2O2; 2-[1,3-dihydro-3-oxo2H-indol-2-ylidene]-1,2-dihydro-3H-indol-3-one) is a blue pigment derived from various species of Indigofera (Eastaugh et al., 2008, p. 200). Indigo, while naturally occurring, can also be synthesized from a coal tar base which was commercially produced in the late 1800s (Figure 5.10). Prussian blue, described as an adulterant of indigo, is “a term which might reasonably be considered applicable to any of the blue hexacyanoferrate (II) pigments (compounds based around [Fe(II)(CN)6]4− which also contain Fe(III) … (with) variations on a composition of M(I)Fe(III)[Fe(II) (CN)6] ⋅ nH2O” (Eastaugh et al., 2008, p. 314). Prussian blue has also been

The Chemistry of Tattoo Inks from Ancient to Modern Times O

N H

107

H N

O

Figure 5.10  Indigo.

CN Fe(III)4

NC NC

Fe(II) CN

CN CN

• × H2O 3

Figure 5.11  Prussian blue.

reported as being a pigment employed in laundry blueing (Figure 5.11). Laundry blueing is a process of adding a blue dye to laundry in order to counteract the yellowing of fabrics and make the fabric appear whiter. Laundry bluing is akin to adding fluorescent optical brighteners or bleach to laundry, both of which are commonly done today. It is reported in the literature that a French forensic scientist, Jean Mathurin Felix Hutin, described the process of tattooing based on a study conducted in the early 1850s. In his account of Hutin’s resultant research, Dye writes, “Colored materials, apparently nearly always Indian or Chinese ink (lampblack mixed with animal glue, sold in solid rolls or cakes), laundry blueing, or vermilion (artificial cinnabar, i.e. alpha mercuric sulfide, ground with white wine and then mixed with white of egg), were prepared with a little water or saliva in small cups or shells” (Dye, 1989, p. 530). Based on the time of Hutin’s research, the materials that could have been used for laundry blueing (and thus tattooing) include ultramarine (likely in its natural form; derived from lapis lazuli, which contains the pigment lazurite (Na6Ca 2Al6Si6O24[(SO4); S; Cl; (OH)]2), although synthetic ultramarine was introduced in the late 1820’s) and smalt (cobalt doped glass, SiO2Cox; i.e., K 2CoSi4O10). Ultramarine is [e]ssentially a three dimensional aluminosilicate lattice with a sodalite structure containing entrapped sodium ions and ionic sulfur groups. The presence of two types of sulfur group, S2 and S3, provides absorption in the ultraviolet and violet (S2) and the green-yellow-orange (S3), making the compound blue. In its simplest form ultramarine has a basic lattice unit of Na7Al6Si6O24S3. However, various synthetic forms are produced deviating from this… The mineral lazurite … is the natural form of this structure and is a member of the sodalite group. (Eastaugh et al., 2008, p. 381); Lazurite

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Forensic Analysis of Tattoos and Tattoo Inks

is a cubic sodic-calcic aluminosilicate sulfate mineral with composition (Na,Ca)8[(Al,Si)12O24](S,SO4)… The structure of lazurite is complex and several polymorphs are known… (Eastaugh et al., 2008, p. 225).

Additional blue pigments include Campeachy wood, or log wood, a bluepurple dye in which hematoxylin from plants of the Haemotoxylum genus is oxidized to pH sensitive haematin, which thus allows for a wide range of colors from red to purple to blue and even black (Eastaugh et al., 2008, p. 248), and cobalt aluminate (Al2O3CoO), also referred to as cobalt aluminum oxide (CoAl2O4), and cobalt blue.

Purple Tattooing Pigments Manganese oxide has been reported as the pigment used in purple tattoo inks. According to the literature, manganese oxides (and some hydroxides) are a group of black pigments while manganese phosphates are purple pigments (Eastaugh et al., 2008, p. 257).

White Tattooing Pigments The pigments reported for white tattoo inks include Chinese white (zinc white, zinc[II] oxide, ZnO), lead carbonate (lead white, PbCO3), lead oxide, and titanium dioxide (TiO2). While the lead oxides are characteristically yellow, brown, or red, it is reported that lead hydroxide was found in lead white, which is lead carbonate hydroxide, PbCO3 ⋅ Pb(OH)2 (Eastaugh et al., 2008, p. 234). Titanium dioxide white is a general term for various titanium dioxide pigments, specifically the anatase and rutile forms of titanium (IV) oxide. With regard to white tattoo pigments reported in the literature, Cohen notes, “The Japanese at first used the highly toxic white lead, lead oxide, to produce the white tattoo… Zinc oxide then replaced the lead oxide as less toxic. Finally, the extremely intense artist’s color of titanium dioxide replaced both … (Titanium white) is an inert, harmless compound found in the best artists paints such as Grumbachers” (Cohen, 1994, p. 270).

Brown Tattooing Pigments Brown inks were reported to contain Sepia (predominantly Sepia officinalis cuttlefish ink sac), ox gall, viridian, cadmium sulfide, and iron oxide. The pigment from Sepia species contains melanin, with the cuttlefish ink containing

The Chemistry of Tattoo Inks from Ancient to Modern Times O

O

HO

H2C

OH

H3C

O

H N

NH

HN

H N

O

O NH

O HN

NH

CH3

CH2

N

H 3C

CH3

HOOC Bilirubin

109

COOH Biliverdin

Figure 5.12  Natural brown pigments.

black eumelanin (Eastaugh et al., 2008, p. 343). Ox gall is a yellowish pigment derived from the bile of bovine gall bladders. Bile is composed mainly of bilirubin and biliverdin (Figure 5.12), which are breakdown products of hemoglobin (Eastaugh et al., 2008, p. 170).

Modern Tattooing Pigments In the twentieth century, several studies were published which focused on the chemical composition of tattoo inks. Some of these studies were scientific, using instrumental methods to determine the chemical composition of selected tattoo inks, while other studies focused on reporting the content of tattoo inks based on their labeling or communication with the manufacturers or distributors of the tattoo inks. Much of the impetus for these research projects appears to be related to health and safety; in the first half of the twentieth century, much of the research was the result of allergic reactions attributed to the heavy metals found in the inks. In the second half of the twentieth century and into the twenty-first century, with the introduction of synthetic organic pigments into tattoo inks, medical, and scientific professionals had become more concerned with what individuals were injecting into their skin and what long-term effects could arise from their presence in the tissue. Even with the introduction of organic synthetic pigments into tattoo inks, much of the literature has focused on the heavy metal content of tattoo inks as well as what potential effects these ingredients could have on the tattooed individual. Recently, interest has focused on tattoo removal and the potential effects of the products released into the body upon photodecomposition of these synthetic pigments and subsequent distribution of the byproducts within the tissues. To a lesser extent, hygiene in the tattoo parlor

110

Forensic Analysis of Tattoos and Tattoo Inks

remains an issue and is now partially regulated by regional health departments, largely through the dissemination of licenses for both the parlor and the individual artist. Conducting a case study in 1950, Rostenberg et  al. made a search of the literature for information regarding pigments used for tattooing and “found this to be very sparse” (Rostenberg et al., 1950, p. 545). According to the authors, “Through the courtesy of the Food and Drug Administration, Federal Security Agency, Washington D.C., and of Fezandie and Sperrle, Inc. of New York, N.Y., we obtained the names, and, in part, the chemical composition of the materials used for tattoo designs. In view of the fact that these are not generally known, we think it worth while to list the various substances with some information about them” (Rostenberg et al., 1950). The information reported to the authors is presented in Table 5.1. The authors add It should be realized that these substances are sold under a great variety of trade names and code numbers. However, regardless of the name used, [the materials listed in the table are], as far as we could determine, the ones employed to obtain the named different colors and shades seen in tattoo designs. Another point to be borne in mind is that the pigments employed can be obtained in varying degrees of purity and, consequently, the color range for any given compound can vary considerably. The nature and dilution of the fluid used to make the paste that is actually put on the tattoo needle also influence the shade obtained (Rostenberg et al., 1950).

In a footnote, the authors also acknowledge the use of gold and platinum salts being used for medical tattooing. The list reported by Rostenberg et al. was reproduced by Beerman and Lane in their 1954 article. The latter authors add, “Certain additions and alterations to the list may be suggested. Cinnabar or red mercuric sulfide, is synonymously known as vermilion and as Chinese red… Another chemical, not mentioned in the list, used to produce the red color is carmine (carminum)” (Beerman and Lane, 1954, p. 446). In his 1961 article, Watkins lists the common pigments for use in tattooing in which, from his dermatological standpoint, “the following have been tolerated in the skin to varying degrees of satisfaction” (Watkins, 1961, p. 306). While his list is consistent with that of the earlier literature, he adds lithium oxide (Li2O) as a source of white pigment used in tattooing (Table 5.2). In 1984, Slater and Durrant conducted x-ray microanalysis on the tattoos of 17 patients in conjunction with light and transmission electron microscopy (TEM) examinations. The results of their study (tattoo color and corresponding elemental composition) are reported in Table 5.3.

The Chemistry of Tattoo Inks from Ancient to Modern Times

111

Table 5.1  Pigment Information Provided by Rostenberg et al. (1950) Pigments or Dyes Used to Produce Different Colors in Tattoos Blacks

Carbon—finely dispersed carbon in an ammoniacal solution. Phenol is also usually present. Iron oxide-also known as black oxide and magnetic oxide. It is also ferrosoferric oxide [Fe3O4 or FeO ⋅ Fe2O3 or Fe(OH)2 ⋅ Fe2OH3]. Logwood—probably logwood black, also known as campeachy black, diamond black, neutral black, and by many other names. This is an extract of logwood from the tree Haematoxylum campechianum. It is made into a lake with potassium dichromate so that as it is applied there is a considerable amount of chromate present.

Blue

Cobaltous aluminate-CoO Al2O3, also known as azure blue and cobalt ultramarine and by many other names.

Brown

Ochre—a natural ferric hydrate and basic ferric sulfate containing alumina, silica, and lime, among other substances. It occurs in a wide variety of shades and is sold under many names, including ochre, with all sorts of descriptive adjectives, such as flame ochre and imperial ochre. It is also known as Chinese yellow, imperial yellow, sienna, mahogany brown, Roman earth, Mars yellow, Mars orange, Mars red, Mars brown.a

Flesh

Iron oxides—these, as a rule, are impure and are a variety of ochre (see brown).

Green

Chrome oxide green—chromic oxide or chromium sesquioxide (Cr2O3), also known as casalis green. Guignet’s green—hydrated chromium sesquioxide Cr2O(OH)4 or mixtures of Cr4O3 (OH)6 and Cr4O(OH)10 with Cr2O3 together with 0.5% to 10% of boric acid. It is also known as emerald green and Pannetier’s green.b Phthalocyanine dyes—usually as copper salts and sometimes mixed with other coal tar dyes, especially Hansa yellow G (fanchon yellow; ext. D&C yellow #5), which is alpha-(O-Nitro-p-tolylazo)-acetoacetanilide.

Red

Cadmium selenide—also known as cadmium red. Cinnabar—mercuric sulfide (HgS). Sienna—see ochre under brown.

Violet

Manganese violet—probably NH4Mn2 (P2O7)2.

White

Titanium white—titanium dioxide (TiO2). Zinc white—zinc oxide (ZnO), also known as Chinese white.

Yellow

a

b

Cadmium yellow—cadmium sulfide (CdS), also known as radiant yellow. It may also be mixed with zinc sulfide and barium sulfate. Ochre—see under brown.

The Mars colors are artificial ochres which are made by precipitating a mixture of a soluble iron salt (ferrous sulfate) and alum (or aluminum sulfate) with an alkali like lime or potash (Gettens and Stout, 1966, p. 129). According to Gettens and Stout, emerald green is not synonymous with Guignet’s green (viridian). The authors state that emerald green is copper aceto-arsenite and is both poisonous and dangerous to handle (Gettens and Stout 1966, p. 113).

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Forensic Analysis of Tattoos and Tattoo Inks

Table 5.2  Pigment Information Provided by Watkins (1961) Orange and red Yellow Green Blue Violet Black Brown White

Mercuric sulfide, cadmium selenide, and ferric hydrate, carmine Cadmium sulfide Salts of chromium and coal tar dyes Cobaltous aluminate (azure blue or cobalt ultramarine) Manganese violet Carbon of some type or iron oxide Ochre-ferric hydrate and basic ferric sulfate Lithium oxide or zinc oxide

Table 5.3  Pigments Reported by Slater and Durrant (1984) Color Red Blue/green Yellow Brown Red Red Blue/red Yellow Purple Blue Red Blue/red Yellow Green/blue Red Green Red/green

Metals Aluminum, chlorine Copper, titanium Iron Iron No elements detected Mercury, chlorine Chromium, mercury Cadmium, lead, phosphorous Manganese Cobalt Mercury Chromium, mercury No elements detected Titanium, copper Mercury Chromium Mercury, titanium

The Transition from Natural to Synthetic Pigments in Tattoo Inks At some point, there was a shift from the mineral pigments, specifically the heavy metal containing pigments routinely encountered in the early twentieth century, to the synthetic organic pigments presently found in tattoo inks. A 1988 study by Lehmann and Pierchalla notes this transition. The authors analyzed nine different tattoo inks (white, yellow, orange, red, two blues, violet, green, and black) using analytical chemical methods to detect the inorganic components as well as thin layer chromatography (TLC) and spectrometry (specifically UV/Vis, IR, and NMR) to detect the organic components. Lehmann and Pierchalla subsequently reported finding mixtures of organic dyes and inorganic fillers. According to the authors, the inorganic

The Chemistry of Tattoo Inks from Ancient to Modern Times

113

filler consisted mainly of titanium dioxide (TiO2) and the colors detected were as given in Table 5.4. The authors conclude, “Heavy metals, e.g. mercury, cadmium, or chrome as the common components of the traditional tattoo dyes, are capable of evoking unwanted skin reactions, but were not detected… Our results suggest that classic dyes have been superseded by newer, mainly synthetic dyes” (Lehmann and Pierchalla, 1988, p. 152). Tattoo inks containing heavy metals were still reported in the late twentieth century, as reported in 1991 when Sowden et al. examined histological sections of red tattoos in eighteen patients and determined the chemical composition of the pigments using x-ray microanalysis.* The elements reported included iron, sulfur, titanium, phosphorous, aluminum, silicon, calcium, mercury, and cadmium. In addition, the details as listed in Table 5.5 were reported in a 1994 study by de Groot et al., in the 2003 Workshop on Technical/Scientific and Regulatory Issues in the Safety of Tattoos, Body Piercing and of Related Practices. In 1997, Waldman and Vakilzadeh reported “While in the past these (allergic) reactions have been ascribed to mercury salts (cinnabar) and cadmium sulfide, now synthetic inorganic azo dyes have also been found to be responsible for such reactions” (Waldman and Vakilzadeh, 1997, p. 667). In their study, the authors detected Naphthol AS (Naphthol Red, Pigment Red 170) and Pigment Red 23 via patch testing (Figure 5.13). In determining the transition from natural to synthetic pigments being routinely employed in tattoo inks, a review of the tattoo literature as well as correlation to the development, manufacture and use of synthetic pigments, it is possible to develop a time frame in which synthetic pigments became the standard in tattoo ink composition. Based on the observations and conclusions reported by Lehmann and Pierchalla as well as Waldman and Vakilzadeh the transition from tattoo inks composed of heavy metals to synthetic organic pigments likely began in the late twentieth century (1980s and 1990s) and continued into the early twenty-first century (in general, prior to 2010). Although the literature and robust scientific studies are sparse, one can effectively theorize that the use of inorganic natural pigments had fallen out of use and been replaced by synthetic pigments during this time frame. It should be noted that several studies in the early twenty-first century continued to report the presence of heavy metals, but in some instances no information was provided regarding the date of manufacture of the tattoo ink or the date that tattoo was obtained, making it difficult to pinpoint a specific transition period. In addition, some studies rely on atomic spectroscopic

* The authors do not indicate when each of the patients had acquired their tattoos, only that they conducted their study in a two-year period up to December 1988 on patients exhibiting inflammatory reactions to their red tattoos. It is unknown how much time elapsed between tattoo acquisition and the inflammatory response that resulted in the patient seeking medical treatment.

114

Table 5.4  Pigments Reported by Lehmann and Pierchalla (1988) Color White Red

Pigments Titanium dioxide, TiO2 (rutile) Pigment Red 22 Titanium dioxide, TiO2 (rutile) Barium sulfate, BaSO4

OH O

N

N

O

N

N H

O

Pigment Red 22 Pigment Yellow 83 Titanium dioxide, TiO2 (rutile)

CI

OCH3

H3C

Cl O H H3CO

N

N

N N

H

O

N N

H

H O

OCH3

Cl

O CH3

H3CO

CI

Pigment Yellow 83 Orange

Pigment Orange 16 N H HO

H3C OCH3 N N O

O N N CH3

OH H N

H3CO

Pigment Orange 16 (Continued)

Forensic Analysis of Tattoos and Tattoo Inks

Yellow

Color Green

Pigments Pigment Yellow 74 Titanium dioxide, TiO2 (rutile) Pigment Blue 15 (copper phthalocyanine)

O

O O

N

HN N O

N

O

O

Pigment Yellow 74a Blue

Pigment Blue 15 (copper phthalocyanine) Titanium dioxide, TiO2 (rutile)

N N

N Cu

N N

N N

N

Pigment Blue 15 Violet

Pigment Violet 19 Titanium dioxide (rutile)

H

O

N N O

H

The Chemistry of Tattoo Inks from Ancient to Modern Times

Table 5.4 (Continued)  Pigments Reported by Lehmann and Pierchalla (1988)

Pigment Violet 19 a

Elemental carbon

 

Pigment Yellow 74 is also known as Dalamar yellow, which is reported as a pigment used in tattoo inks by Cohen (1994, p. 267).

115

Black

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Forensic Analysis of Tattoos and Tattoo Inks

Table 5.5  Pigments Reported by de Groot et al. (1994) Color

Coloring Material

Blue Green Red Yellow Purple

Cobalt blue (cobaltous aluminate) and indigo Trivalent chromic oxide and hydrated chromium sesquioxide Mercury sulfide (cinnabar) Cadmium sulfide, ochre (ferric oxide), and curcuma yellow (curcumine) Manganese

H5C2O OCH3

H OH N

H2NOC N

N

O

O 2N

Pigment Red 170

N

OH

H

N

N

NO2 O

Pigment Red 23

Figure 5.13  Pigments detected by Waldman and Vakilzadeh (1997).

techniques and not molecular techniques, in which the latter could provide more specific information regarding molecular structure and subsequent elucidation of the specific pigment employed and whether or not it was a metal complex in a synthetic pigment.

Additional Studies and Reports on Tattoo Ink Composition In 2000, Bäumler et al. analyzed 41 tattoo pigments (blues, greens, yellows, oranges, reds, and violets) using visible absorption spectroscopy, FT-IR ­spectroscopy, XRD, mass spectrometry (MS), and TEM. The samples were taken from a variety of wholesalers from the United States, the United Kingdom, the Netherlands, and Germany. The authors identified the pigments in the tattoo inks as given in Table 5.6. Table 5.6  Pigments Reported by Bäumler et al. (2000) Color Reds Orange Yellows Green Blue Violet

Pigments Pigment Red 5, 9, 22, 112, 122, 170 (naphthol red) Pigment Orange 13 Pigment Yellow 14 (diarylide yellow), 55, 74 (hansa yellow), 83, 87 Pigment Green 7 (chlorinated copper phthalocyanine) Pigment Blue 15 (copper phthalocyanine) Pigment Violet 23

The Chemistry of Tattoo Inks from Ancient to Modern Times

117

NH2

Figure 5.14  Aniline.

In 2001, Timko et  al. analyzed 29 tattoo inks (Huck Spaulding Enter­ prises, Inc., USA) and India ink using SEM/EDS and compared the resultant data to that reported on manufacturer MSDS (Material Safety Data Sheet). The authors reported the presence of titanium, aluminum, silica, copper, chromium, iron, chlorine, sulfur, carbon, oxygen, and magnesium. In another 2001 study, authors Reus and van Buuren visited tattoo shops in Amsterdam as well as suppliers of permanent makeup and tattoo inks and conducted experiments on a selection of inks in an effort to determine the presence of azo dyes, heavy metals, and alkaline earth metals. The authors conducted both microbiological and chemical examinations. To detect the presence of azo dyes, the authors used gas chromatography-mass spectrometry (GC-MS), and to detect the presence of heavy metals, the authors used both graphite furnace and flame Atomic Absorption Spectroscopy (GF-AAS and AAS, respectively). The authors identified aromatic amines including aniline (Figure 5.14). Reus and van Buuren reported the heavy metals in their ink colors as given in Table 5.7. In 2002, Lundsgard presented the results of interviews with both “traditional” tattooists and “cosmetic” tattooists in addition to communication with pigment suppliers and manufacturers in an effort to identify the pigments used in tattoo inks found in the Danish market. The author was able to identify a total of seventeen pigments used in traditional (“general”) tattooing and eleven pigments used in cosmetic tattooing. No chemical or instrumental tests were conducted to confirm the reports of the tattoo artists and suppliers/manufacturers. The author notes, “The pigments mentioned … have all been positively identified through information from the suppliers of tattoo colours … [the list] does not represent all pigments used in the Table 5.7  Pigments Reported by Reus and van Buuren (2001) Heavy Metal Manganese Nickel Chromium Strontium Barium Lead Cobalt Cadmium Zinc

Ink Colors Brown, black, red, and yellow Brown Brown and black Orange, red, yellow, black, and green Green, blue, red, white, and yellow White and purple Brown and red Orange and brown Orange, green, blue, and black

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Forensic Analysis of Tattoos and Tattoo Inks

Table 5.8  Pigments Reported by Lundsgard (2002) Pigments Used in General Tattoo Colors Pigment Orange 36 Pigment Yellow 74 Pigment Red 170 Pigment Yellow 97 Pigment Red 146 Pigment Brown 2 (hostaperm brown) Pigment Red 266 Pigment Violet 23 Pigment Red 122 Pigment Yellow 1 Pigment Orange 43 Pigment Green 7 (chlorinated copper phthalocyanine) Pigment White 6 Pigment Red 101 Pigment Blue 15 (copper phthalocyanine) Pigment Blue 15:3 (copper phthalocyanine) Pigment Black 7 (carbon black)

Pigments Used in Cosmetic Tattoo Colors Pigment White 6 (titanium dioxide) Pigment Brown 6 (iron oxide) Pigment Red 101 (iron [III] oxide) Jernoxid (iron [II] oxide) Pigment Yellow 42 Sudan red Food Yellow 13 (quinoline yellow) Mangan violet (Pigment Violet 16) Food Red 1 Food Blue 2 Acid Red 87 (Eosine A)

products in the Danish market but solely comprises the pigments found on the basis of information from the suppliers who wanted to participate in this investigation” (Lundsgaard, 2002, p. 14). Table 5.8 summarizes Lundsgaard’s findings. In 2003, Hupe-Norenberg used energy dispersive x-ray spectroscopy to study tattoo inks. The compositions reported were given in Table 5.9. Aberer and Kranke reported (Table 5.10) on the tattoo inks encountered in allergic reactions resulting from tattoos in the 2003 Workshop on Technical/Scientific and Regulatory Issues in the Safety of Tattoos, Body Piercing and of Related Practices (Aberer and Kranke, 2003, p.  55). The authors also state that the other colors (pigments) used for tattooing that may or may not contain metals include the list as given in Table 5.11 (Aberer and Kranke, 2003). Table 5.9  Pigments Reported by Hupe-Norenberg (2003) Color

Composition

Red Yellow Green Blue

Titanium, silicon, potassium, chlorine, and aluminum Silicon, aluminum, titanium, and sulfur Aluminum and titanium Titanium, copper, aluminum, silicon, and potassium

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Table 5.10  Pigments Reported by Aberer and Kranke (2003) Color

Reported Allergen (Color Composition)

Red Yellow Green

Mercury (mercury sulfide, cinnabar, and vermilion) Cadmium (cadmium sulfide) Chromium (chrome green, casalic green, and Guignet’s green [mixture of hydrous chromium oxides]) Cobalt (cobalt blue, azure blue, and cobaltus aluminate)

Blue

Table 5.11  Additional Pigments Reported by Aberer and Kranke (2003) Color

Composition

Black

Logwood (containing chrome), black waterproof ink (containing charcoal suspended in ammoniacal solution containing phenol), and carbon dioxide (sic.) Venetian red (hydrate of ferric oxide) and cadmium salts and ferric sulfate Titanium or zinc oxide and lead carbonate Manganese violet Manganese oxide Iron oxide Aside from mercury sulfide, nonmetallic red colors in tattoos may include an organic pigment (organic lake), carmine (dried insect bodies/ cochinilla), cadmium red (selenide), and sienna Chlorinated copper (phthalocyanine) may be employed in green tattoos, copper salts mixed with azo dyes In some blue tattoos copper phthalocyanine may be used; indigo is occasionally added

Brown White Violet Purple Flesh Red Green Blue

In their presentation “Chemicals used in tattooing and permanent makeup products” during the 2003 Workshop on Technical/Scientific and Regulatory Issues in the Safety of Tattoos, Body Piercing and of related Practices, Baeumler et al. came together to report the results of additional surveys of “market players,” providing reports of their permanent make up and tattoo ink contents, with “to some extent also scientific articles in the medicinal literature have been used as a source of information” (Baeumler et al., 2003, p. 22). Table 5.12 lists colors “in current use” based on input from Norway, Denmark, and Finland (Baeumler et al., 2003, p. 24). Table 5.13 lists colors reported based on input from Germany from the year 2001 (Baeumler et al., 2003, p. 25). Table 5.14 lists colors reported based on input from Danish authorities (Baeumler et al., 2003, p. 26). In 2004, Schmitz and Muller conducted elemental analysis of tattoo inks using SEM-EDS. The authors obtained the results as given in Table 5.15.

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Forensic Analysis of Tattoos and Tattoo Inks Table 5.12  Pigments Reported by Bäumler et al. (2000) Pigment reds Pigment oranges Pigment yellows Pigment greens Pigment blues Pigment violets Pigment browns Pigment blacks Pigment whites Acid red Acid yellow Acid blue Basic violet Solvent red Food red Natural red

22, 23, 7, 170, 210, 57:1, 57:2, 181, 122, 101, and 102 16 74, 87, 42, and 43 7 (chlorinated copper phthalocyanine), 36, and 17 15 (copper phthalocyanine), 29 (ultramarine blue), and 27 (Prussian blue) 16 (manganese violet) 25, 6, and 7 6 and 7 (graphite), 11 6 (titanium dioxide) 18, 51, and 87 3, 9, and 23 9 10 1 17 22/23

Table 5.13  Pigments Reported by Bäumler et al. (2000) Pigment reds Pigment oranges Pigment yellows Pigment greens Pigment blues Pigment violets Pigment browns Pigment blacks Pigment whites

22, 23, 170, 146, 49, 181 (vat red 1), 122, 15, 101, and 102 13, 34, 16, and 43 1, 74, 83, 42, and 43 7, 17 15 19, 23 25, 6, and 7 6 and 7 (graphite), 11 6 (titanium dioxide), 4

Table 5.14  Pigments Reported by Bäumler et al. (2000) Pigment reds Pigment oranges Pigment yellows Pigment greens Pigment blues Pigment violets Pigment browns Pigment blacks Pigment whites

266, 170, 146, 101, and 102 43 1, 74, 97, and 36 7 15 19 25, 6, and 7 6 and 7 (graphite) 6 (titanium dioxide)

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Table 5.15  Pigments Reported by Schmitz and Muller (2004) Color

Composition

Black Violet Green

(Mainly carbon), phosphorous, and sulfur, a little silicon, and aluminum Aluminum, phosphorous, silicon, chlorine, titanium, and chromium Aluminum, phosphorous, chlorine, titanium, copper, some clays, and copper-free Aluminum, silicon, sulfur, and chlorine Silicon, aluminum, titanium, and sulfur Sodium, aluminum, silicon, phosphorous, sulfur, chlorine, titanium, copper, potassium, and calcium

Red Yellow Blue

In 2008, Beute et  al. measured the absorption spectra of twenty-eight pigments and India ink, which were mixed in an agar medium prior to instrumental analysis. The samples used in their study were the same inks and pigments used from the 2001 research of Timko et  al. The authors reported that black inks exhibited absorption over the entire spectrum with no true peak, white pigments increased in absorbance from 404 nm to peak at 790 nm and flesh inks had no maximum absorption (Timko et al., 2001, p. 510). The results were reported as provided in Table 5.16. Poon et al. published a study in 2008 reporting the results of the analysis of a selection of modern tattoo inks using Raman spectroscopy. This study Table 5.16  Pigments Reported by Beute et al. (2008)

Color Black India ink Browns Blue (misty, new blue) Blue green Permanent green Emerald green Pine green Parrot green Misty green Yellow (tulip and lemon) Orange (Florida orange and blush) Red (cerise, fire red, devils’ red, crimson red, tulip red, lotus, wild violet, and peony) Flesh White

Max. Absorption (nm) 600–800 600–800 410–550 590–770 656–808 570–800 602–680 620–785 420–480 440–480 470–485 420–540 500–570 None 790

Lowest Absorption (nm)

730–740 460–490 488 492 532 512 532 532 580 580–610 615–654 600–800

Secondary Peak (nm)

450 470 620–740 630–710 780–795

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Forensic Analysis of Tattoos and Tattoo Inks

Table 5.17  Pigments Reported by Poon et al. (2008) Color

Pigments

Red Yellow Green

Pigment Red 170 (naphthol AS), Pigment Yellow 14 (diarylide yellow) Pigment Yellow 14 (diarylide yellow), titanium dioxide Pigment Green 7 (chlorinated copper phthalocyanine), pigment Yellow 14 (diarylide yellow) Pigment Blue 15:1 (copper phthalocyanine) Carbon black

Blue Black

was a portion of a larger research project by the primary author that considered the analysis of both traditional and modern pigments. The authors analyzed five inks form Millennium Colorworks, Inc. (West Babylon, NY), specifically a blue, yellow, red, green, and black ink, with the results as summarized in Table 5.17. Forte et al. conducted a study in 2009 in which they examined tattoo inks using sector field inductively coupled plasma mass spectrometry (SF-ICP-MS) in order to quantify the metal content of tattoo inks. The authors tested 13 tattoo inks (black, brite orange, canary yellow, country blue, deep blue, deep green, deep brown, deep turquoise, deep violet, golden yellow, lime green, red scarlet, and white brite) for the presence of cadmium, mercury, cobalt, chromium, and nickel. According to their analyses, Forte et al. found that all the metals were present in all the 13 tattoo inks except for mercury, which was absent in black, country blue, and white brite. The same authors also published a more comprehensive survey of metals contained in tattoo inks in the same year. In this study, the authors used SF-ICP-MS in order to quantify the metal content of 56 tattoo inks. Specifically, the elements examined were aluminum, barium, cadmium, cobalt, chromium, copper, iron, mercury, manganese, nickel, lead, antimony, strontium, and vanadium. As in the former study, all the measured metals were detected in all the colors with mercury being under the level of detection for 16 of the 56 inks. Furthermore, the authors reported that chromium showed the highest concentration, followed by nickel and then cobalt. As regard the origin of colors, the natural black ink is obtained from magnetite and wustite (iron oxides) or amorphous carbon from combustion. Other sources normally used are represented by the India ink (containing carbon particles) and logwood which is extracted from the plant Haematoxylum campechisnum (containing chromium)… Blue pigments from minerals include copper (II) carbonate (azurite), sodium aluminum silicate (lapis lazuli), calcium copper silicate (Egyptian blue), copper phthalocyanine, cobalt aluminum oxides and chromium oxides (p. 6000)… The ingredient used to produce the green pigments is mainly chromium oxide but other compounds such as copper salts (Copper phthalocyanine and malachite), lead

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chromate (chrome  yellow) and ferro-ferricyanine (Prussian blue) are also used (p. 6001)… The red coloring is usually due to mercury sulphide, in alternative, cadmium sulphide and cadmium selenide might also be used as well as iron oxide (rust) and ferric hydrate (sienna/red ochre)… White pigments are nowadays derived from titanium dioxide naturally present in the environment as anatase or rutile. This compound has been used to replace the adoption of other salts such as barium sulphate and the most toxic lead carbonate or lead white (Forte et al., 2009a, p. 6002).

In February of 2011, an article appeared in the New York Times reporting that a German study found “dangerous materials” in tattoo inks. The Chemischen und Veterinäruntersuchungsämter (CVUA) Freiburg and Karlsruhe examined thirty-eight red, orange, and yellow tattoo inks in a 2010 study and evaluated the ingredients listed on the labels. The inks were found to contain “prohibited” pigments and/or dyes including materials that are not regulated for tattooing or cosmetic use and some ingredients that are considered harmful and/or carcinogenic. The pigments are listed in Table 5.18. In a 2012 article by Ortiz and Alister meant to “raise awareness of the dangers of cosmetic tattoos” (Ortiz and Alister, 2012, p. 424), the authors report on the pigment components found in tattoo inks (Table 5.19). Table 5.18  Results of 2011 German Study of Pigments in Tattoo Inks Pigment Reds Pigment Oranges Pigment Yellows Other

170, 179, 210, 254, and 266 13, 34 65, 74, 97, 138, and 151 Titanium dioxide

Table 5.19  Pigments Reported by Ortiz and Alster (2012) Color Red Yellow Green Blue Violet White Tan Brown Black

Pigment Mercury sulfide (cinnabar), cadmium selenide (cadmium red), sienna (red ochre, ferric hydrate, ferric sulfate), azo dyes, and hematite Cadmium sulfide (cadmium yellow), ochre, curcumin yellow, azo dyes, limonite, and anthraquinone Chromium oxide (casalis green), hydrated chromium sesquioxide (Guignet green), malachite green, lead chromate, ferro-ferric cyanide, curcumin green, and phthalocyanine dyes (copper salts with yellow coal tar dyes) Cobalt aluminate (azure blue), phthalocyanine, ferric ferrocyanide, and indigoid Manganese violet and indigoid Titanium dioxide (rutile), zinc oxide (zincite), and corundum Iron oxides Ochre India ink, carbon, iron oxide, logwood extract, magnetite, and charcoal

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According to the authors, “Mercury and cadmium salts are no longer found in tattoo inks because of their toxicity. Synthetic organic pigments, such as anthraquinone (yellow), phthalocyanine (blue green), azo (mostly yellow, orange, red, magenta, purple), and indigoid (violet-blue), are synthesized chemical compounds that create brighter, more diverse colors” and “the majority of tattoo ink is industrial grade color intended for use as a printer ink or automobile paint” (Ortiz and Alister, 2012, p. 425).

The Liquid Composition of Modern Tattoo Inks In general, modern tattoo inks are composed of pigment particles mixed with a solution to disperse them. The pigment portion is comprised of organic pigments such as azo dyes (reds, oranges, yellows), polycyclic amines, oxazines (magentas, purples, violets), phthalocyanines (greens, blues), quinacridones (reds), and arylides. Modern tattoo inks can also contain mineral pigments such as titanium dioxide (whites, lighteners) or iron oxide (reds, yellows, and browns). The solution portion of tattoo inks can be composed of a variety of components including a vehicle (to facilitate transfer of the pigment particles into the needle and the skin), additives (such as wetting agents, preservatives, stabilizers, thickeners, and pH regulators), and solvents. Since there is currently no strict regulation of tattoo ink compositions, the variation is extensive and subject to change based upon material availability, manufacturer capabilities, and fiscal considerations. Water may function as a vehicle in the liquid portion of the tattoo ink; its function is to keep the pigment evenly distributed in the fluid matrix, and carry the pigments from the bottle to the needle of the tattoo machine and into the dermis of the skin. Wetting agents can include glycerine, which affects the viscosity of the ink and acts as a thickener and alcohols such as ethanol or isopropanol, which thin the ink. Barium sulfate may be added as a stabilizer, and preservatives can include witch hazel and benzoic acid. According to the packaging labels, the tattoo inks in the 2012 study conducted by Miranda contained the liquid and additive components as given in Table 5.20. A review of updated Material Safety Data Sheets (MSDS) for the inks examined in Miranda’s study demonstrated the presence of propylene glycol [OHCH2CHOHCH3] as an ingredient also (Figure 5.15). In addition to their reports on pigments, Bäumler et al. provide information concerning the liquid portion of the inks, including auxiliary ingredients. The authors report the list (Table 5.21) of auxiliary ingredients (Bäumler et al., 2000, p. 29), which are “based on direct contact by the authors to market players” (Bäumler et al., 2000, p. 22).

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Table 5.20  Liquid Components of Tattoo Inks Reported by Miranda (2012b) Distilled water

dH2O

Isopropanol (isopropyl alcohol)

CH3CHOHCH3;

Glycerine

  CH2OHCHOH CH2OH;

Polyethylene glycol

  HOCH2(CH2OCH2)nCH2OH;

OH

HO

OH OH H

  Witch hazela

O HO

O

OH

OH

OH

OH

O

O

O

HO

OH

OH

OH n

O

OH

OH HO

O

OH OH

OH O HO

OH

HO OH a

Dried leaves of Hamamelis virginiana; Using HPLC, Wang et al. (2003) identified hamamelitannin, catechins, and gallic acid in the leafy and woody portions of the H. virginiana plant.

OH H3C

OH

Figure 5.15  Propylene glycol.

Additional auxiliary ingredients from a study by the Danish authorities included thickening powder (not specified; cellulose-based thickener is used in at least one case), emulsifier (unspecified), resin (unspecified; in the drawing ink it was linseed oil), aqua rosae, as well as the list given in Table 5.22 (Bäumler et al., 2000, p. 30). The authors add that listerine and vodka have been reported as being used as a means of thinning the tattoo ink prior to its use (Bäumler et al., 2000).

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Table 5.21  Liquid Components of Tattoo Inks Reported by Bäumler et al. (2000) Distilled water Ethanol

dH2O CH3CH2OH;

H H H C C O H

Isopropanol

H H   CH3CHOHCH3; OH

Glycerol

OHCH2CHOH CH2OH;

  OH OH

  HO Hydrochloric acid Sodium hydroxide Benzoic acid

Poloxamer 407

HCl NaOH O

OH

HO[CH2CH2O]x[C(CH3)HCH2O]y [CH2CH2O]zH, where x = 98, y = 67, z = 98; CH3 O HO

O a

O

a

H

b

Rosa canina extract Barium sulfate Aluminum hydroxide Rosina

  BaSO4 Al[OH] 3 H

HO

Neodecanoic acid

H O

C10H20O2;

O OH

  Butanamid

O NH2

Amorphous silica (silicon dioxide)

SiO2 (Continued)

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Table 5.21 (Continued)  Liquid Components of Tattoo Inks Reported by Bäumler et al. (2000) Kaolin

Al2Si2O5[OH] 4;

Aroma

Could be many different chemicals mixed together

a

H2O H2O O O O Al Si Si Al O O O O

Pine resin, mainly composed of abietic acid.

Table 5.22  Auxiliary Ingredients of Tattoo Inks Reported by Bäumler et al. (2000) Sodium hyalonate

OH

OH HO

O

O

HO

NH

n

O

O O

O–Na+

O

Methylparaben

OR  where R = CH3

O

OH

Dexpanthenol

C9H19NO4; 

H OH H N

HO

OH

O

Urea

(NH2) 2CO; 

O H2N

Phenol

C

NH2

OH

Additional Studies of Modern Tattoo Inks and Pigments Additional studies concerning tattoo inks include an examination of pigment particle size, microbial status of tattoo inks, and the effects of laser-induced breakdown spectroscopy (LIBS) on the inks in tissue. In 2011, Høgsberg et al.

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classified the particle sizes of tattoo inks using laser diffraction,* TEM, SEM, and XRD. They determined there were three classes of particles: 1. Smallest-black particles (carbon black; mean diameters of 41–165 nm) 2. Intermediate-color particles (green, blue, red, and yellow; in the size range between the black and white pigments) 3. Largest-white particles (titanium dioxide; mean diameters of 317–738 nm) In 2013, Høgsberg et  al., conducted a study in an effort to analyze the microbial product safety of tattoo inks in terms of packaging, labeling, preservation, and sterility of newly acquired stock bottles of ink. The authors found bacteria, but no yeasts or molds in the tattoo inks sampled. Furthermore, they determined that, “labeling was widely inadequate or misleading, and the packaging/sealing was defective in many cases” (Høgsberg et al., 2013, p. 79). The effects of photodecomposition on tattoos have been of interest throughout tattoo history, with much of the focus on the resultant fading of tattoos over a period of time, especially with regard to older tattoos. In addition to the depth of deposition of the pigment (in which too shallow could result in loss over time due to the sloughing off of skin cells and in which too deep pigments could be subjected to macrophages and the natural healing processes of the body, resulting in removal of the pigments as foreign bodies), the chemical nature of the pigment plays a major role in the retention and indelibility of that tattoo. In general, the effect of natural light (specifically ultraviolet radiation, 250–400 nm) on tattoos with regard to exposure, penetration, and absorption of radiation by both the dermis and the tattoo pigments can lead to decomposition of the pigments, which is viewed as fading and degeneration of the tattoo design. Of course, with the introduction and current use of stable, light fast synthetic organic pigments, as well as the increased use of tattoo machines that provide a controlled and uniform depth of insertion of these pigments, the visual effects of fading and loss of detail have declined. Presently, the interest is not so much in the inherent, repeated exposure of a tattoo to natural daylight, but the use and effects of various light sources of varying wavelengths on tattoos for removal purposes. Studies have suggested that the average ink particle is fractured into 10–100 smaller fragments upon laser irradiation (Goldman and Fitzpatrick, 1994, p.  15). Furthermore, studies suggest that the primary effects of laser removal treatment are fragmentation of ink particles, release into the extracellular dermal * Particles passing through a laser beam will scatter light at an angle that is inversely proportional to their size (Mie theory).

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space, partial elimination of ink in a scale crust, probably greater elimination into lymphatics, and rephagocytosis of laser altered residual tattoo ink particles (Goldman and Fitzpatrick, 1994). In a series of studies, Engel, Vasold et al. investigated the laser induced breakdown of pigments to evaluate the effects of laser tattoo removal on tattoo pigments in order to understand the chemical nature of the break down products. The authors were concerned with understanding the mechanism of laser light cleavage of the pigment molecule followed by the formation of decomposition products as a result of tattoo removal. With regard to laser removal, the authors describe that the (high intensity and pulsed) laser light is absorbed by the pigment particles and, at a high temperature, a buildup of heat is achieved in the pigments within nanoseconds. As a consequence, the pigment particles fragment or explode, changing the shape and the size of the tattoo particles significantly, as well as the resultant molecular make-up of the fragments. Subsequently, the fragments will be transported away as part of the natural healing process and removal of foreign materials from the body. Both effects, namely the laser cleavage and subsequent healing process, lead to a decrease in the local pigment concentration and, consequently, to fading of the tattoo color in the skin (Vasold et al., 2004, p. 185). While this fading is certainly the desired effect of laser tattoo removal, the resultant fragments released into the body upon ‘explosion’ of the pigment particles is reported to have the potential to be problematic due to the chemical nature of these fragments and their subsequent effects on the body. Many of these breakdown products are believed to be carcinogenic, and researchers assert the long-term effects of these breakdown products in the tissues require further study. In their study described earlier, Regensburger et al. studied the presence of PAHs in black tattoo inks to assess the potential hazardous nature of tattoo inks placed in the skin. The authors note that while the risks posed by PAHs include carcinogenicity, mutagenicity, and the generation of singlet oxygen under UV-irradiation, which could affect the cellular integrity of the skin (Regensburger et al., 2010, p. e275), “it is unknown so far whether PAHs in black tattoo inks can contribute to any carcinogenic risk for tattooed humans” (Regensburger et al., 2010, p. e278).

Alternate Sources of Tattoos and Tattoo Inks

6

In addition to the materials reported in the previous chapter, alternate sources of tattoo inks and pigments have been reported in historical literature. For example, pigments routinely used for cosmetic purposes, pigments used in art and manufacturing, writing inks and household chemicals and products have found alternate uses as tattoo inks. This chapter addresses many of the less traditional materials used in tattooing. Many pigments that were used for temporary, yet routine, repeated purposes such as ritual body painting, medical treatments, and cosmetics have evolved into being applied in a more permanent fashion, namely tattooing. It is likely that many practices started as temporary, such as the use of cosmetics or body painting for cultural, ritual, magical, and religious purposes. Whether by necessity or accident, at some point it was determined that by inserting the pigments into the skin, the symbols, designs, and overall staining treatments would last for a longer period of time, if not permanently. Of course, it is likely that this transition was based on experimentation and trial-and-error, as was observed with the reports of tattoo artists in the eighteenth and nineteenth centuries.

Pigments for Medicinal Purposes Pigments, as well as substances that were believed to be magical, have been placed in and on the skin for medicinal, or healing purposes. Among the many and varied uses of body marking, we find instances of the art being employed to attract the opposite sex, not by adding artificial ornament to enhance natural charms, but because there is faith in the magical potence of particular drugs and substances, especially if they are applied in a ceremonial manner. The Burmese have such strong faith in tattooed charms … The usual color is vermilion which is pricked in with the tattooing needle. Along with the colouring matter is mixed a drug which varies with the object of the tattooing …” (Hambly, 1925, p. 126).

In addition to lampblack, obtained by the burning of sesamum oil mixed with water, and vermilion, drugs and solutions may also be added to the ink (Yoe, 1896, p. 42). According to Yoe, a drug of tenderness, which enables a 131

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man to get the woman he loves, is “composed of vermilion mixed with a variety of herbs and curious things, prominent among which is the bruised, dry skin of the toukteh, the trout-spotted lizard…*” (Yoe, 1896). In another instance, Yoe mentions “tattooing … with singular drugs” as a form of what he describes as charmed tattooing. In addition to being used for magical purposes, some “drugs” used in tattooing elixirs were purported to be medicinal in nature. Ilani et  al. analyzed a red powder found in a sealed silver tube within a gravesite in Israel using inductively coupled plasma atomic absorption spectroscopy (ICPAES), ICP-MS, SEM-EDS, and XRD. The red powder contained hematite (Fe2O3), malachite (Cu2[CO3][OH]2), cassiterite (SnO2), galena (PbS), kaolinite (Al2O3 ⋅ 2SiO2 ⋅ 2H2O), and calcite (CaCO3) (Ilani et  al., 1999, p.  1324). Subsequent evaluation and comparison of the chemical composition indicated that the material in the tube is a medicine dating back to the Late Roman period. The authors add, “… many medicines were a ‘cocktail’ composed of many materials … (It is reported that) red and yellow iron oxides (ochre), green copper carbonates, lead sulphide (galena) as well as calcium carbonate (calcite) and antimony sulphide, alone or in a mixture, were the most commonly used metals in Roman pharmacy …” (Ilani et al., 1999, p. 1325). As such, it is reasonable to correlate early medicines and ointments with tattooing, whether intentional or accidental, due to the overlap in chemical composition as well as application. Recall that Ötzi’s tattoos are believed to be the result of medical treatments, specifically as acupuncture likely to relieve pain and tension (see Samadelli et al., 2015 for recent findings on Ötzi’s tattoos). Tattooing has also been employed in surgical procedures, for cosmetic and healing therapies. Mercury sulfide is an example of a chemical that was used to treat cutaneous lesions arising from a variety of ailments such as syphilis (Turrel and Marino, 1942, p. 126). The authors specifically report on the use of tattooing with mercuric sulfide for lesions resulting from pruritus ani. A 1937 article in Science News Letter reports the tattooing of the eye with gold and platinum in an effort to improve vision. According to the report, Tattooing the cornea actually dates back to the second century A.D. when Galen used a half iron rod, powdered pomegranate bark and copper salts to * Here is an example of the shortcomings inherent in the translation and reporting of tattoo tradition; regarding this statement by Shway Yoe (cited from his 1896 book), the following is found in Schiffmacher’s 2010 Encyclopedia for the Art and History of Tattooing, “Mister Shawy Yoe’s publication … one would mix the skin of a trout and of a gecko with the pigment ….” (Schiffmacher, 2010, p. 245). While the name change may have been an oversight or an editing error, the contents of the pigment have changed from the skin of a trout-spotted lizard to the skins of a trout and a gecko. According to Cumings, the toukteh, pronounced tuctoo, is a member of the family Geckotidce and is otherwise known as the trout-spotted lizard; his color “pale brown and liberally embellished all over with pink spots” (Cumings, 1893, p. 44).

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make indelible coverings for opaque spots on the cornea…When superficial opaque spots develop on the cornea, especially near the pupil, they greatly interfere with vision … by dispersing the light that passes through the translucent area. Tattooing is used to close up the spaces between the opaque spots and allow lights to pass through a concentrated area. Tattooing also has been used to improve the appearance of the eye in certain conditions … in which the eyes would be white instead of blue or brown or some in between color. India ink and many other substances were tried in corneal tattooing … Gold was first used in 1911 and platinum in 1928. The metals, in the form of chlorides, are used in a solution which, after preliminary preparation of the eye, is placed on the opaque spot for two or three minutes. Then adrenalin chloride is added and the gold changes chemically so that a dark brown, almost black, coloring is produced (n.a., 1942, p. 312).

Pigments for Cosmetic Purposes Research and fieldwork have found extensive use of pigments being placed both on and in the skin for cosmetic purposes. One of the oldest applications of cosmetics is kohl, commonly applied to the eyes. Kohl is described as soot from the burning of various materials (such as the cheaper kind of frankincense or the shells of almonds, the qurtum plant [Carthamus tinctorius] and vegetable matter), carbonate of lead, black oxide of copper, brown ochre, magnetic oxide of iron, black manganese of oxide, sulfide of antimony, malachite (a green ore of copper), and chrysocolla (a greenish blue ore of copper) and galena (a dark gray ore of lead) (Lucas, 1930, p.  42). Interestingly, the chemical composition of some apparent cosmetics reported in historical literature has correlation to the “medicine” reported by Ilani et al. (1999). Lucas aptly notes that scientific studies of recovered specimens are often inconclusive with regard to the specific uses of the residues; usually reported as having a possible cosmetic or medicinal purpose, with tattooing often being overlooked (Lucas, 1930, p. 42). A 2011 article reports on the finding of pigments in a South African cave estimated to be 100,000 years old. These cave artisans had stones for pounding and grinding colorful dirt enriched with a kind of iron oxide to a powder, known as ocher. This was blended with the binding fat of mammal bone marrow and a dash of charcoal … [This finding] is the earliest example yet of how emergent homo sapiens processed ocher, one of the species’ first pigments in wide use … The early humans may have applied the concoction to their skin for protection or simply decoration … (Wilford, 2011, p. A14).

Face paint has also been reported in the literature as being oxide of iron, red ocher (Lucas, 1930, p. 44). The most commonly referenced form of body

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Forensic Analysis of Tattoos and Tattoo Inks

paint is that of woad, which was mentioned by Julius Caesar. Other pigments used for body paint as referenced in the literature include charcoal, red ocher, and “earth.” In a 2012 study, Domenech-Carbo et al. reported their results of chemical analysis from samples of pigmenting materials contained in vessels found in a burial site. Using a variety of analytical techniques, including FT-IR, SEM-EDS, and XRD, the authors report finding chemicals consistent with those reported for tattooing (e.g., charcoal, cinnabar, iron oxide, and barium sulfate). The authors conclude that the samples were likely used for cosmetic purposes and for funerary rituals.

Pigments Used in Art and Manufacturing Literature has noted the correlation between tattoo designs and shapes, particularly those classified as “tribal,” and decorated individuals on ancient pottery, statues and figurines, structures (houses, caves, burial chambers), artwork, and so on, uncovered during archaeological excavation and exploration. The correlation between the process of scrimshaw, a pastime of sailors in which designs and artwork were carved, pricked or drawn into bones, teeth, and tusks of various land and sea creatures, and tattooing was reported in Caplan, “the description of scrimshaw work could just as well be a description of 19th century tattooing techniques … The scrimshander’s techniques and tools and pigments were equally serviceable for tattooing and no doubt were used for exactly that purpose too” (Caplan, 2000, p. xxiii). With regard to the process of scrimshaw and the pigments employed Frank describes A sailmaker’s needle, graver’s burin or sharp pointed knife was used to prick a series of holes through the outline of [a] picture, thus making a corresponding mark in the ivory or bone … These pock marks … form an outline of the desired image … The process then becomes a matter of engraving, or carefully connecting the dots with a blade or burin; or stippling, using dots rather than lines to fill out the picture. When pigment or ink is painted on and then went off before it dries or hardens remnants remain in the grooves or dots … The most common pigment used for scrimshaw was lampblack, a carbon suspension in oil or grease that is the residue of combustion in lamps and candles and tryworks, ubiquitous on shipboard. However India ink (also called China ink) was also occasionally used. (The ludicrous myth of tobacco juice as a coloring agent has no foundation in empirical facts; no actual evidence has ever been produced to support it). Few specifics are known about the colors on pictorial scrimshaw. As far as is known, the whalemen left no written record of what pigments and inks they used, nor has evidence emerged of their buying colors for scrimshaw, though commercially made watercolors were much in evidence on shipboard … Certainly verdigris, the emerald green rust produced by the

Alternate Sources of Tattoos and Tattoo Inks

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oxidation of copper and brass, was widely employed; probably also analogous home-brewed and shipboard made concoctions, such as variants of such fruit based colors familiar to agrarian America as blueberry and oxblood milk paint (Frank, 2012, p. 153).

In mentioning the presence of commercially made watercolors on board ships and their apparent use by sailors, the use of artists and decorators paint for tattooing was to be expected, and references to such use can be found throughout the literature. References to specific “brands” of paint products employed in early tattooing can be found; Cohen writes, “the beautiful vivid blues and permanent greens of present day tattooing are the copper phthalocyanine compounds … They are used in Grumbacher artist’s paints and in the printing industry” (Cohen, 1994, p.  268). Cohen also adds that Grumbacher’s are the best artists’ paints (Cohen, 1994, p. 270). According to Mayer, M. Grumbacher, Inc. was based in Cranbury NJ and it is not clear as to whether this company was a manufacturer or distributor of pigments* (Mayer, 1991, p. 666). Other references to artists materials refer to tempera paint (distemper) and poster colors. Distemper was a term employed in Great Britain to designate aqueous paints made with a simple glue-size or casein binder, such as are used for flat indoor wall painting or decoration. Among the American products that may be classified under this heading are calcimine, cold water paints, and showcard and poster colors. The term is rather more descriptive of bulk or house paints than of artists’ paints (Mayer, 1991, p. 643). When referring to a fellow tattooist, Steward writes, “He used tempera colors in the skin-colors which were neither inert nor pure—but very cheap…he went right on with the dangerous pigments” (Steward, 1990, p. 26). Collins reports the use of Prang colors, “[Charlie Wagner] used to spit in a box of kids’ Prang water colors and use that for red, green and yellow …” (Hardy, 2007, p. 116). Cohen describes doxime carbazole; “The rare purple or violet pigment given to a select few of the tattooing world 20 years ago was doxime carbazole, used in photographic plate production and as a paint pigment … Carbazole is an extremely weak base and very insoluble in water” (Cohen, 1994, p. 268). This description corresponds to pigment violet 23 (Carbazole dioxazine/carbazole violet), although the nomenclature reported by Cohen is slightly different and possibly due to typographical oversight.

* According to their website, Grumbacher has been providing artists materials and tools since 1905 (http://www.grumbacherart.com/). Max Grumbacher is described as a master brush maker, and when his business grew after he immigrated to America in 1903, he partnered with a German manufacturer of artists paint and began to import and sell artists’ colors. By the early 1930s, he began to manufacture artists’ colors in the United States (https://www.maxgrumbachergallery.com/static_pages/about).

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Forensic Analysis of Tattoos and Tattoo Inks

Writing Inks It is quite logical to reason that experimentation with writing inks for their ability to be used as tattoo inks would be expected throughout time. It is not surprising to find that individuals have improvised by using pen ink as the source of pigments for tattooing. As previously described, the use of pen ink has been reported as used for homemade, amateur and prison tattooing practices as well as being used by professional tattoo artists. It is worthwhile to have knowledge of writing ink history and chemical compositions over time when studying tattooing practices and materials, both ancient and modern. “Generally speaking, during the entire history of mankind, in all corners of the globe, there have been just three different types of ink: a pigment plus a binder (like ink sticks and gouache), a chemical precipitation (like iron gall ink), and a dyestuff (like any modern fountain pen ink)” (Thompson, 1996, p. 42). Throughout the literature, India ink and Chinese ink are reported as being used for black tattoo inks. According to Thompson (1996), Stick ink was invented in China … In England, India sometimes is thought of as its originator which can be seen from its English name, Indian ink … Soot and glue are the two most important ingredients in ink sticks, or ink cakes, as they are also called. The soot has just one purpose: to give color to the ink. Soot consists of nearly pure carbon … The glue in ink sticks normally is animal glue, originally made from deer bones. It acts as an adhesive to bond the soot particles… This glue also governs the flow properties of the ink … Fragrance, additional colorants (to produce certain hues) etc. can also be added … (p. 44) … Roughly speaking, the soot used in ink sticks belong to one of three categories: vegetable oils soot, pine soot, petroleum based or synthetic oil soot (p. 50).

The chemistry and pigment composition of writing inks have changed over time, similar to the changes observed in tattoo ink chemistry. Historically, India/carbon inks were used from 618–906 ad, iron gallotannate inks were used in about 600 ad, and in about 1954, chelated metalized dyes began to be used, that is, copper phthalocyanines (Brunelle, 2003, p. 7). While straightforward, carbon-based, sooty inks were likely the easiest to produce and exhibited high degrees of robustness and permanency, other inks were likely experimented with in the art of tattooing. In general, writing inks have a similar composition to that of tattoo inks; containing dyes or pigments, solvents and vehicles, resins, lubricants, and other materials depending on the desired properties of the ink. Much like tattoo inks, writing inks are not pure, and they can exhibit extensive variation with respect to chemical composition. According to Brunelle (2003),

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137

The solvents and vehicles found in writing inks may be primarily water or entirely organic solvents; glycol solvents are the most commonly used in ballpoint pens although benzyl alcohol has become a common solvent used in ballpoint pens (p. 24) … The principle change in the last fifteen years is the elimination of toluene; common writing pen solvents and vehicles include dipropylene glycol, butylene glycol, phenyl glycol, and benzyl alcohol (p. 25) … Resins in writing inks are used for adjusting the viscosity of ballpoint pen ink and for increasing film strength and lubricant qualities of the ink … Some resins impart color to the inks and can include coal tar, pine tar, and various resins (p. 28) … Lubricants include oleic acid (also used as a drying agent and to adjust the viscosity of the ink) (p. 29) … Other additives include biocides (prevent microbial growth), surfactants (adjust surface tension of the mixture, aid in wetting), corrosion inhibitors (preserved metal components), sequestrants (hold a substance in solution by complexing action), shear thinning agents (permit flow), preservatives and diluting agents (tertiary butyl hydroperoxide), emulsifying agents, diluting agents, preservatives, buffers, additives to adjust pH, viscosity, polymerization and blockage prevention (p. 29).

With regard to the pigment component of writing inks, “Although dyes from any Society of Dyers and Colourists dye constitution class could appear in the formulations of writing inks, there are four classes that are of particular interest to ink analysts: arylmethane, azo, phthalocyanine and azine (nigrosine) dyes” (Brunelle, 2003, p. 15). Arylmethane dyes are those that are derived from methane, with hydrogen atoms being replaced by aryl rings (Brunelle, 2003, p. 15). Nigrosine writing ink dyes are acid dyes of the azine (pyridine) or aniline (aminobenzene) chemical classes with many contaminants, especially metals (Brunelle, 2003, p. 16). Other inks that have been reported in the literature are the iron gall inks. Iron gall containing tannic acid was used to make manuscript inks and may have been used for body painting and possibly tattooing. Tannic acid occurs in two basic forms, pyrogallol and catechol (Figure 6.1). One group of tannins can be converted into metagallic acid and yield pyrogallol, the other tannins produce metagallic acid and catecol (Mitchell and Hepworth, 1904, p. 50). “Inks made from catechol tannins, such as those extracted from hemlock or pine bark will give a greenish black ink …” while “pyrogallol tannins, such as those extracted from galls, cherry bark, and oak bark will give a blueblack ink …” (Thompson, 1956, 1996, p. 5). Ancient writings and literature may be especially useful for providing recipes that may have been used to tattoo in ancient times. The review of texts such as the Mappae Clavicula (Smith and Hawthorne, 1974) and other documents that discuss medieval bookmaking and the chemistry of writing inks (e.g., Levey (1962); Mitchell and Hepworth, 1904) can provide insight into pigment chemistry and tattoo ink compositions reported in historical documents.

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Forensic Analysis of Tattoos and Tattoo Inks OH

HO

HO

HO O

HO HO

HO HO

OH

O O

HO

OH

OH O

O

O O

O O HO

O

O

O O O

OH

OH OH

O O

O

O

OH OH

O

OH O

HO

OH

OH O

HO HO

OH

Tannic acid COOH

OH

OH OH

OH HO

OH OH Gallic acid

OH Pyrogallol

Catecol

Figure 6.1  Pigments related to iron gall inks.

In 1993, “the primary supplier of inks to tattoo artists throughout the word (Spaulding and Rogers) states that they use Pelikan Ink, a brand name of India ink, as their black pigment” (Goldman and Fitzpatrick, 1994, p. 165). A “bottle of German black Pelikan ink” was a component of the “Professional” Tattoo Outfit offered by Spaulding and Rogers in their 1950 Tattooing Catalogue (Morse, 1977, p. 42). Sailor Jerry Collins also refers to the use of Pelikan drawing ink (Hardy, 2007, p.  82), and Pelikan black drawing ink, Talens black (drawing) ink, and Higgins black ink (Sanford) have been reported on tattoo ink distributor websites (Figure 6.2). Miranda notes, The Sanford logo is more commonly associated with clerical ink and inscription, and a subsequent search of this ink lists it as for use with technical pens, airbrushes, dip pens or brushes (not tattoo inks). In another instance, it was alleged that Pelikan ink (advertised as a drawing/fountain pen ink) was being used as a tattoo ink but was later removed from the market because its usage as

Alternate Sources of Tattoos and Tattoo Inks National tattoo supply

Email this to friend Higgins black magic ink ***Made in the U.S.A***

139

Talens and Pelikan drawing inks, not for tattooing

HBN

#5K932 Pelikan A, 1000 mL $69.00

#5K931 Pelikan A, 250 mL $38.50

#5K901 Talens #5K931 Talens drawing ink #700 Indian ink 490 mL 490 mL 12-Oz, $42.00 (12-Oz), $42.00

Figure 6.2 Left: Higgins ink, which was available for sale on the National

Tattoo Supply website in 2012 but is no longer listed on their website (as of 2014). Right: Talens and Pelikan Inks available for sale on the Unimax Supply Co. Inc. website (as of 2014). Note the presence of “Not for Tattooing” above the inks (http://store.unimaxshop.com/talens—pelikan-black-inks-p2309.aspx).

a tattoo ink caused allergic reactions and led to legal ramifications (Miranda, 2012b, p. 101).

In addition to pen ink, the use of pencils was also reported. During an interview with an inmate, Haines and Huffman report the inmate “used pencil lead* and hair oil” as the tattoo ink (Haines and Huffman, 1956, p. 109). Other materials reported to have been used for tattooing included household products such as laundry/washing blue, brick dust,† and ash, all of which have been discussed earlier. With regard to a specific use of the latter, memorial, or mourning tattoos are described as ash tattoos in which “… the ink has been mixed with the ash of the deceased.” (Schiffmacher, 2010, p. 301). Gold flakes have also been reported; “Tattoo artists have often tried to incorporate gold as an ingredient of their tattoo pigments” (Schiffmacher, 2010, p. 144). By entering the phrase “homemade tattoo ink” as an online search query, a variety of “do-it-yourself” tattoo ink recipes are available, many listing household products and writing inks (e.g., inks from ballpoint pens, artist’s pen inks) as the sources of pigments. Extensive literature pertaining to the scientific study of writing inks is available in both forensic and general periodicals and texts, which provides myriad information on ink chemical composition. Components of inks include dyes, pigments, vehicles

* Likely graphite. † Recall that this term was synonymous with cinnabar/vermilion. Whether or not individuals took the terminology literally and attempted to inject brick dust into the skin is unknown.

140

Forensic Analysis of Tattoos and Tattoo Inks HO

O

O

COOH

Figure 6.3 Fluorescein, the basic building block for its various derivatives, including those listed in the Table 6.1.

(oils, solvents, resins), and other additives such as driers, plasticizers, surfactants, and waxes (Zlotnick and Smith, 1999, p. 267). More recently, the introduction of tattoo pigments that exhibit luminescent properties (fluorescence, phosphorescence) has resulted in the trend of glow-in-the-dark tattoos (Figure 6.3). No comprehensive scientific studies concerning the luminescence of tattoo inks and corresponding chemical composition of luminescent tattoo inks has been identified, the FDA website provides a list of chemicals/pigments that are luminescent (Table 6.1). Table 6.1  Pigments That Exhibit Luminescent Properties Color Name D&C Orange No. 5 (CI 45370:1) D&C Orange No. 10 (CI 45425:1) D&C Orange No. 11 (CI 45425) D&C Red No. 21 (CI 45380:2) D&C Red No. 22 (CI 45380) D&C Red No. 27 (CI 45410:1) D&C Red No. 28 (CI 45410) Luminescent zinc sulfide a

b

Compositiona,b Sodium salt of 4′,5′-dibromofluorescein 2′,4′,5′-tribromofluorescein 2′,4′,5′,7′-tetrabromofluorescein 4′,5′-diiodofluorescein 2′,4′,5′-triiodofluorescein 2′,4′,5′,7′-tetraiodofluorescein Disodium salts of 4′,5′-diiodofluorescein 2′,4′,5′-triiodofluorescein 2′,4′,5′,7′-tetraiodofluorescein 2′,4′,5′,7′-tetrabromofluorescein 2′,4′,5′-tribromofluorescein 2′,4′,7′-tribromofluorescein Disodium salt of 2′,4′,5′7′-tetrabromofluorescein Disodium salts of 2′,4′,5′-tribromofluorescein 2′,4′,7′-tribromofluorescein 2′,4′,5′,7′-tetrabromo-4,5,6,7-tetrachlorofluorescein Disodium salt of 2′,4′,5′,7′-tetrabromo-4,5,6,7-tetrachlorofluorescein Zinc sulfide containing a copper activator

http://www.ecfr.gov/cgi-bin/retrieveECFR?gp=&SID=17723345ba7c363ef25a68e9776aa2cd &r=PART&n=21y1.0.1.1.28#se21.1.74_11255 http://www.ecfr.gov/cgi-bin/retrieveECFR?gp=&SID=17723345ba7c363ef25a68e9776aa2cd &r=PART&n=21y1.0.1.1.27#se21.1.73_12995 (luminescent zinc sulfide)

Alternate Sources of Tattoos and Tattoo Inks

141

According to the FDA website Only the following fluorescent colors are approved for use in cosmetics, and there are limits on their intended uses: D&C Orange No. 5, No. 10, and No. 11; and D&C Red No. 21, No. 22, No. 27, and No. 28 … Luminescent zinc sulfide is the only approved glow-in-the-dark color additive … No color additives are approved for injection into the skin, as in tattoos and permanent makeup.*

Other sources of tattoos, specifically temporary designs, include henna, “fake” tattoos, and ink-based stamp pads. To apply a temporary tattoo, the design is cut from the sheet, placed face down on the skin, and the back of the tattoo is wet with a damp cloth. After approximately 30 s, the backing can be peeled off and the tattoo will remain on the skin. To remove the tattoo, it is recommended that alcohol is applied to the area and by rubbing the design, it will be removed. According to one design sheet (Figure 6.4), the following is reported (Table 6.2): Ingredients: PVA copolymer resin, modified varnish, deodorized petroleum, silicon dioxide, aluminum silicate, iron oxide, FD&C Yellow #5 and 6 aluminum lake, D&C Red #7, FD&C Blue #1 aluminum lake. (All colors are FDA certified.)

Figure 6.4  A sheet of temporary tattoos. * http://www.fda.gov/ForIndustry/ColorAdditives/ColorAdditivesinSpecificProducts/ InCosmetics/ucm110032.htm; the FDA describes fluorescent colors as “neon or day glow” and luminescent colors as “glow in the dark”… “luminescent zinc sulfide…[can be] recognize[d] by its whitish-yellowish-greenish glow;” (http://www.fda.gov/­cosmetics/ productsingredients/products/ucm143055.htm); “Following excitation by daylight or a suitable artificial light, luminescent zinc sulfide produces a yellow-green phosphorescence with a maximum at 530 nanometers” (see footnote a in Table 6.1).

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Forensic Analysis of Tattoos and Tattoo Inks

Table 6.2  Pigments Reported in Temporary Tattoo Design Sheets Color Name D&C Yellow 5 (CI 19140) D&C Yellow 6 aluminum lake (CI 15985:1) D&C Red 7 (CI 15850:1) D&C Blue 1 aluminum lake (CI 42090:2)

a

b

Compositiona,b Trisodium salt of 4,5-dihydro-5-oxo-1-(4-sulfophenyl)-4[4-sulfophenyl-azo]-1H-pyrazole-3-carboxylic acid Disodium salt of 6-hydroxy-5-[(4-sulfophenyl)azo]-2naphthalenesulfonic acid, and Trisodium salt of 3-hydroxy-4-[(4-sulfophenyl)azo]-2,7naphthalenedisulfonic acid Calcium salt of 3-hydroxy-4-[(4-methyl-2-sulfophenyl) azo]-2-naphthalenecarboxylic acid Disodium salt of ethyl [4-[p-[ethyl (m-sulfobenzyl) amino]-α-(o-sulfophenyl) benzylidene]-2,5-cyclohexadien1-ylidene] (m-sulfobenzyl) ammonium hydroxide inner salt with smaller amounts of the isomeric disodium salts of ethyl [4-[p-[ethyl(p-sulfobenzyl) amino]-α-(o-sulfophenyl) benzylidene]-2,5-cyclohexadien-1-ylidene] (p-sulfobenzyl) ammonium hydroxide inner salt and ethyl [4-[p-[ethyl (o-sulfobenzyl) amino]-α-(o -sulfophenyl) benzylidene]2,5-cyclohexadien-1-ylidene] (o-sulfobenzyl) ammonium hydroxide inner salt

http://www.ecfr.gov/cgi-bin/retrieveECFR?gp=&SID=17723345ba7c363ef25a68e9776aa2cd &r=PART&n=21y1.0.1.1.28#se21.1.74_1101. Lakes are made by extending on a substratum of alumina…combining such color with the basic radical aluminum or calcium (http://www.ecfr.gov/cgi-bin/retrieveECFR?gp=&SID= 17723345ba7c363ef25a68e9776aa2cd&r=PART&n=pt21.1.82#se21.1.82_151).

A 2005 study by Rastogi and Johansen regarding the colorants in transferable picture tattoos (temporary tattoos) was conducted for dermatological purposes; specifically to detect the presence of allergens in temporary tattoos. Using UV/VIS spectroscopy and HPLC, the authors extracted the pigments of 36 picture tattoos, using citric acid tetrabutylammonium hydroxide, acetonitrile/tetrahydrofuran acid as the extraction solvent. According to their study, Rastogi and Johansen identified the following colorants: solvent orange 1, acid yellow 9, acid dye, acid blue 169, pigment red 57, acid red 18, acid green 22, acid red 52, acid red 50, direct blue 86, and natural yellow 3 (curcumin). The authors note, “The blue color could not be extracted … This may also be the reason for nonidentifiable green (blue + yellow) and violet (blue + red) …” (Rastogi and Johansen, 2005, p. 208). The inability to extract, and thus identify the blue-containing portions of the tattoos was likely due to inefficient extraction of the phthalocyanines; this extraction would require a stronger acid due to the phthalocyanines exhibiting characteristics of an inorganic molecule because of the presence of copper and possibly chlorine and bromine.* Rastogi and Johansen also note that they were unable to identify the black  color. * See Chapter 9.

Alternate Sources of Tattoos and Tattoo Inks O

NH2

OH

O

H N

H2N O Lawsone, 2-hydroxy-1, 4-naphthoquinone

143

N H

Para-phenylenediamine

O

Indigo

Figure 6.5  Pigments found in various types of henna products.

They  report previous studies in which para-phenylenediamine (a coal tar derivative) was the black coloring agent identified in temporary tattoos. Henna is another popular temporary option for skin decoration. There are three types of henna reported for use to stain the skin, red henna, black henna, and blue henna (Figure 6.5). With red henna (Lawsonia inermis), the active ingredient is naphthoquinone (lawsone, 2-hydroxy-1,4-naphthoquinone). When mixed with water, a reddish brown paste is produced, which leaves a similar color on the skin. Black henna contains the active ingredient para-phenylenediamine (PPD), which is a dark brown dye. When mixed with water, a dark brown paste is produced, which leaves a similar color on the skin. Blue henna is characterized by an indigo blue, which is a blue black dye (Aberer and Kranke, 2003, p. 55). The use of stamp ink being used as a pigment intended to create a permanent tattoo has been reported. During their research regarding the prevalence of tattoos in a prison environment, a 22-year-old inmate informed Haines and Huffman that his tattoos were made with “just a sewing needle and the stamping ink that is used to put on your clothing” (Haines and Huffman, 1956, p. 108). Indeed, the use of stamp pads to generate a temporary, inked mark is well-established. Ink-based stamps, while not typically used as a temporary tattoo in the decorative sense, may be used to mark and subsequently track individuals. Stamps are often used to designate entry into various public venues, from arenas hosting sporting events, concerts and trade shows to social events at clubs and bars. In addition, stamps may also be used at attractions which host children, such as theme parks, carnivals, and indoor family-themed entertainment. For example, Chuck E. Cheese’s®, a family-oriented restaurant and game room, has a Kid Check® program stating, “Every member of a party—adult and kid; family or group—who enters Chuck E. Cheese’s gets a unique hand stamp that is verified upon their exit to assist in our objective that families who come together leave together.”* These hand stamps at any of the above-mentioned venues may be latent or patent; *

http://www.chuckecheese.com/experience/our-promise.

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Forensic Analysis of Tattoos and Tattoo Inks

the latent stamps often employing a luminescent dye that can be detected using a “black light”* or alternate light source and the patent stamps being any color based on the stamp pad employed. In 1989, Jasuja et al. examined black, violet, green, and red Indian brand stamp inks using TLC. The authors reported that It is evident … that the dye constituents of all the four brands could be successfully separated with four different solvent systems using one system for each colour. Among these inks, the black, green, and red inks of four brands were found to be non-identical in their dye compositions, whereas all the four violet inks showed [the] same dye constituents as is evident from the same number of color spots with same shades and R f values. After trying a number of solvent systems and their mixtures in various proportions, it was also observed that the dye constituents of all the four colour[s] could not be separated with one solvent system, rather different solvent system[s] for each color had to be evolved (Jasuja et al., 1989, p. 256).

The authors did not attempt to identify the chemical compositions of the inks or the individual constituents resolved on the TLC plates. Lee et al. studied five red sealing inks from Korean markets (manufacturers included those from Korea, Japan, and China), and using time-of-flight secondary ion mass spectrometry (TOF-SIMS), atomic absorption spectroscopy (AAS), and ICP-MS, determined elemental composition and evaluated the use of instrumental methods to differentiate ink samples. On the basis of inorganic elemental analysis and organic analysis, the authors concluded that sealing inks were able to be differentiated based on TOF-MS (Lee et al., 2008, p. 1524). In a similar study, Dirwono et  al. studied 13 red sealing inks from Korean stores (manufacturers included those from Korea, Japan, and China). Upon visual examination, the authors report that the colors of the inks varied, some exhibiting a red color and others exhibiting a purple red color (Dirwono et al., 2010, p. 7). Using FT-IR, specifically ATR, the authors compared spectra in blind studies to determine whether or not the inks could be differentiated by analytical means and conducted studies comparing the seal inks to ballpoint pen inks (Dirwono et al., 2010, p. 8). As a result, the authors determined that it was possible to distinguish inks from different manufacturers. In their 2013 publication, Raza and Saha examined nine blue color stamp inks manufactured in India; the authors reported that upon initial examination, the colors appeared different when stamped on a piece of paper, with some appearing violet, one appearing blue-black and one * A black light is a mercury-vapor tube coated with phosphors on the inside. When stimulated by the mercury vapors in the tube, the phosphors emit longer wave UV near the violet portion of the visible spectrum. The range is approximately 300–400 nm, corresponding to long wave UV and visible violet regions (Petersen, 2000, p. 640).

Alternate Sources of Tattoos and Tattoo Inks

145

appearing blue. The authors reported crystal violet as being a component in some of the stamp pads analyzed and that classification of the inks based on Raman spectroscopy resulted in the ability to classify the nine stamp inks in five groups. Whether using inorganic pigments, organic pigments or common household products for tattooing, a thorough understanding of chemical composition is necessary to evaluate the pigment’s role in forensic investigations. By determining tattoo ink composition, specifically with regard to the pigment portion, it may be possible to detect the pigments in human tissue and thus determine the presence or absence of a tattoo as well as its physical characteristics. It may also be possible to determine whether or not residues are consistent with a tattoo ink, which can aid in criminal investigations.

Modern Tattoo Inks

III

7

Modern Organic Pigments

The color of a substance is determined by its absorption spectrum in the visible region (~400–700 nm). Colorants are generally classified as to whether they are organic or inorganic, natural or synthetic, and whether they are dyes or pigments. Further classification is done according to their method of application onto a substrate (such as textile dyes), according to the chemical class of the chromophore, or on the basis of their color. According to Mayer, pigments may be classified according to their color, use, permanence, and so on. It is customary, however to classify them according to their origin, as follows (Mayer, 1991, p. 31): I. Inorganic (mineral) a. Native earths (ocher, raw umber, etc.) b. Calcined native earths (burnt umber, burnt sienna, etc.) c. Inorganic synthetic colors (cadmium oxide, zinc yellow, etc.) II. Organic a. Vegetable (gamboges, indigo, madder) b. Animal (cochineal, Indian yellow, etc.) c. Synthetic organic pigments With regard to classification, Mattiello takes a slightly modified approach, first assigning the broad general classes: colored, white, black and metallic element and alloy followed by further delineation according to composition and hue (Mattiello, 1946, p. 3): I. Colored a. Organic i. Synthetic—chemically manufactured ii. Natural b. Inorganic i. Synthetic—chemically manufactured ii. Natural II. White a. Opaque i. Synthetic—chemically manufactured ii. Natural 149

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Forensic Analysis of Tattoos and Tattoo Inks

b. Nonopaque extender i. Synthetic—chemically manufactured ii. Natural III. Black a. Organic i. Synthetic—chemically manufactured ii. Natural b. Inorganic IV. Metallic element and alloy a. Inorganic i. Synthetic—chemically manufactured Organic pigments are carbon hydrogen derivatives while inorganic pigments are not formed from carbon and hydrogen, but contain metal atoms. To change the solubility of organic molecules, metals can be added to the molecule. Often, these molecules retain their classification as organic although a metallic component has been added (Mayer, 1991, p. 63). An example of this classification is the phthalocyanines. Dyes are coloring materials that are partially or completely soluble in a variety of liquids, and can be applied to a variety of substrates based on their affinity to a particular substrate. Dyes are those that dissolve in liquids and impart their color effects to materials by staining or being absorbed (Mayer, 1991, p. 29). Classification of dyes can be based upon the method of application or their structure (Gettens and Stout, 1966, p. 112). They consist in structure of a chromophore group and a salt-forming (anchoring) group (Gettens and Stout, 1966, p. 112). Pigments are small, dry particles that are virtually insoluble in liquids and the media in which they are applied. When a pigment is mixed or ground in a liquid vehicle to form a paint, it does not dissolve but remains dispersed or suspended in the liquid (Mayer, 1991, p. 29). The same is true for inks. Dyes and pigments are similar with respect to chemistry and structure and tend to differ in application and usage. Lomax and Learner define synthetic organic pigments as referring to manufactured colorants that have carboxylic ring skeletons as part of their structure, with many of the ring systems being aromatic in nature, as well as potentially consisting of a variety of functional groups and metal ions (Lomax and Learner, 2006, p. 108). The authors add that synthetic organic pigments, true pigments and not dyes, must be distinguished from those natural organic pigments that are now synthesized; as such, they define synthetic organic pigment as referring specifically to those pigments that have no counterparts in nature, but are manufactured in a laboratory to achieve a specific color or application (Lomax and Learner, 2006, p. 108). Organic pigments are carbon-based, polycyclic compounds that contain one or more characteristic functional groups called chromophores. The shades

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and physical properties of organic pigments depend on the nature and number of chromophores and salt forming groups within the molecular species and the relative disposition of these functional groups within the molecule. Chromophores are classified as either chromogens, which are color generating functional groups, or auxochromes, which are color augmenting functional groups. Molecules referred to as chromogens possess the potentiality for developing color even if they are not in themselves intensely colored (Patterson, 1967, p. 26). Auxochromes produce shifts in the absorption bands of the molecule, which can develop color in the molecule (Figure 7.1). Hypsochromic, or blue shifts are those in which the absorption band moves to a shorter wavelength and bathochromic, or red shifts are those in which the absorption band moves to a longer wavelength (Patterson, 1967). Color-displaying molecules vary in the amount and type of functional groups they contain, which will impact the color they exhibit. The production of color is related to the resonance by delocalization of the π electrons from the presence of conjugated unsaturated systems. The intensity of the color can depend on the width of the band and other colors may display more than one band in an absorbance spectrum. Common chromogens include: C═C and ─C═C─C═C─, C═O (carbonyl), C═S (thiol), CH═N (azomethine), N═N (azo), N═N+O−, N═O (nitroso), NO2 (nitro), and ringed structures (note the presence of unsaturated (double) bond systems, which contribute the π electrons). Common auxochromes include: ─OCH3, ─OH, ─NH2, NH─R, NR 2, O─R, halogens, Hyperchromic

Hypsochromic

Bathochromic

Hypochromic

Abs.

Wavelength (nm)

Figure 7.1  Shifts observed in UV/Vis spectrophotometry.

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salts, phenyls and naphthyls, and other conjugated heterocyclic groups. The carbonyl and vinyl groups have chromophoric properties only when they are present in the molecule in multiple conjugated order (Juster, 1962, p. 598). The structural features responsible for color are also responsible for absorption in the ultraviolet, as well as the visible, region of the electromagnetic spectrum. Table 7.1 demonstrates the colors of substances showing single absorption bands in the visible region of the electromagnetic spectrum. In 1856, with the discovery of mauve, the modern synthetic dye industry began. In 1865, with the nature of benzene described,* more sophisticated preparations of natural and synthetic dyes arose (Zollinger, 2003, p. 6). Since this time, millions of colored compounds have been synthesized. Synthetic organic dyes and pigments are synthesized from five basic raw materials: benzene, toluene, xylene, naphthalene, and anthracene (Mayer, 1991, p. 478). These are aromatic hydrocarbons produced by the distillation of coal tar—a byproduct of the coal gas and coke industry, and from some petroleum residues (Mayer, 1991). As such, colors derived in this manner are collectively referred to as coal tar dyes and pigments (Figure 7.2). According to the Pigment Compendium, “the term coal tar appears to have been used primarily from the late eighteenth through to the earlier twentieth century, aniline colours being an essentially synonymous term. Both are now wholly superseded by the use of the chemical nomenclature of the azo and polycyclic pigment groups” (Eastaugh et al., 2008, p. 117). Fay (1919) provides a detailed description of the process of obtaining coal tar and its products: When bituminous coal is thoroughly ignited in stoves and furnaces and a draught of air freely circulates through the mass, three principle products Table 7.1  Absorption Characteristics of Colors Wavelength (nm) 200–300 300–400 400–435 435–480 480–490 490–500 500–560 560–580 580–595 595–605 605–750

Color of Light Absorbed — — Violet Blue Green–blue Blue–green Green Yellow–green Yellow Orange Red

Color of Compound — — Yellow–green Yellow Orange Red Purple Violet Blue Green–blue Blue–green

* Described by Kekule; the normal vibration modes of benzene have also been diagrammed by Varsanyi.

Modern Organic Pigments

153 CH3

Benzene

Toluene

Naphthalene

Anthracene

CH3

Xylene

CH3

Figure 7.2  Coal tar dyes. are formed: one is water vapor, a second carbon dioxide and third the ash. If coal be heated equally hot, but inside a long cast iron or earthen retort shut off from all contact with the oxygen of the air…[an] operation known as destructive distillation… four chief products result from the destructive distillation of bituminous coal…: coal gas, ammoniacal liquor, coal tar and coke (p. 5)… The constituents of tar may, according to their chemical reactions, be divided into three classes: first, the hydrocarbons (composed of carbon and hydrogen), second, the phenols (consisting of carbon, hydrogen and oxygen), third, the nitrogenous compounds (composed of carbon, hydrogen and nitrogen) (p. 6).

Synthetic organic pigments exhibit a wide range of physical and chemical properties, including light fastness, heat stability, solubility in water or organic solvents, reactivity and stability to recrystallization (Lomax and Learner, 2006, p. 108). Chemical robustness is essential to the quality of synthetic pigments. The overall permanence of the pigment can be affected by sunlight (or any exposure to ultraviolet radiation), the atmosphere (such as atmospheric gases and moisture), the medium, and the action of the pigments when mixed together as well as the chemical properties of the pigment itself. Mayer provides a list of preferred requirements for ideal paint pigments, and these can be applied to the pigments used in tattoo inks as well: 1. Should be a smooth, finely divided powder 2. Should be insoluble in the medium in which it is used 3. Should withstand the action of sunlight without changing color, under conditions in which the painting may be exposed 4. Should not exert a harmful chemical action upon the medium or upon other pigments with which it is to be mixed 5. Should be chemically inert and unaffected by materials with which it is to be mixed or by the atmosphere 6. Should have proper degree of opacity or transparency to suit the purpose for which it is intended

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Forensic Analysis of Tattoos and Tattoo Inks

7. Should be of full strength and contain no added inert or loading ingredients 8. Should conform to accepted standards of color and color quality and exhibit all the desirable characteristics of its type 9. Should be purchased from a reliable house that understands and tests its colors, selects them from worldwide sources, and can furnish information as to origin, details of quality, and so on* Synthetic organic pigments include azo compounds, phthalocyanines, oxazines, and quinacridones. Azo pigments are characterized by the presence of the chromophore azo group ─N═N─. Lomax and Learner further specify that most of the α-keto azo pigments exhibit tautomerism with a ketohydrazone form (Lomax and Learner, 2006, p. 110), which was also described in Zollinger (2003, p. 327) (Figure 7.3). The azo pigments are described as the largest class of synthetic pigments and are subdivided into the following classes based upon their general formulae: monoazo (one azo group), disazo (two azo groups), trisazo (three azo groups), and additional polyazo (four or more azo groups) classes. From the point of view of use, azo coloring matters can be classed into acid, mordant, direct, disperse, azoic, and solvent dyes, as well as into pigments, and a few azo compounds appear among basic and vat dyes (Zollinger, 1961, p. 219). Pigment red 146 (PR 146, 2-hydroxy-3-naphtharylide azo pigment), pigment red 170 (PR 170, 2-hydroxy-3-naphtharylide azo pigment), pigment yellow 3 (PY 3, Hansa Yellow 10G, acetoacetarylide azo pigment), and pigment yellow 151 (PY151, Hansa Yellow H4G) are examples of monoazo pigments. PR 146 and PR 170 are further characterized as aromatic azo compounds, with the general formula Ar─N═N─Ar′ (Figure 7.4). Pigment orange 16 (PO 16, dianisidine orange), pigment orange 34 (PO 34), and pigment yellow 83 (PY 83, permanent yellow HR) are examples of a disazo pigments (Figure 7.5). Phthalocyanines, organometallic compounds, consist of dyes and pigments that contain the tetrabenzoporphyrazine (TBP) nucleus (Figures 7.6 and 7.7). R

N

N

CH (R’, R”)

N

N

C (R’, R”)

Figure 7.3  Hydroxyazo-ketohydrazone tautomerism, in which the structure on the left represents the α-keto azo form and the structure on the right represents the ketohydrazone form.

* It should be noted that while stringent practices may be employed by the pigment supplier, this is not a guarantee that tattoo ink manufacturers will follow stringent quality control measurements in mixing the pigments with the liquid components.

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CI O O

HN

O

HO

O

N

N

O H2N

O

OH

NH

N

Pigment red 146

O

N

N H

O

Pigment red 170

CI O N+ CI

N

H N

N

O

O– CH3

O

O

Pigment yellow 3

N

H N

O

N O

H N N H

O

OH Pigment yellow 151

Figure 7.4  Monoazo pigments.

The color attributed to the phthalocyanines is due to both the inorganic metal ion of the central copper atom* and the organic conjugated bond system of the annulated system. The principal metal ion is copper and peripheral substituents are chlorine and bromine. Pigment green 7 (PG 7, phthalocyanine green) and pigment blue 15 (PB 15, phthalocyanine blue) are examples of phthalocyanines. Pigment blue is characterized by the copper centered within the TBP nucleus (copper-tetrabenzo-tetraazo-porphin), and pigment green is characterized by the chlorination of the benzene rings with the copper centered TBP nucleus (chlorinated copper-tetrabenzo-tetraazo-porphin). According to Thomson, the halogen bromine may also be incorporated along with the chlorine, where the more bromine used, the more yellow the resultant shade. This phthalocyanine is known as pigment green 36 (PG 36, phthalo green) (Thomson, 1977, p. 447). Phthalocyanines are subject to modifications through substitutions, and reports of α, β, γ, δ, ε, π, ρ, and R crystal forms of metal * Described in the crystal field theory developed by Bethe and van Vleck.

156

Forensic Analysis of Tattoos and Tattoo Inks O H N

N

N O

O

O

O N

N

N H

O Pigment orange 16

OH N

N N

N

N N

N N CI

HO

CI

Pigment orange 34 O O O CI

N

CI O

N

NH

CI

HN

O

N CI

N

O O

O

Pigment yellow 83

Figure 7.5  Disazo pigments.

H C H

N

C H C H C C

C

C

C

C

H

H

C

C

C

C

C

C

C H

N * NH

*HN N

N

H H C

C

C

C

C

C

C

H

H

H

N C

C

C

C

N C H

Figure 7.6  Tetrabenzoporphyrazine nucleus.

H

C H

C H C H

Modern Organic Pigments CI

CI

CI

CI

CI

CI

N N

Cu N

CI

CI

N

Br CI

CI

Br

N

CI CI

CI

CI

CI

N

N

N

N

Cu

N

N

N N

CI

Br

CI

N

CI

CI

157

CI

N

CI Br

CI Br

Pigment green 7

Br

N

CI

CI

CI

CI

Pigment green 36

N N

N Cu

N

N N

N N

Pigment blue 15

Figure 7.7  Phthalocyanines.

phthalocyanines have been described. Pigment blue 15 is the primary blue pigment in the phthalocyanines class, with nine forms of copper phthalocyanine being reported, including four crystal forms of copper phthalocyanine. According to the Pigment Compendium, PB 15 is an unstabilised (against crystal modification), non-halogenated copper phthalocyanine with the α-crystal modification, 15:1 is the same but with 0.5–1 chlorine substitutions, 15:2 is a non-flocculating version of 15:1, 15:3 is an unsubstituted β-copper phthalocyanine, 15:4 is a non-flocculating version of 15:3, and 15:6 is a stabilized, unsubstituted ε-modification form. Pigment blue 16 designates a metal-free phthalocyanine and Pigment Blue 7 is a cobalt phthalocyanine. Pigment Green 7 describes a copper phthalocyanine with 14–15 chlorine substitutions and Pigment Green 36 is a copper phthalocyanine with 4–9 bromine and 8–2 chlorine substitutions (Eastaugh et al., 2008, p. 305).

Oxazines are characterized by the presence of the chromophore oxazine ring, which forms the center of three condensed rings (Figure 7.8). The oxazines are subdivided into mono oxazines (one auxochrome is a free or

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Forensic Analysis of Tattoos and Tattoo Inks

CI

N C

C

C

C O +

N

C2H5 N

O

N

O

CI

N Oxazine ring bound into a three ringed structure

Oxazine ring

N C

O

Pigment violet 23

Figure 7.8  Oxazines.

substituted amino group), dioxazines (two oxazines are condensed together), and oxazones (the auxochromes are hydroxyl groups) (Color Index). Pigment violet 23 (PV 23) is an example of a dioxazine, a linear system of five anellated rings. According to The Pigment Compendium, PV 23 is used to shade phthalocyanine pigments, to counteract the yellowish cast of titanium dioxide whites and to shade carbon-based blacks that have a brownish cast (Eastaugh et  al., 2008, p.  309). Polymorphisms of PV 23 exist as α and β polymorphs. Quinacridones are a ring system with the following general structure (the linear, trans form is shown in Figure 7.9, at left). Color modification of the quiacridones can be done by substitution of side groups, crystal modification, and particle size (Patterson, 1967, p. 61). Pigment red 122 (PR 122), 2, 9-dimethyl-quinacridone, is an example of a quinacridone. It is described as a linear cis-quinacridone and is reported to have α, β, and γ forms. An extensive amount of literature concerning the chemical analysis of pigments can be found within a vast array of scientific journals, with the focus of these articles addressing color science, forensic science, and art conservation science. A study by Palenik et al., published in 2011, was conducted in an effort to classify and identify pigments using Raman spectroscopy specifically in the context of forensic investigations. Using excitation wavelengths of 785 and 514 nm, the authors analyzed pigments from a reference H

O

N

C

C

N

O

H

Quinacridone general structure

Figure 7.9  Quinacridones.

H2C

H N

O

O

N H

Pigment red 122

CH3

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collection which includes “approximately 1,200 pigment and >5,500 dye samples … includ(ing) 300 unique organic and inorganic pigments” (Palenik et al., 2011, p. 13). In addition, the authors “verified pigment identity” using energy dispersive spectroscopy (EDS), XRD, FTIR, and polarized light microscopy (PLM) (Palenik et al., 2011, p. 28). Prior to the Palenik et al. (2011) study, Scherrer et al. (2009) appeared to have one of the most comprehensive Raman spectral reference collections of synthetic organic pigments to date, which included approximately 120 pigments. The majority (“about 90%”) of samples were analyzed using a 785 nm excitation wavelength while the remaining samples were analyzed using an excitation wavelengths of 514 and 633 nm. The pigments analyzed included in Table 7.2 (Scherrer et al., 2009, p. 508). A 2008 article by Schulte et al. contains reference spectra of 23 pigments, included in Table 7.3 (Schulte et al., 2008, p. 1457). A 2000 article by Vandenabeele et  al. contains reference spectra of 21 azo pigments. This database is limited to red and yellow pigments, and the excitation wavelength used was 780 nm. The pigments compromising the database are included in Table 7.4 (Vandenabeele et al., 2000, p. 510). A 2010 article by Colombini and Kaifas contains reference spectra of 23 orange and yellow organic pigments (in addition to fluorescent orange and yellow pigment samples), which were analyzed using 514 and 785 nm excitation Table 7.2  Pigments Analyzed by Scherrer et al. (2009) Pigment reds Pigment oranges Pigment yellows Pigment greens Pigment blues Pigment violets Pigment browns

2, 3, 4, 5, 7, 8, 9, 10, 11, 12, 16, 18, 48:3, 49, 49:1, 49:2, 53, 53:1, 57, 57:1, 68, 83:1, 112, 122, 144, 146, 149, 166, 170, 179, 185, 187, 188, 214, 242, 254, 255, 264 5, 13, 34, 36, 43, 48, 49, 62, 73 1, 1:1, 2, 3, 5, 10, 16, 65, 73, 74, 81, 83, 93, 95, 97, 109, 111, 120, 129, 139, 150, 151, 154, 155, 175, 181, 194 7, 9, 36 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60 5, 19, 23, 32, 36, 37 23, 25

Table 7.3  Pigments Analyzed by Schulte et al. (2008) Pigment reds Pigment oranges Pigment yellows Pigment greens Pigment blues Pigment violets

2, 49, 83:1, 88, 122, 123, 146, 176, 179, 181 13, 34, 43 3, 83, 109, 110 7 15:3 1, 2, 5:1, 19

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Forensic Analysis of Tattoos and Tattoo Inks Table 7.4  Pigments Analyzed by Vandenabeele et al. (2000) Pigment reds Pigment yellows

3, 8, 9, 17, 22, 23, 49:1, 52:1, 53:1, 57:1, 112, 170 1, 3, 12, 13, 14, 17, 83, 65, 74

Table 7.5  Pigments Analyzed by Colombini and Kaifas (2010) Pigment oranges Pigment yellows

34, 36, 43, 48, 49, 59, 61, 65, 73 1, 3, 16, 24, 74, 83, 109, 129, 138, 139, 151, 154, 173

wavelengths. The pigments compromising the database are included in Table 7.5 (Colombini and Kaifas, 2010, p. 17). Ropret et al. (2008) presented a reference library of 21 yellow pigments, which were analyzed with an excitation wavelength of 785 nm. The yellow pigments analyzed include PY 6, 73, 75, 97, 111, 213, 100, 55, 81, 16, 155, 95, 128, 151, 154, 129, 153, 109, 110, 173, and 139 (Ropret et al., 2008, p. 488). Using pigment spectral data, such as those publications reported above, as well as conducting computer searches of existing pigment libraries, Miranda conducted a preliminary evaluation of the pigments present in select tattoo inks (Miranda, 2012b). Following preliminary evaluation of pigment composition based on reported data in the literature, it is essential to obtain pigment standards for comparison and subsequently analyze the pigment standards under analytical conditions similar to that of tattoo inks. When these conditions are met, accurate determination of pigment compositions can be made with confidence. More detailed examination with microscopy as well as the use of a variety of instrumental techniques can provide better conclusions; and finally, interpretation of spectral data to identify specific atomic and molecular features can enable the analyst to explain any effects that may be due to pigment mixtures, contaminants, matrix effects, and so on.

The Chemical Analysis of Modern Tattoo Inks Microscopy

8

In 2012, Miranda conducted a research project concerning the analysis of tattoo inks using microscopy and various spectroscopic techniques. The following chapters review the research conducted. The selection of tattoo inks for the study was based on origin of manufacture (USA, Brazil, and China) and color variation (red, orange, yellow, green, blue, purple, white, brown, gray, and black). Each tattoo ink was obtained in its original bottle and the details of each ink were recorded from the label (including name, ingredients, lot number, and production date). An effort to locate any chemical information was attempted, for example, a search for MSDS through manufacturers. MSDS were located for the U.S. manufactured Skin Candy inks* (these MSDS were dated 2010 and thus did not correspond directly to those in this study in which production dates dated 2008 and 2009). MSDS (or the equivalent) were not found for inks from Brazil and China. The tattoo inks included in the study were as follows: Iron Works Brasil (Made in Brazil): Vermelho (Red), Pink, Citrus (Orange), Amarelo Canario (Canary Yellow), Amarelo Fluor (Fluorescent Yellow), Verde Claro (Green), Azul Royal (Royal Blue), Magenta, Lilas Claro (Lilac/ Light Purple), Preto Escuro (Dark Black) (Figure 8.1).

The contents listed on the packaging for all Iron Works Brasil inks include (translated from Spanish) “mineral/organic pigment, distilled water (dH2O), surfactant, humectants, preservative.” No information was given regarding specific pigment contents. Skin Candy (Made in the United States of America): Candy Apple Red, Red Hot, Marz (Orange), Dolemite (Orange-Yellow), Blisterene (Yellow), Sassygrass (Green), Tastywaves (Blue), Bell Bottom Blue, S.R.V. Teal 2, Razberry Creem (Pink), Muddy Water Blue, Ripple (Purple), San Brownadino (Brown), Whitegirl, Tokyo Pink, Dark Cherry Roan 1, 2, and 3 (Neutral Brown hues) (Figure 8.2).

The contents listed on the packaging for Skin Candy inks include “distilled water (dH2O), polyethylene glycol, witch hazel and ‘proprietary.’” * http://skincandytattoosupply.com/ (Important Links → MSDS Reports).

161

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Forensic Analysis of Tattoos and Tattoo Inks

Figure 8.1  Iron Works Brasil tattoo inks used in Miranda’s study.

(a)

(b)

(c)

Figure 8.2  Skin Candy tattoo inks used in Miranda’s study (Note: the bottle of Whitegirl is not included in the series of photographs).

The Chemical Analysis of Modern Tattoo Inks: Microscopy

163

Information was given regarding specific pigment contents with the exception of Tokyo Pink,* which listed no contents on its bottle. Information concerning the pigment compositions of Skin Candy Tattoo Inks is provided in Table 8.1. Although the inks were dated 2008 and 2009 while the MSDS were labeled 2010, there was agreement between the MSDS and the contents listed on the labels. This indicates that, according to the manufacturer’s records, the chemical composition of these particular tattoo inks had not changed substantially within the couple of years between ink production and MSDS reporting. Flying Tigers (Made in China): Salmon Pink, Pink Red, Magenta, Chinese Red, Bright Red, Rose Red, Mulberry (Red), Dark Red, Orange Red, Orange, Bright Yellow, Mid-Yellow, Yellow, Golden Yellow, Khaki, Grass Hopper (Green), Light Green, Verdancy (Green), Lawngreen, Dark Green, Blue Sky, Turquoise Blue, Cyan, Dark Cyan, Blue, Navy Blue, Dark Blue, Grape (Purple), Table 8.1  Skin Candy Tattoo Inks listed Ingredients (from Bottle Labels) Skin Candy Tattoo Inks (contents, from packaging label: distilled water, polyethylene glycol, witch hazel, “proprietary”) Candy Apple Red Red Hot Marz Dolemite Blisterene Sassygrass Tastywaves Bell Bottom Blue S.R.V. Teal 2 Razberry Creem Muddy Water Blue Ripple San Brownadino Whitegirl

CI 12485 (PR 146) CI 12475 (PR 170) CI 21160 (PO 16) CI 13980 (PY 151), CI 21108 (PY 83) CI 11710 (PY 3), CI 21115 (PO 34), CI 77891 (TiO2) CI 74260 (PG 7), CI 11710 (PY 3), CI 21115 (PO 34) CI 77891 (TiO2), CI 74260 (PG 7) CI 74160 (PB 15), CI 77891 (TiO2) CI 74160 (PB 15), CI 74260 (PG 7), CI 77891 (TiO2) CI 73915 (PR 122), CI 77891 (TiO2) CI 74160 (PB 15) CI 51319 (PV 23), CI 77891 (TiO2) CI 77491 (Fe2O3) CI 77891 (TiO2)

Skin Candy Tattoo Inks (contents, from packaging label: distilled water, witch hazel, polyethylene glycol) Black Cherry Roan 1 CI 12485 (PR 146), CI 77266 (PBl 7—Carbon Black) Black Cherry Roan 2 CI 12485 (PR 146), CI 77266 (PBl 7—Carbon Black) Black Cherry Roan 3 CI 12485 (PR 146), CI 77266 (PBl 7—Carbon Black) * As of 2014, Toyko Pink is described as a vibrant color that is UV reactive and will show up under a blacklight; in addition, it is noted that the ink may fade after 2 years (http:// www.skincandy.net/skincandy-tokyo-pink-tattoo-ink/). According to the MSDS, Tokyo Pink contains distilled water, propylene glycol, witch hazel, pigment red 222, and white pigment 6 (http://skincandytattoosupply.com/pdf/MSDS-TokyoPink.pdf).

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Forensic Analysis of Tattoos and Tattoo Inks

Purple, Violet, Gray, Bright Black, Black, Eggplant Black, Black, Sayonara Suede (Gray), Dark Brown, Light Chocolate, Skin Tone, White (Figure 8.3).

The contents listed on the packaging for all Flying Tigers inks include “isopropanol, water, glycerin and ‘proprietary.’” No information is given regarding specific pigment contents. For the microscopy portion of Miranda’s research study, the tattoo ink samples were placed on a microscope slide and allowed to dry at room temperature for several days in order to allow for evaporation of any volatile solvents. Each prepared slide was examined with a stereomicroscope followed by examination on an Olympus BH metallurgical microscope with Neo objectives using both reflected brightfield and darkfield illumination to observe and document particle and color characteristics (Figure 8.4). In many instances the color observed differed based on the nature of the incident radiation. This is a critical factor to consider with regard to tattoo ink pigments, since the color perceived in the bottle may differ when placed in the skin. Furthermore, this is an important consideration with regard to the forensic examination of pigments, since colors observed may not be a true and accurate representation of the actual color, and examiners may be mislead by the results when only one method of light microscopy is employed in casework. A sample of the ink was scraped off the microscope slide and mounted in a Cargille oil with a refractive index (RI) of 1.5509 [n25°C (±0.0002) D5893Å] for examination with an Olympus BHSP Polarized Light Microscope with DPlan PO achromat objectives.* The selection of an RI oil was made in order to allow for the ability to conduct relative RI measurements on the particles.

Figure 8.3  Flying Tigers tattoo inks used in Miranda’s 2012 study. * The microscope was set up using Köhler Illumination (Goldberg, 1980, p. 20).

The Chemical Analysis of Modern Tattoo Inks: Microscopy

165

Figure 8.4  (a) Olympus BH metallurgical microscope and (b) Olympus BHSP polarized light microscope.

For the identification of materials, once mounted, the sample was viewed with brightfield illumination, plane polarized light, fully crossed polars, and slightly uncrossed polars (5–15° offset). Upon removal of some ink from the slide for microscopic examination, the consistency of the tattoo inks was markedly different from one another. Some samples scraped off with little effort (manual pressure) and were very powdery and dry. Other tattoo inks were difficult to scrape off the microscope slide several and had a “gummy” consistency; as if the solvent had not completely evaporated. This was especially the case for the majority of Flying Tigers tattoo inks (manufactured in China). In some instances, the samples were still “wet,” even a year after having been mounted on the slides, left to dry, and stored in a microscope box, which implied that some pigments may exhibit hydroscopic characteristics. A table of resultant visual and microscopic examinations was prepared to facilitate examination and comparison of the optical characteristics of the pigments, including particle sizes, color, and so on. Visual and microscopic observations were presented in this format in order to conduct comparisons across origin of manufacture and color. The table included images based upon visual/stereoscopic examination; brightfield and darkfield images generated with the metallurgical microscope, crossed and uncrossed polarizers with the polarized light microscope and images generated with the Raman microspectrometer. This information was reported in conjunction with any

166

Forensic Analysis of Tattoos and Tattoo Inks

information concerning the chemical composition as provided through product labels, MSDS, and any additional relevant information pertaining to the ink compositions. When examining pigment (tattoo ink) samples with polarized light microscopy for analytical purposes, the following characteristics should be noted: varieties of materials present in the mixture; whether materials are isotropic or anisotropic; selective absorption and polarization colors, extinction; shape and structure of materials; RI of each material relative to the mounting medium* (Butler, 1973, p. 104). Characterization of pigment particles can be conducted based on documenting physical and optical properties; color (including any illumination conditions and lenses employed), particle size and particle size distribution, particle shape, aggregation, particle surface (texture, relief, fracturing, facets, etc.), inclusions and interparticle relationships, fracture and cleavage, diaphaneity, reflectance, transmission with various filters, fluorescence, pleochroism, RI and relief, dispersion, birefringence, internal reflection, extinction, zoning and twinning, and elongation (Eastaugh et al., 2008, p. 515). Observations of interference figures with conoscopic light can also be conducted to determine a pigment’s optical properties. In addition to the documentation of optical properties and characterization, the resultant data can be compared to pigment databases developed by McCrone (1982), Eastaugh et al. (2008), Mattiello (1946), and so on. Much microscopy of tattoo pigments has focused on the particles within tissue. According to Delly, “The microscopy of tattoos has three important aspects: the identification of the embedded pigments; the histological location of the pigments in the skin; and the pathology resulting from the body’s reaction to the pigment” (Delly, 1986, p.  147). Table 8.2 describes the pigments found in tattoo ink as reported by Delly (Delly, 1986). It is noted that the most prominent optical property of carbon based, black pigments is their strong absorption of radiation in the visible region. Microscopic examination of thin sections with transmitted light as well as examination with reflected light can be used to detect subtle hues such as blues, browns, grays, and silver that can aid in the discriminating power of black pigments in tattoo inks. The power of examining tattoo ink samples using different microscopic methods and lighting techniques should not be underestimated, whether the pigment particles are prepared in a mounting medium or located in a thin section of tissue. Lincoln and Nordstrom highlight the usefulness of polarized light microscopy to render color determination of pigments present in human tissue:

* Becke line measurements.

The Chemical Analysis of Modern Tattoo Inks: Microscopy

167

Table 8.2  Pigments Reported by Delly (1986) Carbon black: Black by both transmitted and reflected light, opaque, and not usually of uniform particle size; as carbon black it is amorphous as graphite and it is hexagonal. Individual carbon particles are 1.78 for red, and 1.74 for blue light. Cadmium sulfide: Yellow; hexagonal with indices of 2.529 (ε) and 2.506 (ω); (+) 0.023 for red to blue-green and (−) for blue-green to blue; hemimorphic crystals … with distinct prismatic cleavage; weakly pleochroic. Ochre and hydrated ferric oxides are sometimes used as yellow pigments. Darker shades of ochre (iron oxide) are used for brown colors, and flesh colors are made from the more hydrated and yellower iron oxides. Manganese containing pigments: Violet Titanium dioxide: White

In studying microscopic sections of tattoos, it was noted that it was impossible to identify the color of the dye or pigment used in the tattooing process … To overcome this problem, stained and unstained tattoo sections were examined under polarized light… Such phenomena are interesting to observe and should be a valuable aid in identifying the … pigment … where multiple colors have been used (Lincoln and Nordstrom, 1958, p. 336).

Iron Works Brasil Tattoo Inks See Figures 8.5 through 8.14.

168

Forensic Analysis of Tattoos and Tattoo Inks (a)

(b)

Dark field, 100×

Bright field, 100× (d)

(c)

In RI 1.550, 400×

Crossed polars, in RI 1.550, 200×

(e)

Raman microscope image, 200×

Figure 8.5  Vermelho. (a)

(b)

Dark field, 100×

Bright field, 100× (d)

(c)

In RI 1.550, 200×

Figure 8.6  Pink.

Crossed polars, in RI 1.550, 200×

The Chemical Analysis of Modern Tattoo Inks: Microscopy (a)

(b)

Bright field, 100× (c)

Dark field, 400× (d)

In RI 1.550, 400×

Crossed polars, in RI 1.550, 200×

Figure 8.7  Citrus.

(a)

(b)

Bright field, 100× (c)

Dark field, 400× (d)

In RI 1.550, 400×

Figure 8.8  Amarelo Canario.

Crossed polars, in RI 1.550, 200×

169

170

Forensic Analysis of Tattoos and Tattoo Inks

(a)

(b)

Bright field, 100×

Dark field, 100× (d)

(c)

In RI 1.550, 400×

Crossed polars, in RI 1.550, 200×

Figure 8.9  Amarelo Fluor. (a)

(b)

Bright field, 400× (c)

Dark field, 400× (d)

In RI 1.550, 400×

Figure 8.10  Verde Claro.

Crossed polars, in RI 1.550, 200×

The Chemical Analysis of Modern Tattoo Inks: Microscopy (a)

(b)

Bright field, 400×

Dark field, 400× (d)

(c)

In RI 1.550, 400×

Crossed polars, in RI 1.550, 200×

(e)

Raman microscope image, 200×

Figure 8.11  Azul Royal. (a)

(b)

Bright field, 100×

Dark field, 100× (d)

(c)

In RI 1.550, 400×

Figure 8.12  Magenta.

Crossed polars, in RI 1.550, 200×

171

172

Forensic Analysis of Tattoos and Tattoo Inks (a)

(b)

Bright field, 100× (c)

Dark field, 100× (d)

In RI 1.550, 400×

Crossed polars, in RI 1.550, 400×

(e)

Raman microscope image, 200×

Figure 8.13  Lilas Claro. (a)

(b)

Bright field, 100×

Dark field, 100×

(c)

In RI 1.550, 400×

Figure 8.14  Preto Escuro.

The Chemical Analysis of Modern Tattoo Inks: Microscopy

Skin Candy Tattoo Inks See Figures 8.15 through 8.31. (a)

(b)

Bright field, 400×

Dark field, 100× (d)

(c)

In RI 1.550, 400×

Crossed polars, in RI 1.550, 400× (f)

(e)

Smear on microscope slide after drying, ~20×

Raman microscope image, 200×

Figure 8.15  Candy Apple Red. (a)

(b)

Bright field, 100× (c)

Dark field, 100× (d)

In RI 1.550, 400×

Figure 8.16  Red Hot.

Crossed polars, in RI 1.550, 400×

173

174

Forensic Analysis of Tattoos and Tattoo Inks (b)

(a)

Bright field, 100×

Dark field, 100×

(c)

(d)

In RI 1.550, 400×

Crossed polars, in RI 1.550, 400× (e)

Postextraction

Figure 8.17  Marz.

The Chemical Analysis of Modern Tattoo Inks: Microscopy (a)

(b)

Bright field, 400×

Dark field, 100× (d)

(c)

In RI 1.550, 400×

Crossed polars, in RI 1.550, 400×

(e)

Postextraction

Figure 8.18  Dolemite. (a)

(b)

Bright field, 100×

Dark field, 100× (d)

(c)

In RI 1.550, 400×

Figure 8.19  Blisterine.

Crossed polars, in RI 1.550, 400×

175

176

Forensic Analysis of Tattoos and Tattoo Inks (a)

(b)

Bright field, 100×

Dark field, 100× (d)

(c)

In RI 1.550, 400×

Crossed polars, in RI 1.550, 400×

(e)

Postextraction

Figure 8.20  Sassygrass. (a)

(b)

Bright field, 100×

Dark field, 100× (d)

(c)

In RI 1.550, 400×

Figure 8.21  Tastywaves.

Crossed polars, in RI 1.550, 400×

The Chemical Analysis of Modern Tattoo Inks: Microscopy (a)

(b)

Bright field, 100× (c)

Dark field, 100× (d)

In RI 1.550, 400×

Crossed polars, in RI 1.550, 400×

(e)

(f)

Smear on microscope slide after drying

Postextraction

Figure 8.22  Bell Bottom Blue. (a)

(b)

Bright field, 100× (c)

Dark field, 100× (d)

In RI 1.550, 400×

Figure 8.23  S.R.V. Teal 2.

Crossed polars, in RI 1.550, 400×

177

178

Forensic Analysis of Tattoos and Tattoo Inks (a)

(b)

Bright field, 100× (c)

Dark field, 100× (d)

In RI 1.550, 400×

Crossed polars, in RI 1.550, 400×

Figure 8.24  Muddy Water Blue. (a)

(b)

Bright field, 100×

Dark field, 100× (d)

(c)

In RI 1.550, 400×

Crossed polars, in RI 1.550, 400×

(e)

Postextraction

Figure 8.25  Razberry Creem.

The Chemical Analysis of Modern Tattoo Inks: Microscopy (a)

(b)

Bright field, 100× (c)

Dark field, 100× (d)

In RI 1.550, 400×

Crossed polars, in RI 1.550, 400×

(e)

Smear on microscope slide after drying

Figure 8.26  Ripple. (a)

(b)

Bright field, 100×

Dark field, 100× (d)

(c)

In RI 1.550, 400×

Figure 8.27  San Brownadino.

Crossed polars, in RI 1.550, 400×

179

180

Forensic Analysis of Tattoos and Tattoo Inks (a)

(b)

Bright field, 100×

Dark field, 100× (d)

(c)

In RI 1.550, 400× (e)

Crossed polars, in RI 1.550, 400× (f)

Smear on microscope slide after drying, ~20×

Raman microscope image, 200×

Figure 8.28  Black Cherry Roan 2.

(a)

(c)

(b)

Bright field, 100×

(d)

Bright field, 100×

Figure 8.29  Roan 1 (a,b) and Roan 3 (c,d).

Dark field, 100×

Dark field, 100×

The Chemical Analysis of Modern Tattoo Inks: Microscopy (a)

(b)

Bright field, 100× (c)

Dark field, 100× (d)

In RI 1.550, 200×

Crossed polars, in RI 1.550, 200×

Figure 8.30  White Girl. (a)

(b)

Bright field, 100×

Dark field, 100× (d)

(c)

In RI 1.550, 400×

Crossed polars, in RI 1.550, 400×

(e)

Raman microscope image, 1000×

Figure 8.31  Tokyo Pink.

181

182

Forensic Analysis of Tattoos and Tattoo Inks

Flying Tigers Tattoo Inks See Figures 8.32 through 8.71. (a)

(b)

Bright field, 100×

Dark field, 100× (d)

(c)

In RI 1.550, 400×

Crossed polars, in RI 1.550, 400×

Figure 8.32  Salmon Pink. (a)

(b)

Bright field, 100×

Dark field, 100×

(c)

Raman microscope image, 1000×

Figure 8.33  Pink Red.

The Chemical Analysis of Modern Tattoo Inks: Microscopy (a)

(b)

Bright field, 100× (c)

Dark field, 100× (d)

In RI 1.550, 400×

Crossed polars, in RI 1.550, 400×

Figure 8.34  Magenta. (a)

(b)

Bright field, 100× (c)

Dark field, 100× (d)

In RI 1.550, 400×

Figure 8.35  Chinese Red.

Crossed polars, in RI 1.550, 400×

183

184

Forensic Analysis of Tattoos and Tattoo Inks

(a)

(b)

Bright field, 100× (c)

Dark field, 100× (d)

In RI 1.550, 400×

Crossed polars, in RI 1.550, 400×

Figure 8.36  Bright Red.

(a)

(b)

Bright field, 100×

Dark field, 100× (d)

(c)

In RI 1.550, 400×

Figure 8.37  Rose Red.

Crossed polars, in RI 1.550, 400×

The Chemical Analysis of Modern Tattoo Inks: Microscopy (a)

(b)

Bright field, 100×

Dark field, 100× (d)

(c)

In RI 1.550, 400×

Crossed polars, in RI 1.550, 400×

(e)

Raman microscope image, 500×

Figure 8.38  Mulberry. (a)

(b)

Bright field, 100×

Dark field, 100× (d)

(c)

In RI 1.550, 400×

Figure 8.39  Dark Red.

Crossed polars, in RI 1.550, 400×

185

186

Forensic Analysis of Tattoos and Tattoo Inks (a)

(b)

Bright field, 100×

Dark field, 100× (d)

(c)

In RI 1.550, 400×

Crossed polars, in RI 1.550, 400×

Figure 8.40  Orange Red. (a)

(b)

Bright field, 100× (c)

Dark field, 100× (d)

In RI 1.550, 400×

Crossed polars, in RI 1.550, 400×

(e)

Raman microscope image, 1000×

Figure 8.41  Orange.

The Chemical Analysis of Modern Tattoo Inks: Microscopy (a)

(b)

Bright field, 100× (c)

Dark field, 100× (d)

In RI 1.550, 200×

Crossed polars, in RI 1.550, 200×

Figure 8.42  Bright Yellow. (a)

(b)

Bright field, 100×

Dark field, 100× (d)

(c)

In RI 1.550, 400×

Figure 8.43  Mid-Yellow.

Crossed polars, in RI 1.550, 400×

187

188

Forensic Analysis of Tattoos and Tattoo Inks

(a)

(b)

Bright field, 100×

Dark field, 100× (d)

(c)

In RI 1.550, 400×

Crossed polars, in RI 1.550, 400×

Figure 8.44  Yellow. (a)

(b)

Bright field, 100×

Dark field, 100× (d)

(c)

In RI 1.550, 400×

Figure 8.45  Golden Yellow.

Crossed polars, in RI 1.550, 400×

The Chemical Analysis of Modern Tattoo Inks: Microscopy (a)

(b)

Bright field, 100×

Dark field, 100× (d)

(c)

In RI 1.550, 400×

Crossed polars, in RI 1.550, 400×

Figure 8.46  Khaki. (a)

(b)

Bright field, 100×

Dark field, 100× (d)

(c)

In RI 1.550, 200×

Figure 8.47  Grass Hopper.

Crossed polars, in RI 1.550, 200×

189

190

Forensic Analysis of Tattoos and Tattoo Inks

(a)

(b)

Bright field, 100×

Dark field, 100× (d)

(c)

In RI 1.550, 400×

Crossed polars, in RI 1.550, 400×

Figure 8.48  Light Green. (a)

(b)

Bright field, 100× (c)

Dark field, 100× (d)

In RI 1.550, 400×

Figure 8.49  Verdancy.

Crossed polars, in RI 1.550, 400×

The Chemical Analysis of Modern Tattoo Inks: Microscopy (a)

(b)

Bright field, 100× (c)

Dark field, 100× (d)

In RI 1.550, 400×

Crossed polars, in RI 1.550, 400×

Figure 8.50  Lawn Green. (a)

(b)

Bright field, 100×

Dark field, 100× (d)

(c)

In RI 1.550, 400×

Figure 8.51  Dark Green.

Crossed polars, in RI 1.550, 400×

191

192

Forensic Analysis of Tattoos and Tattoo Inks

(a)

(b)

Bright field, 100× (c)

Dark field, 100× (d)

In RI 1.550, 400×

Crossed polars, in RI 1.550, 400×

Figure 8.52  Blue Sky. (a)

(b)

Bright field, 100×

Dark field, 100× (d)

(c)

In RI 1.550, 400×

Figure 8.53  Turquoise Blue.

Crossed polars, in RI 1.550, 400×

The Chemical Analysis of Modern Tattoo Inks: Microscopy (a)

(b)

Bright field, 100×

Dark field, 100× (d)

(c)

In RI 1.550, 400×

Crossed polars, in RI 1.550, 400×

Figure 8.54  Cyan.

(a)

(b)

Bright field, 100×

Dark field, 100× (d)

(c)

In RI 1.550, 400×

Figure 8.55  Dark Cyan.

Crossed polars, in RI 1.550, 400×

193

194

Forensic Analysis of Tattoos and Tattoo Inks

(a)

(b)

Bright field, 100×

Dark field, 100× (d)

(c)

In RI 1.550, 400×

Crossed polars, in RI 1.550, 400×

Figure 8.56  Blue. (a)

(b)

Bright field, 100×

Dark field, 100× (d)

(c)

In RI 1.550, 400×

Figure 8.57  Navy Blue.

Crossed polars, in RI 1.550, 400×

The Chemical Analysis of Modern Tattoo Inks: Microscopy (a)

(b)

Bright field, 100× (c)

Dark field, 100× (d)

In RI 1.550, 400×

Crossed polars, in RI 1.550, 400×

Figure 8.58  Dark Blue. (a)

(b)

Bright field, 100×

Dark field, 100× (d)

(c)

In RI 1.550, 400×

Figure 8.59  Grape.

Crossed polars, in RI 1.550, 400×

195

196

Forensic Analysis of Tattoos and Tattoo Inks

(a)

(b)

Bright field, 100×

Dark field, 100× (d)

(c)

In RI 1.550, 400×

Crossed polars, in RI 1.550, 400×

Figure 8.60  Purple. (a)

(b)

Bright field, 100× (c)

Dark field, 100× (d)

In RI 1.550, 400×

Figure 8.61  Violet.

Crossed polars, in RI 1.550, 400×

The Chemical Analysis of Modern Tattoo Inks: Microscopy (a)

(b)

Bright field, 100×

Dark field, 100× (d)

(c)

In RI 1.550, 400×

Crossed polars, in RI 1.550, 400×

Figure 8.62  Grey. (a)

(b)

Bright field, 100× (c)

Dark field, 100× (d)

In RI 1.550, 400×

Figure 8.63  Bright Black.

Crossed polars, in RI 1.550, 400×

197

198

Forensic Analysis of Tattoos and Tattoo Inks (a)

(b)

Bright field, 100×

Dark field, 100× (d)

(c)

Crossed polars, in RI 1.550, 400×

In RI 1.550, 400× (e)

Raman microscope image, 1000×

Figure 8.64  Black.

(a)

(b)

Bright field, 100×

Dark field, 100× (d)

(c)

In RI 1.550, 400×

Figure 8.65  Eggplant Black.

Crossed polars, in RI 1.550, 400×

The Chemical Analysis of Modern Tattoo Inks: Microscopy (a)

(b)

Bright field, 100× (c)

Dark field, 100× (d)

In RI 1.550, 400×

Crossed polars, in RI 1.550, 400×

Figure 8.66  Dark Black. (a)

(b)

Bright field, 100× (c)

Dark field, 100× (d)

In RI 1.550, 400×

Figure 8.67  Sayonara Suede.

Crossed polars, in RI 1.550, 400×

199

200

Forensic Analysis of Tattoos and Tattoo Inks

(a)

(b)

Bright field, 100× (c)

Dark field, 100× (d)

In RI 1.550, 400×

Crossed polars, in RI 1.550, 400×

Figure 8.68  Dark Brown. (a)

(b)

Bright field, 100× (c)

Dark field, 100× (d)

In RI 1.550, 400×

Figure 8.69  Light Chocolate.

Crossed polars, in RI 1.550, 400×

The Chemical Analysis of Modern Tattoo Inks: Microscopy (a)

(b)

Bright field, 100×

Dark field, 100× (d)

(c)

Crossed polars, in RI 1.550, 400×

In RI 1.550, 400× (e)

Raman microscope image, 1000×

Figure 8.70  Skin Tone. (a)

(b)

Bright field, 100×

Dark field, 100× (d)

(c)

In RI 1.550, 400×

Figure 8.71  White.

Crossed polars, in RI 1.550, 400×

201

Part 1—The Chemical Analysis of Modern Tattoo Inks Spectroscopy

9

X-Ray Fluorescence: Theory and Practice X-ray fluorescence (XRF) is a spectroscopic technique in which the elements of a sample are excited by absorption of an incident beam of x-ray radiation and subsequently emit their own characteristic fluorescence x-rays. XRF is routinely employed for the detection and identification of elements having atomic numbers greater than oxygen (although each instrument manufacturer will report its specific qualitative specifications for a given instrument). X-rays are generated in four ways; two primary ways are by bombardment of a metal target with a beam of high energy electrons or by exposure of a substance to a primary beam of x-rays to generate a secondary beam of XRF (Skoog et al., 1998, p. 303). The absorption of x-rays produces electronically excited ions that return to their ground state by transitions involving electrons from higher energy levels (Skoog et al., 1998, p. 309). The series of lines commonly observed in x-ray line spectra are the K series (short wavelength) and L series (long wavelength). Emitted x-rays are named according to the vacancy in the shells that are filled by outer shell electrons, for example, K, L, M, and N. Resultant x-rays are further characterized by the specific energy level within a given series, for example α, β, and γ. X-ray sources, such as an x-ray tube, produce continuum and line spectra, with the line spectrum often being superimposed on the continuum, referred to as Bremsstrahlung (Skoog et al., 1998, p. 303). XRF spectra are plotted as energy (keV) versus relative intensity (counts per unit of time; i.e., seconds).

UV–Vis Spectrometry: Theory and Practice Ultraviolet-Visible (UV-Vis) spectrometry is a molecular absorption spectroscopic technique that is used to determine molecular species, specifically the identification of a molecule’s functional groups. The absorption of ultraviolet or visible radiation generally results from excitation of bonding electrons; as a consequence, the wavelengths of absorption peaks can be correlated to the types of bonds in the species under study (Skoog et al., 1998, p. 330). Skoog 203

204

Forensic Analysis of Tattoos and Tattoo Inks

et al. describe electronic transitions involving σ, π, and n electrons used to categorize absorbing species, noting that absorption of longer wavelength ultraviolet and visible radiation is restricted to chromophores, which contain valence electrons with relatively low excitation energy (Skoog et  al., 1998). Electrons contributing to absorption by an organic molecule are bonding (shared) and nonbonding (unshared); single bonds are designated sigma (σ) molecular orbitals, double bonds contain a sigma molecular orbital and a pi (π) molecular orbital; each also correlating to the name of the corresponding electron. Nonbonding electrons in an organic molecule are designated n and antibonding orbitals are marked with an asterisk (*). The energies of the various molecular orbitals differ, and as such, electronic transitions brought about by the absorption of radiation will take place among certain energy levels (σ, π, n, σ*, π*); four types of transitions are possible: σ → σ*, n → σ*, n → π*, and π → π* (Skoog et al., 1998, p. 331) (Figure 9.1). Absorption maxima due to σ → σ* transitions are never observed in the ordinarily accessible ultraviolet region; the number of organic functional groups with n → σ* peaks in the readily accessible ultraviolet region is relatively small; and most applications of absorption spectroscopy of organic compounds are based on transitions for the n or π electrons to the π* excited state because the energies required for these processes bring the absorption peaks into an experimentally convenient spectral region (200–700 nm). Both transitions require the presence of an unsaturated functional group to provide the π orbitals. Strictly speaking, it is to the unsaturated absorbing centers that the term chromophore applies (Skoog et al., 1998, p. 332).

Energy

Additional characteristics of the molecular species, such as conjugation of chromophores, the presence of aromatic systems, functional group substitutions, the presence of auxochromes, and the presence of inorganic species σ∗

Antibonding

π∗

Antibonding

n

Nonbonding

π

Bonding

σ

Bonding

Figure 9.1  Electronic molecular energy levels and transitions. (Adapted from Skoog, D., F. Holler, and T. Nieman. 1998. Principles of Instrumental Analysis, Fifth edition. Philadelphia, PA: Harcourt Brace College Publishers, p. 331.)

Part 1—The Chemical Analysis of Modern Tattoo Inks

205

can result in wavelength shifts. Solvent effects may also produce shifts in wavelengths. In general, peaks associated with n → π* transitions undergo a hypsochromic shift with increasing solvent polarity while peaks associated with π → π* transitions will usually undergo a bathochromic shift with increasing polarity of the solvent (Skoog et al., 1998). Spectrophotometric measurements made with the UV/Vis require consideration of pigment solubility; the pigments will need to be dissolved in an appropriate solvent (such as acetone [CH3COCH3], methanol [CH3OH], cyclohexane [C6H6], methylene chloride [CH3Cl], or a dilute [0.1M] or concentrated acid [e.g., sulfuric acid, H2SO4]). Due to the change in protonation with a change in pH, any wavelength shifts (bathochromic, or hypsochromic) in the UV/Vis spectra should be documented along with any potential pigment color changes, as these observations can aid in pigment identification and classification. Billmeyer et al. described a range of solvents useful for dissolving organic pigments for solution spectrophotometry. According to the authors, concentrated sulfuric acid (H2SO4) is the most powerful solvent for all organic pigments, having the ability to dissolve virtually all pigments of this type. A series of solvents is listed according to their solubility parameter (defined as a measure of the cohesive energy which must be overcome in the solution process), in which the components of the solubility parameter include dispersion, dipole, and hydrogen bonding. Useful solvents include pentane, cyclohexane, carbon tetrachloride, toluene, xylene, chloroform, methylene chloride, ethyl acetate, acetone, pyridine, ethanol, dimethyl formamide (DMF), and methanol. It is important to consider the effect the solvents will have on the absorption maxima; while these shifts may be useful for identification of the pigment using solution spectrometry, the shifts may provide misleading information pertaining to molecular resonances. This is especially the case with concentrated sulfuric acid, in which the authors note that there are often drastic shifts in absorption maxima and visible color changes when using this solvent (Billmeyer et al., 1981, p. 308). H2SO4 is not only a solvent, but also a sulfonation reagent and catalyst that can cause acid hydrolysis of amide bonds (Zollinger, 2003, p. 414). According to Billmeyer et al. (1981) Pigment Yellow 3 will dissolve in all of the solvents tested but gave different spectra depending on solvent polarity, with a hypsochromic shift occurring with polar solvents and a bathochromic shift occurring with concentrated H2SO4 (308). Pigment Reds 146 and 170 were found to be mostly soluble in all solvents tested with the exception of cyclohexane. Their behavior is reported as being similar to that of Pigment Yellow 3. Disazo pigments, such as Pigment Orange 16 and Pigment Yellow 83 are soluble in toluene, xylene, chloroform, DMF, and concentrated H2SO4. Pigment Violet 23 was reported as being

206

Forensic Analysis of Tattoos and Tattoo Inks

soluble in weak polar solvents such as toluene, xylene, and chloroform, insoluble in acetone and methanol, and soluble in DMF and H2SO4. The authors add that in DMF and H2SO4, the solutions are fluorescent. Pigment Red 122 is soluble in ethanol: NaOH (9:1), DMF, and H2SO4. These solutions also exhibit fluorescence. The phthalocyanines (Pigment Blue 15 and Pigment Green 7) are reported as being only soluble in concentrated H2SO4. The authors add that the absorption maxima of these solutions are shifted from the visible region to the near infrared (between 800 and 900 nm) (309).

Of important note in their research, the authors assert that Beer’s law holds for solutions of inorganic pigments in the solvents used, allowing for the possibility of quantitative analysis to be conducted in addition to the qualitative analysis presented. In addition, an analytical scheme is provided by the authors in order to facilitate the separation and identification of samples that may be composed of two or more pigments (Billmeyer et al., 1981, p. 311). The UV/Vis spectrophotometer is an instrument in which monochromatic light is passed through the sample (which is in a sample holder such as a cuvette made of quartz or silica and having a fixed path length) to the detector. Wavelength selection is done by either a filter or a monochromator. The technique is based upon the detection of electromagnetic radiation generally from the region of 160–780 nm (abscissa) in solution measurements wherein a solution’s percent transmittance (%T) or absorbance (abs.) is plotted on the ordinate. The measurement is made against a reference, which typically consists of the solvent used to dissolve the pigment.

Infrared Spectrometry: Theory and Practice Infrared spectrometry is a branch of vibrational spectroscopy that provides important information about a compound’s chemical nature and molecular structure. For a molecule to absorb infrared radiation, it must undergo a change in dipole moment brought about by its vibrational or rotational motion. A molecule can be continuously rotating and vibrating in space, and infrared active moments are those movements in which the molecule has a change in dipole moment. A dipole moment occurs when atoms within a molecule are chemically different so as to result in an asymmetric distribution of electron density because of unequal electron sharing (separation of charge within a molecule). The magnitude of the moment is determined by the distance between the centers of charge of the atoms and the charge distribution between the atoms. If the frequency of incident infrared radiation is equivalent to the molecule’s natural vibrational or rotational frequency, then a net transfer of energy occurs. This energy transfer causes a change in

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the amplitude of the molecular vibration or rate of rotation, resulting from absorption of the incident infrared radiation. Energy transfer occurs because there is an electronic transition from one vibrational or rotational energy level up to another. The incident infrared radiation will be composed of a continuum of various wavelengths, and thus various frequencies. The frequencies that meet the above criteria will be absorbed by the molecule, while the frequencies that do not will be transmitted. Vibrational modes which do not involve a change in dipole moment are said to be infrared inactive. Fourier transform infrared instruments allow for working with weak signals that may be lost amongst instrumental noise. Due to the decrease in optical elements and types of detectors employed in FT-IR instruments, the power of the radiation that reaches the detector is larger than that in dispersive infrared instruments, and greater signal-to-noise ratios are observed. Fourier transform also results in high resolving power and wavelength reproducibility. An important advantage of Fourier transform is that since all of the wavelengths of the source reach the detector at the same time, an entire spectrum can be obtained within seconds. Non-Fourier transform instruments have to examine each wavelength individually to generate the spectrum, which can take much longer for comparable resolutions. Fourier transform can be described as a mathematical algorithm that is applied to the data generated by the spectrometer. Because the interferometer modulates the infrared light in a very specific way, the Fourier transform algorithm enables the instrument to process all of the wavelengths of infrared light at once. This produces a high quality spectrum almost immediately. Fourier transform spectroscopy incorporates an interferometer for the purpose of achieving usable frequency-domain spectroscopy from timedomain (changes in radiant power with time) data through a series of mathematical computations and signal modulations. The interferometer splits a beam of radiation into two beams of nearly equal power and then recombines them such that the intensity variations of the combined beam can be measured as a function of differences in the path lengths of the two beams. After a signal called an interferogram is generated, the mathematical Fourier transform of this signal occurs and is plotted. These interference patterns undergo data processing to produce a “readable” spectrum; the interferogram shifts from the faster light frequency to a slower audio frequency, which can be “read” by the detector and subsequently plotted. The common Michelson interferometer possesses both a fixed and a movable mirror. The movable mirror travels away from and toward the beamsplitter with a constant velocity allowing for its location to be determined by fluctuations in the power of the reference laser radiation incident on a detector. The difference in path length that the infrared light travels can be determined at any point in time by reference to the interference pattern generated by the laser. The difference between this path length and the path length that

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the infrared light travels to the fixed mirror part of the interferometer is called the optical path difference (OPD). As the optical path difference changes as the moving mirror is moved, the power at the infrared radiation also changes due to the constructive and destructive interferences of the various wavelengths. An interferogram is the result, which is the plot of the infrared energy power (or detector signal) versus the time (a function of the OPD). Although routine infrared spectroscopic analysis is done in absorbance mode, an infrared reflection method can be used. Internal reflection spectroscopy is based on total internal reflection of radiation within an internal reflection crystal. Reflection will occur when radiation moves from a more refractive to a less refractive media, or vice versa. In this method, the more refractive media is the internal reflection element (IRE) and the less refractive is the sample. If the radiation is applied at an angle greater than the critical angle, reflection is described as being complete and total internal reflection occurs. The electric field of the radiation penetrates some distance into the less refractive material and thus can interact with the less refractive material. This distance the field extends into the less refractive media is called the depth of penetration. This depth of penetration depends upon the refractive indices of the sample and IRE, the angle of the incident radiation, and the wavelength of the incident radiation. As the wavelength increases, the wave number decreases and the depth of penetration increases. The electric field that penetrates into the sample is called the evanescent wave. If this radiation is absorbed by the sample, the reflected radiation will be attenuated at the wavelengths corresponding to the sample’s absorption bands. Thus, this technique is called attenuated total reflection (ATR). Using ATR spectroscopy, the sample is placed into direct contact with an internal reflection crystal. For ATR to occur efficiently, the sample must come into contact with an IRE (also called an ATR crystal), which has a higher refractive index (RI) than the sample. Typical IREs are zinc selenide (ZnSe), which has a RI of 2.2, Germanium (Ge), which has an RI of 4 and a composite IRE in which diamond (RI of 2.4) comes into contact with the sample. Most samples have refractive indices between 1.0 and 1.5, so typical IREs are suitable for most sample analysis. ATR is ideal for homogeneous, strongly absorbing and thick samples and a variety of samples that may normally produce intense, saturated peaks difficult to interpret when measured in transmission mode. For routine work, the region of interest is the mid-infrared region from 4000 to 200 reciprocal centimeters (cm−1). Within this range, the commonly displayed infrared spectrum can be split into two major regions, the group frequency region from approximately 4000–1300 cm−1 and the fingerprint region from approximately 1300–400 cm−1 (and down to 200 cm−1). Spectra are displayed as wavenumbers (cm−1) on the x axis and absorbance, reflectance, or percent transmittance on the y axis. When comparing ATR spectra to transmission spectra, the peak locations are very similar (with some

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small shifts occurring), but differ in intensities. One of the major differences between typical absorbance spectra and ATR spectra is the dependency on sample thickness; ATR spectra being generally independent of sample thickness as long as the sample is thicker than the depth of penetration. This is because the radiation penetrates a small distance into the sample, whereas absorption spectra require the incident radiation to traverse the entire sample prior to reaching the interferometer and ultimately the detector. When compared to transmission spectra for a given material, ATR spectra have less intense absorption bands at higher wavenumbers and more intense absorption bands at lower wavenumbers. An ATR reflectance spectrum is a plot of the intensity of the internally reflected radiation as a function of wavelength (or wavenumber). When comparing sample preparation techniques of ATR and transmission, since ATR is based on the reflection of radiation from the surface of the sample, no special sample preparation is needed beyond making sure the sample is in intimate contact with the IRE.

Raman Spectroscopy: Theory and Practice When radiation interacts with matter, several processes can occur, including the absorption, emission, scattering, reflection, and refraction of the incident radiation. The scattering of electromagnetic radiation forms the basis for Raman spectroscopy. The Raman effect is the scattering phenomenon that involves a net energy change between the scattered and incident beams of radiation. In contrast, a scattering process that involves no change in the energy of the scattered beam relative to the incident beam is defined as Rayleigh scattering. Raman scattering is caused by rotational and vibrational transitions in molecules, thereby allowing for structural determination of molecular species. The Raman effect was observed by C.V. Raman in 1928 with the assistance of K.S. Krishnan. According to the literature, the phenomenon of inelastic light scattering was predicted five years earlier by A. Smekal (Haynes et al., 2005, p. 339A) and “figured into the theory of dispersion due to Kramers and Heisenberg and in the papers of Schrödinger” (Raman and Krishnan, 1929, p. 24). Raman found that a small fraction of scattered radiation will differ in wavelength from that of the incident beam and that shifts in frequency depend upon the chemical structure of the molecules causing the scattering. Raman and Krishnan noted that the incident quantum radiation is either scattered as a whole or absorbed in part by the molecules in the medium, where the part absorbed shifts the molecule to an energy level different from its initial state. According to the Raman theory, if an oscillating electric field is incident upon a sample, this field will interact with polarizable electron clouds of the sample molecules. A molecule can undergo a change in polarizability during one of its normal modes of vibration, where polarizability is

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a measure of how efficiently a given incident frequency induces a dipole in a polyatomic molecule. The Raman effect results from the effect of the polarizability with the normal modes of vibration of the molecules. A molecule’s polarizability will vary based upon bond distances and internuclear separations of a molecule. A normal mode that involves a change in polarizability is described as a Raman active mode, whereas a normal mode that results in no change in polarizability is referred to as a Raman inactive mode. In Raman spectroscopy, a dipole moment is induced by an external electric field of light. When a molecule is placed in such an electric field (ε), the induced dipole moment (μi) is given by

µ i = εα

where α is the molecule’s polarizability. Molecular dipoles are generally on the order of one Debye while α values are generally in units of cubic Ångströms. The magnitude of polarizability will vary with the frequency of the incident electric field and can be described as how easily a molecule’s electronic configuration can be distorted by this field. If monochromatic light of frequency (ν0) is incident upon a molecule, then light frequency of ν0 and ν0 ± ν is subsequently emitted from the molecule. In general, Raman scattering occurs when α ≠ 0. From a quantum mechanical viewpoint, the Raman effect involves transitions between energy levels, where molecules in the ground vibrational state can interact with a photon of some energy and reemit a photon of energy at a lower frequency, or molecules in the lowest excited vibrational state can interact with a photon of energy and reemit a photon of energy at a higher frequency. An atomic or molecular system will scatter a photon if the energy of the photon equals the energy difference between the two states of the molecular species. If scattering occurs, the molecular species will occupy a higher energy level known as an excited virtual state. Smith and Dent describe the virtual state as a “complex” between the incident radiation and the molecule; when the oscillating dipole interacts with the molecule, the electrons are polarized to a higher energy state (Smith and Dent, 2005, p. 72). At the instant when the energy is transferred to the molecule, there is a complex that forms between the light energy and the molecule’s electrons in which the nuclei do not have time to move appreciably (Ibid.). The authors add that this virtual state “complex” is unstable and the light is released immediately as scattered radiation. Over time, the excited state will give off energy and the scattering species will return to a lower energy state. With Raman scattering, the amount of energy lost between incident radiation and the resultant emitted photon equals the energy difference between two quantized vibrational energy levels of the molecules causing the scattering. These energy differences are generally characteristic of the molecular species;

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E  = hν = h(c/λ) = hύ in which the energy (E) between the ground state and excited state is directly proportional to the frequency, ν, and inversely proportional to the wavelength, λ, of the absorbed light (where ύ = 1/λ in wavenumbers, cm−1). The intensity of Raman scattering is defined by the equation

I = Klα 2ω 4

in which the intensity is the product of a series of constants (represented by K), the power of the incident laser radiation (l), the polarizability of the molecule, and the frequency of the incident radiation (ω). This equation is important in demonstrating the contribution of the incident frequency on the overall Raman scattering intensity (ω4); specifically, signal enhancement to the fourth power. Resonance Raman scattering is a phenomenon in which the Raman band intensities are enhanced when the excitation wavelength is near that of the electronic absorption band of the molecular species of a sample. This enhancement can be a factor of 102–106, which increases the detection sensitivity by molecules present in a sample at low concentrations. The resonance enhancement effect is observed in those Raman bands associated with functional groups that contain valence electrons with low excitation energies (chromophores). This is due to the presence of absorbing species containing π (bonding) and n (nonbonding) electrons and their transitions to π antibonding electron energy levels. According to White et al., “provided a molecule has a suitable chromophore and the laser excitation wavelength matches, or is very close to the absorbance maximum of the analyte, then under resonance conditions sensitivity can be increased by up to three to four orders of magnitude over traditional Raman spectroscopy” (White et  al., 1998, p. 78). Determination of a sample’s wavelength absorbance maxima using a UV/Vis spectrophotometer can provide the approximate range of excitation wavelengths that are capable of producing the resonance Raman effect. In resonance Raman, an electron is promoted to an excited electronic state followed by instantaneous (10−12–10−14 s) relaxation to a vibrational level within the electronic ground state. In contrast, the relaxation by fluorescence is not instantaneous, but instead involves a relaxation to the lowest vibrational level of the excited electronic state prior to returning to the ground state. In fluorescence, the molecular species emits a new photon after absorption and subsequently returns to the ground state. The lifetime of the excited state is of the order of 10−6–10−8 s in fluorescence. Preresonance Raman spectra are those that are obtained when the excitation sources are set to a frequency slightly lower than that which would cause resonance Raman, thereby resulting in a lower degree of enhancement.

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244 nm

325 nm

Near UV lasers

500 nm

700 nm

300 nm 400 nm

600 nm

200 nm

500 nm

400 nm

As with most spectroanalytical instrumentation, current Raman instrumentation contains a source, a sample holder, a wavelength selector or interferometer, a detector, and a data processing/readout system. With dispersive Raman systems, the wavelength selector is a grating or series of gratings and with Fourier-transform Raman systems, a Michelson interferometer is employed. Sources are almost always lasers, which provide bright, monochromatic radiation. A variety of laser sources are available and selection will vary based upon the instrument, the types of samples being analyzed, and the needs of the analyst (Figure 9.2). In order to evaluate which monochromatic laser excitation wavelength and corresponding laser power (intensity) to apply to the sample being analyzed, it is necessary to consider fluorescence effects, absorption effects, and possible photo decomposition of the sample. Selection of excitation wavelength will also be important when considering desired sample penetration depth, as this may affect resultant spectra, especially in the cases of thin films or layered samples. Raman systems may be stand-alone spectrometers or the Raman spectrometer can be coupled with an optical microscope for the analysis of smaller samples or samples composed of microamounts of molecular species. For stand-alone spectrometers, liquid and solid (e.g., powder) samples may be placed in a capillary tube, sample cell, or alternate sample holder and inserted into the path of the incident beam. For microscopic work, the solid or liquid sample is placed within a sample holder, mounted on a glass or aluminum-coated slide or placed directly on the microscope stage. It is important to note that obtaining Raman spectra is not limited by materials that

600 nm

700 nm

532 nm

633 nm

514 nm 488 nm 473 nm

800 nm

900 nm

785 nm

1064 nm Near IR lasers

617 nm

Figure 9.2  ​Laser excitation wavelengths.

1000 nm

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affect infrared data collection, such as glass sample holders and optical components, aqueous solutions, and some solvents. Many sample types require little to no sample preparation for Raman analysis, which is not always the case with classic infrared analysis techniques, with the exception of ATR. Current Raman instruments are typically of two types, Fourier transform instruments with low band gap semiconductor detectors such as Germanium (Ge) and indium gallium arsenide (InGaAs) or dispersive, multichannel instruments with charge coupled device (CCD) detectors. CCD detectors are not sensitive to the spectral area near the 1064 nm Nd/YAG lasers, and as such, 1064 nm lasers are typically used with a Germanium detector in Fourier transform instruments. With dispersive systems, in order to observe the Raman spectrum, it is necessary to separate the collected Raman scattered light into individual wavelengths, which is accomplished with a grating or series of gratings. Since Raman scattering intensity depends on the fourth power of the frequency (referred to as the ω4 or ν4 rule), the high frequency lasers found in dispersive systems are ideal with respect to increased sensitivity. Conversely, the longer wavelength/shorter frequency of the 1064 nm laser used in FT-Raman instrumentation decreases electron excitation and reduces the chance for fluorescence. Advantages of Fourier transform instruments include the elimination of many fluorescence interferences and acquisition of the full spectrum which minimizes loss of spectral regions (no need to “stitch” spectral regions together when switching between gratings in a dispersive system, and no need to switch gratings to change resolution since the moving mirror controls resolution in an FT system). Additionally, there is an increase of signal to noise ratio with concomitant enhanced sensitivity due to the multiple scan capability with signal averaging and the increased energy throughput of the interferometer. In a dispersive Raman microscope, the laser light travels through the objective, impacts the sample and scatters back through the objective. The Raman scattered light passes through the objective and travels to the spectrometer module. Narrow bandpass interference filters are in place to produce monochromatic incident laser lines and notch filters are in place to block any additional radiation (i.e., Rayleigh) such that only the Raman scattered radiation reaches the detector. The FT-Raman spectrometer uses an interferometer and series of filters to generate spectral data. With Raman spectra, the abscissa (x axis) is the wavenumber shift (the difference in frequency between the observed radiation and the source). This value is usually displayed as wavenumbers (cm−1). The ordinate (y axis) is the Raman intensity and may be labeled as photons per second or arbitrary intensity units. The intensity of a Raman peak is affected by several factors, including but not limited to the molecule’s polarizability, the concentration of the active molecular species within a sample, the intensity of the excitation source, and the efficiency of the detector.

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Raman spectroscopy can be impeded by sample degradation (thermal and photo degradation), inherently weak intensities, fluorescence interferences, and inefficient collection and subsequent detection of radiation. Current instrumentation has been able to overcome these factors, due to the availability of various laser excitation wavelengths, the introduction of interferometer-based instruments, improved detectors and electronics as well as enhancement techniques such as surface enhanced Raman scattering (SERS) and resonance Raman spectroscopy.

SERS: Theory and Practice SERS is the technique employed to enhance the normal Raman signal by a factor of 106 or more by placing a molecular species on or near a metal substrate (e.g., a metal nanoparticle or quantum dots), followed by analysis with standard Raman instrumentation. It has been found that there are three factors which contribute to this enhancement effect, molecular resonance (from the molecular species), surface plasmon resonance (from the conduction band of the metal nanoparticle), and charge transfer resonance (transfer of electrons between the molecule and the metal). In addition to the signal enhancement, there is also a resulting quenching of fluorescence. SERS benefits include the ability to generate high resolution spectra of molecular species in ultratrace concentrations and the ability to generate spectra in cases where fluorescence interference is otherwise overwhelming with normal Raman. Much work has been done to establish the mechanism of the enhancement and to determine the relative effects of the contributing sources. According to Lombardi and Birke, the enhancements can be described by a single expression in which all three resonance effects contribute. Furthermore, these resonances (surface plasmon, charge transfer, and molecular) contribute as multipliers rather than sums. The authors note that the three resonance effects contribute differently to the overall enhancement, depending on several factors. These factors include the nature of both the metal nanoparticle and the molecular species as well as the characteristics of the excitation wavelength. According to the equation that resulted from their research, the enhancement factor (R) can be determined based upon the contribution of the different resonance effects (Lombardi and Birke 1986, p. 5609). Lombardi and Birke determined that the resonances are represented in a single expression linked by coupling terms where the three resonances contribute as multipliers with regard to the overall enhancement. In Figure 9.3, the numerator represents the Raman signal, where I, F, and K represent the ground state (HOMO), a charge-transfer state (Fermi), and an excited molecular state (LUMO) of the molecule–metal system, respectively, and the denominator represents the product of the three resonances (surface plasmon, charge

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Enhancement factor

Transition electron dipole moment (F → K)

Electronic transition (I → K)

215

Hertzberg-Teller coupling (I → F vibronic coupling)

RIFK (ω) = μKIuFKhIF〈i | Qk | f 〉 )2

((ε1(ω) + 2ε0 +

ε22)(ωFK2

– ω2 + γFK2)(ωIK2 – ω2 + γIK2)

Surface plasmon resonance

Charge transfer resonance Imaginary dielectric Molecular resonance constant Damping term

Figure 9.3  ​SERS enhancement factor equation developed by Lombardi and Birke.

transfer and molecular, respectively). In the numerator, hIF{i|Qk|ƒ} ­represents the B-term (nontotally symmetric modes) in the Hertzberg–Teller equation, which gives rise to normal Raman spectra. In the denominator, the values are all energies that are affected by the excitation wavelength. These resonance factors correspond to the surface plasmon resonance, the charge transfer resonance, and electromagnetic resonance. According to the authors, the magnitude of the SERS enhancement, the contribution of each of the three resonance effects and the appearance of the resultant Raman spectra depend on several factors, including the excitation wavelength, the size and shape of the metal nanoparticle, the strength of the oscillator, the energy of the nanoparticle, and the bandwidth of the resonance. Of the metal substrates, copper, gold, and silver are commonly employed for SERS work. Preparation of metal substrates has varied and has included surface roughening by a series of oxidation–reduction cycles, thin film depositions on different substrates by different methods of deposition (i.e., sputtering or evaporation), and the preparation of colloids. A study by Lee and Meisel attempted to detect SERS by examining dyes adsorbed on colloidal gold and silver by preparing a series of silver and gold sols using sodium citrate solution as a reducing agent. In addition to observing the surface enhancement phenomenon due to the molecular species (dyes) adsorbed on the surface of the colloids, the authors demonstrated the efficiency of adsorption of the dye molecules onto the colloids. Many researchers have employed the Lee and Meisel method (or a slightly modified version) since its development to produce silver sols for their SERS work. While effective for SERS, the Lee and Meisel colloids had limited stability and reproducibility with regard to particle size, aggregation, and absorption light maxima. As such, other

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support systems have been developed, such as roughened electrodes, Tollens mirrors,* silver nanoisland films, and alternative metal colloids. In order to improve the analytical performance of SERS in the analysis of microscopic samples, in 2009 Leona developed a sensitive, stable silver colloid support that could be reproducibly prepared by microwave activated reduction of silver sulfate with glucose and sodium citrate. By controlling the reaction and providing rapid, uniform heating, Leona developed a stable silver colloid of narrow particle size range absent of aggregates. Compared to the Lee and Meisel method, the microwave reduction method established by Leona produced a narrow absorption range, narrow particle size distribution, and increased colloid stability over a longer period of time. In 2006, Leona et al. also reported that the poly(l-lysine) used by Lee and Meisel to facilitate the adsorption of dyes onto the silver nanoparticles was not necessary. The authors report that superior results were obtained when using potassium nitrate (KNO3) as the aggregant, or as an alternate, gently heating the microscope slide containing the dye solution-colloid. Sodium chloride (NaCl) has been proposed as a suitable aggregant by Bell et al., where they reported “dramatic growth in the intensity” of the Raman bands resulting from its addition (Bell et al., 2007, p. 1064). The use of other aggregants has been reported (nitrates, chlorates, nitric acid, etc.) and aggregant selection may depend on the nature of the dye or sample being analyzed with regard to its functional groups and charges on the atoms. The presence of a background produced by the citrate-reduced silver colloid from the citrate ion and reduction reaction by-products has been noted by Teslova et al. (2007, p. 807) and should be considered when interpreting SERS spectra that incorporate this type of colloid. Much has been published demonstrating the use of SERS to enhance signals and quench fluorescence. Istvan et al. reported the effect of adding silver sols to TLC spots, stating that the strongest Raman band was enhanced and many additional weak spectral features were then detectable above the noise level (Istvan et al., 2003, p. 1717). SERS has been used in many fields of study, including art conservation and forensic science. SERS has been applied to the analysis of various natural and organic pigments, and dyes, including rhodamine 6G, flavones and derivatives, flavonoids, berberine, alizarin, carminic acid, laccaic acid, photoberberine alkaloids, indanthrone and flavanthrone, and many others. In the forensic science field, SERS has been used to analyze paints, pigments and inks, fibers, and controlled substances such as morphine, codeine and hydrocodone, amphetamines, and methamphetamines (Rana et al., 2011; Taplin, 2011). In addition, several publications have been generated evaluating the contribution of resonance effects to different dye molecules. * Colloidal silver films on a glass substrate.

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Surface enhanced resonance Raman scattering (SERRS) is a technique that couples resonance Raman techniques with those of normal surface enhanced Raman scattering. According to Haynes et al., SERRS occurs when the laser excitation wavelength overlaps with an electronic absorption band, thereby amplifying the Raman scattering intensities of the totally symmetric vibrational modes of the chromophore (Haynes et al., 2005, p. 342A). White et al. analyzed acidic, basic, and neutral dyes using a silver colloid based upon a modified Lee and Meisel method with poly(l-lysine) as the aggregating agent. Using excitation wavelengths of 457.9, 514.5, and 632.7 nm, the authors analyzed an assortment of dyes. They found no difficulties with the analysis of basic dyes and concluded that SERRS analysis is useful for the analysis of dyes in a mixture and the technique demonstrates that it is not necessary to perform any chromatography or extraction on the dyes prior to conducting SERRS (White et al., 1998, p. 86). For acidic and neutral dyes, White et al. found that when ascorbic acid was added to the colloid-aggregant complex, there was an improvement in detection of the dye (White et  al., 1998, p. 80). The authors reported that they were able to distinguish the dyes tested, including geometric isomers and tautomers (White et al., 1998, p. 78). SERRS has been applied to the analysis of several materials encountered in forensic science and art conservation, including colorants, lipsticks, inkjet dyes, and organic pigments and glazes. In order to routinely identify a compound and determine the molecular structure using infrared or Raman spectrometry, correlation charts are used to identify the functional groups in a molecule based upon the observed vibrational bands (see, for example, Colthup et al., 1990; Skoog et al., 1998). After determination of the functional groups based upon the band locations, reference libraries and computer-based searches can be used to aid in the compound identification. For structural determination, calculations can be conducted to provide information about the expected infrared active modes wherein predictions are made about the structure and symmetry of a molecule (e.g., density functional theory calculations; see, for example, Cotton, 1964; Bunker and Jensen, 1998). These calculations are based upon molecular symmetry and group theory considerations. By coupling infrared data with Raman spectrometry, interpretations for qualitative identification can be done with high confidence.

Instrument Calibration, Method Development, and Standard Practices Current trends in the forensic field have been evolving toward increasing the use and development of unified laboratory standards of analysis. A

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publication addressing the current status of forensic science was published in 2009 by the National Academy of Science. Entitled Strengthening Forensic Science in the United States: A Path Forward, the panel of authors addressed several topics, including the accreditation process and standards and guidelines for quality control within the forensic science community. In recent years, accreditation of forensic laboratories has begun shifting from meeting the standards set forth by the American Society of Crime Lab Directors/ Laboratory Accreditation Board (ASCLD/LAB) to those established under the International Organization of Standardization (ISO) ISO/IEC 17025 guideline, which outlines the requirements for the competence of a laboratory to carry out testing and calibrations using standard methods, nonstandard methods, and laboratory-developed methods. Major aspects of any accreditation program are validating and documenting both administrative and technical procedures, developing and maintaining calibration procedures, and using appropriate controls and standards during analytical testing in a forensic laboratory. Any instrumentation to be employed in an accredited forensic laboratory must undergo qualification and calibration, which is a documented process usually done upon instrument installation. In addition, the instrumentation must undergo routine performance monitoring to ensure that the instrument is maintaining a standard level of operation. The establishment of an instrument’s acceptable performance is usually referred to as the instrument qualification. Most forensic laboratories will define how frequently the instrument should be calibrated and what the accepted limits are to declare the instrument suitable for casework. Routine performance checks serve as a check of wavelength accuracy and are usually conducted with a standard that has known, reported peak assignments. The standard selected for performance or function checks is selected based on its ability to provide reproducible results regardless of external conditions such as environment, instrument manufacturer, and so on. For example, a polystyrene standard is employed in order to evaluate the wavelength accuracy of a Fourier-transform infrared spectrometer. Polystyrene has well established, reproducible peaks across the range of the infrared region, making it a suitable standard for routine wavelength correlations and instrument performance verifications. These polystyrene peak values obtained from a laboratory’s FT-IR spectrometer can be compared to known values that have been established in the literature and be recorded and retained. The laboratory will often define an acceptable deviation range for each peak or a number of “major” peaks. Several other measures may be used to ensure good performance the FT-IR spectrometer before use, such as aligning the instrument optics, conducting a battery of tests to evaluate the robustness of the instrument by examining and evaluating the background

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and interferogram, and using the polystyrene for absorbance and resolution tests. These methods may be called the “function check” and are often done prior to use of the instrument. By running a standard, a laboratory is able to evaluate instrument performance on a daily basis and determine whether or not there are problems with the instrument hardware, settings, alignment, or software settings. A validation process known as qualification is used to confirm that the instrumentation employed for routine testing is suitable for intended use. This validation is done by running a set of experiments with a set of standards in order to establish the reliability of the instrument and the specific method that is to be used in routine casework. The accredited laboratory will establish a procedure for qualification of their instrument followed by establishing any methods that are to be used with the instrument. Instrument qualification is a portion of the validation process that verifies that the instrument itself meets required specifications as described by the manufacturer or client. Typically, the qualification of the instrument is conducted upon installation of the instrument; the manufacturing company technician will install and set up the instrument and then run a series of tests to ensure that the instrument has been installed properly and that it meets the required factory specifications. The series of tests will be conducted in order to ensure that the accuracy, precision, and performance characteristics are optimized as per manufacturer’s specifications. After testing and calibrating the instrument, the instrument is considered qualified and the laboratory can proceed to method development for setting standard operating procedures and quality assurance measures. Routine preventative maintenance by the manufacturer and any instrument service are usually stored in a file in order to monitor and support the instrument qualification status. Retention of these records is critical to accreditation and may be critical in legal proceedings, both civil and criminal. Upon instrument installation, the instrument service technician will conduct one or more service tests to ensure that the instrument has been installed properly and is performing according to its specifications. The technician will often provide the laboratory with documents outlining the tests performed and any relevant results. These documents should be retained by the lab, and may often be useful in assisting the analysts with setting up quality assurance procedures to monitor instrument performance. The documentation outlines the procedures used by the technician and demonstrates that the instrument was set up according to its factory specifications. For example, the installation of the Bruker Raman instrument included the following series of tests: a background test, a beam focusing alignment test (using a silicon wafer), a frequency accuracy test (using acetaminophen, a main ingredient in Tylenol®), a spectral resolution test (using a neon lamp),

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a spectral cut-off test (using NIST glass or other fluorescent material), a throughput test (using polystyrene), and a confocal Raman test (using a silicon wafer). Additional information regarding the validation program for the spectrometer is often provided in the Software Users Manual and the Reference Manuals provided by the instrument manufacturer. The latter document may provide a detailed procedure for performance and operational qualifications of the instrument. Materials such as sulfur, cyclohexane, 4-acetamidophenol, polystyrene, silicon, and a 50/50 mixture of acetonitrile/toluene as standards can work for evaluating and monitoring Raman instrument performance. Elemental sulfur is a strong Raman scatterer that has several low-frequency Raman bands that enable the ability to observe low Raman shifts. Cyclohexane and 4-acetamidophenol are also strong Raman scatterers which have a wide frequency range that makes them useful as a standard for spectral resolution. Silicon provides a large, sharp peak at around 520 cm−1, which can make it a useful, rapid check of wavelength accuracy. The peak shift values obtained can be checked against several sources, including ASTM Designation E 1840–96, Standard Guide for Raman Shift Standards for Spectrometer Calibration, and McCreery (2000). In order to monitor and evaluate the UV/Vis spectrophotometer, didymium or holmium oxide standards should be used. For XRF, routine function checks can be performed using copper, tin, or aluminum (Figures 9.4 through 9.17).

300

Cu

200

Sn

100

0

0

10

Figure 9.4  Copper/tin—XRF.

20

-keV-

30

221

Figure 9.5  ​Didimium—UV/Vis.

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Forensic Analysis of Tattoos and Tattoo Inks

Figure 9.6  Holmium oxide—UV/Vis.

222

Part 1—The Chemical Analysis of Modern Tattoo Inks 30,000

223

Cyclohexane (Raman)

Green-488 nm excitation wavelength

20,000

10,000

0

–10,000

Blue-785 nm excitation wavelength Red-633 nm excitation wavelength Black-1064 nm excitation wavelength 500

1000

1500

2000

2500

3000

Intensity/Raman shift (cm–1)

Figure 9.7  ​Cyclohexane—Raman; from top to bottom: λ0 = 488 nm, 785 nm,

Cyclohexane (Raman) 1064 nm excitation wavelength

2923 2937.8

80

2852.4

801.32

633 nm, and 1064 nm.

60

2887.7 2896.7

2632.9 2664.1 2697.2 2799.3 2869.7

1443.6 1465

1266 1347.2

1027.5

382.94 425.85

20

1157.7

40

0 500

1000

1500

2000

2500 3000 Intensity/Raman shift (cm–1)

Figure 9.8  ​Cyclohexane—Raman; λ0 = 1064 nm (major bands labeled).

15,000

Polystyrene (Raman) Green-488 nm excitation wavelength

10,000 5000

Red-633 nm excitation wavelength

0 –5000

Blue-785 nm excitation wavelength 500

1000

1500

2000

2500 3000 Intensity/Raman shift (cm–1)

Figure 9.9  ​Polystyrene—Raman; from top to bottom: λ0 = 488 nm, 633 nm, and 785 nm.

Forensic Analysis of Tattoos and Tattoo Inks

20,000

2851.4 2905.3 2977.4 3001.6 3055.7

1603.6 1667.9

1450.2

1328.9

1000.7 1031.2 794.1 841.74 906.31

619.13

217.28

101.14

10,000

1156.8 1199.3

15,000

5000

Polystyrene (Raman) 488 nm excitation wavelength

3162.1

224

0 500

1000

1500

2000

2500 3000 Intensity/Raman shift (cm–1)

694.76

Figure 9.10  Polystyrene—Raman; λ0 = 1064 nm (major bands labeled).

.6

905.72 841.55

1180.9 1154.2 1068.6 1027.5

1601 1583 1492.1 1451.4 1371.4

3082.2 3059 3024.9 2920.8 2848.8

.2

749.14

.4

0 3500

3000

2500

2000

1500

1000

Figure 9.11  ​Polystyrene—FT-IR (ATR).

Sulfur (Raman)

Black-1064 nm excitation wavelength

15,000 10,000

Green-488 nm excitation wavelength

5000

Red-633 nm excitation wavelength

0

Blue-785 nm excitation wavelength

–5000 100

200

300

400

500

600

Intensity/Raman shift (cm–1)

Figure 9.12  ​Sulfur—Raman; from top to bottom: λ0 = 1064 nm, 488 nm, 633 nm, and 785 nm.

225

Sulfur (Raman) 1064 nm excitation wavelength

472.2

152.98

1500

218.49

Part 1—The Chemical Analysis of Modern Tattoo Inks

1000

246.28

500

0 100

200

300

400

600

500

Intensity/Raman shift (cm–1)

8000

09.236

Figure 9.13  ​Sulfur—Raman; λ0 = 1064 nm (major bands labeled).

Acetominophen (Raman) 785 nm excitation wavelength

1445.8

1323.7 1371.4 1392.5

1236.7 1256.8 1277.9

1105.5

968.78

797.12 834.27

710.82

604.21 627.23 651.24

464.62 503.86

391.24 411.8

328.71

213.77

2000

150.42

4000

1168.2

857.69

6000

0 200

400

600

800

1000

1400

1200

Intensity/Raman shift (cm–1)

Figure 9.14  Acetominophen—Raman; λ0 = 785 nm (major bands labeled).

1003.3

140 120

3167.1

2870.5 2920.4 2981.8 2937.8 3002.7 3055.5

2735.8

2253 2291.8

1585.1 1604.4

1379.9 1440.1

810.44 918.61 991.76

20

217.34

40

346.2 376.51 465.84

60

521.33 622.05

80

1030.2 1156.1 1179.3 1210.3

785.96

100

50/50 Toluene:acetonitrile (Raman) 1064 nm excitation wavelength

0 500

1000

1500

2000

2500

3000 3500 Arbitrary/arbitrary

Figure 9.15 ​50/50 Toluene:acetonitrile—Raman; λ0 = 1064 nm (major bands labeled).

226

Forensic Analysis of Tattoos and Tattoo Inks Silicon (Raman)

1000

Blue-785 nm excitation wavelength

800 600

Green-488 nm excitation wavelength

400 200

Red-633 nm excitation wavelength

0 100

200

300

400

500

600

Intensity/Raman shift (cm–1)

Figure 9.16  ​Silicon—Raman; from top to bottom: λ0 = 785 nm, 488 nm, and 520.83

633 nm.

Silicon (Raman) 785 nm excitation wavelength

500 400 300 200 100 100

200

300

400

500

600

Intensity/Raman shift (cm–1)

Figure 9.17  ​Silicon—Raman; λ0 = 785 nm (major band labeled).

Spectroscopic Analysis of Tattoo Inks Instrumental Analysis: Molecular SpectroscopyRaman and Infrared Spectroscopy The normal Raman spectra of tattoo inks were obtained with a dispersive Raman spectrometer, interfaced with an Olympus microscope. The excitation sources are a blue 488 nm Argon ion (Ar+) laser, a red 632.8 nm (633 nm) Helium/Neon (He-Ne) laser, and a near-infrared 785 nm diode laser. The dried tattoo ink samples that had been placed on the microscope slide were analyzed by placing the microscope slide directly on the sample stage for analysis. The tattoo inks were also analyzed using Fourier-Transform Raman Spectroscopy with a near-infrared 1064 nm neodymium-yttrium aluminum garnet (Nd/YAG) laser excitation source. A portion of the ink on the

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227

microscope slide was scraped off and placed into the sample holder for analysis using FT Raman. In instances of overwhelming fluorescence and the presence of highly absorbing species (blacks, browns, grays, and the darker purples, blues, and greens), the pigment was ground with potassium bromide (KBr) and put in a glass capillary tube prior to analysis in the FT Raman. SERS was conducted on some of the tattoo ink pigment extracts as well as the powder pigment standards. The silver colloid was prepared using Leona’s microwave digestion method. Spectra were obtained using the dispersive Raman instrument with an excitation wavelength of 488 nm. The resultant spectra were compared to the normal Raman spectra at 488 nm in an effort to evaluate whether or not there was any improvement in using SERS to generate spectral information, especially with samples that exhibited overwhelming fluorescence with normal Raman. A drop of colloid was placed directly on the tattoo ink smear and allowed to sit for several minutes followed by addition of the potassium nitrate and subsequent analysis with the instrument. This technique proved to be quite successful in generating interactions between the pigment and the colloid, which resulted in quality SERS spectra for several of the tattoo inks and pigments. Examination and comparison of the Raman spectra (normal and Fourier transform) for a given pigment were conducted in order to determine whether there is band shifting and changes in relative band intensities due to changing the excitation wavelength. While the band locations are relative for a given molecular species and most literature indicates that resultant Raman spectra of a sample are independent of the incident energy, it is anticipated that when changing from 488 to 633 nm and 785 to 1064 nm laser excitation wavelengths, there may be some shifting of bands and changes in band relative ratios. This evaluation was used to assert that the excitation wavelength is an important factor in the evaluation and comparison of questioned and known samples and should thus be noted in any Raman analysis, especially when reporting band locations in both tabular and spectral formats. Examination and comparison of the normal Raman spectra and SERS spectra were conducted to evaluate whether or not SERS was useful in enhancing weak signals and quenching fluorescence. In addition, any variations in band locations and relative band intensities were noted. The infrared spectra of tattoo inks was obtained with a Nicolet FT-IR spectrometer with an ATR attachment for ATR measurements. A portion of the ink on the microscope slide was scraped off and placed into the internal reflecting element for direct analysis without any additional sample preparation. X-ray fluorescence spectra were also obtained from the tattoo ink samples in order to gain information regarding the atomic composition of the samples. For all resultant infrared and Raman spectra, peak identification was conducted in order to label and classify the strongest bands (major) for

228

Forensic Analysis of Tattoos and Tattoo Inks

comparison to pigment reference material and to determine the modes of vibration based on previously published correlation tables. All tattoo inks were evaluated to determine possible pigment compositions based upon band locations and comparison to pigment standards. Reference pigments were obtained and analyzed, where possible, in an effort to have a set of standard pigments that have been analyzed on the same instruments and under the same conditions as the tattoo inks; these reference samples were used to compile known pigment databases for the various instrumental techniques employed. A list of known pigment standards obtained and analyzed in Miranda’s (2012b) study can be found in Table 9.1. The spectra from the reference pigments and tattoo inks were compared to data tables that are available in the literature, specifically articles by Vandenabeele et  al. (2000), Ropret et al. (2007), Schulte et al. (2008), Scherrer et al. (2009), and Colombini and Kaifas (2010).

Chemistry and UV–Vis Spectroscopy The primary examination of the pigment samples was done without separating the pigment from the carrier solution, which means that there are potential matrix interferences inherent in all instrumental examinations. For example, a portion of the solution in which the pigment(s) is dispersed may produce fluorescence that inhibits the detection of the pigment. It is expected that the SERS technique will be the best way to reduce fluorescence and at the same time, enhance the signal of the pigment. Matrix effects may also render the pigment molecule unable to bind to the colloid. The solution may also present solubility issues that introduce problems in UV/Vis spectrometric measurements, which determine the absorption maxima (useful for resonance Raman). One method to minimize matrix effects is to conduct extractions of the tattoo inks in order to remove any residues from the solution and any inorganic materials. As such, a solvent extraction similar to the procedure used by Poon et al. was conducted on a selection of tattoo inks to separate the pigment from the carrier solution and any inorganic substances. The extraction method was conducted and evaluated in order to provide an accurate method for the extraction and recovery of the organic pigment portion of the tattoo ink. The extraction procedure was also able to elucidate whether or not an inorganic pigment such as titanium dioxide was present in the tattoo ink. This extraction process would allow for recovery and subsequent instrumental analysis of any inorganic portion in order to confirm its presence and identify any potential polymorph. A selection of extracted pigments were analyzed using both Raman (normal and FT-Raman) and infrared (ATR) techniques, and a comparison

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229

Table 9.1  Standard Pigments Analyzed in Miranda’s (2012b) Study Reference Pigments

Chemical Structure

Pigment Blue 15 Pigment Blue 15.1 Pigment Blue 15.2 Pigment Blue 15.3

N N

N Cu

N N

N N

N

Pigment Green 7

CI CI

CI

CI

CI

CI

N CI

CI

N

N Cu

N N

N N

N CI(3–4)

CI(3–4)

Pigment Orange 16

O

H N

N O

N O

O

N

O

N

N H

O

Pigment Orange 34 N

N O

N

N CI

CI

N

Pigment Orange 62

O N

N N

CH3 O O2N

N NH

NH O NH HN

O

(Continued)

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Forensic Analysis of Tattoos and Tattoo Inks

Table 9.1 (Continued)  Standard Pigments Analyzed in Miranda’s (2012b) Study Reference Pigments

Chemical Structure

Pigment Red 122

O CH3

NH NH

H3C O

Pigment Red 146

Cl

CH3 O CONHC6H5

O CH3

NH O

O

NH N O CH3

Pigment Red 170

H5C2O NH O

O H2NOC

NH N

Pigment Red 255 O NH

NH

O

Pigment Yellow 3

Cl

NO2 HN

N

H N

H3C O

Cl

O

(Continued)

Part 1—The Chemical Analysis of Modern Tattoo Inks

231

Table 9.1 (Continued)  Standard Pigments Analyzed in Miranda’s (2012b) Study Reference Pigments

Chemical Structure

Pigment Yellow 73

Cl

NO2 HN

NH

H3C O

Pigment Yellow 83

O

O O O

N

CH3

O

N

Cl N

NH

CI

Cl

O HN

O

N

N Cl

Pigment Yellow 151

O O

O

CH3 O N NH O

NH O NH

OH

HN

O

Pigment Violet 23 Cl

CH3 N

N

O

O

N Cl

N

CH3

of spectral data between direct analysis of the tattoo ink and the extracted pigment(s) was conducted to elucidate any differences in data according to the state of the sample. In order to assess the resonance effects of the tattoo inks, some of the tattoo inks were analyzed using UV/Vis spectrometry. The region of absorption of the tattoo ink can provide additional insight into the best excitation wavelength necessary to get maximum signal and quality

232

Forensic Analysis of Tattoos and Tattoo Inks

spectra due to resonance effects. The solubility of the pigments and additional wet chemistry methods may provide insight into chemical composition and lends itself to tattoo ink differentiation. It should be noted that there may be problems associated with extraction techniques, including contamination, incomplete or inefficient extraction of the pigment and possibility of changing the form of the chromophore or overall structure of the molecule. With regard to extractions, White et al. report that it is important to control both the pH and solvent polarity during extraction to ensure there are no changes in the chemical structure of the dye, as this change my impact the resultant Raman spectrum and lead to problems with identification (White et al., 1998, p. 82). With regard to differentiation of organic and inorganic pigments, separation was conducted using solvent extraction methods. Generally, inorganic pigments are expected to be heavier than the organic components, and it is expected that centrifugation coupled with solvent extraction will aid in the separation of organic and inorganic components. Due to its extensive use as a lightener, it is hypothesized that the majority of inorganic material recovered will consist of titanium dioxide. Caution must be taken during extraction, since some organic pigments, such as the phthalocyanines, may behave more like inorganics due to their composition and molecular structure, specifically with regard to the presence of the copper and chlorine atoms. Pigment standard samples and pigment extracts from the selected tattoo inks were dissolved in concentrated sulfuric acid. Concentrated sulfuric acid was used as the solvent in order to ensure complete dissolution of the pigment. Although this solvent can have a great effect on the molecular chemistry of the pigments, it is well-suited for the dissolution of the phthalocyanines and their metal complexes. The initial color change upon addition of the pigment particles into the concentrated sulfuric acid was recorded (Figure 9.18), and absorption measurements were extended beyond the visible region of the electromagnetic spectrum (approximately 400–700 nm) into the near

Figure 9.18  Tattoo ink pigment extractions dissolved in concentrated H 2SO4

in fused silica cuvettes in preparation for UV/Vis analysis Candy Apple Red, Red Hot, Marz, Dolemite, Blisterine Sassygrass, Tastywaves, Bellbottom Blue, SRV Teal 2, Muddy Water Blue, Ripple, Razberry Creem, San Brownadino, Tokyo Pink, Black Cherry Roan 2.

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233

infrared region (to approximately 900 nm) to account for any bathochromic and hypsochromic shifts due to the use of the concentrated H2SO4. Visual color characteristics, UV/Vis spectrometry, and color changes of the pigment upon introduction of the concentrated sulfuric acid solvent system were recorded in an effort to characterize the pigments and the tattoo inks. Although it is not possible to establish structural information of the pigment molecule from “coloristics” and solution chemistry, it is possible to gain information regarding the color class, functional groups (specifically chromophores), and resonance wavelength (for Raman spectroscopy) based upon visual characteristics and absorption maxima. Since the tattoo inks contain an abundance of various additives, including the presence of more than one pigment, it is recommended that pigment extracting be conducted prior to UV/Vis and wet chemistry methods. A proposed alternative to the extraction method conducted in this research is the use of the separation method TLC. Separation by a TLC plate in an appropriate solvent system followed by removal of the zone from the plate, extraction with an appropriate solvent system, and any necessary filtration and evaporation methods would be another option for separating the inks and extracting any pigments for spectroscopic analysis. A general scheme of analysis for tattoo inks includes microscopic examination (such as polarized light microscopy to determine optical properties in addition to particle dispersion and particle size), wet chemistry (solvent extractions and solubility testing), and instrumental analysis (UV/Vis, Raman spectroscopy, infrared spectroscopy). Additional analytical techniques to determine the inorganic composition of the tattoo inks should be conducted to include bulk XRF or electron microprobe analysis using low vacuum SEM/EDS instrumentation (although care should be taken in interpretation due to the potential difference in results from a bulk technique and a more area specific technique such as SEM/EDS). Chromatography can also be used to identify ink composition, including TLC, GC, and HPLC. All techniques employed should consider both the pigment portion and vehicle portion of the tattoo inks.

Tattoos in Tissue Upon completion of the analysis portion of the tattoo inks, a study of tattoo inks in tissue was conducted. Known tattoo ink was injected into pigskin using a tattoo machine and standard tattooing procedures and an attempt was made to analyze the inks and evaluate the potential interferences from the tissue substrate (Figure 9.19). Tattooed pigskin was preserved by either freezing the tissues or storing the tissues in formalin in order to assess the effects of preservation methods on the tissue and tattoo ink. Formalin

234

Forensic Analysis of Tattoos and Tattoo Inks (a)

(b)

Figure 9.19  Tattooing of pigskin (a) and resultant tattoos (b).

fixation preserves the tissue by preventing autolysis and stabilizing tissue structure and formalin fixation promotes the cross-linkage of amine groups in collagen (Huang et al., 2003, 649). A section of pigskin was obtained from a local butcher and stored in a refrigerator prior to tattooing. A tattoo artist was directed to tattoo two series of seven successive dots into the pigskin using the same Skin Candy tattoo inks analyzed in Miranda’s (2012b) research as follows: White Girl, Red Hot, Marz, Blisterine, Tastywaves, Muddy Water Blue, and Ripple. One set of colored dots was placed in formalin and the other set was frozen. The tattooed skin samples were then analyzed with the dispersive Raman using the three laser excitation wavelengths available (488, 633, 785 nm). Literature concerning the vibrational spectroscopic analysis of human tissue has been reported, with regard to biological implications with focus on dermatology and oncology (Williams et al., 1993; Gniadecka et al., 1998; de Faria and de Souza, 1999; Caspers et  al., 2003; Huang et  al., 2003) and

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anthropological and archeological implications with focus on mummified remains (Edwards et al., 2002; Petersen et al., 2003). These studies demonstrate the ability of Raman spectroscopic methods to generate spectra of human skin, both normal (“fresh”) and mummified, as well as human tissues from biopsies. de Faria and de Souza evaluated human skin and nail using an excitation wavelength of 632.8 nm and compared their resultant data to that reported in the 1992 literature by Barry et al. and Williams et al. in 1993 (in which an excitation wavelength of 1064 nm was employed). The results of de Faria and de Souza demonstrated good agreement between reported and experimental data. Gniadecka et  al. employed FT-Raman spectroscopy to investigate the molecular conformation of proteins, lipids and water in human stratum c­ orneum, whole skin, nail, and hair (Gniadecka et al., 1998, p. 394). The authors provided Raman spectral data of intact skin along with the band assignments and they added that skin spectra were highly reproducible, with only minor differences occurring in spectra with pigmented skin samples. These differences showed increased background fluorescence as a result of increased pigmentation (Gniadecka et al., 1998). With regard to mummified remains, research has been conducted on remains preserved by desiccation in various environments, including artificial mummification processes employed by ancient cultures. Overall, mummified skin exhibited bands characteristic of proteins and lipids, and the remains tended to exhibit weaker hydroxyl (–OH) and amide (–NH) bands due to the decrease in water content which results from the desiccation process (Petersen, 2000, p. 376). In the article by Edwards et  al., the authors provide a series of important observations that resulted from their comparisons of mummified and normal human skin, including the differences in Raman bands with regard to presence and absence, intensity variations, fluorescence, and general features characteristic of the type of skin analyzed (Edwards et  al., 2002, p.  8). Generally, bands from tissue proteins (including collagen, phospholipids, etc.) are found in the regions of 1640–1680 cm−1 (amide I), 1220–1300 cm−1 (amide III) and in the regions associated with C–C vibrations, aromatic ring vibrations, and assorted C–H vibrational modes. Differences may exist in band intensity, width, and overall shape depending on the quality and moisture content of the tissue sample. Huang et al. addressed the effect of formalin fixation on Raman studies of human tissues. According to the authors, major Raman bands associated with formalin can be found in the ranges 980–1100 cm−1 and 1480–1650 cm−1, with notable formalin peaks at 907, 1041, and 1492 cm−1 (Huang et al., 2003, p.  651). Their results showed that formalin fixation caused minimal influence on the tissue Raman spectra (Huang et al., 2003), but the authors note that the effect of formalin on overall Raman spectra may be tissue-specific (i.e., animal vs. human, epithelial vs. tumor, etc.). Notably, an increase in

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Forensic Analysis of Tattoos and Tattoo Inks

formalin fixation time will decrease the overall Raman intensity of the skin and related proteins due to the formalin dehydrating the tissue (Huang et al., 2003, 654) and changing the molecular structure of the tissue proteins. It should be noted that this is a positive aspect of formalin fixation with regard to this research, as the prolonged exposure of formalin to the tattooed tissue will reduce, if not eliminate, potential band interferences from the tissue substrate (as well as reducing potential fluorescence that could result from the analysis of tissue). This is clearly demonstrated in the pigskin study, as little to no evidence of the tissue substrate is present. Furthermore, there appears to be little effect of the formalin on the resultant Raman spectra, with little to no evidence of the characteristic formalin Raman bands present in the fixed pigskin samples. Even with the tissue substrate and the formalin fixative, it was still possible to identify the pigments present in the pigskin by comparing the resultant spectra to the previously obtained spectra of the tattoo ink and pigment standards. When analyzing tattooed human tissue (whether normal, mummified, charred, or decomposed) using vibrational spectroscopic methods, it is essential that the analyst be aware of the potential bands that could result from the tissue substrate in order to ensure proper interpretation of the resultant data and correct assignment of bands to the pigments present. In addition, the analyst should be aware of any bands that may arise from the fixation method, such as formalin. Barry et al. reported both the FTIR and FT Raman spectra (λ0 = 1064 nm) of human stratum corneum in an effort to assign the observed vibrational modes (Barry et al., 1992, p. 641). The results provide reference spectra for comparison and, if necessary, spectral subtraction of any bands detected in the tattooed skin samples that result from the tissue matrix can be conducted. A correlation to the resultant data with effects of the environmental conditions that produce postmortem changes in tissue such as charring, decomposition, and mummification are made. Consideration is also given to the possibility of detecting tattoo inks and pigments in instances where the tissue has healed and the pigment was able to migrate deeper into the skin. A proposed timed study analyzing a tattoo via Raman spectroscopy as the pigments migrate into the deeper layers of tissue and as the tissue heals is presented. The goal is to develop a method for detecting tattoo inks in situ with the most minimally invasive techniques, including conducting an analysis without the need to excise tissue from the body. Due to the current trends toward hand-held Raman spectrometers, this would be ideal and allow for more routine analysis of living and cadaveric tissue, and tissue in which removal of samples is undesired or nearly impossible, such as forensic specimens of limited size and historical samples in museums.

Part 2—The Chemical Analysis of Modern Tattoo Inks Spectroscopy

10

Results: Pigment Standards The pigment standards were first examined to evaluate their band locations relative to those reported in the literature* and in order to assign characteristic vibrational modes to the primary functional groups of the pigment molecule. Comparison of normal Raman and SERS spectra were also conducted with the pigment standards. General observations followed by correlation of the experimental data to the literature of the resultant spectra for the pigments are summarized below. The complete experimental spectral libraries can be found in Miranda (2012b). Pigment Red 122 With an increase in the excitation wavelength (λ0) from 488 nm to 785 nm, there is a substantial decrease in signal observed. The best normal Raman spectrum was obtained with λ0 = 488 nm. No spectrum was generated using the FT-Raman, even after mixing the pigment with KBr in order to minimize sample heating and reduce fluorescence. The spectrum obtained with SERS corresponds to the peaks observed with the normal Raman spectrum at λ0 = 488 nm. There was not any apparent signal enhancement observed going from normal Raman to SERS at this excitation wavelength. The FT-IR/ATR spectrum generated a number of well-resolved peaks; the peaks characteristic of quinacridones are apparent with the series of peaks in the region of 1630–1550 cm−1, and the peaks located at 1472 cm−1 and 1335 cm−1. With regard to UV/Vis, the absorbance maximum of Pigment Red 122 was 302.0 nm, likely a bathochromic shift that resulted from the solvent system (concentrated H2SO4). This is supported by the change in color observed (red to a bluish-red, or purple shade). Correlation can be made between the * In the literature, the peaks are labeled very strong (vs), strong (s), and medium to strong (m-s), and so on by the authors (a subjective determination based on peak intensities of the resultant spectra). These “strong” peaks were compared to the experimental data. The experimental spectra used for comparison were selected based on which λ0 for that particular pigment exhibited the highest number of peaks and best peak resolution. If there was more than one spectrum that fit the criteria, the spectrum with the λ0 closely matching the λ0 of the literature was selected.

237

238

Forensic Analysis of Tattoos and Tattoo Inks O NH

CH3

H 3C

NH O

Figure 10.1  ​Pigment Red 122.

experimental data and reported data for PR 122 (Scherrer et al., 2009; Schulte et al., 2008) (Figure 10.1). Pigment Red 146 (Figure 10.2) Raman bands were resolved with Raman spectra at λ0 = 488, 785, and 1064 nm. Overwhelming fluorescence was observed with λ0 = 633 nm and no useful data were obtained at this excitation wavelength. The spectrum obtained with SERS corresponds to the peaks observed with the normal Raman spectrum at λ0 = 488 nm. Signal enhancement was observed when going from normal Raman to SERS as well as resolution of peaks not observed in the normal Raman spectrum (Figure 10.3). The FT-IR/ATR spectrum generated a number of well-resolved peaks. With regard to UV/Vis, the absorbance maximum of Pigment Red 146 was 317.0 nm, likely a bathochromic shift that resulted from the solvent system (concentrated H2SO4). This is supported by the change in color observed (red to a bluish-red or purple shade). Correlation can be made between the experimental data and reported data for PR 146 (Scherrer et al., 2009; Schulte et al., 2008). Pigment Red 146 exhibits bands characteristic of a monoazo. Specifically, the C–N symmetric stretch at 1157 cm−1 and the N═N stretching at 1426 and 1449 cm−1. In addition, the characteristic bands associated with naphthalene can be found at 955, 1363, 1552, and 1581 cm−1. CI CH3 O

O CONHC6H5 O NH N O CH3

Figure 10.2  ​Pigment Red 146.

CH3

NH O

400 Pigment Red 146 normal Raman 488 nm

1584.2

1553.4

1489.7 1511.1

1448.7

1336 1334.7

239

1581.9

1552.3

1485.1 1508.3

1448.7

1363.7

1159.1

1283.3 Pigment Red 146 SERS 488 nm

1157.7

600

957.65

800

955.79

927.75

1000

1047.2

1200

1282.4

1400

1365.7

Part 2—The Chemical Analysis of Modern Tattoo Inks

200 0 600

1000

800

1200

1400 1600 Intensity/Raman shift (cm–1)

Figure 10.3  ​Comparison of Pigment Red 146 obtained with normal Raman (red) and SERS (green), λ0 = 488 nm.

Pigment Red 170 (Figure 10.4) Bands were resolved with Raman spectra at all four excitation wavelengths. The best normal Raman spectrum was with λ0 = 633 nm. The spectrum obtained with SERS corresponds to the bands observed with the normal Raman spectrum at λ0 = 488 nm. Substantial signal enhancement was observed when going from normal Raman to SERS as well as resolution of bands not observed in the normal Raman spectrum (Figure 10.5). The FT-IR/ ATR spectrum generated a number of well-resolved peaks. With regard to UV/Vis, the absorbance maximum of Pigment Red 170 was 312.50 nm, similar to that of Pigment Red 146. Correlation can be made between the experimental data and reported data for PR 170 (using Scherrer et al., 2009; Vandenabeele et al., 2000). Pigment Red 255 Pigment Red 255 (Figure 10.6) is classified as a polycyclic diketopyrrolo-­ pyrrole, and has a structure different from the azo pigments that characterize H5C2O NH O H2NOC

Figure 10.4  ​Pigment Red 170.

NH N

O

0

1486.7 1510.5

1550.3 1548.3

1451 1449.1

1384.8 1360.1

1242.3

1507.3

Pigment Red 170 SERS 488 nm

1282.2

1105.9

1160.4

963.76

1013.8 1047.3

730.05

961.72

500

609.95

1000

925.9

1500

1162.7

2000

1286.3

1361.8

2500

1602.9

Forensic Analysis of Tattoos and Tattoo Inks

1604.8

240

Pigment Red 170 normal Raman 488 nm

400

600

800

1000

1200

1400 1600 Intensity/Raman shift (cm–1)

Figure 10.5  ​Comparison of Pigment Red 170 obtained with normal Raman (red) and SERS (green), λ0 = 488 nm.

many of the red pigments. Bands were resolved with normal Raman spectra with all three excitation wavelengths. The best normal Raman spectrum was with λ0 = 785 nm. The spectrum obtained with SERS corresponds to the peaks observed with the normal Raman spectrum at λ0 = 488 nm. Signal enhancement was observed when going from normal Raman to SERS (Figure 10.7). The FT-IR/ATR spectrum generated a number of well-resolved peaks. With regard to UV/Vis, the absorbance maximum of Pigment Red 255 was 521.50 nm. This absorbance shift to a longer wavelength is in contrast to the apparent color change observations in which the red/orange color of Pigment Red 255 changes to a yellow color upon introduction of concentrated H2SO4. Correlation can be made between the experimental data and reported data for PR 255 (Scherrer et al., 2009). Evaluation of the spectra of Pigment Red 255 exhibits bands characteristic of ring breathing (in the region of 930–1052 cm−1), C═C stretching (in the region of 1560–1602 cm−1) and amide III and I bands at 1309 cm−1 and 1661 cm−1, respectively.

O NH O

Figure 10.6  ​Pigment Red 255.

NH

1629.7

1128.9

1049.6

1002.4

1660.4

1344.3

1028.1 1045.3

926.8

2000

1558.2 1582.4

Pigment Red 255 SERS 488 nm 997.48

4000

928.3

6000

1098.1

8000

241

1601.8

1294

1400

10,000

1433.2

Part 2—The Chemical Analysis of Modern Tattoo Inks

0 Pigment Red 255 normal Raman 488 nm 800

900

1000

1100

1200

1300

1400

1500 1600 1700 Intensity/Raman shift (cm–1)

Figure 10.7  ​Comparison of Pigment Red 255 obtained with normal Raman (red) and SERS (green), λ0 = 488 nm.

Pigment Orange 16 (Figure 10.8) Raman bands were resolved with Raman spectra at λ0 =  633, 785, and 1064  nm. Overwhelming fluorescence was observed with λ0 = 488 nm and no useful data were obtained at this excitation wavelength. The spectrum obtained with SERS corresponds to the bands observed with the normal Raman spectrum at λ0 = 633 and 785 nm. Substantial signal enhancement was observed when going from normal Raman to SERS with λ0 = 488 nm since no bands were observed in the normal Raman spectrum (Figure 10.9). The FT-IR/ATR spectrum generated a number of well-resolved peaks. With regard to UV/Vis, the absorbance maximum of Pigment Orange 16 was 541.0 nm, likely a bathochromic shift that resulted from the concentrated H2SO4. This is supported by the change in color observed (orange to a reddish pink shade). No reference Raman spectra could be found for Pigment Orange 16 in the literature. The following major peaks are reported (assigned very strong [vs] and strong [s] according to peak intensity) for the spectrum with λ0 = 785 nm: 1601.8vs, 1397.3s, 1323.5vs, 1259.6s, 1123.4s, 669.65s, 371.07s, 120.07s (Figure 10.10). O H N

N O

N O

O N

O N O

Figure 10.8  ​Pigment Orange 16.

N H

242

Forensic Analysis of Tattoos and Tattoo Inks

70,000 60,000 50,000 40,000 30,000 20,000 10,000 400

600

800

1000

1200

1400

1600

8000

1627.6 1645.9

1501.2 1545.8 1557.2

1447.9

1173.5

1113.3

1062.7

998.31

924.03 949.61

696.61

613.1 643.77

464.33

9000

524.74

10,000

1323.7

1261.3

11,000

1394.7

1600.9

200

Pigment Orange 16 SERS 488 nm

400

600

800

1000

1200

1400 1600 Intensity/Raman shift (cm–1)

Figure 10.9  Comparison of Pigment Orange 16 obtained with normal Raman

4000

1601.8

1323.5

(top spectrum) and SERS (bottom spectrum), λ0 = 488 nm.

1660.8

1533.1 1561.7

1471.8

1397.3

1241.8 1259.6 1274.6 1305.7

1175.8

1123.4 1000.2

912.99 927.63 950.76

613.25 623.92 669.65

526.74

371.07

304.02

1000

184.04

2000

120.07

3000

0 200

400

600

800

1000

1200

1400

1600

Figure 10.10  ​Pigment Orange 16, λ0 = 785 nm. (Intensity/Raman shift [cm−1].)

Part 2—The Chemical Analysis of Modern Tattoo Inks

243

Pigment Orange 34 (Figure 10.11) Bands were resolved with Raman spectra with all four excitation wavelengths (Figure 10.12). The spectrum obtained with SERS corresponds to the bands observed with the normal Raman spectra. There was not any apparent signal enhancement observed when going from normal Raman to SERS. The FT-IR/ATR spectrum generated a number of well-resolved peaks. With regard to UV/Vis, the absorbance maximum of Pigment Orange 34 was 517.0 nm, likely a bathochromic shift that resulted from the concentrated H2SO4. This is supported by the change in color observed (orange to a reddish pink shade). Correlation can be made between the experimental data and reported data for PO 34 (Colombini and Kaifas, 2010; Scherrer et  al., 2009; Schulte et al., 2008). Pigment Orange 34 differs from pigment orange 16 with the presence of two methyl groups, with each group found on the outer-most rings located N N N O

N CI

CI

N

O N N N

1596.7

Figure 10.11  ​Pigment Orange 34. 2500

2000

1537.3

1420

1478.9

1286.9 1297.7

1237.2

1159.1

1048.6

997.93

915.24

767.97

669.25

539.93

290.94

500

122.6

1000

368.76 393.13

1272.7

1500

0 200

400

600

800

1000

1200

1400

1600

Figure 10.12  ​Pigment Orange 34, λ0 = 785 nm (Intensity/Raman shift [cm−1]).

An interesting feature of the above Raman spectrum for PO 34 is the appearance of evenly spaced, bands of relative intensity. This may be due to the high molecular symmetry or the fundamental and overtones of a vibration (Franck-Condon scattering).

244

Forensic Analysis of Tattoos and Tattoo Inks

200,000

150,000

Pigment Orange 34, 785 nm

100,000 Pigment Orange 34, 488 nm 50,000 Pigment Orange 34, 633 nm 200

400

600

800

1000

1200

1400 1600 Intensity/Raman shift (cm–1)

Figure 10.13 ​ Comparison of Pigment Orange 34 at different excitation wavelengths.

para to the rest of the molecule. Pigment Orange 34 exhibits bands characteristic of a disazo. Specifically, the C–N symmetric stretch at 1159 cm−1 and the N═N stretching at 1420 cm−1. A band at 1596 cm−1 is characteristic of the C═C (ring breathing) stretch. Pigment Orange 34 exhibited well-resolved peaks across all excitation wavelengths. When comparing the three normal Raman spectra, it is apparent that using the 633 nm (red) laser resulted in the most peaks being resolved and the highest intensity peaks followed by the 785 nm (red/near IR) laser (Figure 10.13). Pigment Orange 62 Bands were resolved with normal Raman spectra with all three excitation wavelengths. The spectrum obtained with SERS corresponds to the bands observed with the normal Raman spectra. There was not any apparent signal enhancement observed when going from normal Raman to SERS. The FT-IR/ ATR spectrum generated a number of well-resolved peaks. With regard to UV/Vis, the absorbance maximum of Pigment Orange 62 was 401.5 nm, likely a hypsochromic shift that resulted from the concentrated H2SO4. This is supported by the change in color observed (orange to a yellowish shade). Correlation can be made between the experimental data and reported data for PO 62 (Scherrer et al., 2009). Pigment Orange 62 (Figure 10.14) exhibits bands characteristic of a monoazo. Specifically, the C–N symmetric stretch at 1164 cm−1 and the N═N stretching at 1403 cm−1. In addition, bands likely associated with the double annulated structure can be found at 1336 and 1600 cm−1. Pigment Orange 62

Part 2—The Chemical Analysis of Modern Tattoo Inks CH3 N NH

O2N

245

O NH

O NH HN

O

Figure 10.14  Pigment Orange 62.

100,000

Pigment Orange 62, 785 nm

80,000

60,000 Pigment Orange 62, 488 nm 40,000

20,000

Pigment Orange 62, 633 nm 200

400

600

800

1000

1200

1400 1600 Intensity/Raman shift (cm–1)

Figure 10.15 Comparison of Pigment Orange 62 at different excitation wavelengths.

exhibited well-resolved peaks across all three excitation wavelengths. When comparing the three spectra, it is apparent that using the 633 nm (red) laser resulted in the most bands being resolved and the highest intensity peaks followed by the 785 nm (red/near IR) laser (Figure 10.15). Pigment Yellow 3 Bands were resolved with normal Raman spectra with all three excitation wavelengths. The spectrum obtained with SERS corresponds to the bands observed with the normal Raman spectra. There was not any apparent signal enhancement observed when going from normal Raman to SERS. The FT-IR/ ATR spectrum generated a number of well-resolved peaks. With regard to UV/Vis, Pigment Yellow 3 dissolved in concentrated H2SO4 produced a yellow color, with a corresponding absorbance maximum of 424.5 nm. No major shifts were observed. Correlation can be made between the experimental data and reported data for PY 3 (Colombini and Kaifas, 2010; Scherrer et al., 2009; Schulte et al., 2008; Vandenabeele et al., 2000).

246

Forensic Analysis of Tattoos and Tattoo Inks CI

NO2 HN

N

CI

H3C

NH O

O

Figure 10.16  ​Pigment Yellow 3.

Pigment Yellow 3 (Figure 10.16) exhibits bands characteristic of a monoazo. Specifically, the C–N symmetric stretch at 1140 cm−1, the C–N symmetric bend at 1170 and 1191 cm−1, and the N═N stretching at 1387 cm−1. Nitro group stretching can be found at 825, 1336, and 1566 cm−1. Amide III and I bands can be found at 1244 cm−1 and 1675 cm−1, respectively. The bands located at 650 cm−1 and 709 cm−1 are due to the C–Cl stretching vibrations. Pigment Yellow 3 exhibited well-resolved peaks across all three excitation wavelengths. When comparing the three spectra, it is apparent that using the 488 nm (green) laser resulted in the most peaks being resolved and the highest intensity peaks followed by the 633 nm (red) laser (Figure 10.17). This is likely due to the resonance effects; recall the absorbance maximum of Pigment Yellow 3 was 424.5 nm in the UV/Vis spectrophotometer. Pigment Yellow 73 Bands were resolved with normal Raman spectra with all three excitation wavelengths. The spectrum obtained with SERS corresponds to the bands Pigment Yellow 3, 785 nm 8000

6000 Pigment Yellow 3, 488 nm 4000 Pigment Yellow 3, 633 nm 2000

200

400

600

800

1000

1200

1400 1600 Intensity/Raman shift (cm–1)

Figure 10.17  Comparison of Pigment Yellow 3 at different excitation wavelengths.

Part 2—The Chemical Analysis of Modern Tattoo Inks

247

CI

NO2 HN

N

O

CH3

NH

H3C O

O

Figure 10.18  ​Pigment Yellow 73.

observed with the normal Raman spectra. There was not any apparent signal enhancement observed when going from normal Raman to SERS. The FT-IR/ ATR spectrum generated a number of well-resolved peaks. With regard to UV/Vis, Pigment Yellow 73 dissolved in concentrated H2SO4 produced a yellow color, with a corresponding absorbance maximum of 428.0 nm. No major shifts were observed. Correlation can be made between the experimental data and reported data for PY 73 (Ropret et al., 2007; Scherrer et al., 2009). Pigment Yellow 73 (Figure 10.18) exhibits bands characteristic of a monoazo. Specifically, the C–N symmetric stretch at 1137 cm−1, the C–N symmetric bending at 1197 cm−1, and the N═N stretching at 1390 cm−1. Nitro group stretching can be found at 824, 1335, and 1565 cm−1. Amide III and I bands can be found at 1249 cm−1 and 1676 cm−1, respectively. Pigment Yellow 83 (Figure 10.19) Bands were resolved with normal Raman spectra with all three excitation wavelengths. The spectrum obtained with SERS corresponds to the bands observed with the normal Raman spectra. Signal enhancement was observed when going from normal Raman to SERS as well as resolution of peaks not observed in the normal Raman spectrum (Figure 10.20). The FT-IR/ATR spectrum generated a number of well-resolved peaks; PY 83 contains a large band from about 1450–1500 cm−1, which is due to the strong N═N azo O O

N

O

NH

CI

O

CI N

N CI

Figure 10.19  ​Pigment Yellow 83.

N O

O

CI

HN

O O

Forensic Analysis of Tattoos and Tattoo Inks 1593.7

248 14,000

662.72

2000

1153.4

Pigment Yellow 83 normal Raman 488 nm 539.42

4000

920.4 923.62

6000

0 Pigment Yellow 83 SERS 488 nm 600 800

1000

1200

1596.3 1527.5

1400.4 1398.3

1222.5

8000

1254.3

1253.8

10,000

1289.8 1290.1 1334.6

12,000

1400 1600 Intensity/Raman shift (cm–1)

Figure 10.20  ​Comparison of Pigment Yellow 83 obtained with normal Raman (red) and SERS (green), λ0 = 488 nm.

vibrations. In addition, the series of peaks at around 1180–1310 cm−1 indicates a disazo, as well as the three peaks located around 850–980 cm−1. With regard to UV/Vis, Pigment Yellow 83 dissolved in concentrated H2SO4 produced an orange color, with an absorbance maximum of 487.0 nm. This color shift observed is consistent with the bathochromic shift absorbed instrumentally. Correlation can be made between the experimental data and reported data for PY 83 (Scherrer et al., 2009; Schulte et al., 2008; Vandenabeele et al., 2000). Pigment Yellow 83 exhibits bands characteristic of a disazo. Specifically, the N═N stretching at 1400 cm−1. A band at 1596 cm−1 is characteristic of the C═C (ring breathing) stretch. A band representing the C–Cl stretching is present at 662 cm−1 and symmetric C–O–C stretching band is present at 920 cm−1. Pigment Yellow 151 (Figure 10.21) Bands were resolved with normal Raman spectra with all three excitation wavelengths. The spectrum obtained with SERS corresponds to the bands CH3 O N NH

NH O

O OH

Figure 10.21  ​Pigment Yellow 151.

NH HN

O

Part 2—The Chemical Analysis of Modern Tattoo Inks

249

observed with the normal Raman spectra. Signal enhancement was observed when going from normal Raman to SERS (Figure 10.22). The FT-IR/ATR spectrum generated a number of well-resolved peaks. With regard to UV/ Vis, the absorbance maximum of Pigment Yellow 151 was 272.50 nm, likely a hypsochromic shift that resulted from the concentrated H2SO4. Correlation can be made between the experimental data and reported data for PY 151 (Colombini and Kaifas, 2010; Ropret et al., 2007; Scherrer et al., 2009). Pigment Yellow 151 exhibits bands characteristic of a monoazo. Specifically, the C–N symmetric stretch at 1143 cm−1 (and 1600 cm−1) and the N═N stretching at 1386 cm−1. In addition, bands likely associated with the double annulated structure can be found at 1579 and 1600 cm−1. Amide III and I bands can be found at 1247 and 1651 cm−1, respectively.

8000

Pigment Yellow 151 normal Raman (488 nm) Pigment Yellow 151 SERS (488 nm)

6000

4000

2000

0

552.8 571.66 585.86 613.87 660.27 708.75

474.32

386.63

2000

1712.1

1712.8

1600 1800 Intensity/Raman shift (cm–1) 1454.1 1495.7 1514.7 1567.6 1588.6 1601.8 1626.5 1653.2

1247.7 1291.3 1314.3 1325.4 1387.8

1132.4 1144.2 1153.7 1200.4

1386.2

Pigment Yellow 151 normal Raman (488 nm) 133.24 171.34 196.37

4000

1400

1453.3 1492.7 1512.4 1566.2 1579.4 1600.8 1626.1 1651.8

6000

1200

1085.1 1131.1 1143.8 1152.7 1200.3 1247.3 1289.3 1312.9 1322.1

956.74

875.63

1022.9

1000

956.74

800

709.13

550.75 586.17 614.18

474.72

388.13

8000

600

Pigment Yellow 151 SERS (488 nm) 197.85 225.32

10,000

136.12

12,000

400

1021.5

200

0 200

400

600

800

1000

1200

1400

1600

1800

Intensity/Raman shift (cm–1)

Figure 10.22  ​Comparison of Pigment Yellow 151 obtained with normal Raman

(red) and SERS (green), λ0 = 488 nm. The top window is displaying the spectra in “overlaid” form to demonstrate increased signal from normal (red) to SERS (green) and the bottom window displays the spectra in “stacked” form to demonstrate band location correlations.

250

Forensic Analysis of Tattoos and Tattoo Inks

Pigment Green 7 Bands were resolved with Raman spectra at all four excitation wavelengths. There was not any apparent signal enhancement observed when going from normal Raman to SERS. The FT-IR/ATR spectrum generated a number of wellresolved peaks. With regard to UV/Vis, absorbance maxima for Pigment Green 7 dissolved in concentrated H2SO4 were observed at 859.50 and 815.0 nm. This was an obvious absorbance shift (bathochromic) from the purple region to the near infrared region, which is consistent with that reported in the article by Billmeyer et al. (1981). Correlation can be made between the experimental data and reported data for PG 7 (Scherrer et al., 2009; Schulte et al., 2008). Pigment Green 7 (Figure 10.23) exhibited well resolved bands across all three excitation wavelengths. Interestingly, the spectra were quite different with a change in excitation wavelength, which is due to the resonance effects resulting from the Δλ0 on the molecular structure of the phthalocyanine (Figure 10.24). This is important in that it not only lends support to the CI

CI

CI

CI

CI

CI

N CI

CI

N

N Cu

N

N N

N N

CI(3–4)

CI(3–4)

200

400

600

1000

1200

1522.3 1491.3

1436.6

1534.3

1375.9 1414.7 1379.3

1277.6

1334.2

1543.2

1322.7

1270.7

1198.0 1205.6

1199.7

1073.6

813.93 843.71

800

1079.2

640.6

505.59 541.92

288.84

193.45

Pigment Green 7, 633 nm 2000

973.35

682.11

4000

736.34 771.33 813.39

640.1

505.15

347.56 368.41

289.8

235.22

6000

146.82 162.72

Pigment Green 7, 488 nm

736.16 769.1

680.77

8000

736.79 760.91

Pigment Green 7, 785 nm 106.39 140.77 160.89 196.11

10,000

681.69

Figure 10.23  Pigment Green 7.

1600 1400 Intensity/Raman shift (cm–1)

Figure 10.24  ​Comparison of Pigment Green 7 at different excitation wavelengths.

Part 2—The Chemical Analysis of Modern Tattoo Inks

251

assertion that all reported Raman spectra should have the corresponding λ0 listed, but it indicates that comparisons between two or more spectra should be done where the same λ0 was used to generate the spectra. Bands characteristic of the breathing and deformations of the phthalocyanine TBP nucleus can be found at around 680 cm−1 and in the region from about 750 to 800 cm−1. The band located at around 230–235 cm−1 corresponds to the N–Cu metal bond. As the excitation wavelength changes, the relative ratios of these bands associated with the TBP nucleus also change. In some instances, the bands may not even be resolved above the background. The band located around 1520–1535 cm−1 remains dominant in the spectra and can be attributed to the ring breathing of the molecule. Pigment Blue 15, 15:1, 15:2, 15:3 Bands were resolved with normal Raman spectra with all three excitation wavelengths. Only Pigment Blue 15 (Figure 10.25) was available for SERS. There was not any apparent signal enhancement observed when going from normal Raman to SERS. The FT-IR/ATR spectrum generated a number of well-resolved bands (Note: there was a very small amount of Pigment Blue 15 available for FT-IR/ATR. Spectral quality was not very high for Pigment Blue 15, but peaks were still resolved). With regard to UV/Vis, absorbance maxima for Pigment Blue 15 dissolved in concentrated H2SO4 were observed at 791.0 and 700.50 nm. This was an obvious absorbance shift (bathochromic) from the orange region to the red/near infrared region, which is consistent with that reported in the article by Billmeyer et al. (1981). Correlation can be made between the experimental data and reported data for PB 15 (Scherrer et al., 2009). Correlation between reported spectra and experimental spectra for the polymorphs of pigment blue were also made. In comparing experimental spectra with that in the literature, it became apparent that, while in most cases, band locations were relatively consistent with changing excitation wavelength (although variation in

N N

N Cu

N N

N

Figure 10.25  ​Pigment Blue 15.

N N

252

Forensic Analysis of Tattoos and Tattoo Inks

band presence/absence can be seen), the excitation wavelength used would affect the relative band intensities (Figure 10.26). This could be problematic in interpretation when comparing spectra of the same substance that were generated with different excitation wavelengths. When individuals report intensities in the literature (e.g., vs, s, s-m, etc.), an analyst should bear in

174.2

256.79 233.59

482.73

847.75 829.26

774.68 746.05

1036.2 1006.8

1192 1142.3 1127.4 1106.5

1334.4 1306.2

500

1478.2 1447.3 1406.6

1602.4 1584.9

1000

595.07

1500

679.28

1519.8

Pigment Blue 15, 488 nm

0 1000

800

594.26

949.75

1209.2 1187.9 1140.4 1105.9

1516.4 1443.9

1500

1332.7 1302.7

2500 Pigment Blue 15, 785 nm

2000

600

400 200 Intensity/Raman shift (cm–1)

256.46 232.73

1200

481.38

1400

677.4

1600

744.97

1800

1000

500

256.46 232.73

400 200 Intensity/Raman shift (cm–1)

174.2

256.79 233.59

774.68 746.05

847.75 829.26

949.75 1036.2 1006.8

1332.7 1302.7

1209.2 1187.9 1140.4 1105.9 1192 1142.3 1127.4 1106.5

500

1334.4 1306.2

1000

1602.4 1584.9

1500

1478.2 1447.3 1443.9 1406.6

1515.1 1519.8

Pigment Blue 15, 785 nm

594.26

2500 2000

600

481.38

800

482.73

1000

595.07

1200

677.4

1400

744.97

1600

679.28

1800

0 Pigment Blue 15, 488 nm 1800

1600

1400

1200

1000

800

600

400 200 Intensity/Raman shift (cm–1)

Figure 10.26  ​Pigment Blue 15 spectra λ0 = 488 nm (top spectrum) and λ0 = 785 nm

(middle spectrum) and both spectra overlaid. (Note: Spectra are reversed for comparison to reference spectrum presented in Scherrer.)

Part 2—The Chemical Analysis of Modern Tattoo Inks

253

mind that these values are subjective and will vary depending on the excitation wavelength. This variation in Raman spectra with a change in excitation wavelength can be attributed to resonance effects, specifically selective enhancement from resonance with different electronic states. It is reported that phthalocyanine molecules have a B (or Soret) band in the blue region of the absorption spectrum and a Q (π → π* transition) band in the red region of the absorption spectrum. The B and Q bands are associated with vibronic bands and the use of visible excitation wavelengths in these regions (blue and red, respectively) will give rise to resonance or pre-resonance enhancements (Bovill et  al., 1986, p. 569). The metal ion incorporated into the porphyrin ring system can also affect the resultant spectra and band locations. The band located around 1520–1530 cm−1 remains dominant in the spectra and can be attributed to the ring breathing of the molecule (C–N). Bands characteristic of the breathing and deformations of the phthalocyanine TBP nucleus can be found at around 680 cm−1 (C–N–C, N–C, N–C–C) and in the region from about 750 to 800 cm−1 (C–N–C, Cu–N). The band located at around 230–235 cm−1 corresponds to the N–Cu metal bond. As the excitation wavelength changes, the relative ratios of these bands associated with the TBP nucleus also change. In some instances, the bands may not even be resolved above the background. Copper phthalocyanine is a planar molecule consisting of 57 atoms. It has 165 normal vibrations and is in the symmetry group D4h. The following irreducible representations are reported (Basova and Kolesov, 2000, p. 771):

Γ vib = 14A1g +13A 2g +14B1g +14B2g +13E g + 6A1u + 8A 2u

+ 7B1u + 7B2u + 28E u

in which the A1g, B1g, and B2g modes are Raman active and the A2u and Eu modes are infrared active (Li et al., 2005, p. 192), respectively. Experimental and calculated vibrational and absorption spectra of the phthalocyanines and their metal complexes have been reported in the literature along with detailed assignment of vibrational modes (Basova and Kolesov, 2000; Bovill et  al., 1986; Li et  al., 2005; Liu et  al., 2007). Basova et  al. report, “…some contradictory assumptions concerning the assignments of the bands in (various phthalocyanines) still exist. The agreement between the data of symmetry assignments of the bands in IR spectra of CuPc obtained by different authors is good, while the assignments in the Raman spectra are often very different” (Basova et al., 2009, p. 2081). The authors further add that the discrepancies in Raman band assignments are largely due to the lack of experimental support of the theoretical, calculated data. Evaluation of the data obtained by Basova et  al. (2009) correlates to the data reported by Bovill et  al. in 1986 (concerning α copper phthalocyanine) and Li et al. in 2005. It is important to

254

Forensic Analysis of Tattoos and Tattoo Inks

25 20 15 10 5 0 500

1000

1500

2000

2500

Figure 10.27  ​Characteristic fluorescence superimposed on a blue tattoo ink containing copper phthalocyanine.

note that with regard to experimental data, the authors of the various studies report the use of different excitation lasers (ranging in the blue, green, and red regions), with some authors not specifically reporting the λ0 used to generate their experimental data (they instead refer the reader to the literature in which the experimental data was acquired; see Li et al., 2005 and Liu et al., 2007). Copper phthalocyanine is described as “unusual” in regard to the fact that there is an increase in observed fluorescence with an increase in excitation wavelength (contrary to the tendency of fluorescence to decrease as the source approaches near infrared wavelength status). This fluorescence displays itself in a characteristic manner, and can be a means for preliminary identification of the copper phthalocyanines (blues and greens). It is believed that this phenomenon is due to the presence of the copper transition metal (Figure 10.27). Pigment Violet 23α (Figure 10.28) Bands were resolved with normal Raman spectra with λ0 = 488 nm. Overwhelming fluorescence was observed with λ0 = 633 and 785 nm, and

CH3

CI N

O

N O

N CI

Figure 10.28  Pigment Violet 23.

N

CH3

500

1480.2 1480.8

1326.7

1406.7 1404.8

1166.1

1339.4

1261.8

1500 1000

1283.8

2000

255

1166.8

928.26

1046.9

2500

1128.6

3000

1287.3

Part 2—The Chemical Analysis of Modern Tattoo Inks

Pigment Violet 23α SERS 488 nm Pigment Violet 23α normal Raman 488 nm

0 700

800

900

1000

1100

1200

1300

1400 1500 Intensity/Raman shift (cm–1)

Figure 10.29  Comparison of Pigment Violet 23α obtained with normal Raman (red) and SERS (green), λ0 = 488 nm.

no useful data were obtained at these excitation wavelengths. No spectrum was generated using the FT-Raman, even after mixing the pigment with KBr in an effort to minimize sample heating and reduce fluorescence. The spectrum obtained with SERS corresponds to the bands observed with the normal Raman spectrum at λ0 = 488 nm. Signal enhancement was observed when going from normal Raman to SERS as well as resolution of bands not observed in the normal Raman spectrum (Figure 10.29). The FT-IR/ATR spectrum generated a few broad peaks. With regard to UV/ Vis, Pigment Violet 23α underwent a hypsochromic shift when dissolved in concentrated H2SO4, the absorbance maximum being located at 317 nm. The color exhibited upon mixing the powder with the concentrated H2SO4 was a faint pinkish/red. No reference Raman spectra could be found for Pigment Violet 23α in the literature. The following major bands are reported for the spectrum with λ0 = 488 nm: 1481.1, 1406.8, 1329.2, 1283.5, and 1166.7. Pigment Violet 23β Bands were resolved with Raman spectra at all four excitation wavelengths. The spectrum obtained with SERS corresponds to the bands observed with the normal Raman spectra. Signal enhancement was observed when going from normal Raman to SERS (Figure 10.30). The FT-IR/ATR spectrum generated a number of well-resolved peaks. With regard to UV/Vis, Pigment Violet 23β underwent a hypsochromic shift when dissolved in concentrated H2SO4, the absorbance maximum being located at 313 nm. Correlation can be made between the experimental data and reported data for PV 23β (Scherrer et al., 2009).

Forensic Analysis of Tattoos and Tattoo Inks

1444.2

1590.3 1611.2 1587 1608.3

1346.8

1388.6 1427.4 1442.1

1255.7

1047.1

920.68

671.72

10,000

591.28 618.81

315.43

485.23 528.66

12,000 Pigment Violet 23β SERS 488 nm

1131.4 1167.2 1207.9

14,000

1392.4 1431.3

256

1400

1600

8000 6000

0 200

400

600

800

1000

1343.4

1204.6

1253

1164.3

917.96

671.33

591.04 618.13

2000

484.77

313.97

4000 Pigment Violet 23β normal Raman 488 nm

1200

Intensity/Raman shift (cm–1)

Figure 10.30  ​Comparison of Pigment Violet 23β obtained with normal Raman (red) and SERS (green), λ0 = 488 nm.

1480.8 1587 1608.3

1253

1164.3 1204.6

917.96

671.33

591.04 618.13

313.97

484.77 527.84

Pigment Violet 23β normal Raman (488 nm)

1343.4

1300.6

4000

2000

1406.7

Pigment Violet 23α normal Raman (488 nm)

1427.4 1442.1

6000

1339.4

1166.8

8000

1283.8

When comparing the Raman spectra of Pigment Violet 23α and Pigment Violet 23β, there are obvious differences. This indicates that it is possible to distinguish between the two polymorphs with Raman spectroscopy (Figure 10.31). It is interesting to note the difference between α and β forms with regard to the normal Raman spectra, the SERS spectra, the infrared spectra and the absorption spectra (Figure 10.32). These differences indicate that PV23α and PV23β likely differ in molecular structure or chemical constitution (e.g., isomorphism) and not just in crystal form of the same molecule, making the “polymorph” designation a misnomer. To test this hypotheses, crystal structure determination of α and β forms can be carried out by XRD. Additional evaluation of different molecular conformations (S-shape vs. linear, cis vs. trans) using density functional theory (DFT) calculations may

0 200

400

600

800

1000

1200

1400 1600 Intensity/Raman shift (cm–1)

Figure 10.31  ​Comparison of the normal Raman spectra of Pigment Violet 23α (green spectrum) and Pigment Violet 23β (red spectrum) [λ0 = 488 nm].

Part 2—The Chemical Analysis of Modern Tattoo Inks 1.000

257

n–π transitions

0.800

0.600 Pigment Violet 23β 0.400

0.200 π–π transition Pigment Violet 23α 0.000 200.00

300.00

400.00

500.00

600.00

Figure 10.32 Comparison of Pigment Violet 23α and β absorbance spectra. Note the additional band at 482 nm present in the β polymorph.

also enable the correlation of experimental spectral data with theoretical spectral data, allowing for the determination of correct molecular structure designations for PV23α and PV23β.

Results: Tattoo Inks Skin Candy The Skin Candy Tattoo Ink set was analyzed extensively due largely to the fact that it was the only tattoo ink set that had available pigment composition data. This allowed for attainment of pigment standards that could be analyzed with similar instrumental parameters, facilitating spectral comparisons. Of the analyses conducted on the Skin Candy tattoo inks, the following was considered: • Comparisons of the inks at different excitation wavelengths (Normal Raman-488 , 633, and 785 and FT-Raman-1064 nm) to evaluate the consistency of spectra with changing λ0. • Comparison of the pigment extractions at the different excitation wavelengths (Normal Raman-488, 633, and 785 and FT-Raman-1064 nm) to evaluate the consistency of spectra with changing λ0. • Comparison of the tattoo ink to the pigment extraction to evaluate any spectra differences between direct analysis of the ink and the pigment extracted from the ink. • Comparison of the tattoo ink to the pigment(s) listed on the bottle label to determine whether there is consistency with contents and

258

Forensic Analysis of Tattoos and Tattoo Inks

ingredients listed on the label. In addition, this comparison may aid in determining whether or not there are other materials within the tattoo ink. • Comparison of the tattoo ink analyzed with normal Raman and SERS to further evaluate and validate the use of SERS. • Comparison of the SERS spectrum of the pigment extraction of the tattoo ink and the SERS spectrum of the pigment(s) listed on the bottle label also to further evaluate and validate the use of SERS. • Comparison of absorbance spectra of the tattoo ink pigment extraction and the corresponding pigment standard. In addition to the above, information pertaining to the visual and microscopic examinations, UV/Vis, FT-IR (ATR), and XRF spectra were collected and reported in order to characterize and develop comprehensive tattoo ink spectral databases.* Overall, there were no substantial differences between the spectra of the tattoo inks and their pigment extractions. The extraction procedure was effective in separating the pigments and pigment additives such as titanium dioxide. In the case of the phthalocyanines (blue and green pigments), although considered organic pigments, this class exhibited extraction characteristics consistent with inorganic pigments due to the metal complex, which made the extraction procedure less efficient when carbon tetrachloride was used as a solvent. Candy Apple Red (Figure 10.33) Correlation was found between Candy Apple Red and Pigment Red 146 (Figure 10.34). Signal enhancement was observed when SERS was employed (Figure 10.35). XRF indicated the presence of titanium, chlorine, and iron. It is probable that the titanium is due to the presence of titanium dioxide. Red Hot (Figure 10.36) Correlation was found between Red Hot and Pigment Red 170 (Figure 10.37). Signal enhancement was observed when SERS was employed (Figure 10.38). XRF indicated the presence of chlorine and iron. Marz (Figure 10.39) Correlation was found between Marz and Pigment Orange 16 (Figure 10.40). XRF indicated the presence of titanium, chlorine, and iron. It is probable that the titanium is due to the presence of titanium dioxide.

* See Miranda (2012b).

Part 2—The Chemical Analysis of Modern Tattoo Inks

259

10,000 8000

Candy Apple Red tattoo ink 1064 nm

6000 Candy Apple Red tattoo ink 488 nm 4000 2000 0

Candy Apple Red tattoo ink 633 nm Candy Apple Red tattoo ink 785 nm 200

400

600

800

1000

1200

1400 1600 Intensity/Raman shift (cm–1)

Figure 10.33  ​Raman spectra of Candy Apple Red ink at different excitation

–600

Candy Apple Red tattoo ink 900 1000 800

1100

1200

1300

1581.9

1552.3 1554.9

1582.3 1582.4

1485.1 1508.3 1485.4 1508.4

1554.2

1448.7 1451.1

1486.1 1507.9

1451.1

1334.7

1363.7 1363.7 1363.9

1335.3

1282.4 1294.7

957.67

Candy Apple Red pigment extraction 1114.4

–400

958.36

–200

1113.7

200 Pigment Red 146 (Standard) 0

1157.7

400

1113.7

600

955.79

wavelengths.

1400 1500 1600 Intensity/Raman shift (cm–1) Excitation wavelength 488 nm

Figure 10.34  ​Normal Raman spectra of Candy Apple Red ink and pigment

Candy Apple Red normal Raman 900 1000 800

1100

1200

1400

1554.1

1554.3 1582.1

1608.3

1582.5

1482.7 1507.8 1486.1 1508.4

1427.7 1450.1

1363.7

1363.9

1293.3

1300

1428.5 1450.3

1218.8

1175.6

957.71

50

1278.3 1293.2 1317 1335.8

Candy Apple Red tattoo ink SERS

150 100

1265.8

1146.1

1218.8

1113.6

1147.2

200

1091.8 1114.2

250

956.7

300

1172.9

350

1320.8 1335.5

extraction compared to Pigment Red 146.

1500 1600 Intensity/Raman shift (cm–1) Excitation wavelength 488 nm

Figure 10.35  Normal Raman spectrum of Candy Apple Red ink compared to SERS spectrum of Candy Apple Red ink.

260

Forensic Analysis of Tattoos and Tattoo Inks

12,000 10,000 8000 6000

Red Hot tattoo ink 1064 nm

Red Hot tattoo ink 488 nm

4000 2000

Red Hot tattoo ink 633 nm

0 Red Hot tattoo ink 785 nm 200

400

600

800

1000

1200

1400 1600 Intensity/Raman shift (cm–1)

1604.9

1551.1

1362.1 1384.2

1420.3 1451.5 1488.2 1511.7

1286.8

1332.2

1164.6

1225.5 1243.5

1114.2

964.06

1010.9 1042.7

863.2

732.81

777.66

478.13 494.59 510.12 539.28 573.94 611.27

365.77

267.71

187.73

–40,000

1605.2 1604.8

1488.7 1511.8 1551.8

1362.4 1385.7 1420.6

1287.3

1333 1287.6

1226.9 1244.3

1165.3

964.5

733.3

779.2

611.96

478.67 495.13 510.91 540.24 574.8

258.72 268.28

422.79

Red Hot tattoo ink –20,000

1332.7 1362.8 1384.3 1421.2 1451.7 1488.7 1511.9 1551.3

1244.1

1165.2

1114.3 1115.3

964.98

1014.4 1015.2

728.59 733.49

777.57

422.08 452.46 477.66 494.92 510.07 540.21 574.22 612.25

334.75

0

Pigment Red 170 (Standard) 113.13

20,000

112.98

40,000

421.89

Figure 10.36  ​Raman spectra of Red Hot ink at different excitation wavelengths.

Red Hot pigment extraction 200

400

600

800

1000

1200

1400 1600 Intensity/Raman shift (cm–1) Excitation wavelength 633 nm

Figure 10.37  Normal Raman spectra of Red Hot ink and pigment extraction

50

600

800

1000

1595 1608.7

1452.9 1475.8 1487.3 1512.2 1453.5

1488.6 1503.2

1362.8

1346.8 1362.7

1287.6

1243.4 1242.8

1200

1209.3

1164.7 1108.6

963.74 964.25

Red Hot normal Raman 731.19

100

610.79

150

Red Hot tattoo ink SERS

608.55

200

1164.4

compared to Pigment Red 170.

1400 1600 Intensity/Raman shift (cm–1) Excitation wavelength 488 nm

Figure 10.38  Normal Raman spectrum of Red Hot ink compared to SERS spectrum of Red Hot ink.

Part 2—The Chemical Analysis of Modern Tattoo Inks

261

40,000 35,000 30,000

Marz tattoo ink 785 nm

25,000 20,000 Marz tattoo ink 1064 nm 15,000

Marz tattoo ink 633 nm

10,000

400

200

600

800

1000

1200

1400 1600 Intensity/Raman shift (cm–1)

1601.8 1660.8

1533.1 1561.7

1661.1

1397.5

1602

1661.2

1602 1533.2 1562.4 1533.7 1562.6

1397.3

1471.8

1397.7

1457.8 1472.8 1472.3

1124

1176.6

1242.7 1260.2 1275.2 1306.3 1324.1

1124.1

670.22 670.23

1176.7

613.67 624.4 613.69 624.75

527.35

305.58

120.59

371.6 371.58

527.6

–8000

304.82

–6000

Marz pigment extraction

120.76

–4000

184.19

–2000

181.64

0 Pigment Orange 16 (Standard)

1242.3 1260.1 1275.1 1292.3 1306.2 1323.9

1123.4

1000.2 1000.6 1000.5

1175.8

912.99 927.63 950.76 914.02 928.26 951.13 913.75 928.1 951.05

669.65

613.25 623.92

526.74

371.07

304.02

120.07

2000

184.04

4000

1241.8 1259.6 1274.6 1305.7 1323.5

Figure 10.39  ​Raman spectra of Marz ink at different excitation wavelengths.

Marz tattoo ink 200

400

600

800

1000

1200

1400 1600 Intensity/Raman shift (cm–1) Excitation wavelength 785 nm

Figure 10.40  Normal Raman spectra of Marz ink and pigment extraction compared to Pigment Orange 16.

Dolemite (Figure 10.41) A comparison of Dolemite and the reported pigment composition is described below. XRF indicated the presence of titanium and iron. It is probable that the titanium is due to the presence of titanium dioxide. According to the bottle label, Dolemite is supposed to contain Pigment Yellows 83 and 151. There is very little evidence to support the presence of PY 83, PY 151, or a mixture of the two (Figures 10.42 and 10.43). XRF did not disclose the presence of chlorine, which is found in PY83. Based on the literature, it appears that the bands present are more consistent with Pigment Yellow 74 (Colombini et al., 2010; Scherrer et al., 2009; Vandenabeele et al., 2000). Comparison between the spectrum of pigment yellow 74 (Figure 10.44) reported in Scherrer et al. (2009) with the experimental data demonstrates

262

Forensic Analysis of Tattoos and Tattoo Inks

10,000

8000 Dolemite tattoo ink 488 nm 6000

4000

Dolemite tattoo ink 1064 nm

2000 Dolemite tattoo ink 785 nm 0

400

200

600

800

1000

1400 1600 Intensity/Raman shift (cm–1)

1200

Figure 10.41 ​ Raman spectra of Dolemite ink at different excitation wavelengths.

1667.8

1596.2 1592.8

1489.6 1511.2

1400.9 1404.2

1580.5 1601.8

1490.3 1511.8 1549.6 1593.3 1495.1

1402.2 1438.8

1453.8

1387.3

1263.5 1297.8 1325.7 1352.4 1326 1352.3

1334.4

1247.3

1254.1 1290.5 1263.4

1159.4

1088.6

801.17

403.52

184.69

–1000 Pigment Yellow 83 –2000

1312.2

1159.3 1169.7

1067.7 1088.6

1018.1

919.34

661.87

536.22

1143.5

955.46

613.8

Pigment Yellow 151 (Standard)

0

1022.2

917.81 953.16

780.53 801.67 826.32 845.51

623.19 645.74

401.76

463.82

318.8

386.96

Dolemite tattoo ink

342.96

1000

359.71

142.43

2000

185.64 224.81 261.38

a correlation between 38 of the bands labeled in the spectrum of Dolemite (Figure 10.45). The effect of mixtures cannot be ruled out as an important factor in evaluating spectral data. Extraction of the Dolemite tattoo ink resulted in the visualization of three components, a white portion which is likely to be titanium dioxide, a large yellow portion and a small orange portion (Figure 10.46). Based upon the disproportionate amount of yellow and orange pigment, two scenarios are possible: the pigment detected for Dolemite was the yellow portion, with the small concentration of orange portion either being undetected or overwhelmed by the yellow; or the resultant spectra for Dolemite are a combination of the yellow and orange portions, with some spectral bands arising from the yellow portion and some spectral bands arising from the orange portion. As such, it is recommended that

Dolemite pigment extraction 200

400

600

800

1000

1200

1400

1600

1800

Intensity/Raman shift (cm–1) Excitation wavelength 785 nm

Figure 10.42  Normal Raman spectra of Dolemite ink and pigment extraction compared to Pigment Yellow 151 and Pigment Yellow 83.

Part 2—The Chemical Analysis of Modern Tattoo Inks

263

Dolemite tattoo ink (IR) Pigment Yellow 83 (IR) Pigment Yellow 151 (IR) 0.6

0.4

0.2

0 1400

1600

1200

1000

800 Absorbance/wavenumber (cm–1)

Figure 10.43  FTIR (ATR) spectra from the “fingerprint” region (1700–650 cm−1) of

Dolemite and Pigment Yellows 83 and 151. Note the lack of correlation of the pigment standards with the tattoo ink. Band assignments with infrared spectra similar to that done with Raman spectral data can be useful for providing information concerning the characteristic functional groups of the pigment molecules. For example, the disazo PY 83 (in blue) contains a large band from about 1450–1500 cm−1, which is due to the strong N═N azo vibrations. This band is also present, but much weaker in monoazo PY 151 and Dolemite (which is thought to be consistent with the monoazo PY 74). In PY 83, the series of peaks at around 1180–1310 cm−1 indicates a disazo, as well as the three peaks located around 850–980 cm−1.

O

O

O N N

O

N

HN O

O

1667.8

1438.8 1454.1 1459.1 1490.3 1499.1 1549.6 1511.8

1402.2

1200

500

1593.3

1352.4

1263.5 1143.8 1159.3 1169.7 1200.7 1245.5

1000

1297.8

917.81 953.16 1002.3 1018.1 1045.8 1067.7 1088.6

801.67 826.32 845.51

741.62 780.52

1000

600.68 623.19 645.74 661.19

185.64

318.8 359.71 401.76 442.76 463.82 496.24 523.26 539.02

1500

224.81 261.38

2000

142.43

2500

98.584

Dolemite tattoo ink (785 nm) 3000

1325.7

Figure 10.44  ​Pigment Yellow 74.

0 200

400

600

800

Figure 10.45  ​Dolemite tattoo ink showing band locations.

1400

1600

Intensity/Raman shift (cm–1)

264

Forensic Analysis of Tattoos and Tattoo Inks

Figure 10.46  ​Resultant extraction of Dolemite tattoo ink. Note the presence of three distinct color profiles—white (bottom), orange, and yellow (top).

an extraction or separation method be employed in order to determine the amount of pigments present and to isolate each pigment for subsequent qualitative spectroscopic analysis. In addition, the ratios of pigments (either relative ratios or more detailed quantitative analysis) may be a means to distinguish similar colors from different manufacturers or brands. Furthermore, Colombini and Kaifas state “PY83 is supposed to be containing some unknown percentage of PY1,” adding that this class of pigment is often used in mixtures, making them complex to study (Colombini and Kaifas, 2010, p. 18). Blisterine (Figures 10.47 and 10.48) A comparison of Blisterine and the reported pigment composition is described below. XRF indicated the presence of titanium and iron. It is probable that the titanium is due to the presence of titanium dioxide. According to the bottle label, Blisterine is supposed to contain Pigment Yellow 3 and Pigment Orange 34 (Figures 10.49 through 10.51). There is very little evidence to support the presence of PY 3 and PO 34. Based on the literature, it appears that the bands present are more consistent with Pigment Yellow 74 as seen with the Dolemite Tattoo Ink. In addition, no chlorine was detected by XRF, which is found in both PY3 and PO34. Comparison between the spectrum of Pigment Yellow 74 (Figure 10.44) reported in Scherrer et al. (2009) with the experimental data demonstrates

Part 2—The Chemical Analysis of Modern Tattoo Inks

265

10,000 8000 Blisterine tattoo ink 1064 nm 6000 4000 Blisterine tattoo ink 488 nm 2000 0 –2000

Blisterine tattoo ink 633 nm

Blisterine tattoo ink 785 nm 400 200

600

800

1000

1200

1400 1600 Intensity/Raman shift (cm–1)

–40,000

1667.6

1667.9

1245.4 1263.4 1298.8 1326.4 1352.8 1404.3 1422.8 1439.2 1459.4 1489.6 1511.8 1550.3 1592.4 1263.3 1298.3 1325.8 1352.7 1404.2 1422.7 1438.9 1459.3 1489.4 1511.8 1550.1 1592.4 1598.8

1159.9 1170.7

1245

1067.4 1088.7

1159.6 1170.3

929.79 926.83 953.16

1067.7 1089.2

802.27 801.72

701.01

600.78 623.84 645.57

524.2

360.76 402.23

–20,000

Blisterine normal Raman

185.05

0

601.22 624.51 646.06

185.74

360.23 403.17

20,000

524.91

Figure 10.47  Raman spectra of Blisterine ink at different excitation wavelengths.

Blisterine tattoo ink SERS 200

400

600

800

1000

1200

1400

1600

Intensity/Raman shift (cm–1) Excitation wavelength 488 nm

Figure 10.48  ​Normal Raman spectrum of Blisterine ink compared to SERS

800

1000

1667.7

1592.2 1592.8 1596.7 1613.8

1489.8 1511.7

1549.7

1537.3

1478.9

1404 1438.1 1420

1667.8

1243.3 1263.6 1298.2 1324.7 1329.7 1334.5 1352.3 1403.7 1244.9 1268.6 1297.8 1325.8 1352.4

1200

1464.6 1495.2

1188.6

1237.2 1272.7 1286.9 1297.7

1159.1 1139.7

1048.6

997.93

1036.5

915.24

767.97

669.25

600

856.82

400

746.32

200

–2000 Pigment Yellow 3

623.48 649.94

395.23 405.25 412.84

110 135.74

186.81 281.89

0 Pigment Orange 34 (Standard)

539.93

368.75 393.13

290.94

122.6

Blisterine pigment extraction 2000

1244.8 1275.9 1302.8 1309.7 1336.8 1386.1 1403.3

1158.3 1169.7 1159.3 1169.8

1066.8 1088.5

801.5 826.25

645.74

463.91

401.8

358.14

317.73

185.67

225.41 257.65

4000

107.5

6000 Blisterine tattoo ink

1067.2 1088.9

801.6 826.05

621.97 645.51

439.97 464.78

401.64

317.7

185.24 221.52 257.97

8000

359.79

spectrum of Blisterine ink.

1400 1600 Intensity/Raman shift (cm–1) Excitation wavelength 785 nm

Figure 10.49  ​Normal Raman spectra of Blisterine ink and pigment extraction compared to Pigment Orange 34 and Pigment Yellow 3.

400

200

600

800

1000

1400

1667.6

1594.7 1612.1

1560.8

1493.7

1418.1 1387.4

1535.7

1244.8 1263.2 1298.3 1325.8 1352.7 1404.2 1422.6 1438.9 1459.3 1489.3 1511.8 1549.9 1592.4 1598.8 1236.7 1271.9

1200

1297.7 1335.6

1226.2

1157.6

1067.2 1088.7

926.61

Pigment Yellow 3 (Standard) SERS

744.61

–500

1047.3

914.29

537.9

0

1099 1138.4

801.71

623.74 645.51

Pigment Orange 34 (Standard) SERS 369.09

500

184.85

1000

402.17

Blisterine tattoo ink SERS

1159.5 1170.3

Forensic Analysis of Tattoos and Tattoo Inks

926.77

266

1600

Intensity/Raman shift (cm–1) Excitation wavelength 488 nm

Figure 10.50  SERS spectra of Blisterine tattoo ink compared to Pigment Orange 34 and Pigment Yellow 3. Blisterine tattoo ink (IR) 0.7 Pigment Yellow 3 (IR) Pigment Orange 34 (IR) 0.6 0.5 0.4 0.3 0.2 0.1 0 1600

1400

1200

1000

800 Absorbance/wavenumber (cm–1)

Figure 10.51  ​Infrared spectra from the region of 1750–650 cm−1 of Blisterine

tattoo ink and Pigment Yellow 3 and Pigment Orange 34. Note the lack of correlation of the pigment standards with the tattoo ink.

a correlation between 34 of the bands labeled in the spectrum of Blisterine (Figure 10.52). Due to the resultant Raman data and subsequent comparison to pigment standards, it is apparent that the labeling on the Blisterine packaging does not correspond to the actual ingredients. An overlay of the Raman spectra for Dolemite and Blisterine demonstrates that they are similar in chemical composition (Figure 10.53), in addition to an overlay of the infrared spectra (Figure 10.54). Sassygrass (Figure 10.55) Additional bands were detected when using SERS (Figure 10.56). XRF indicated the presence of titanium, chlorine, iron, and copper. It is probable that

1400

Blisterine tattoo ink (785 nm) 1263.6

1200

267

1324.7 1329.7 1334.5 1352.3

Part 2—The Chemical Analysis of Modern Tattoo Inks

1667.7

1421.71403.7 1431.4 1437.2 1458.4 1511.8 1548.7 1592.2

1298.2

1017.6 1046.1 1066.8 1088.5 1125.5 1158.3 1169.7 1180.7 1243.3

917.03

780.84 801.6 826.05 845.77

400

600.39 623.31 645.51

600

317.92 359.79 401.64 441.05 464.38

800

98.16 107.07 185.24 222.99 258.18

1000

200 200

400

600

800

1000

1200

1400

1600

Intensity/Raman shift (cm–1)

Figure 10.52  Blisterine tattoo ink showing band locations. Blisterine tattoo ink (785 nm) 3000 Dolemite tattoo ink (785 nm) 2500 2000 1500 1000 500 0 200

400

600

800

1000

1200

1400

1600

Intensity/Raman shift (cm–1)

Figure 10.53  Overlay of Dolemite and Blisterine, Raman spectra. Blisterine tattoo ink (IR) Dolemite tattoo ink (IR) 0.6

0.4

0.2

0 1600

1400

1200

1000

800 Absorbance/wavenumber (cm–1)

Figure 10.54  ​Overlay of Dolemite and Blisterine, infrared spectra.

268

Forensic Analysis of Tattoos and Tattoo Inks

2500 2000

Sassygrass tattoo ink 1064 nm

1500 1000

Sassygrass tattoo ink 488 nm

500 0 Sassygrass tattoo ink 633 nm –500 Sassygrass tattoo ink 785 nm 200

400

600

800

1000

1200

1600

1400

Intensity/Raman shift (cm–1)

Figure 10.55  Raman spectra of Sassygrass ink at different excitation wavelengths.

the titanium is due to the presence of titanium dioxide and the chlorine and copper are indicative of Pigment Green 7. Many of the bands present in the Sassygrass tattoo ink correspond to the bands present in Pigment Green 7 (Figure 10.57). Because Sassygrass is a green tattoo ink, it is probable that the majority of the pigment is green, thus rendering it difficult to detect any other pigments present in trace quantities, such as the Pigment Orange 34 and Pigment Yellow 3 that are supposed to be present according to the ingredients listed on the label (Figures 10.58 and 10.59).

1667.2 1693.4 1686.8

1403.3 1422.8 1439.3 1488.9 1509.8 1548.7 1591.9 1404.3 1422.8 1438.7 1489.3 1511.8 1549.7 1592.2

1667.5

1262.2 1298.3 1331.3 1350.4

1159.4 1170.2

1067.9 1088.4

927.15

600.78 623.75 645.57

524.2

402.57

360.2

185.18

–40,000

801.71

0 Sassygrass normal Raman –20,000

1244.9 1263.2 1298.2 1325.7 1352.7

1159.7 1169.7 1213.2

1084.4

926.32

600.48 623.34 645.66 685.5

525.24

359.8 402.58

20,000

184.73

40,000

801.74

Tastywaves (Figure 10.60) XRF indicated the presence of titanium, chlorine, copper, and bromine. It is probable that the titanium is due to the presence of titanium dioxide and the

Sassygrass tattoo ink SERS 200

400

600

800

1000

1200

1400

1600

Intensity/Raman shift (cm–1) Excitation wavelength 488 nm

Figure 10.56  ​Normal Raman spectrum of Sassygrass ink compared to SERS spectrum of Sassygrass.

200

400

600

1000

1436.6

1534.3

1396 1426.7 1449.3 1478.4 1505.3 1536.7

1281.3

1338.2

1334.2 1379.3

1212 1079.2 1200

269

1277.6

1082.4

1205.6 800

973.35

640.6

505.59 541.92

288.84

193.45

–500

98.743

Pigment Green 7 (633 nm)

736.34 771.33 813.39

682.11

0

956.15 979.07

508.71 546.37

500

291.42 333.27

165.61 197.71

99.989

Sassygrass tattoo ink (633 nm)

642.94 677.31 684.75 740.36 776.16 818.15

Part 2—The Chemical Analysis of Modern Tattoo Inks

1400 1600 Intensity/Raman shift (cm–1)

Figure 10.57  ​Sassygrass tattoo ink compared to Pigment Green 7 standard.

chlorine, copper, and bromine are indicative of Pigment Green (Cu, Cl, Br). The presence of the bromine suggests Pigment Green 36 (in addition to or instead of Pigment Green 7) in which some of the chlorines are replaced with bromine (Figures 10.61 and 10.62). Bellbottom Blue (Figure 10.63) XRF indicated the presence of titanium and copper. It is probable that the titanium is due to the presence of titanium dioxide and the copper is indicative of Pigment Blue (Figure 10.64). UV/Vis data correlated to that of Pigment Blue 15. SRV Teal 2 (Figure 10.65) XRF indicated the presence of titanium, chlorine, and copper. It is probable that the titanium is due to the presence of titanium dioxide and the chlorine 200,000

Sassygrass tattoo ink

150,000 100,000 Sassygrass pigment extraction 50,000 0

Pigment Orange 34 (Standard) Pigment Yellow 3 (Standard)

–50,000 –100,000 Pigment Green 7 (Standard) 200

400

600

800

1000

1200

1400

1600

Intensity/Raman shift (cm–1) Excitation wavelength 633 nm

Figure 10.58  Normal Raman spectra of Sassygrass ink and pigment extraction compared to Pigment Orange and Pigment Yellow 3 and Pigment Green 7.

270

Forensic Analysis of Tattoos and Tattoo Inks Pigment Yellow 3 Pigment Orange 34 Pigment Green 7 Sassygrass 6

10

3.000

7

9

8

4

Abs.

3

2.000

400.00

nm.

600.00

800.00

2 2

11

3

5 42

3 5 7

0.000 210.00

4 6

8

9

5

4

6

6

7

7

5

8

2

1

1.000

900.00

Figure 10.59  ​U V/Vis spectra of Sassygrass and corresponding pigments (according to manufacturer).

and copper are indicative of Pigment Green and Pigment Blue (Figures 10.66 through 10.68). Muddy Water Blue (Figure 10.69) XRF indicated the presence of copper. The copper is indicative of Pigment Blue, which is consistent with the observations of the Raman spectra (Figure 10.70). UV/Vis data correlated to that of Pigment Blue 15. Ripple (Figure 10.71) XRF indicated the presence of titanium and chlorine. It is probable that the titanium is due to the presence of titanium dioxide. Spectra observed 800

600 Tastywaves tattoo ink 1064 nm

400

200

Tastywaves tattoo ink 488 nm Tastywaves tattoo ink 785 nm

200

400

600

800

1000

1200

1400

1600

Intensity/Raman shift (cm–1)

Figure 10.60 ​ Raman spectra of Tastywaves ink at different excitation wavelengths.

1482.1 1505.9 1550.7 1562.3 1506.5 1541.4 1550.1 1563

1483.7

1543.2

1491.8

1389.3 1423.8 1359.3 1890.1 1375.9

1414.7

1282.2

271

1282.7

1188.7 1200.8 1213.9 1189.7 1201.2 1214.5

1073.6

1199.7

1083.6 1084.1

823.27 823.83 813.93 843.71

685.8

741.37 773.02

680.77 736.16 769.1

640.1

505.15

347.56 368.41

2000

235.22

146.82 162.72

4000

289.8

6000 Tastywaves pigment extraction

686.24

644.21

576.07

511.16

330.35 352.37 370.24

8000

263.28

149.28 166.45

10,000 Tastywaves tattoo ink

741.79 773.42

613.35 643.61

445.78

510.57

12,000

334.59 349.39 370.95

148.4 165.36

14,000

235.14 264.03

Part 2—The Chemical Analysis of Modern Tattoo Inks

0 Pigment Green 7 (Standard) 200

400

600

800

1000

1200

1400

1600

Intensity/Raman shift (cm–1) Excitation wavelength 488 nm

Figure 10.61  Normal Raman spectra of Tastywaves ink and pigment extraction compared to Pigment Green 7.

Cl

Cl

Br Cl Br Cl

Cl N

N

N

N

Cu

N

N

N

Br

Cl Br Cl

N

Cl

Br

Cl Cl

Br

Figure 10.62  Pigment Green 36. 5000 4000 3000

Bellbottom Blue tattoo ink 488 nm

2000 1000 0 –1000

Bellbottom Blue tattoo ink 633 nm

Bellbottom Blue tattoo ink 785 nm

–2000 200

400

600

800

1000

1200

1400

1600

Intensity/Raman shift (cm–1)

Figure 10.63 ​Raman spectra of Bellbottom Blue ink at different excitation wavelengths.

1591 1610.5

1393.3 1412.5 1431 1452.2 1470.8 1484 1527.8

1590.6 1610 1584.9 1602.4

1406.6

1447.3 1478.2

1192

679.28

482.73

1306.2 1334.4

1519.8

1339.7

832.2 848.77

1209.8

776.86

829.26 847.75

681.25

595.38 595.07

484.6

234.71 257.75

Pigment Blue 15 (Standard) 233.59 256.79

1000

177.88

2000

Bellbottom Blue pigment extraction

174.2

3000

746.05 774.68

4000

1392.3 1411.2 1429.4 1451.3 1470.4 1483.1 1526.4

1308.8 1340.7

1108.8 1131.6 1108.6 1130.7 1144.4 1106.5 1127.4 1142.3

1207.6

1008.9 1039.2 1008.7 1038.7 1006.8 1036.2

832.74 847.75

777.25

447.18

235.25 257.72

143.11

485.16

Bellbottom Blue tattoo ink 5000

681.76

Forensic Analysis of Tattoos and Tattoo Inks 595.48 610.25

272

0 400

200

600

800

1000

1200

1400

1600

Intensity/Raman shift (cm–1) Excitation wavelength 488 nm

Figure 10.64 Normal Raman spectra of Bell Bottom Blue ink and pigment extraction compared to Pigment Blue 15. 16,000

SRV Teal 2 tattoo ink 785 nm

14,000 12,000 SRV Teal 2 tattoo ink 488 nm 10,000 8000

SRV Teal 2 tattoo ink 633 nm 200

400

600

800

1000

1200

1400

1600

Intensity/Raman shift (cm–1)

Figure 10.65  Raman spectra of SRV Teal 2 ink at different excitation wavelengths. 5000

SRV Teal 2 tattoo ink

4000 3000 2000 1000

SRV Teal 2 pigment extraction

Pigment Blue 15 (Standard)

0 –1000 –2000

Pigment Green 7 (Standard) 200

400

600

800

1000

1200

1400 1600 Intensity/Raman shift (cm–1) Excitation wavelength 488 nm

Figure 10.66  ​Normal Raman spectra of SRV Teal 2 ink and pigment extraction compared to Pigment Blue 15 and Pigment Green 7.

–2000

200

400

1000

1200

1390.7

1584.9 1602.4

1543.2

1491.3

1519.8

1482.3 1506.8 1529.8 1562.7

1457.3 1486 1507.1 1530.3 1563.6 1592.6 1613.3 1447.3 1478.2

1389.5 1406.6

1414.7

1306.2 1334.4

1338.1

1340.8

273

1375.9

1215.1 1200.9 1214.2 1199.7

1192

1040.6

800

1084.4 1108.6 1083.7

1006.8 1036.2

1073.6

772.55

685.9

823.46 829.26 847.75 813.93 843.71

746.05 774.68

679.28

600

680.77

640.1

505.15

347.56 368.41

289.8

235.22

–1000

146.82 162.72

0 Pigment Green 7 (Standard)

736.16 769.1

595.14

643.86

595.07

Pigment Blue (Standard)

482.73

1000

SRV Teal 2 pigment extraction 233.59 256.79

2000

174.2

3000

510.73

4000

1106.5 1127.4 1142.3

SRV Teal 2 tattoo ink

686.76

5000

597.49

Part 2—The Chemical Analysis of Modern Tattoo Inks

1400 1600 Intensity/Raman shift (cm–1) Excitation wavelength 488 nm

Figure 10.67  Normal Raman spectra of SRV Teal 2 ink and pigment extraction compared to Pigment Blue 15 and Pigment Green 7 (with peak labels).

4000

SRV Teal 2 tattoo ink (488 nm) Pigment Green 7 (488 nm) Pigment Blue 15 (488 nm)

3000

2000

1000

0 200

400

600

800

1000

1200

1400

1600

Intensity/Raman shift (cm–1)

Figure 10.68  Overlaid Raman spectra of SRV Teal 2 with Pigment Green 7 and

Pigment Blue 15. SRV Teal 2 does appear to exhibit bands present in both pigments. 2500 2000

Muddy Water Blue tattoo ink 1064 nm

1500 1000

Muddy Water Blue tattoo ink 488 nm

500 0 Muddy Water Blue tattoo ink 633 nm –500 Muddy Water Blue tattoo ink 785 nm 200

400

600

800

1000

1200

1400

1600

Intensity/Raman shift (cm–1)

Figure 10.69  Raman spectra of Muddy Water Blue ink at different excitation wavelengths.

1525.9

1391.7

1428.9 1450.8

1339.2

1108.8

1038.8

832.02

483.71

595.2

Muddy Water Blue pigment extraction 257.77

3000

681.23

4000

1588.1 1606.7 1590.4

1390.8 1408.5 1428.3 1449.2 1469.3 1479.7 1523.9

1308.3 1337.8

1205.3

1107.8 1130.3

1007.8 1037.8

830.85 847.16

680.59

484.3

Muddy Water Blue tatto ink 234.01 257.59

5000

Forensic Analysis of Tattoos and Tattoo Inks 594.92 619.26

274

1519.8

1584.9 1602.4

1406.6

1447.3 1478.2

1306.2 1334.4

1192

1106.5 1127.4 1142.3

1006.8 1036.2

829.26 847.75

746.05 774.68

482.73

174.2

233.59 256.79

Pigment Blue 15 (Standard) 1000

679.28

595.07

2000

0 200

400

600

800

1000

1200

1400

1600

Intensity/Raman shift (cm–1) Excitation wavelength 488 nm

Figure 10.70  ​Normal Raman spectra of Muddy Water Blue ink and pigment extraction compared to Pigment Blue 15.

for ripple tattoo ink are consistent with pigment violet 23β (Figures 10.72 through 10.74). Razberry Creem All normal Raman spectra exhibited overwhelming fluorescence, with a few very weak bands observed with λ0 = 488 nm (Figure 10.75). SERS produced spectra with marked fluorescence, but additional bands were resolved (Figures 10.76 and 10.77). XRF indicated the presence of titanium. It is probable that the titanium is due to the presence of titanium dioxide. UV/Vis data exhibited correlation to the spectrum of Pigment Red 122 (Figures 10.78 and 10.79). 5000 4500

Ripple tattoo ink 1064 nm

4000 3500 3000

Ripple tattoo ink 488 nm

2500 Ripple tattoo ink 785 nm 2000 200

400

600

800

1000

1200

1400

1600

Intensity/Raman shift (cm–1)

Figure 10.71  ​Raman spectra of Ripple ink at different excitation wavelengths.

0 200

400

600

800

1000

1701.1

1589.7 1587.9 1609.5 1639

1344.3 1390.4 1428.7 1444.9

1200

1587 1608.3

1164.3 1204.6 1253

917.96

671.33

591.04 618.13

313.97

484.77 527.84

Pigment Violet 23β (Standard)

2000

1343.4 1300.6 1427.4 1442.1

1169.9 1208.1 1108.8 1132 1165.1 1187.2 1205.3 1254.2

919.23

671.76

591.4 618.68

416.68

485.55 528.59

315.35

Ripple pigment extraction

6000 4000

671.05

486.36

10,000 8000

592.47 620.19

12,000 Ripple tattoo ink

275

1347.8 1394 1432.4 1445

Part 2—The Chemical Analysis of Modern Tattoo Inks

1400 1600 1800 Intensity/Raman shift (cm–1) Excitation wavelength 488 nm

Figure 10.72 ​Normal Raman spectra of Ripple ink and pigment extraction compared to Pigment Violet 23β.

Black Cherry Roan 2 (Figure 10.80) The Roan color series is described as neutral brown hues that are meant to be used to produce sepia-toned tattoos, often used with portrait or memorial tattoos. Although these colors appear as different shades of brown (with Roan 1 being the darkest brown, almost black and Roan 3 being the lightest brown of the set), microscopic examination disclosed the presence of green and reddish-pink/purple pigments, which ratios varied depending on the numerical assignments of the Roan color (Figure 10.81). In addition to Raman spectra data, UV/Vis data correlated to that of Pigment Red 146 (Figure 10.82).

800

1200

1255.7

1131.4 1167.2 1207.9

1047.1 1000

1591.2 1611.4

1347.1

1590.3 1611.2

Pigment Violet 23β (Standard) SERS 0 600 200 400

920.68

485.23 528.66

2000

315.43

4000

1346.8

Ripple tattoo ink SERS

6000

1392.4 1431.3 1444.2

1167.6 1207.3

672.1 671.72

920.91

591.4 619.16 591.28 618.81

8000

485.3

10,000

315.54

12,000

1256.7

14,000

1393.4 1431.9 1444.7

San Brownadino (Figure 10.83) The bands observed are consistent with iron oxide. According to Bell et al., (1997) synthetic iron (III) oxide, Fe2O3, exhibits bands at 224vs, 291vs, 407m,

1400

1600

Intensity/Raman shift (cm–1) Excitation wavelength 488 nm

Figure 10.73  SERS spectra of Ripple ink compared to Pigment Violet 23β.

276

Forensic Analysis of Tattoos and Tattoo Inks Pigment Violet 23α Pigment Violet 23β Ripple

3

4

0.000 200.00

300.00

400.00 nm

5

7

3

6 2

8 9

10

0.500

5

Abs.

4

5

1.000

6

1.500

500.00

600.00

Figure 10.74  ​Comparison of Ripple tattoo ink and two polymorphs of PV23 (α and β).

494w, 608m (λ0 = 632.8 nm). XRF indicated the presence of iron, which is indicative of iron oxide.

1668.7

1648.5

Whitegirl (Figure 10.84) The bands observed at the lower shifts are consistent with titanium dioxide, specifically rutile. According to Burgio and Clark (2001) the rutile form of titanium dioxide exhibits bands at 144(w), 232(m), 447(s), and 609(s)cm−1 (λ0 = 1064 nm). XRF indicated the presence of titanium, which is indicative 80,000

1313.7

75,000

1235.8

70,000

65,000 Razberry Creem tattoo ink 488 nm 1200

1250

1300

1350

1400

1450

1500

1550

1600

1650

Intensity/Raman shift (cm–1)

Figure 10.75  Normal Raman spectrum of Razberry Creem tattoo ink from the

region of 1200 nm to 1660 nm (λ0 = 488 nm). The overwhelming fluorescence can be seen in the region from 70 nm to 1660 nm (inset).

1639.2 1649.1

1598.4

1490.1

1516.4

1002.4

1160.1

7000

1205.7

8000

1236.1

9000

1414.3

1315.7 1328.4

10,000

6000

277 1567.7

Part 2—The Chemical Analysis of Modern Tattoo Inks

5000 Razberry Creem tattoo ink 488 nm SERS 1100

1000

1200

1300

1400

1500 1600 Intensity/Raman shift (cm–1)

Figure 10.76  ​SERS spectrum of Razberry Creem tattoo ink from the region of

1000 nm to 1660 nm (λ0 = 488 nm). Although fluorescence is still apparent, the use of SERS enabled the resolution of additional bands.

of titanium dioxide. According to Ropret et al. (2008), the anatase form of titanium dioxide is characterized by bands at 398, 515, and 639 cm−1. Most literature reports anatase as having three major bands (395, 515, and 640 cm−1) and rutile as having two major bands (450 and 610 cm−1).

1567.7 1598.6 1639.3 1649.2 1649.4

1454.9 1485 1514.6

1380.8

1315.3

1197.2

1568 1595.2

1478.2 1489.8 1516.1

1414.3

1357.6

1315.3

1159.7 1205.2 1235.7

1111.3

1002.3 1002.3 1031.5

952.66

876.09 889.1

809.8

721.39

613.31 502.69 542.3 555.28

.45

Razberry Creem tattoo ink 1064 nm 143.53 189.52 225.9

.5

451.1

Razberry Creem tattoo ink 488 nm SERS

.55

343.82

.6

126.98 150.6

Tokyo Pink Tokyo Pink tattoo ink exhibited overwhelming fluorescence for normal Raman at all three excitation wavelengths. At λ0 = 785 nm, two very weak bands were detected among the background (Figure 10.85). No information was obtained when attempting SERS on Tokyo Pink. FT-Raman was successful in producing a detailed spectrum (Figure 10.86). The two bands identified

.4 200

400

600

800

1000

1200

1400

1600

Intensity/Raman shift (cm–1)

Figure 10.77  ​SERS spectrum and FT-Raman spectrum of Razberry Creem tattoo ink (baseline correction has been applied to both spectra).

1639.3 1644.5 1644.3 1648.8

1598.6

1567.7

1595.8

1566.8

1596.3

1565.5 1567.6

1595.2

1509.4 1516.3 1513.2

1408.3 1411.7

1382.1

1516.1 1527.6

1471.2 1489.8

1407.8

1414.3 1433.2

1315.3 1336.1 1350.9 1357.6 1364.8 1310.7 1315.3 1314

1235.7

1205.2

1260.9 1258.4 1262.7

1234.8

1202.8

1233.8

1100.1

–2000

Pigment Red 122 Standard (SERS)

953.25

–1000

1203.1

0 Pigment Red 122 (Standard)

1235.2

Razberry Creem tattoo ink (SERS) 1000

1205.2

1159.7

1183.4

1111.3

1065.7 1076.7

1027.8

2000

1002.3

Forensic Analysis of Tattoos and Tattoo Inks 959.21 974.06

278

Razberry Creem pigment extraction 1000

1200

1100

1300

1400

1500

1600

Intensity/Raman shift (cm–1) Excitation wavelength 488 nm

Figure 10.78  ​SERS spectrum of Razberry Creem tattoo ink and normal Raman

1639.3 1649.2

1598.6

1644.5

1595.8

1566.8

1516.1

1478.2 1489.8

1414.3

1315.1

1407.8

1000

1234.8

1202.8

1500

1310.7

1235.7

1205.2

1159.7

1111.3

2000

1002.3

2500 Razberry Creem tattoo ink 488 nm SERS

1567.7

spectrum of Razberry Creem pigment extraction compared to the normal Raman and SERS spectra of Pigment Red 122.

Pigment Red 122 (Standard) 488 nm 500 1000

1100

1200

1300

1400

1500

1600

1700

Intensity/Raman shift (cm–1)

Figure 10.79  ​Comparison of SERS spectra of Razberry Creem tattoo ink and Pigment Red 122.

Figure 10.80  Photomicrograph of Roan tattoo ink (stereomicroscope, ~20×).

279

1582.3 1553.7

1507.7

1485.7

1450

1334.3

1314.8

1292

1218.7

1146.2

1172.7

1089.7

1200

978.37

956.71

1400

1112.3

1600

1426.5

1362.7

Black Cherry Roan 2 tattoo ink 633 nm

1800

1581.5

1555.2

1507.7

1485.3

1425.3

1362

1314.7 1331.7

1278.6 1291.7

1216.1 1221.7

1145.4

2000

1172

2200

1112.4

952.85 958.29

Part 2—The Chemical Analysis of Modern Tattoo Inks

Black Cherry Roan 2 tattoo ink 488 nm

1000

1000

1100

1200

1300

1400

1500 Intensity/Raman shift (cm–1)

Figure 10.81 Comparison of Black Cherry Roan tattoo ink at λ0 = 488 nm

–200

1448.7 1485.1 1508.3

1552.3 1581.9

1426.5 1450 1485.7 1507.7

1553.7 1581.5

1282.4

1292 1314.8 1334.3 1362.7

1218.7

956.71 978.37

748.56

553.39

0

1089.7 1112.3 1146.2 1172.7

Pigment Red 146 (Standard)

638.21

200

1157.7

400

1113.7

955.79

600

1334.7 1363.7

(green) and 633 nm (red).

Black Chery Roan 2 tattoo ink

400

800

600

1000

1200

1600 1400 Intensity/Raman shift (cm–1) Excitation wavelength 488 nm

Figure 10.82  ​Comparison of Black Cherry Roan tattoo ink (blue) and Pigment

1000

607.85

497.54

612

291.82

409.05 405.95 410.14

2000

291.98

San Brownadino tattoo ink 488 nm

3000

292.26

4000

223.43

San Brownadino 5000 tattoo ink 785 nm

225.79

6000

224.68

Red 146 pigment standard (red).

San Brownadino tattoo ink 633 nm

100

200

300

400

500

600

700

Intensity/Raman shift (cm–1)

Figure 10.83 ​Raman spectra of San Brownadino ink at different excitation wavelengths.

1001.8 1001.2

600

800

1000

Whitegirl tattoo ink 1064 nm

1452.4

1000.8 814.89

611.27

400

200

1002.1 1032.2

446.79

610.76

142.93

232.33

440.26

610.18

–10,000

447.79

0

232.13

10,000

143.14

20,000

142.92

30,000

238.13

40,000

440.15

232.15

50,000

608.3

Forensic Analysis of Tattoos and Tattoo Inks 142.22

280

Whitegirl tattoo ink 488 nm

Whitegirl tattoo ink 633 nm

Whitegirl tattoo ink 785 nm 1200

1400

Intensity/Raman shift (cm–1)

Figure 10.84 ​ Raman spectra of Whitegirl ink at different excitation wavelengths.

1002.6

350 300 250

1601.8

200 150 Tokyo Pink tattoo ink 785 nm 100 600 800

1000

1200

1400

1600

Intensity/Raman shift (cm–1)

1601.7

1

78.066

Figure 10.85  ​Normal Raman spectrum of Tokyo Pink (λ0 = 785 nm).

0

3066.3

1648.7

1158.1 1180.1 1284.9 1307.5 1382.8 1412.4 1449 1496.9 1536.2

787.35 828.1 850.55

619.35 666.37

.2

406.5

.4

241.91

.6

981.49 1028.6

1003

.8

Tokyo Pink tattoo ink 785 nm 500

1000

1500

2000

2500

3000

Intensity/Raman shift (cm–1)

Figure 10.86  FT-Raman spectrum of Tokyo Pink (λ0 = 1064 nm).

Part 2—The Chemical Analysis of Modern Tattoo Inks

281

with normal Raman at λ0 = 785 nm were detected in the FT-Raman spectrum (λ0 = 1064 nm). The spectrum does not appear consistent with that of any pigment standards analyzed in Miranda’s research. The strong band at 1601.7 cm−1 is consistent with that observed with Pigment Orange 16 and 62, a disazo and monoazo pigment, respectively. The band at 1601.7 cm−1 is due to the C═N stretching vibration, and the band at 1003 cm−1 is due to ring breathing. XRF indicated the presence of titanium, chlorine, and iron. It is probable that the titanium is due to the presence of titanium dioxide. Iron Works Brasil Vermelho High quality spectra were resolved with normal Raman at all three excitation wavelengths and with FT-Raman. The FT-IR (ATR) spectrum also displayed a number of well-resolved peaks. XRF indicated the presence of iron, zinc, and titanium. It is probable that the titanium is due to the presence of titanium dioxide. Microscopic examination of the Vermelho slide preparation proved to be very interesting, and lent support to the importance of microscopically examining the samples prior to instrumental analysis. Microscopic examination displayed a large concentration of red pigment particles, but a small aggregate of blue pigment particles was also discovered (Figure 10.87). The region was subsequently analyzed using normal Raman along with the red region. Based on comparison to the pigment standards, the blue region was consisted with Pigment Blue 15 and the red region was consistent with Pigment Red 170 (Figures 10.88 through 10.90). Pink Overwhelming fluorescence was observed with normal Raman at all three excitation wavelengths. A high quality spectrum was obtained with

Figure 10.87  Image of region of Vermelho tattoo ink slide preparation through dispersive micro-Raman. Magnification is approximately 500×.

282

Forensic Analysis of Tattoos and Tattoo Inks 20,000

Raman intensity

15,000

10,000

5000

0

200

400

600

800

1000

1200

1400

1600

Figure 10.88  ​Overlay of red region (red) and blue aggregate (blue) from Vermelho sample (λ0 = 785 nm).

FT-Raman (Figure 10.91). SERS was useful in resolving Raman bands (Figure 10.92). The FT-IR (ATR) spectrum also displayed a number of well-resolved peaks. XRF indicated the presence of titanium. It is probable that the titanium is due to the presence of titanium dioxide. No pigment standard could be correlated to the resultant spectral data. Citrus Overwhelming fluorescence was observed with normal Raman at all three excitation wavelengths. A high quality spectrum was obtained with FT-Raman (Figure 10.93). The FT-IR (ATR) spectrum also displayed a number of well-resolved peaks. XRF indicated the presence of titanium. It is

Pigment Red 170

1604.9

1164.6 1207.1 1225.5 1243.5 1286.8

1114.2 1138.3

964.06 1010.9 1042.7

335.04 365.77

267.71

732.81 777.66 805.28 850.41 863.2

20,000

112.98

25,000

187.73

30,000

421.89 478.13 494.59 510.12 539.28 573.94 611.27 631.91 664.78

35,000

1332.2 1364.2 1384.2 1420.3 1451.5 1488.2 1511.7 1551.1

1362.1

40,000

15,000 10,000 Vermelho tattoo ink (Red) 200

400

600

800

1000

1200

1400

1600

Intensity/Raman shift (cm–1) Excitation wavelength 633 nm

Figure 10.89  Red region of Vermelho and Pigment Red 170.

1335.8 1342.8 1363.2

1288.3

1143.4 1158.9 1183.8

1106.3

1007.3

952.14

777.05

730.43

593.81

485.12

257.24

6000

96.445

8000

679.97

10,000

1451.2 1488.7

12,000

747.6

145.52

Vermelho Blue aggregate (785 nm)

1606.4

14,000

283 1526

Part 2—The Chemical Analysis of Modern Tattoo Inks

4000 200

400

600

800

1000

1200

1400

1600

Intensity/Raman shift (cm–1)

Figure 10.90  ​Blue aggregate of Vermelho. The region appears consistent with Pigment Blue 15 (no polymorph specified due to the lack of information and comprehensive comparison data).

probable that the titanium is due to the presence of titanium dioxide. No pigment standard could be correlated to the resultant spectral data. Correlation exists between the FT-Raman spectra of Pink and Citrus, which indicates that both pigments have similar, but not identical, molecular composition (Figure 10.94).

1362.5 1382.8 1454 1508.5 1553.3 1575.1 1598.7 1649.3

1155.3

1186.4 1201.8 1284.4 1307.7

978.86

1000

1048.4 1091.9

796.74

636.69 689.07

397.07

291.06

600

1200

1400

1600

2929.5

Intensity/Raman shift (cm–1)

3068.2

400

1598.7

978.86 1048.4 1092.1 1155.3

796.74

636.69 688.47

516.2 542.4

397.07

200

291.06

.2

800

.15

.6 .4

516.2 542.4

.2

197.34

.25

Pink (1064 nm)

1508.5

.8

3

1362.5

1

Pink (1064 nm)

70.759

1.2

144.66

Amarelo Canario Fluorescence was observed at λ0 = 488 nm, but some bands were present (1598, 1400.2, 1289.8, and 1247.8 cm−1). High quality spectra were obtained with λ0 = 633, 785, and 1064 nm (Figure 10.95). SERS was useful in resolving

0 500

1000

1500

2000

2500

3000

Intensity/Raman shift (cm–1)

Figure 10.91  FT-Raman spectrum of Pink, with a close-up of the region from 170 to 1700 cm–1 (inset).

Pink SERS (488 nm)

1680.7

1509.7 1472.3 1418.8

932.58

637.68 661.07

5600

1089.7 1126.9

5800

1185.4

6000

1311.7

773.35

6200

1577.4

1363.4

6400

1651.4

Forensic Analysis of Tattoos and Tattoo Inks 613.09

284

5400 5200

200

400

600

800

1000

1200

1400

1600

Intensity/Raman shift (cm–1)

1598 1154.9 1188.7 1203 1234.2 1288.9 1313 1363.4 1382.1 1427.4 1456.6 1510.9 1549.9

1048.1 1093.7

978.53

915.54

796.72

.1 400

600

800

1000

1200

1400

1600

Intensity/Raman shift (cm–1) 2927.9

978.53 1048.1 1093.7 1154.9 1203 1234.2 1288.9 1363.4 1382.1 1427.4 1510.9 1549.9 1598

796.72

396.87

291.06

196.88

515.17 542.28 636.63 690.63

200

1

3065.4

1.5

.5

636.63

.2

515.17 542.28

.3

396.87

71.806

.4

291.06

.5

2.5 2

Citrus (1064 nm)

.6

690.63

.7

Citrus (1064 nm)

196.88

3

144.08

Figure 10.92  SERS spectrum of Pink (baseline corrected).

0 500

1000

1500

2000

2500

3000

Intensity/Raman shift (cm–1)

Figure 10.93  FT-Raman spectrum of Citrus, with a close-up of the region from 170 to 1700 cm–1 (inset). Citrus (1064 nm) Pink (1064 nm) .6

.4

.2

0 500

1000

1500

2000

2500

3000

Intensity/Raman shift (cm–1)

Figure 10.94  Spectral comparisons of IWB tattoo inks Citrus and Pink demonstrating the high degree of correlation between the two inks.

Part 2—The Chemical Analysis of Modern Tattoo Inks

285 1598.3 1673.1 1597.9

1674.6

1598.7

1492.7 1522 1553.6 1491.2 1522.9

1399.2

1257.7 1286 1314.1

1144.7

938.21 952.81

620.78 638.48 657.17

513.44

398.4

1634.5

1399.4

1247.5 1257.7 1287.1 1314.7

1492.8 1519.4 1524.7 1554.8

1399.4

1145.4 1144.7 1182.6

1446.3

1048.8 1066.8 1048.6 1066.4

1258 1287.9 1315.2

908.45 937.91 953.15 910.76 938.28 953.02

638.52

721.13 788.12

542.18

492.91

620.26 635.24 640.88 656.74 674.7 712.75

492.6 515.3 541.28 563.74

397.92

345.26

398.65 420.57 444.6

275.13 344.24

–10,000

Amarelo Canario (785 nm) 272.31

0

113.54 143.08 169.33 196.91

10,000

Amarelo Canario (633 nm)

112.78 142.7

20,000

272.63

113.92 143.46

30,000

196.95

40,000

197.3

50,000 Amarelo Canario (1064 nm)

–20,000 200

400

600

800

1000

1200

1400

1600

Intensity/Raman shift (cm–1)

Figure 10.95 Comparison of Amarelo Canario and different excitation wavelengths.

Raman bands (Figure 10.96). The FT-IR (ATR) spectrum also displayed a number of well-resolved peaks. XRF indicated the presence of titanium. It is probable that the titanium is due to the presence of titanium dioxide.

1400

1600

1663.3 1674.6

1493.7 1522.3

1399.7

1598

100,000

1400.2

1247.3 1287.8

Amarelo Canario SERS

1247.8 1289.8

150,000

1116.1 1144.3

200,000

937.79

657.59

250,000

1574.8

1598.3

Amarelo Fluor Overwhelming fluorescence was observed with normal Raman at λ0 = 488 and 633 nm. A spectrum was obtained at λ0 = 785 and a high quality spectrum was obtained at 1064 nm (Figure 10.97). The FT-IR (ATR) spectrum also displayed a number of well-resolved bands. XRF indicated the presence of titanium. It is probable that the titanium is due to the presence of titanium dioxide. No pigment standard could be correlated to the resultant spectral data.

50,000 Amarelo Canario normal Raman 0 200

400

600

800

1000

1200

Intensity/Raman shift (cm–1) Excitation wavelength 488 nm

Figure 10.96 Comparison of normal Raman and SERS spectra of Amarelo Canario.

Forensic Analysis of Tattoos and Tattoo Inks

1549.4 1359.2 1382 1398.8 1426.7 1456.2

1155

1203.2 1234.4 1257.6 1288.6 1316.9

979.08

1095.2

1048.2

773.54 796.78

914.26

850.12

0 200

400

600

800

1000

1200

1400 1600 Intensity/Raman shift (cm–1)

2927.1

3066

1234.4 1257.6 1288.6 1382 1398.8 1426.7 1456.2

1155

1203.2

979.08

1048.2 1095.2

636.98

773.54 796.78

692.28

291.32

397.32

.5

515.17 542.43

1549.4

1

1673.3

1597.7

0.2

475.74 515.17 542.43

291.32

0.4

692.28

636.98

0.6

71.344

1.5

Amarelo Fluor (1064 nm)

0.8

397.32

143.78

1

Amarelo Fluor (1064 nm)

1597.7

286

0 500

1000

1500

2000

2500 3000 Intensity/Raman shift (cm–1)

Figure 10.97 FT-Raman spectrum of Amarelo Fluor, with a close-up of the region from 170 to 1700 cm–1 (inset).

The FT-Raman spectra of Amarelo Fluor and Citrus are very similar, with little differences between the spectra (Figure 10.98). Verde Claro Overwhelming fluorescence was observed at λ0 = 488 nm. A high quality spectrum was observed with λ0 = 633 nm and spectra were observed with λ0 = 785 and 1064 nm (bands resolved at 146.84 and 1539.7 cm−1). The FT-IR (ATR) spectrum also displayed a number of well-resolved peaks. XRF indicated the presence of titanium, copper, and bromine. It is probable that the titanium is due to the presence of titanium dioxide and the copper and bromine are indicative of Pigment Green. Verde Claro contains Pigment Green 7 1

Amarelo Fluor (1064 nm) Citrus (1064 nm)

.8 .6 .4 .2 0 500

1000

1500

2000

2500

3000

Intensity/Raman shift (cm–1)

Figure 10.98  Spectral comparison of Amarelo Fluor and Citrus tattoo inks.

1536.9 1436.6

1379.3

1534.3

1337.6 1359.8 1388 1394.4 1435.5 1444.9 1479.4 1492.2 1506.9

1280.4 1277.6

1205.6 736.34 771.33 813.39

682.11 640.6

505.59 541.92

288.84

193.45

98.743

0

287

1334.2

1079.4 1083.8 1079.2

Verde Claro (633 nm) 2000

1212.8

979.67

643.23

508.73

291.27

4000

98.492 145.58

6000

973.35

683.04 687.78 706.01 738.32 742.76 773.43 778.42 816.25

Part 2—The Chemical Analysis of Modern Tattoo Inks

Pigment Green 7 (633 nm) 200

400

600

800

1000

1200

1400

1600

Intensity/Raman shift (cm–1)

Figure 10.99  Comparison of Verde Claro with Pigment Green 7 standard.

(Figure 10.99). The presence of bromine indicates that Verde Claro may also contain a trace amount of a bromine-containing pigment such as Pigment Green 36. Microscopic examination of the tattoo ink provided information concerning the composition of verde claro, which would likely not have been discerned from “bulk” spectroscopic analyses. Polarized light microscopy of verde claro disclosed the presence of colorless, green, yellow, and blue pigment particles (Figure 10.100).

Figure 10.100 Photomicrograph of Verde Claro tattoo ink (polarized light

microscopy, 1.550 RI mounting media, 400×). Note the presence of colorless, green, yellow, and blue pigment particles of varying particle size.

288

Forensic Analysis of Tattoos and Tattoo Inks

Azul Royal High quality spectra were resolved with normal Raman at all three excitation wavelengths and a spectrum was obtained with FT-Raman. The FT-IR (ATR) spectrum also displayed a number of well-resolved peaks. XRF indicated the presence of titanium and copper. It is probable that the titanium is due to the presence of titanium dioxide and the copper is indicative of Pigment Blue 15 or a related polymorph. Magenta Overwhelming fluorescence was observed at λ0 = 633 and 785 nm. Spectra were observed with λ0 = 488 and 1064 nm. SERS was useful in resolving Raman bands (Figure 10.101). The FT-IR (ATR) spectrum also displayed a number of well-resolved peaks. XRF indicated the presence of titanium. It is probable that the titanium is due to the presence of titanium dioxide. No pigment standard could be correlated to the resultant spectral data.

–1000

1648.3

1567.2 1567.3

1515.1

1415.7

1308

1202.2 1232.8

617.82

Magenta normal Raman (488 nm)

1316.3

0

1205.3 1234.8

1000

394.74

2000

202.63

3000

152.62

Lilas Claro High quality spectra were obtained with all excitation wavelengths (both normal Raman and FT-Raman). Examination of the Raman spectra (Figures 10.102 and 10.103) indicates the presence of titanium dioxide, anatase form (“light region” of the photomicrograph displayed in Figure 10.104) and Pigment Violet 23, specifically the β polymorph (“dark region” of the photomicrograph displayed Figure 10.104). The FT-IR spectrum resolved a few peaks and XRF indicated the presence of titanium. This titanium is due to the presence of titanium dioxide.

–2000 Magenta SERS (488 nm) 200

400

600

800

1000

1200

1400

1600

Intensity/Raman shift (cm–1)

Figure 10.101  ​Comparison of normal Raman and SERS spectra of Magenta.

Part 2—The Chemical Analysis of Modern Tattoo Inks

289

Figure 10.102  Photomicrograph of region of Lilas Claro tattoo ink slide prepa-

143.75

ration through dispersive the micro-Raman instrument, demonstrating the dark and light regions. Magnification is approximately 2000×. 10

636.99

143.42

6

513.62

196.69

395.76

Titanium dioxide (1064 nm)

8

4

638.6

515.44

196.94

396.81

Lilas Claro (light region) 1064 nm

2 0 100

200

300

400

500

600

700

Intensity/Raman shift (cm–1)

400

600

800

1000

1200

1590.8 1611.4 1643

1392.7 1431.4

1400

1587 1608.3

1427.4 1442.1

1343.4

1164.3 1204.6

917.96

671.33

484.77 527.84

313.97 200

591.04 618.13

Pigment Violet 23β (488 nm) –50,000

1253

1388.6

0

1444.4

1256.1

1167.1 1207.4

921.05

591.03 618.61 636.85 671.28

484.82

395.22 415.98

315.56

142.14

50,000 Lilas Claro (dark region) 488 nm

1346.6

Figure 10.103  ​Normal Raman of Lilas Claro compared to titanium dioxide.

1600

Intensity/Raman shift (cm–1)

Figure 10.104  ​Normal Raman of Lilas Claro compared to Pigment Violet 23β pigment standard.

290

Forensic Analysis of Tattoos and Tattoo Inks

5000 4000 3000 Salmon Pink tattoo ink (785 nm) 2000 1000

Pigment Orange 34

0 200

400

600

800

1000

1200

1400

1600

Intensity/Raman shift (cm–1)

Figure 10.105  Comparison of Salmon Pink tattoo ink and PO 34 standard.

Flying Tigers Salmon Pink Correlation was found between Salmon Pink and Pigment Orange 34 (Figure 10.105).

400

600

1000

1608.2

1551.7

1400

1602.9

1550.3

1451 1486.7 1510.5

1361.7

1425.9 1453.7 1485.1

1361.8 1384.8

1242.3

1047.3

1162.7 1200

1283.8

1237.8

1161.5

967.05 800

963.76

Pigment Red 170 (SERS 488 nm)

730.4

–5000

925.9

0

1286.3

Pink Red (flying tigers), 488 nm

737.76

5000

1108.5

Pink Red Comparison of the spectrum obtained at 488 nm exhibited correlation with the SERS (488 nm) spectrum of Pigment Red 170. The SERS spectrum was employed because there were more, better resolved peaks observed when compared to the normal Raman spectrum (488 nm) of Pigment Red 170 (Figure 10.106). Due to the detection of zinc by XRF and the microscopic appearance of pink red, it is likely that zinc oxide (white) is present in the tattoo ink (Figure 10.107).

1600

Intensity/Raman shift (cm–1)

Figure 10.106  Comparison of Pink Red tattoo ink and PR 170 standard.

Part 2—The Chemical Analysis of Modern Tattoo Inks

291

Figure 10.107  ​Flying Tigers Pink Red tattoo ink (darkfield microscopy 100×,

left and Raman microscope, 1000×, right). Note the aggregates of pink/red particles and the aggregates of white particles. This can also be seen in the image from the XRF (bottom right), which detected zinc.

Reds Chinese Red: Correlation was found with Pigment Red 170, specifically with regard to the more intense bands at 1163 (C–N symmetrical bend), 1283, 1360 (naphthalene), 1424 (N═N stretch), 1484, 1548, 1609 cm−1 (benzene stretch). There are a large number of unassigned bands, indicating that this tattoo ink is an azo dye in the red class and possibly a mixture. Similar conclusions can be drawn about the Rose Red tattoo ink, which exhibited peaks at 1289, 1360, 1424, 1486, 1547, and 1607 cm−1 and the Mulberry tattoo ink, which exhibited peaks at 1160, 1285, 1360, 1424, 1485, 1549, and 1609 cm−1(Figure 10.108). An additional band was found at 1580 cm−1 for Rose Red and Mulberry, which was not present in Pigment Red 170. The intensity of the band at 1580 cm−1 is similar to that of the band at 1609 cm−1. Similar results were found with Dark Red. In summary, the selection of red tattoo inks exhibit characteristic Raman spectra consistent with azo dyes. Correlation was made between Pigment Red 170 and the Bright Red tattoo ink, with intense bands found at 1282, 1360, 1422, 1484, 1549, and 1609 cm−1 (Figure 10.109). Orange Red and Orange Correlation was found between Orange Red, Orange, and Pigment Orange 34. After closer inspection with the literature, better correlation was found between Orange Red, Orange, and Pigment Orange 13 (Scherrer, et al., 2009), with the most intense peaks at 1280, 1555, and 1599 cm−1 (Figure 10.110).

292

Forensic Analysis of Tattoos and Tattoo Inks

2

1.5

1

.5

0 Rose Red (FT), 1064 nm (red spectrum); Mulberry(FT), 1064 nm (blue spectrum) 200 400 600 800 1000

1200

1400

1600

Intensity/Raman shift (cm–1)

Figure 10.108  Comparison of Rose Red (red) and Mulberry (blue) spectra demonstrating correlation between the two inks.

8

6

4

2

0 Bright Red (FT), 1064 nm (red spectrum); Pigment Red 170, 1064 nm (blue spectrum) 200

400

600

800

1000

1200

1400

1600

Intensity/Raman shift (cm–1)

Figure 10.109  Comparison of Bright Red tattoo ink (red) and PR 170 pigment standard (blue).

N N O

N

N Cl

Cl N

Figure 10.110  Pigment Orange 13.

N

O N N

Part 2—The Chemical Analysis of Modern Tattoo Inks

293

3000 2000 1000 0

Orange Red 785 nm

–1000 –2000 –3000

Orange 785 nm

1800

1600

1400

1200

1000

800

600

400

200

Intensity/Raman shift (cm–1)

Figure 10.111  ​Orange Red (red spectrum) and Orange (blue spectrum) Flying

Tigers tattoo inks (all spectra acquired with 785 nm laser excitation). Note the symmetry in bands.

Pigment Orange 13 (Figure 10.111) is structurally similar to Pigment Orange 34, the difference being the two methyl groups present of the outermost benzene rings (para orientation). The high degree of symmetry observed in the Raman spectrum of Pigment Orange 34 is also observed in that of Pigment Orange 13 (as reported in Scherrer et al., 2009). Yellows Mid-Yellow, Yellow, and Golden Yellow tattoo inks appear to have similar pigment compositions, at least with respect to the most abundant pigment in each ink (Figure 10.112). The spectra exhibit major bands at 1596 cm−1 (aromatic

2000

Yellow 785 nm (blue spectrum) Mid-Yellow 785 nm (black spectrum) Golden Yellow 785 nm (red spectrum)

1500

1000

500

0 200

400

600

800

1000

1200

1400

1600

Intensity/Raman shift (cm–1)

Figure 10.112  ​Comparison of yellow tattoo inks; Yellow (blue spectrum), MidYellow (black spectrum), and Golden Yellow (red spectrum).

294

Forensic Analysis of Tattoos and Tattoo Inks

ring vibrations), 1399 cm−1 (azo N═N symmetric stretch), 1293 cm−1 (C–C stretching and CH bending vibrations, specifically the characteristic vibration between the C–C bridge between phenyl groups at the center of the molecule) and 1251 cm−1 (amide III band, with the amide I band around 1660 cm−1, and benzylamide band at 950 cm−1). The spectra clearly indicate a disazo pigment, specifically a diarylide. Bright Yellow has major bands at 1252, 1330, 1347, 1503, 1596, and 1404 cm−1 and Khaki has major bands at 1251, 1292, 1398, and 159.4 cm−1, indicative of azo pigments. Greens XRF disclosed the presence of copper, chlorine, and bromine in the Grass Hopper, Light Green, and Dark Green tattoo inks, and copper and chlorine in the Verdancy and Lawn Green tattoo inks. All the green pigments exhibited bands at around 685 and 740 cm−1, which is indicative of the vibrations inherent in the TBP nucleus characteristic of phthalocyanines. These two bands, along with the XRF data, assert that all of the green tattoo inks contain phthalocyanines. The presence of bromine indicates PG36 and the lack of bromine indicates PG7. Blues XRF disclosed the presence of copper in Blue Sky, Turquoise Blue, Cyan, Dark Cyan, Blue, Navy Blue, and Dark Blue. Cyan and Dark Cyan also contained chlorine, and Navy Blue contained chlorine and bromine in addition to the copper. All the blue pigments exhibited bands at around 680 and 740 cm−1, which is indicative of the vibrations inherent in the TBP nucleus. These two bands, along with the XRF data, assert that all the blue tattoo inks contain phthalocyanines. Although the spectral differences with a change in the excitation wavelength have been addressed earlier in this document, one important observation is worth adding. In the blue tattoo inks, examination of the normal Raman spectra at 488 nm shows a strong band around 680 cm−1 with little to no band around 745 cm−1. The absence of this band may lead an inexperienced analyst to conclude that the TBP nucleus (ring vibrations) characteristic of the phthalocyanines is absent. These bands are present and of equal intensity in the normal Raman spectra at 785 nm. Purple and Violet Correlation was found between Purple, Violet, and Pigment Violet 23β (Figures 10.113 and 10.114). Dark Brown and Light Chocolate XRF indicated the presence of chlorine, chromium, iron, copper, and zinc in Dark Brown and the presence of chlorine, chromium, iron, nickel, and zinc in Light Chocolate. Correlation was found between Dark Brown and Light Chocolate Raman spectra (Figure 10.115).

Part 2—The Chemical Analysis of Modern Tattoo Inks 4000

295

Purple tattoo ink (488 nm) Pigment Violet 23β (488 nm)

3000

2000

1000

0 200

400

600

800

1000

1200

1400

1600

Intensity/Raman shift (cm–1)

Figure 10.113  ​Comparison of Purple tattoo ink and PV 23β pigment standard. Violet tattoo ink (488 nm) Pigment Violet 23β (488 nm) 3000

2000

1000

0 200

400

600

800

1000

1200

1400

1600

Intensity/Raman shift (cm–1)

Dark Brown tattoo ink (488 nm) 200

400

600

800

1000

1200

1484.4

1533 1556.1 1590.6 1533.9 1556.7 1590.8

1361.3 1362.2 1400

1484.7

1280.5

1232.9 1235.3

–2000

791.94

–1000

1165.1

Light Chocolate tattoo ink (488 nm)

914.97 968.74 968.74

0

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Figure 10.114  ​Comparison of Violet tattoo ink and PV 23β pigment standard.

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Intensity/Raman shift (cm–1)

Figure 10.115 ​Comparison of Light Chocolate and Dark Brown tattoo inks demonstrating pigment composition correlation.

Forensic Analysis of Tattoos and Tattoo Inks 141.87

296

637.09

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195.74

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196.69

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Figure 10.116  Comparison of White tattoo ink with titanium dioxide (anatase).

Skin Tone No quality data was obtained with Raman, and some peaks resolved with IR. XRF indicated the presence of zinc. This tattoo ink was still “wet,” even a year after being mounted on a glass slide and stored at room temperature in a microscope slide box. White XRF indicated the presence of titanium, which was consistent with the Raman spectrum corresponding to the titanium dioxide standard, specifically the anatase polymorph (Figure 10.116).

Results: Pigskin (Figure 10.117) Preliminary examinations were used to compare the resultant spectra of the tattooed regions to the known pigments and to evaluate the effect of tissue preservation methods on the resultant spectra, specifically fixing the tissue using formalin versus freezing the tissue (Figures 10.118 through 10.124). Based on the spectra, no major differences were observed between formalin fixation and freezing of the samples. The first attempt, which was to directly analyze the tattooed regions, was successful, and no additional methodology needed to be used (i.e., thin sectioning; the addition of silver colloid and employment of SERS; or the use of the hydroxyl gel to extract the tattoo ink from the pigskin). For direct analysis, the sectioned, tattooed pigskin was placed in a glass Petri dish and subsequently placed on the sample stage of the Raman microscope. The sample was viewed under the microscope and focused on prior to Raman analysis. Minimal to no interferences from the tissue matrix (skin) as well as fixation methods (formalin) were observed. It is reasonable to conclude that the

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Figure 10.117  ​Section of pigskin with series of Skin Candy tattoo inks.

direct analysis of unhealed, tattooed skin would easily disclose the presence of tattoo ink pigments due to both the absence of interfering layers of skin that would result from healing and due to the lack of migration of the pigments into deeper layers of skin also due to the healing process. Although alternate methods were not employed, their use may become paramount in instances when the superficial, surface layers of tissue have

150,000

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White tattoo ink in pigskin, fixed (488 nm)

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Intensity/Raman shift (cm–1)

Figure 10.118  ​Comparison of white tattoo ink in pigskin (fixed and frozen) with Skin Candy Whitegirl tattoo ink.

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2500 Red tattoo ink in pigskin, fixed (785 nm)

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Figure 10.119  ​Comparison of red tattoo ink in pigskin (fixed and frozen) with Skin Candy Red Hot tattoo ink. 10,000

Orange tattoo ink in pigskin, fixed (785 nm)

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Figure 10.120  Comparison of orange tattoo ink in pigskin (fixed and frozen) with Skin Candy Marz tattoo ink.

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Figure 10.121  ​Comparison of yellow tattoo ink in pigskin (fixed and frozen) with Skin Candy Blisterine tattoo ink.

Part 2—The Chemical Analysis of Modern Tattoo Inks

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Green tattoo ink in pigskin, fixed (785 nm)

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Green tattoo ink in pigskin, frozen (785 nm)

Tastywaves tattoo ink (785 nm)

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Intensity/Raman shift (cm–1)

Figure 10.122  Comparison of green tattoo ink in pigskin (fixed and frozen) with Skin Candy Tastywaves tattoo ink. 12,000 10,000 Blue tattoo ink in pigskin, fixed (785 nm) 8000 Blue tattoo ink in pigskin, frozen (785 nm) 6000 4000 2000 Muddy water blue tattoo ink (785 nm) 200

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Intensity/Raman shift (cm–1)

Figure 10.123  ​Comparison of blue tattoo ink in pigskin (fixed and frozen) with Skin Candy Muddy Water Blue tattoo ink. 2500 2000

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Figure 10.124  ​Comparison of purple tattoo ink in pigskin (fixed and frozen) with Skin Candy Ripple tattoo ink.

1606.3

1362.2 1331.3

1486.2 1513.7 1548.9

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Forensic Analysis of Tattoos and Tattoo Inks 328.88

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Figure 10.125 ​ Cadaver tissue cross section, red region of tattoo (Raman, λ0 = 785 nm).

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healed and the pigment is embedded and stored in the deeper dermal layers. Direct analysis should be attempted first, with special attention paid to the excitation wavelength and its relative depth of penetration, as the source may be able to reach and therefore detect the pigments without intervention or destructive methodology. As described earlier, the longer wavelengths (such as 785 nm for dispersive Raman and 1064 nm for FT-Raman) penetrate deeper into the tissue and thus may be more useful in detecting the pigment particles that make up the tattoo. Preliminary research into the analysis of tattoo inks in human tissue has demonstrated the ability to locate and isolate the pigment layer within a cross section of excised, fixed tissue, and subsequently detect the pigments via micro-Raman spectroscopic methods. A section of tattoo exhibiting the colors black, red, yellow, and green was obtained for a portion of the study. The following are Raman spectra (unprocessed, raw data) of the preliminary test results on cadaver tissue in Figures 10.125 through 10.128 (Miranda, unpublished study).

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Figure 10.126  ​Cadaver tissue cross section, orange region of tattoo (Raman, λ0 = 785 nm).

1666.3

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Part 2—The Chemical Analysis of Modern Tattoo Inks

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Figure 10.127  ​Cadaver tissue cross section, yellow region of tattoo, λ0 = 785 nm.

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Figure 10.128  Cadaver tissue cross section, green region of tattoo, λ0 = 785 nm.

Based on preliminary studies, Raman spectroscopy is capable of detecting tattoo inks in human tissue. As was observed with the pigskin, minimal to no interferences from the tissue matrix as well as fixation methods, namely vibrational modes from either skin or formalin respectively, were observed. Pigment spectral bands in the preliminary research studies can be correlated to the both tattoo ink and pigment reference standards, even without any spectral processing, as demonstrated in the series of spectra obtained from tattoo inks in human tissue.

Further Studies and Conclusions

IV

11

Current Status and Future Work

Scientific Inquiries The study conducted by Miranda (2012b) was able to determine the pigment compositions of a variety of tattoo inks, which varied in terms of color and origin of manufacture. Databases of tattoo inks were created with regard to microscopic characteristics, normal Raman data at different wavelengths of excitation, FT-Raman data, surface enhanced Raman scattering, FT-infrared data via attenuated total reflection, and XRF. Similar pigments were found in tattoo inks from different manufacturers, which did not allow for individualization of tattoo inks based upon country of origin (with the limitation being the samples set examined). A revised hypothesis might include a more detailed evaluation of the microscopic and optical properties of the pigment particles and qualitative analysis of pigments within each tattoo ink in addition to an evaluation of the liquid portion of the inks. Microscopy was an extremely useful tool for evaluating the physical properties of the tattoo inks. By examining the tattoo inks using bright field and dark field microscopic techniques, information concerning the uniformity and pigment distribution within the inks was able to be ascertained. It is highly recommended that any examination concerning tattoo inks and pigments (even paints and inks, in general) begin with a thorough microscopic examination, beginning with stereomicroscopy, followed by bright field and dark field microscopy methods, and polarized light microscopy of the pigment particles. Further analysis using scanning transmission electron microscopy (S-TEM) may also be useful in disclosing characteristics of the particles. Examination of the pigment particles can disclose additional information including particle size, crystal morphology (forms) and class, and optical data such as (relative) RIs, birefringence, extinction characteristics, and so on. While it did not necessarily improve the resultant spectral data, extractions of the tattoo inks were useful in resolving and isolating the individual pigments and separating the organic pigments from the inorganic, mineral pigments (such as titanium dioxide). Extractions allow for a more thorough qualitative assessment of the pigment composition of the inks and may be useful for determining quantitative aspects of pigment composition by evaluating relative ratios of the pigment present. 305

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Forensic Analysis of Tattoos and Tattoo Inks

In analyzing samples in a laboratory, it is essential to employ the instrumentation that will provide information concerning both the organic and inorganic fractions of the samples. Both Raman spectroscopy and infrared spectroscopy/attenuated total reflection provided a great deal of information concerning the chemical structure of the pigments that make up the inks, and either one of these techniques can be used to obtain detailed information about a sample. There is a great benefit to using Raman spectroscopy due to the ability to use different excitation wavelengths to generate a useable spectrum. In addition, the use of SERS as an analytical tool in Raman spectroscopy is paramount; SERS is a simple, yet powerful technique that enables the analyst to obtain data in instances where optical and physical characteristics of the sample would normally preclude the resolution of Raman bands. The microwave synthesis technique described by Leona demonstrates the ease with which a suitable colloid can be prepared and used for SERS work. In addition, XRF provided a simple, rapid method for obtaining data concerning the inorganic, atomic composition of the tattoo inks. The advancement of analytical techniques and instrumentation coupled with the paradigm shift to a more objective, analytical approach to forensic science provides fertile ground for research that can contribute to forensic science and criminal justice, art conservation and cultural heritage, as well as anthropology and art history. During the course of Miranda’s research, it became apparent that there are many additional studies that could be done with tattoo inks or related materials. A summary of future projects is presented; the list is not intended to be exhaustive, as the evolution of tattoo inks and the needs of the forensic science community will surely guide the course of future research. General instrumental techniques would be extremely useful for further classifying each ink, namely x-ray diffraction (XRD) on the tattoo inks in an effort to elucidate specific structural information. XRD data would be an added tool, especially in instances where computational chemistry, or density functional theory (DFT) calculations are to be made. Molecular electronic fluorescence spectroscopy would prove useful in the analysis of the tattoo inks and pigments in solution. A vast undertaking to understand the solubility of the inks and pigments with a variety of solvents using wet chemistry coupled with UV/Vis spectrophotometry and fluorescence spectrometry may provide increased discriminating power between tattoo inks and pigments. Additional microchemistry and solution chemistry (including color and microcrystalline tests) could be conducted to enhance any analytical schemes developed for identification and comparison of tattoo inks and pigments. Density functional theory calculations should be conducted for all the pigments represented in this study, with detailed vibrational modes being assigned to the calculated and experimental Raman and infrared

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bands. Additional SERS spectra should be obtained, with the use of alternate excitation wavelengths and aggregants used in an effort to evaluate optimum sample preparation methods of the tattoo inks. Quantitative analysis of the tattoo inks in an effort to determine relative pigment abundances is another approach that could be undertaken in the characterization and discrimination of tattoo inks. By determining concentrations of specific pigments (both organic and inorganic fractions) and demonstrating batch consistency, it may be possible to statistically assign an unknown tattoo ink to a particular manufacturer (or country of origin) based upon the relative ratios of pigments. A more detailed analysis of both the inorganic portions of the tattoo inks along with a thorough investigation of the liquid portion of the inks may prove useful in discriminating ink brands and origins of manufacture. Aside from the need to continue building up databases and libraries by analyzing more tattoo inks and powder pigments, there are other substances similar to tattoo inks (in usage and application) that should be studied and characterized, both on and off the skin. These include henna, nonpermanent, “fake” tattoos, and ink-based stamp pads. Detailed, comprehensive analyses of stamp inks, coupled with chemometrics, may prove useful in discriminating these inks and could be useful in forensic investigations. In addition to evaluating the chemical composition of temporary tattoos and ink pads, evaluating the persistence and detection of such residues in human tissue would be of value. Should human remains be discovered and temporary tattoos or a hand stamp detected, the pattern of the design as well as the chemical composition of the residue in the epidermis may provide information concerning the source of the design. Depending on the distribution and persistence studies, information concerning the approximate time since application may also be ascertained. It is apparent that it is possible to distinguish polymorphs of a given pigment, as reported in the literature (e.g., authors in Venkataraman’s text report on distinguishing the different polymorphs of Pigment Blue 15 using infrared spectroscopy and comparative x-ray powder data, p. 446 and p. 289, respectively) and based on the experimental data presented in Miranda’s 2012 research (both IR and Raman). One future research project that could be applied to increasing the discrimination power of pigment blue 15 is through the use of chemometrics. Specifically, by using software for data analysis that incorporates statistical computing and graphical display methodologies.* By inputting the spectral data (peak locations) for the various pigment blues into the computer program, it is possible to use a discrimination algorithm such as partial least squares (PLS) analysis to determine the relationships between * Such as The R Project for Statistical Computing, http://www.r-project.org

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Forensic Analysis of Tattoos and Tattoo Inks

the data and determine if samples within the data set can be distinguished. This use of statistics could also be applied to tattoo inks and manufacturers. This is an excellent way to support the paradigm shift from subjective analysis and interpretation within forensic science to the desired objective, statistical support for interpretations and conclusions regarding inclusions and exclusions. Additionally, like Raman spectroscopy, x-ray powder diffraction is a useful tool for differentiating between the different polymorphs of a given pigment. XRD coupled with wet chemistry methods to facilitate crystal growth or isolation of a crystal form is a viable project that could provide insight into the polymorphs of existing synthetic/organic pigments. Caution must be taken during sample preparation methods to prevent the chance of changing the crystal form upon the application of pressure or solvents (e.g., according to Thompson, “The (infrared) spectrum (of the Pigment Blue polymorph) must be run in Nujol since the high pressures involved in the potassium bromide [KBr] disk techniques effect changes in crystal form and hence in the peak ratio” (Thomson, 1977, p. 447). Since similar pigment types were found across the three origins of manufacture (U.S., Brazil, and China), further microscopic and spectroscopic studies should be conducted in an effort to distinguish the pigment manufacturers based on a more comprehensive study of the pigment polymorphs present in the tattoo inks. The crystal form of the pigment is a key factor in the physical properties of the resultant tattoo ink. According to Brostoff et al. slight variations in the manufacturing process [of artists’ pigments] including pH, drying processes and corresponding temperatures, and any milling methods can cause the transformation of polymorphs and affect the crystallinity and crystal quality of the pigment (Brostoff et  al., 2009, p.  6097). An evaluation of the pigment manufacturing processes along with the manufacturing processes of the tattoo inks should be conducted and used to characterize tattoo inks originating from different sources. Since evaluation of the physical and optical characteristics of the pigment particles is critical to determining the color characteristics of a sample, more detailed evaluation of the particles in tattoo inks should be explored (although control over the drying, extraction, and any additional isolation and preparation methods would be paramount to prevent modification of the crystals [i.e., polymorph changes]). Again, microscopy would prove to be an extremely powerful tool for evaluating the pigment distribution, particle size, and particle shapes. Expanding or improving upon any work presented in this research would be beneficial, specifically with regard to SERS. This should be done in order to further validate the use of SERS as a routine analytical tool to be used in the lab, whether it be a forensic lab, conservation lab, industrial lab, or any other laboratory setting (cosmetic, pharmaceutical, color chemistry, etc.). The increased application and validation of SERS in the forensic field

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will help meet the criteria set forth in courtroom admissibility guidelines such as those in Daubert.* In general, good laboratory practices in the form of standard operating procedures, proper training, and certification of laboratory analysts and quality assurance measures should be developed and adhered to in the laboratory. It is imperative that any instrument be checked prior to analysis in order to ensure that the instrument is operating according to its specifications, and laboratories should maintain records demonstrating that their instruments are working properly in order to meet any quality assurance standards set forth by the laboratory or any accrediting agency. Literature providing standards and corresponding spectral data (including electronic databases) is readily available and should be referred to in order to ensure that the instrument is performing properly. The analytical schemes for a tattoo analysis provided in this chapter should be employed for routine and uniform examination of tattoo inks in crime labs and tattoos in the autopsy suite of medical examiner offices. Manufacture and Distribution “There is no point in asking a tattooist whether he uses mercury, cadmium, or cobalt salts. He will reply that he gets his colors from a supplier in the United States or Australia and that he finds from experience that the effect is what he wants. This is not good enough. Supplies should only be obtained from reputable manufacturers whose lists include the chemical nature of the pigment” (Scutt and Gotch, 1974a and b, p. 135). A thorough evaluation of the hierarchy of manufacturers, distributors, brands of tattoo inks, and pigments should be ascertained in an effort to understand production, bottling and packaging, as well as sourcing of pigments used to manufacture the tattoo inks (Figure 11.1). Product searches of tattoo ink brands demonstrate that brands offer tattoo inks that have different labels and lines; for example, a tattoo brand may offer a line of colors under the name of a particular tattoo artist or a limited edition color palette. Whether or not these are just packaging changes as a marketing strategy or actual inks of different chemical compositions requires further investigation. One challenge is the lack of regulation of the contents; it is reasonable to hypothesize that manufacturers will vary their product based on their business model, specifically pigment cost, pigment availability, manufacture costs, as well as availability and cost of chemicals, and so on. In 2 012, Miranda reported A search of manufacturers and distributors was conducted in an attempt to assess the variation in tattoo ink manufacturing. It is apparent that some tattoo * Daubert versus Merrell Dow Pharmaceuticals, Inc., 509 U.S. 579 (1993) [Daubert I]; Daubert v. Merrell Dow Pharmaceuticals, Inc., 43 F.3d 1311 (9th Cir. 1995) [Daubert II].

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Forensic Analysis of Tattoos and Tattoo Inks

Figure 11.1  Various tattoo inks exhibiting different brands, packaging labels, and color arrays.

ink manufacturers will generate different brand names under their main company name. For example, Skin Candy Tattoo Inks list separate ink brands under the “Skin Candy” umbrella, including Skin Candy, Bloodline, Kabuki, Tribal One, Eternal, Dynamic, Panther, and Roan Bloodline. Additional tattoo inks from other manufacturers include Intenze, Starbrite, Iron Butterfly, Alla Prima, Silverback, Black Buddha, Dynamic Color Co., Scream, Immortal, National, Fusion, Eternal, Dispersion, Talons/Talens, Joker, Katana, Twilight MOMs Millennium and MOMs Nuclear (where MOMs is labeled as a distributor) and Chameleon (the latter two are newer, “Blacklight UV Reactive” inks),

Current Status and Future Work

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Sta-Glo and Cosmetic Colors (Huck Spaulding Distributors), Prizm, Ichiban Sumi, Forever Natural, Lightning, Flesh-Tone, EO One, and Infinitink. It is difficult in many instances to ascertain common origin from distributors and may be possible by looking at the information on the bottle label (to correlate manufacturer name, location/address, etc.). Tattoo ink lines named after famous tattoo artists are also available, and generally are an “artist series” of a particular manufacturer (i.e. Feldman’s Inks). The primary Japanese manufactured tattoo ink is Kuro Sumi (a Kokkai Sumi ink was found at one distributor’s website, likely a cheaper alternative to the well-known Kuro Sumi brand). One supply company offered powder pigment for tattoo inks and recommended mixing their colors with witch hazel, their own dispersing solution (listed as “Made in the U.S.A.,” but no additional information was made available), Listerine or alcohol.*

An example of the ink variation can be quickly ascertained by a review of a Tattoo Supply Catalog or website, or attendance at a Tattoo Convention. From the 2013 Unimax Supply Company Catalog, the following inks are available for purchase (56–77): Electra Pro Stormy Wash Series by Unimax Mom’s Black Pearl Series Mom’s Black Onyx Ink Kuro Sumi Outlining Ink and Gray Wash (Outlining, Graywash, Light Graywash) Kuro Sumi Bronze Shading Kuro Sumi Cherry Shading Intenze Black and Gray Wash (True Black, Lining Black, Sumi Wash, Gray Wash Set) Intenze Zuper Black Intenze Japaneze Tattoo Ink Set (Japaneze Black Sumi, Dark Gray, Light Gray) Intenze Suluape Black Mark Mahoney Gangster Gray (Intenze) Bob Tyrrell Advanced Black and Gray Formula (Intenze) Alla Prima Zao Black, Prima Black, Graywash Set Eternal Ink Triple Black and Lining Black, Graywash Set Starbrite Colors Starbrite Blacks, Black Outlining, Tribal Black, Alley Cat Black EO One EO Tribal, Wash, Black Sets, Gray Sets Panthera Black Ink (Black Tribal XXX, Dark Sumi Wash, Light Sumi Wash, and Black Ink Lining)

* http://www.nationaltattoo.com/index.asp?PageAction=VIEWCATS&Category=3.

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Forensic Analysis of Tattoos and Tattoo Inks

London Smoke,* Gray Color Variations Talens Drawing Ink† Silverback Ink, Silverback black, XXX Black, XXX Gray Washes, X4 Gray Wash Series (Black/Brown hue), FRESH Gray Wash Series (Purple Hue), MOLD Gray Wash Series (Green Hue) Electra Pro Ultra Modern Color Palette and Modern Blacks (approximately 41 colors, including blacks, whites, grays, and neutral [earth/ flesh] tones) Intenze Palettes (approximately 80 colors, including blacks, whites, grays, and neutral [earth/flesh] tones) Intenze Sets‡; Mario Barth Gold Label, Mike DeMasi Color Portrait Set, Boris from Hungary Tattoo Set, Bob Tyrell and Mark Mahoney Sets, Dragon Color Set, Intenze Bowery Ink by Bowery Stan Moskowitz Intenze Essential Silver Set (Blue Silver, Purple Silver, and Titanium Silver) Moms Millennium Ink (approximately 41 colors, including blacks, whites, grays, and neutral [earth/flesh] tones) Mom’s NUCLEAR COLORS (Backlight UV Set of 9), UV Blacklight Clear Mom’s Millennium Sets Eternal Ink (approximately 62 colors, including blacks, whites, grays, and neutral [earth/flesh] tones) Eternal Ink Sets Kuro Sumi Ink (approximately 59 colors, including blacks, whites, grays, and neutral [earth/flesh] tones) Kuro Sumi Ink Sets Starbrite Colors Ink (approximately 40 colors, including blacks, whites, grays, and neutral [earth/flesh] tones) Starbrite Sets Alla Prima Ink (approximately 32 colors, including blacks, whites, grays, and neutral [earth/flesh] tones) Alla Prima Sets EO One Ink (approximately 50 colors, including blacks, whites, grays, and neutral [earth/flesh] tones) EO One Sets The brands are Electra Pro, Moms, Kuro Sumi, Intenze, Alla Prima, Eternal Ink, Starbrite Colors, EO One, and Silverback Ink, but the color * The catalog notes that Panthera and London Smoke are CE Certified Ink Approved for European Union (59). † The catalog notes Now Labeled “Not for tattoo” (59). In addition, the website (http:// www.unimaxsupply.com/) also sells Pelikan ink and Talens Indian ink, which are also listed as “Talens & Pelikan Drawing Inks, Not for Tattooing.” ‡ Many of these sets are named for specific tattoo artists.

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palettes vary extensively within a given brand as well as across brands. Other tattoo ink brands/names not available in this catalog include, but are not limited to, Cheyenne Ink, Derma Medical Permanent Cosmetic Colors, Dispersion Colors, Cover up Tattoo Ink, Irezumi Tattoo Ink, Philadelphia Eddie’s Traditional Inks, Paolini Sacred Color Tattoo Inks, Tony Polito Inks, Spaulding Tattoo Colors, VooDoo Ink, Prime Pigments, World Famous Tattoo Ink, Atomic Ink, Solid Ink, Bloodline Tattoo Inks, Platinum Ink, Platinum 2 Ink, Dynamic Ink, Dermalgo Ink (UK), Evil Ink, Jet Tattoo Ink, Pro Tattoo Ink, U.S. Tattoo Supply Ink, Black Tiger Tattoo Ink, Infiniti Tattoo Ink, Infiniti Painless Tattoo Ink, Internal Glow Tattoo Ink, Crow Tattoo Ink, and so on. In addition, an effort to understand the use and preference of tattoo inks by tattoo artists would help the forensic scientist understand the prevalence* of tattoo inks used by tattooists. Whether or not an artist consistently uses a specific ink brand for his or her work as opposed to switching products routinely based on cost, availability, recommendations, and so on, could make a substantial difference in an investigation. The possibility of counterfeiting may also affect tattoo ink contents (Figure 11.2). According to Miranda One problem in attempting to understand the trends in manufacture and distribution of tattoo inks is the potential for counterfeit products; for example, a search of tattoo inks on popular online marketplaces offers brand-name tattoo inks at a fraction of the cost, and a careful examination of packaging (bottle type and shape, labels) demonstrates differences between the ‘originals’ and those offered at a discount through online marketplaces. It is possible that the

Figure 11.2  Some packaging and advertisements feature a licensed logo such as these, likely in an effort to demonstrate that they are selling the original products and not counterfeit inks. * An internet search of “Tattoo Supply” will provide an extensive array of suppliers; by navigating to suppliers websites and shopping their Tattoo Ink sections, the extent of tattoo ink brands/names becomes apparent.

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determination of counterfeiting based on comparison of chemical composition of the real and counterfeited product (as well as chemical composition and physical characteristics of the packaging and associated labels) may further enhance the usefulness of tattoo ink databases and methods of analysis (Miranda, 2012b, p. 102).

Legislation and Regulation Concerning Tattooing Many facets of tattooing legislation and oversight are regulated based on jurisdiction and can be determined by state statutes or local ordinances. Much concern has been given to health regulations and codes directed toward the tattoo artist and tattoo parlors, largely to ensure the safety of the patrons and to prevent transmission of infection and disease. Such regulations and guidelines include mandating tattooing be conducted by licensed tattoo artists, while some states/cities may require certification, taking courses and passing exams relating to tattooing, health and safety, and so on (Armstrong, 2005, p. 39). Some jurisdictions require tattoo parlors be registered and also meet requirements of the local Board of Health. Additional legal matters are concerned with the prohibition of tattooing while incarcerated; prohibition of tattooing of persons under the influence of drugs or alcohol; as well as the prohibition of the tattooing of minors (under that age of 18), while some states will allow the tattooing of minors with written consent from a parent. For example, according to the New York State Penal Law §260.21 Unlawfully dealing with a child in the second degree, a ­person is guilty of unlawfully dealing with a child in the second degree when “…He marks the body of a child less than eighteen years old with indelible ink or pigments by means of tattooing” (NYS Penal Law, 2013, p. 152). Recently, much attention has focused on the regulation of tattoo parlors, tattoo artists, tattoo equipment (such as pigments and inks), as well as the methods of sanitizing equipment and maintaining health codes. Regulation and oversight by both the FDA and the Department of Health has been proposed. According to the FDA’s website FDA considers the inks used in intradermal tattoos, including permanent makeup, to be cosmetics… The pigments used in the inks are color additives, which are subject to premarket approval under the Federal Food, Drug, and Cosmetic Act. However, because of other competing public health priorities and a previous lack of evidence of safety problems specifically associated with these pigments, FDA traditionally has not exercised regulatory authority for color additives on the pigments used in tattoo inks. The actual practice of tattooing is regulated by local jurisdictions.* * http://www.fda.gov/Cosmetics/ProductsIngredients/Products/ucm108530.htm.

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With regard to the FDA and the Federal Food, Drug, and, Cosmetics Act, Ortiz and Alster report that the FDA is investigating the chemical composition of tattoo inks, the way they are metabolized by the body, short and long term safety, and interactions with light and lasers (Ortiz and Alster, 2012, p. 425). Much attention is focused on allergic reactions, introduction of microbial contamination and, the potential dangers of long-term exposure to tattoo pigments and photodecomposition products. Currently, no tattoo ink or additive is FDA approved; no color additives are FDA approved for injection into the skin. More recently, the District of Columbia Department of Health gave notice [O]f the intent to adopt new body art regulations in Title 25 (Food Operations and Community Hygiene Facilities), Subtitle G (Body Art Establishment Regulations) of the District of Columbia Municipal Regulations…The purpose…is to provide regulatory oversight of body art pursuant to the recently enacted Regulation of Body Artists and Body Art Establishments Act of 2012… This legislation provides the Department of Health with exclusive regulatory oversight of body art establishments in Title 25, Subtitle G of the District of Columbia Municipal Regulations and will enable the District of Columbia to protect public health and safety in body art procedures.*

The regulations proposed include matters related to qualifications and training of licensed tattoo artists, pre- and post-operating procedures, preventing contamination, record keeping and record maintenance, shop structure and operation, facility maintenance, license and registration requirements, inspections and reporting of findings from inspections, hazards and violations, administrative matters (including equipment maintenance), hearings, civil and criminal sanctions, as well as reviews and appeals. With regard to inks and pigments, Section 300 is concerned with preventing contamination, and Section 801 is concerned with the examination, sampling and testing: 300.1 All body artists shall use only sterile water to mix and dilute inks, dyes or pigments and shall not use tap water or distilled water (p. 13); 300.2 All tattoo artists shall use inks, dyes and pigments that are specifically manufactured for performing body art procedures in accordance with manufacturer’s instructions (p. 14); 801.1 The Department may examine, collect samples, and test equipment, water, inks, dyes, pigments, reusable instruments, disposable items, jewelry, sharps, marking instruments and stencils, and furnishings without cost and test as necessary to determine compliance with these regulations (p. 50). * http://www.dcregs.dc.gov/Gateway/NoticeHome.aspx?noticeid=5009873.

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The regulations also require the conspicuous posting of a disclosure sign which contains the excerpt, “There may be a risk of carcinogenic decomposition associated with certain pigments when the pigments are subsequently exposed to concentrated ultra-violet light or laser irradiation” (p. 10). Recordkeeping practices require maintaining a list of actual pigments used in the particular establishment (314.1.a) as well as using suppliers and manufacturers of pigments that are registered in the District (706.2.j). Whether or not these proposals will become policies and whether or not other jurisdictions adopt similar policies remains to be seen. Furthermore, the degree of enforcement and what affects these policies have on law enforcement and legal matters will need to be considered upon implementation. Without a comprehensive analysis and a thorough understanding of the composition of tattoo inks as well as definitive establishment of manufacturing guidelines, some aspects of the proposed regulations may be difficult to enforce. With tattoos no longer a characteristic of the marginalized and individuals on the fringe of society, and, therefore, present on a large portion of the population, tattoos provide a fertile ground for identification and individualization in forensic investigations. Forensic scientists and crime laboratories should establish tattoo ink databases using microscopic and spectroscopic methods and researchers should continue to study tattoo ink compositions, much the way there have been myriad studies of artist’s, architectural and automotive paints and pigments as well as writing and artist’s inks. Forensic scientists should also work with medicolegal investigators and medical examiners to search for, examine and document the presence of tattoos on human remains, especially in instances where the remains are decomposed, charred or in a state such that their resolution and visualization may be the best means of conducting an identification. In addition, portions of the tattoos should be excised such that laboratory analysis of the pigments within the tissue can be conducted microscopically and spectroscopically. Tattoos are now quite ubiquitous and unique to the wearer—factors such as design, size, color, placement as well as relative amounts and locations of multiple tattoos on an individual lend themselves to identification and, in many instances, individualization. Locating, enhancing, resolving and documenting tattoos is rapid and straightforward and can provide substantial investigatory information in less time than many forensic identification techniques (e.g., dental, radiological, fingerprinting, DNA). Forensic experts and law enforcement personnel should not underestimate the power and weight of the tattoo and should make every effort to include such evidence in their analyses and investigations.

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Youssef, N. 2006. These tattoos aren’t artful-they help identify Iraq’s dead, McClatchy Newspapers, October 31, http://www.mcclatchydc.com/2006/10/31/14926/ these-tattoos-arent-artfulthey.html. Yules, R., D. Laub, R. Honey, A. Vassiliadis, and L. Crowley. 1967. The effect of Q-switched ruby laser radiation on dermal tattoo pigment in man, Archives of Surgery, 95(2), 179–180. Yurkew v. Sinclair, 495 F.Supp. 1248, 1980. Zeis, M. 1947. Tattooing the World Over. Rockfort, IL: Zeis Studio Publications. Zeis, M. 1953. Tattooing: As Ancient as Time, as Modern as Tomorrow. Rockfort, IL: Zeis Studio Publications. Zeis, M. 1960. Tattoo Artist Course: Secrets of the Art of Tattooing. Rockford, IL: Zeis Studio Publications. (Reproduction). Zeis, M. 1968. Tattooing the World Over, Second edition. Rockfort, IL: Zeis Studio Publications. Zieba-Palus, J. and M. Kunicki. 2006. Application of the micro-FTIR spectroscopy, Raman spectroscopy and XRF method examination of inks, Forensic Science International, 158(2–3), 164–172. Zieba-Palus, A. Michalska, and A. Weselucha-Birczynska. 2011. Characterisation of paint samples by infrared and Raman spectroscopy for criminalistic purposes, Journal of Molecular Structure, 993(1–3), 134–141. Zimmerman, M. 1979. Suits for malpractice based on alleged unsightly scars resulting from removal of tattoos, Journal of Dermatologic Surgery and Oncology, 5(11), 911–912. Zlotnick, J. and F. Smith. 1999. Chromatographic and electrophoretic approaches to ink analysis, Journal of Chromatography B, 733, 265–272. Zollinger, H. 1961. Azo and Diazo Chemistry—Aliphatic and Aromatic Compounds. New York, NY: Interscience Publishers. Zollinger, H. 2003. Color Chemistry: Syntheses, Properties, and Applications of Organic Dyes and Pigments, third edition. Switzerland: Wiley-VCH.

Index

A AAS, see Atomic absorption spectroscopy (AAS) ABO system, 33 Acetone (CH3COCH3), 86, 205, 206 Additives, 83, 84, 94, 124, 137, 140 color, 314, 315 pigment, 258 Adulterants, 101, 102, 103, 104, 106 Alizarin (C14H6O2(OH)2), 101, 102, 103, 216 Aloe, 105, 106 α-keto azo pigments, 154 Amarelo Canario, 161, 283, 285 comparison of Amarelo Canario and excitation wavelengths, 285 comparison of normal Raman and SERS spectra of, 285 tattoo ink, 169 Amarelo Fluor, 161, 285–286 FT-Raman spectra of, 286 spectral comparison of, 286 tattoo ink, 170 Amateur tattoos, 7, 8, 9, 35, 61, 62 American oak, 105, 106 American Society of Crime Lab Directors/ Laboratory Accreditation Board (ASCLD/LAB), 218 Aniline, 117, 137, 152 Anthropometry, 32, 34 Approaching individualization, 34 Argon ion laser (Ar+ laser), 226 Arylmethane dyes, 137 ASCLD/LAB, see American Society of Crime Lab Directors/Laboratory Accreditation Board (ASCLD/ LAB) Atomic absorption spectroscopy (AAS), 144 ATR, see Attenuated total reflection (ATR) Attenuated total reflection (ATR), 208, 305, 306 attachment for ATR measurements, 227

exception, 213 FT-IR/ATR spectrum, 240, 241, 282, 288 spectra, 209 Azo pigments, 154 α-keto, 154 disazo pigments, 156, 205 monoazo pigments, 155 reference spectra, 159 Azul Royal, 288 tattoo ink, 171

B Barium sulfate (BaSO4), 84, 103, 104, 124 Beer’s law, 206 Bellbottom Blue, 269 normal Raman spectra, 272 Raman spectra, 271 tattoo ink, 177 Benzophenone (BP), 100 Bile pigments, 63 Bilirubin, 63, 109 Biopsy specimens, 61, 62 Black Cherry Roan 2, 275 comparison, 279 and Pigment Red 146, 279 tattoo ink, 180 Black colors, 98 Black light, 144 Black tattooing pigments, 98; see also Blue tattooing pigments; Brown tattooing pigments; Green tattooing pigments; Orange tattooing pigments; Purple tattooing pigments; Red tattooing pigments; White tattooing pigments; Yellow tattooing pigments black colors, 98 chemical composition of pigments, 100 gunpowder, 99

353

354 Black tattooing pigments (Continued ) lampblack, 99 principle colorants, 99 Black tattoo ink, 17, 100, 198 PAHs in, 129 Blanket method of tattooing, 66 Blisterine, 264 Pigment Orange 34 and Pigment Yellow 3, 266 Pigment Yellow 74spectrum vs., 264–265 tattoo ink, 175 Blood grouping, 33 Blood typing, see Blood grouping Blue sky tattoo ink, 192 Blue tattooing pigments, 106; see also Black tattooing pigments; Brown tattooing pigments; Green tattooing pigments; Orange tattooing pigments; Purple tattooing pigments; Red tattooing pigments; White tattooing pigments; Yellow tattooing pigments Campeachy wood, 108 Indigo, 106, 107 Laundry blueing, 107 Prussian blue, 106 Blue tattoo ink, 194, 294 characteristic fluorescence superimposed on, 254 in pigskin, 299 Blue tattoos, 59 Bone black, 98, 99, 100 BP, see Benzophenone (BP) Brazilin (C16H14O5), 101, 102, 103 Brazilwood, 98 extract, 102 principle colorants in, 103 Brick dust, 87, 88, 101, 139 Bright black tattoo ink, 197 Bright red tattoo ink, 184, 291, 292 Bright yellow tattoo ink, 187, 294 Brown tattooing pigments, 108–109; see also Black tattooing pigments; Blue tattooing pigments; Green tattooing pigments; Orange tattooing pigments; Purple tattooing pigments; Red tattooing pigments; White tattooing pigments; Yellow tattooing pigments Business in tattooing, 89

Index C Cadmium carbonate (CdCO3), 104 Cadmium mercury sulfide S (CdHg S), 104 Cadmium oranges, 104 Cadmium oxalate (Cd[C2O4]), 104 Cadmium oxide (CdO), 104 Cadmium selenide (CdS), 101, 104, 123 Cadmium sulfide (CdS), 104, 105, 108 Calcite (CaCO3), 132 Campeachy wood, 106, 108 Candy Apple Red, 258, 259 normal Raman spectra, 259 Raman spectra, 259 tattoo ink, 173 Carbazole, 135 Carbon-based black pigments, 97, 101 Carbon-based blacks, 98, 158 Carbon hydrogen derivatives, 150 Carmine (C22H22O13), 31, 87, 101, 103 Carminic acid, see Carmine Cassiterite (SnO2), 132 CCD detectors, see Charge coupled device detectors (CCD detectors) Charge coupled device detectors (CCD detectors), 213 Chemical methods, 62, 69 Chemischen und Veterinäruntersuchungsämter (CVUA), 123 China ink, see India ink Chinese red tattoo ink, 105, 110, 183, 291 Chinese stick ink, 89 Chrome pigments, 104 Chromogens, 151 Chromophores, 74, 150 conjugation, 204 nature and number of, 151 within skin, 74 Cicatrization, 4, 5, 7, 22 Cinnabar, 31, 60, 88, 101, 110 adulterants in, 102 synthetic form, 101 Circumin, 105 Citrus tattoo ink, 169, 282–283 FT-Raman spectrum, 284 spectral comparison with Amarelo Fluor ink, 286 Classes of particles, 128 Coal tar dyes, 152, 153 Cobalt aluminate (Al2O3CoO), 106, 108

Index Cobalt aluminum oxide (CoAl2O4), see Cobalt aluminate (Al2O3CoO) Colorants, 80, 83, 103, 142, 149, 217 Color perception, 55, 58 assessment of color perception of veins within tissue, 57 light and, 58 Copper phthalocyanine (CuPc), 122, 135, 136, 253–254 characteristic fluorescence superimposed on blue tattoo ink, 254 crystal forms, 157 Courtroom Court of Appeals, 53 Dawson’s First Amendment rights, 51 defendant’s tattoos, 49 Greer’s Fifth Amendment rights, 50 information rich tattoos, 47 interpretation of teardrop tattoos, 48 prejudicial effect, 52 tattoos in, 46 Cover-ups, 8, 65, 67 examples of tattoo, 67 skin-colored cover-ups, 66 Criminal atavism, 26 Criminal investigations, 45 2010 New Hampshire case homemade tattoo machine, 46 shape of damage to boxer shorts, 45 tattoos and, 44 Criminological theories, 25 criminal atavism, 26 diagrams from Lombroso’s text, 28 statistical study of physical features of convicts, 29 tattoo diagrams from Lombroso’s book, 27 tattoos and, 25 Crocetin, 105 CVUA, see Chemischen und Veterinäruntersuchungsämter (CVUA) Cyan tattoo ink, 193 Cyclohexane (C6H6), 205

D Daddy’s Boy (DB), 46 Dark black tattoo ink, 199 Dark blue tattoo ink, 195

355 Dark brown tattoo ink, 200, 294, 295 Dark cyan tattoo ink, 193 Dark green tattoo ink, 191 Dark red tattoo ink, 185, 291 Dawson’s First Amendment rights, 51 DB, see Daddy’s Boy (DB) DBF, see Dibenzofuran (DBF) DBP, see Dibutyl phthalate (DBP) Defendant’s tattoos, 47, 49, 51 Density functional theory (DFT), 256, 306 Deoxyribonucleic acid (DNA), 20, 34 analysis, 39, 43 fingerprint, 34 forensic, 34 profile, 39 results, 40 Depth of penetration, 56, 60, 208, 209, 300 Dermal layer, 6, 55, 63, 300 Dermis, 55, 56, 59, 61, 64, 124 Design modification, 66 Destructive distillation, 153 Destructive method, 63 DFT, see Density functional theory (DFT) Dibenzofuran (DBF), 100 Dibutyl phthalate (DBP), 100 1,2-dihydroxy-9, 10-anthracenedione, see Alizarin (C14H6O2(OH)2) 1,2-dihydroxyanthraquinone, see Alizarin (C14H6O2(OH)2) Dimethyl formamide (DMF), 205 Disazo pigments, 154, 156, 205 distilled water (dH2O), 71, 161 DMF, see Dimethyl formamide (DMF) DNA, see Deoxyribonucleic acid (DNA) Dolemite, 261–264 band locations, 263 extraction, 262, 264 FTIR spectra, 263 normal Raman spectra, 262 spectrum of pigment yellow 74 vs., 261–262 tattoo ink, 175 Dyes, 80, 83, 150, 215, 217 adsorption, 216 arylmethane, 137 chelated metalized, 136 coal tar, 153 madder, 103 organic, 112 synthetic inorganic azo, 113 tattoo, 66, 113

356 E Eagle tattoo, 60 EDS, see Energy dispersive spectroscopy (EDS) Eggplant black tattoo ink, 164, 198 Electromagnetic spectrum, 55, 58, 62, 152, 232 Energy dispersive spectroscopy (EDS), 159 Energy dispersive x-ray spectroscopy, 97, 118 Epidermis, 55, 63, 307 Euxanthic acid, 104 Evanescent wave, 208 Extradermal tattoos, 18

F Feldman’s inks, 311 Ferric oxide (Fe2O3), 103 Fingerprinting, 33 Flash, 11 Fleming adds, 4 Fluorescence, 283 Flying Tigers tattoo inks, 163, 164, 182; see also Iron Works Brasil tattoo inks; Skin Candy tattoo inks black tattoo ink, 198 blue sky tattoo ink, 192 blue tattoo ink, 194, 294 bright black tattoo ink, 197 bright red tattoo ink, 184 bright yellow tattoo ink, 187 Chinese red tattoo ink, 183 cyan tattoo ink, 193 dark black tattoo ink, 199 dark blue tattoo ink, 195 dark brown tattoo ink, 200, 294, 295 dark cyan tattoo ink, 193 dark green tattoo ink, 191 dark red tattoo ink, 185 eggplant black tattoo ink, 198 golden yellow tattoo ink, 188 grape tattoo ink, 195 grass hopper tattoo ink, 189 greens, 294 grey tattoo ink, 197 khaki tattoo ink, 189 lawn green tattoo ink, 191 light chocolate tattoo ink, 200, 294, 295 light green tattoo ink, 190 magenta tattoo ink, 183

Index mid-yellow tattoo ink, 187 mulberry tattoo ink, 185 navy blue tattoo ink, 194 orange red and orange, 291, 293 orange red tattoo ink, 186 orange tattoo ink, 186 pink red tattoo ink, 182, 290–291 purple tattoo ink, 196, 294, 295 reds, 291 rose red tattoo ink, 184 salmon pink tattoo ink, 182, 290 sayonara suede tattoo ink, 199 skin tone tattoo ink, 201, 296 turquoise blue tattoo ink, 192 verdancy tattoo ink, 190 violet tattoo ink, 196, 294, 295 white tattoo ink, 201, 296 yellow tattoo ink, 188, 293–294 Folk remedies, 72 Forced idleness, 25 Forensic investigations, 29 anthropometry, 32 identity based on character of pattern, 30 research collections, 31 tattoos and, 29 Forensic serology, 33 Fourier transform, 207 Fourier transform infrared spectroscopy (FT-IR), 100 FT-IR/ATR spectrum, 241, 243 Fumigation method, 7 Function check, 219

G Galena (PbS), 132 Gas chromatography-mass spectrometry (GC-MS), 100, 117 Germanium (Ge), 208, 213 GF-AAS, see Graphite furnace and flame Atomic Absorption Spectroscopy (GF-AAS) Glycerine, 84 Golden yellow tattoo inks, 188, 293–294 Grape tattoo ink, 195 Graphite furnace and flame Atomic Absorption Spectroscopy (GF-AAS), 117 Grass hopper tattoo ink, 189 Greens tattoo ink, 294, 299

Index Green tattooing pigments, 106; see also Black tattooing pigments; Blue tattooing pigments; Brown tattooing pigments; Orange tattooing pigments; Purple tattooing pigments; Red tattooing pigments; White tattooing pigments; Yellow tattooing pigments Greer’s Fifth Amendment rights, 50 Grey tattoo ink, 197 Gunpowder, 99 Gunpowder tattooing removal, 69

H HCBD, see Hexachloro-1,3-butadiene (HCBD) Helium/Neon laser (He-Ne laser), 226 Hematite (Fe2O3), 132 Henna, 143 Hertzberg–Teller equation, 215 HET, see Hexamethylenetetramine (HET) Hexachloro-1,3-butadiene (HCBD), 100 Hexamethylenetetramine (HET), 100 High-pressure liquid chromatography (HPLC), 100 Homemade tattoo inks, 84–86 Homemade tattoo machine, 46 HPLC, see High-pressure liquid chromatography (HPLC) Human skin, 55 anatomy, 55 assessment of color perception of veins within tissue, 57 electromagnetic spectrum, 58 factors, 58–59 layers, 56 light scattering, 56–57 optical pathways, 57 Human tissues, 55 tattoo pigments and, 59–61 Hydrogen peroxide (H2O2), 62 Hydroxides, 103 Hydroxyazo-ketohydrazone tautomerism, 154

I ICP-MS, see Inductively coupled plasma mass spectrometry (ICP-MS) ICPAES, see Inductively coupled plasma atomic absorption spectroscopy (ICPAES)

357 Identifications-based tattoos, 40 Identification tattoos, 35 Imiquimod, 73 India ink, 85, 134 Indigo, 106, 107 Indigotin disulphonic acid, 71 Indium gallium arsenide (InGaAs), 213 Inductively coupled plasma atomic absorption spectroscopy (ICPAES), 132 Inductively coupled plasma mass spectrometry (ICP-MS), 100 Information rich tattoos, 47 Infrared spectrometry, 206 ATR reflectance spectrum, 209 depth of penetration, 208 Fourier transform infrared instruments, 207 Infrared spectrum, 308 Inorganic colorants, 149 Inorganic pigments, 145 Instrument qualification, 218 Intermediate-color particles, 128 Internal reflection element (IRE), 208 International Organization of Standardization (ISO), 218 IRE, see Internal reflection element (IRE) Iron oxides, 103 Iron Works Brasil study, 161 Iron Works Brasil tattoo inks, 162, 167; see also Flying Tigers tattoo inks; Skin Candy tattoo inks Amarelo Canario tattoo ink, 169, 283, 285 Amarelo Fluor tattoo ink, 170, 285–286 Azul Royal tattoo ink, 171, 288 Citrus tattoo ink, 169, 282–283 Lilas Claro tattoo ink, 172, 288 Magenta tattoo ink, 171, 288 Pink tattoo ink, 168, 281–282 Preto Escuro tattoo ink, 172 Verde Claro tattoo ink, 170, 286–287 Vermelho, 281 ISO, see International Organization of Standardization (ISO) Ivory black, 99

J Jagger, 14 Japanese-style tattoos, 91

358 K Kaolinite (Al2O3⋅2SiO2⋅2H2O), 132 Keloid, 5 Keratin-rich epidermis, 6 Khaki tattoo ink, 189

L Lampblack, 99 Largest-white particles, 128 Laser-induced breakdown spectroscopy (LIBS), 127 Laser tattoo removal, 73, 74 dermatological and histological studies, 75 for different color pigments, 76 Q-switched ruby laser, 75 suitability of lasers for different tattoo colors, 77 thermal decomposition, 73 Laundry blueing, 107 Lawn green tattoo ink, 191 LIBS, see Laser-induced breakdown spectroscopy (LIBS) Light, 58 scattering, 56–57 Light chocolate tattoo ink, 200, 294, 295 Light green tattoo ink, 190 Lilas Claro tattoo ink, 172, 288 photomicrograph of region, 289 Listerine, 84, 90 Lithium oxide (Li2O), 110 Logwood (Haematoxylum campechianum), 99 Lymphatic ganglion, 61

M Magenta tattoo ink, 171, 183, 288 Malachite (Cu2(CO3)(OH)2), 132 Manganese oxide (MnO), 101, 103 Market players, 119 Marz, 258, 261 Marz tattoo ink, 174 Mass spectral data (MSD), 101 Mass spectrometry (MS), 116 Material Safety Data Sheets (MSDS), 124 Mechanical methods, 68, 69 Mercuric sulfide pigment, 101 Methanol (CH3OH), 205 Methylene chloride (CH3Cl), 205

Index Microscopy, 161, 305 Flying Tigers tattoo inks, 163, 164 Iron Works Brasil tattoo inks, 162, 167–172 Miranda’s research study, 164 Olympus BH metallurgical microscope, 165 pigment samples, 166 pigments reported by Delly, 167 Skin Candy tattoo inks, 162, 173–181 Skin Candy tattoo inks ingredients, 163 tattoo inks, 161 Mid-yellow tattoo inks, 187, 293–294 Miranda’s research, 305–306 Modern tattooing pigments, 109 pigment information, 111, 112 x-ray microanalysis, 110 Modern tattoo inks, 124; see also Tattoo inks additional studies of, 127–129 auxiliary ingredients, 125 liquid composition of, 124–127 propylene glycol, 125 Moko pattern, 34 Molecular spectroscopy-Raman and infrared spectroscopy, 226 He-Ne laser, 226 Nd/YAG laser, 226–227 reference pigments, 228 SERS, 227 Monoazo pigments, 155 MS, see Mass spectrometry (MS) MSD, see Mass spectral data (MSD) MSDS, see Material Safety Data Sheets (MSDS) Muddy Water Blue tattoo ink, 178, 270 Raman spectra, 273, 274 Mulberry tattoo ink, 185

N National Institute of Standards and Technology (NIST), 101 Natural brown pigments, 109 Natural color pigments, 97 Natural pigments, 101 Natural red pigments, 103 Natural yellow pigments, 106 Navy blue tattoo ink, 194 Needle cartridges, 15 Neodymium-yttrium aluminum garnet laser (Nd/YAG laser), 226–227 New York-based tattoo artists, 96

Index 9F, see 9-fluoronone (9F) 9-fluoronone (9F), 100 NIST, see National Institute of Standards and Technology (NIST) ν4 rule, 213

O Ochres, 103 ω4 rule, 211, 213 OPD, see Optical path difference (OPD) Optical path difference (OPD), 208 Orange red tattoo inks, 186, 291, 293 Orange tattooing pigments, 104–105; see also Black tattooing pigments; Blue tattooing pigments; Brown tattooing pigments; Green tattooing pigments; Purple tattooing pigments; Red tattooing pigments; White tattooing pigments; Yellow tattooing pigments Orange tattoo inks, 186, 291, 293, 298 Organic colorants, 149 Organic pigments, 124, 149 absorption characteristics of colors, 152 carbon hydrogen derivatives, 150 chromogens, 151 coal tar dyes, 153 disazo pigments, 156 hydroxyazo-ketohydrazone tautomerism, 154 monoazo pigments, 155 oxazines, 157–158 phthalocyanines, 154–155, 157 pigments analysis, 159–160 quinacridones, 158 shifts in UV/Vis spectrophotometry, 151 structural features for color, 152 synthetic, 153, 154 tetrabenzoporphyrazine nucleus, 156 Oxazines, 124, 154, 157–158 Ox gall, 108–109

P PAHs, see Polycyclic aromatic hydrocarbons (PAHs) Painting, 4, 5, 70, 92, 131, 135, 137 Para-phenylenediamine (PPD), 143 Partial least squares analysis (PLS analysis), 307

359 Particle encapsulation delivery system (PEDS), 79 PB 15, see Pigment Blue 15 (PB 15) PEDS, see Particle encapsulation delivery system (PEDS) Pelican ink, 85 Permanent decorations, 5 PG 36, see Pigment Green 36 (PG 36) PG 7, see Pigment Green 7 (PG 7) Photothermolysis, 73, 74 Phthalocyanines, 154–155, 157 Pigment Blue 15 (PB 15), 155, 157, 251, 252 variation in Raman spectra, 253 Pigment Green 36 (PG 36), 155, 157, 271 Pigment Green 7 (PG 7), 155, 157, 250–251 Pigment Orange 16 (PO 16), 154, 241–242 Pigment Orange 34 (PO 34), 154, 243–244 Pigment Orange 62 (PO 62), 244–245 Pigment Orange tattoo inks 13, 292, 293 Pigment Red 122 (PR 122), 158, 237–238 Pigment Red 146 (PR 146), 154, 238–239 Pigment Red 170 (PR 170), 154, 239 Pigment Red 255, 239 comparison, 241 FT-IR/ATR spectrum, 240 Pigments, 83 additional studies of, 127–129 in art and manufacturing, 134–135 chemistry, 58 for cosmetic purposes, 133–134 detection in tattooed skin, 61–62 exhibits luminescent properties, 140 in henna products, 143 for medicinal purposes, 131–133 related to iron gall inks, 138 in temporary tattoo design, 142 Pigment standards, 237 PB 15, 251–254 PG 7, 250–251 Pigment Red 255, 239–241 Pigment Violet 23α, 254–255 Pigment Violet 23β, 255–257 Pigment Yellow 15, 248–249 PO 16, 241–242 PO 34, 243–244 PO 62, 244–245 PR 122, 237–238 PR 146, 238–239 PR 170, 239 PY 3, 245–246 PY 73, 246–247 PY 83, 247–248

360 Pigment Yellow 151 (PY151), 154, 248–249 Pigment Yellow 3 (PY 3), 245–246 Pigment Yellow 73 (PY 73), 246–247 Pigment Yellow 83 (PY 83), 154, 247–248 Pigskin, 296 Raman spectra, 300, 301 with series of Skin Candy tattoo inks, 297 Pink red tattoo ink, 182s, 290–291 Pink tattoo ink, 168, 281–282 SERS spectrum, 284 PLM, see Polarized light microscopy (PLM) PLS analysis, see Partial least squares analysis (PLS analysis) PMI, see Postmortem interval (PMI) PO 16, see Pigment Orange 16 (PO 16) PO 34, see Pigment Orange 34 (PO 34) PO 62, see Pigment Orange 62 (PO 62) Polarized light microscopy (PLM), 159 Polycyclic aromatic hydrocarbons (PAHs), 100, 101, 129 Postmortem interval (PMI), 63 Potassium bromide (KBr), 227, 308 Potassium nitrate (KNO3), 216 PPD, see Para-phenylenediamine (PPD) PR 122, see Pigment Red 122 (PR 122) PR 146, see Pigment Red 146 (PR 146) PR 170, see Pigment Red 170 (PR 170) Preto Escuro tattoo ink, 172 Pricking methods, 6 Printer inks, 85 Prison tattoos, see Amateur tattoos Professional tattoo inks, 87; see also Tattoo inks Bowery neighborhood of New York City, 88 business in tattooing, 89 colors and pigments in tattooing, 94–95 contradictory information, 92 cover-up and top portion of tattoo, 93 Japanese-style tattoos, 91 listerine, 90 New York-based tattoo artists, 96 pamphlet for Zeis School of Tattooing, 89 pigments, 87 tattaugraphs, 88 Zeis Publications, 90 Professional tattoos, 8 Propylene glycol, 125 Prussian blue, 106, 107

Index Purple tattooing pigments, 108; see also Black tattooing pigments; Blue tattooing pigments; Brown tattooing pigments; Green tattooing pigments; Orange tattooing pigments; Red tattooing pigments; White tattooing pigments; Yellow tattooing pigments Purple tattoo ink, 196, 294, 295, 299 PY151, see Pigment Yellow 151 (PY151) PY 3, see Pigment Yellow 3 (PY 3) PY 73, see Pigment Yellow 73 (PY 73) PY 83, see Pigment Yellow 83 (PY 83)

Q Q-switched ruby laser, 75 Qualification, 218–220 Quinacridones, 158

R Raman active mode, 210 Raman effect, 209 Raman inactive mode, 210 Raman scattering intensity, 211 Raman spectroscopy, 209, 237, 301, 306 intensity of Raman scattering, 211 laser excitation wavelengths, 212 Raman effect, 209, 210 Raman instruments 213 by sample degradation, 214 stand-alone spectrometers, 212 Razberry Creem tattoo ink, 178, 274–275 and Pigment Red 122, 278 Raman spectrum, 276 SERS spectrum, 277, 278 SERS spectrum and FT-Raman spectrum, 277 Red henna (Lawsonia inermis), 143 Red Hot tattoo ink, 173, 258, 260 Red tattooing pigments, 101; see also Black tattooing pigments; Blue tattooing pigments; Brown tattooing pigments; Green tattooing pigments; Orange tattooing pigments; Purple tattooing pigments; White tattooing pigments; Yellow tattooing pigments adulterants, 102

Index cinnabar and vermilion, 101 iron oxides and hydroxides, 103, 104 natural pigments, 101 Red tattoos, 59 inks, 291, 298 Reflected infrared photography, 63 Refractive index (RI), 164, 208 Resonance Raman scattering, 211 Retention of pigments, 59 RI, see Refractive index (RI) Ripple tattoo ink, 179, 270 polymorphs of PV23, 276 Raman spectra, 274, 275 Roan 1 tattoo ink, 180 Roan 3 tattoo ink, 180 Roan color series, 275, 278 Rose Red tattoo inks, 184, 291, 292

S S-TEM, see Scanning transmission electron microscopy (S-TEM) Saffron, 105 Salabrasion, 69 Salmon pink tattoo inks, 182, 290 San brownadino tattoo ink, 179, 275–276 Raman spectra, 279 Santalin, 102, 103 Sassygrass tattoo ink, 176, 266–268 Sayonara suede tattoo ink, 199 Scanning electron microscopy (SEM), 61 Scanning electron microscopy/energy dispersive spectroscopy (SEMEDS), 100, 119, 132, 134 Scanning transmission electron microscopy (S-TEM), 305 Scarification, 4, 5, 7, 22 Scientific inquiry, 53–54 Sector field inductively coupled plasma mass spectrometry (SF-ICP-MS), 122 SEM-EDS, see Scanning electron microscopy/energy dispersive spectroscopy (SEM-EDS) SEM, see Scanning electron microscopy (SEM) Sepia species, 108–109 SERRS, see Surface enhanced resonance Raman scattering (SERRS) SERS, see Surface enhanced Raman scattering (SERS)

361 7-a-d-glucopyranosyl-9,10-dihydro-3,5,6,8tetraahydroxy-1-methyl-9,10dioxo-2-anthracenecarboxylic acid, see Carmine (C22H22O13) Sewing technique, 6 SF-ICP-MS, see Sector field inductively coupled plasma mass spectrometry (SF-ICP-MS) Siennas, 103 Silver colloid, 216–217, 227 Skin-colored cover-ups, 66 Skin Candy study, 161 Skin Candy tattoo inks, 162, 173, 257; see also Iron Works Brasil tattoo inks; Flying Tigers tattoo inks Bell Bottom Blue tattoo ink, 177, 269 Black Cherry Roan 2 tattoo ink, 180, 275 Blisterine tattoo ink, 175, 264–266 Candy Apple Red tattoo ink, 173, 258, 259 Dolemite tattoo ink, 175, 261–264 Marz tattoo ink, 174, 258, 261 Muddy Water Blue tattoo ink, 178, 270 Razberry Creem tattoo ink, 178, 274–275 Red Hot tattoo ink, 173, 258, 260 Ripple tattoo ink, 179, 270, 274 Roan 1 tattoo ink, 180 Roan 3 tattoo ink, 180 San brownadino tattoo ink, 179, 275–276 Sassygrass tattoo ink, 176, 266–268 S. R. V. Teal 2 tattoo ink, 177 SRV Teal 2, 269–270 Tastywaves tattoo ink, 176, 268–269 tattoo inks ingredients, 163 Tokyo pink tattoo ink, 181, 277, 281 White girl tattoo ink, 181, 276–277 Skin pigmentation process, 4 Skin tone tattoo ink, 201, 296 Smallest-black particles, 128 Sodium chloride (NaCl), 216 Spectroscopy acetominophen—Raman, 225 copper/tin—XRF, 220 cyclohexane—Raman, 223 didimium—UV/Vis, 221 50/50 toluene, 225 holmium oxide—UV/Vis, 222 infrared spectrometry, 206–209 instrument calibration, method development, and standard practices, 217 instrument qualification, 218

362 Spectroscopy (Continued ) polystyrene—Raman, 223–224 Raman spectroscopy, 209–214 SERS, 214–217 silicon—Raman, 226 sulfur—Raman, 224–225 UV-Vis spectrometry, 203–206 UV/Vis spectrophotometer, 220 validation process, 219 XRF, 203 S. R. V. Teal 2 tattoo ink, 177 SRV Teal 2 ink, 269–270 Raman spectra, 272–273 Standard tattoo flash, 11 Stratum corneum, 55, 56, 235, 236 Street tattoos, see Amateur tattoos Strong (s) peak, 241 StyrofoamTM cup, 86 Subconscious sadism, 25 Sulfuric acid (H2SO4), 205 Surface enhanced Raman scattering (SERS), 214, 215, 306 analytical performance, 216 conducting on tattoo ink pigment, 227 enhancement factor equation, 215 metal substrate preparation, 215–216 SERRS, 217 Surface enhanced resonance Raman scattering (SERRS), 217 Synthetic color pigments, 97 Synthetic organic pigments, 83, 87, 109, 112, 113, 124, 128, 150, 153, 154, 159, 308

T Tannic acid, 70, 71, 137, 138 Tapping, 7 Tastywaves tattoo ink, 176, 268–269 Raman spectra, 270, 271 Tattaugraphs, 88 Tattoo(s) advertisement for tattooing of blood types, 36 aid in identification, 39 cinnabar, 60 in courtroom, 46–53 and criminal investigations, 44–46 and criminological theories, 25–29 designs visible under charring, 44 eagle tattoo, 60 fingerprinting, 33

Index and forensic investigations, 29–33 forensic medicine and pathology, 38 Guldensuppe case, 41–42 historical practices, 34 historical tissue samples, 40 human tissue, 59–61 identification and individualization, 33–44 lymphatic ganglion, 61 physical characteristics, 40 pigments, 59–61, 79 prison tattoos, 35 recognition and identification, 43 and scientific inquiry, 53–54 series of cases, 42–43 tattooing individualizing marks, 37 Tattoo colors, 85–86, 110 cosmetic, 8 pigments, 76, 78 suitability of lasers for, 77 Tattooed skin, pigments detection in, 61–62 Tattooing, 3, 5, 131 basic stages, 19 colors and pigments in, 94–95 early tattoo machine designs, 10 evidence of tattoos, 20 flash, 11 fumigation method, 7 images from Bulwer’s 1653 text, 21 jagger, 14 layers, 18 legislation and regulation, 314–316 modern tattoo machine, assembly diagram, 11 needle cartridges, 15 painting, 4 permanent decorations, 5 pigments for medicinal purposes, 131–133 professional tattoos, 8, 9 sewing and pricking, 6 in surgical procedures, 132 tattoo artist, 8 tattoo design drawn freehand without use of stencils, 18 tattoo machine designs and modifications, 12–14 tattoo prevalence and interpretation, 20–23 tattoos in New York City c. 1950, 16 temporary henna tattoo, 19 terminology and technique, 4–19

Index Thermal Machine Stencil Paper Instructions, 17 transfer of tattoo design to skin, 17 Zeis flash sheet, 16 Tattoo inks, 57, 83; see also Writing inks chemistry, 228–233 databases, 305 elemental analysis of tattoo inks, 119 energy dispersive x-ray spectroscopy, 118 green tattoo ink spot on white paper, 84 homemade tattoo inks, 85–86 liquid composition of, 84–85 manufacture and distribution, 309–314 market players, 119 molecular spectroscopy-Raman and infrared spectroscopy, 226–228 pigments, 83, 114–116 pigment composition, 80, 85 quantitative analysis, 307 using Raman spectroscopy, 121 results of German study of pigments in, 123 using SF-ICP-MS, 122 spectroscopic analysis, 226 standard pigments analyzing in Miranda’s study, 229–231 studies and reports, 116–124 synthetic organic pigments, 124 transition from natural to synthetic pigments in, 112–116 UV–Vis spectroscopy, 228–233 Tattoo removal methods, 67 folk remedies, 72 list, 72–73 mechanical methods, 68, 69 pure acetic acid and axunge, 70 removing gunpowder tattooing, 69 tattoo marks, 71 tattoos as punishment, 67 TBP nucleus, see Tetrabenzoporphyrazine nucleus (TBP nucleus) TEM, see Transmission electron microscopy (TEM) Temporary henna tattoo, 19 Tetrabenzoporphyrazine nucleus (TBP nucleus), 154–156, 251, 253, 294 3, 4′, 5′, 7-tetrahydroxy-2, 3′-methelenneoflavan, see Brazilin Thermal cautery, 73 Thermal decomposition, 73 Thermal Machine Stencil Paper Instructions, 17

363 Thin layer chromatography (TLC), 112, 144, 216, 233 Time-of-flight secondary ion mass spectrometry (TOF-SIMS), 144 Tissue, tattoos in, 233 FT-Raman spectroscopy, 235 human tissue, 236 tattooing of pigskin, 234 Titanium dioxide (TiO2), 113 Titanium dioxide white, 108, 158 TLC, see Thin layer chromatography (TLC) TOF-SIMS, see Time-of-flight secondary ion mass spectrometry (TOF-SIMS) Tokyo Pink tattoo ink, 181, 277, 281 FT-Raman spectrum, 280 Raman spectrum, 280 Traditionalism, 26 Transmission electron microscopy (TEM), 110, 116 Traumatic tattoo, 8 Tri-Luma, 73 Turquoise blue tattoo ink, 192

U Ultraviolet-Visible spectrometry (UV-Vis spectrometry), 203, 228 Beer’s law, 206 electronic molecular energy levels and transitions, 204 molecular species, 204 organic and inorganic pigments, 232 pigment standard samples, 232 spectrophotometric measurements, 205 standard pigments analyzing in Miranda’s study, 229–231 visual color characteristics, 233 Umbers, 103

V Validation process, 219 Verdancy tattoo ink, 190, 294 Verde Claro tattoo ink, 170, 286–287 Vermelho tattoo ink, 168, 281 Vermilion, 101 Very strong (vs) peak, 241 Violet tattoo ink, 196, 294, 295 Visualization of tattoos, 62; see also Tattoo bile pigments, 63

364 Visualization of tattoos (Continued ) blanket method of tattooing, 66 chemical methods, 62 design modification, 66 destructive method, 63 infrared photography in resolving tattoos, 64 relative penetration depths of different wavelengths, 64 stage of decomposition, 65 tattoo cover-ups, 67

W Wetting agents, 84, 100, 124 Whitegirl tattoo ink, 162, 181, 276–277 Raman spectra, 280 White tattooing pigments, 108; see also Black tattooing pigments; Blue tattooing pigments; Brown tattooing pigments; Green tattooing pigments; Orange tattooing pigments; Purple tattooing pigments; Red tattooing pigments; Yellow tattooing pigments White tattoo ink, 201, 296 Writing inks, 136 chemistry and pigment composition, 136 fluorescein, 140 Higgins ink, 139 using inorganic pigments, 145 pigments exhibits luminescent properties, 140 pigments in henna products, 143 pigments in temporary tattoo design, 142

Index pigments related to iron gall inks, 138 red sealing inks, 144 tannic acid, 137 temporary designs, 141 using UV/VIS spectroscopy and HPLC, 142

X X-ray diffraction (XRD), 100, 306, 308 X-ray fluorescence (XRF), 203, 220 X-rays, 34, 37, 203

Y Yellow tattooing pigments, 105–106; see also Black tattooing pigments; Blue tattooing pigments; Brown tattooing pigments; Green tattooing pigments; Orange tattooing pigments; Purple tattooing pigments; Red tattooing pigments; White tattooing pigments Yellow tattoo inks, 188, 293–294, 298

Z Zeis flash sheet, 16 Zeis School of Tattooing colors, 90 pamphlet for, 89 Zinc carbonate (ZnCO3), 104 Zinc oxide (ZnO), 104 Zinc selenide (ZnSe), 208 Zinc sulfide (ZnS), 104