High Resolution Continuum Source AAS -Atomic Absorption Spectroscopy With Only

High Resolution Continuum Source AAS -Atomic Absorption Spectroscopy with only one light source – the only innovation of the XXI century in Atomic Absorption and a new challenge for Environmental Analysis

Why to buy a contrAA??????

?

HR Continuum Source AAS –

HR-CS AAS

HR-CS AAS - it´s something in between AAS and ICP OES !!
One light source for all elements
Real multi element AAS
Simultaneous background correction
Recording of reference spectra
More spectral information
Wider working range
Better detection limits

It is still routine AAS but includes powerful features of an ICP OES

Key components AAS: HR-CS AAS vers LS AAS

1. Radiation source ⇒Xenon – short arc lamp/ HCL, EDL, boosted HCL 2. Atomizer

⇒ identical atomizer for flame technique

3. Monochromator ⇒ High resolution / > 1:140000 4. Detector

⇒ CCD array detector/

5. Software

⇒ Aspect CS/

low resolution 1:10000 single spot detector (PMT) WinAAS

Flame AAS – a phase-out model of Atomic Spectrometry?

To many limitations of traditional LS flame AAS No flexibility , only defined lines Less information - interferences, no vicinity

But

 robustness, simple to operate, fastness, low costs

..... – or basis of a new generation in atomic spectrometry the HR-CS AAS?
HR- CSAAS brings a new dimension of capabilities to AAS
All flame elements are permanently available from one source
Routine flame applications can be run as simple as in LS AAS
Detection limits are improved
All AAS correction modes are simultaneous and permanent
Additional sources of noise can be understood and corrected for
The method is not limited to atomic lines
Complex determinations due to spectral overlap can be corrected with reference spectra
There is space for research in flame AAS

The most important reasons to buy an contrAA !

1. SIMPLY THE BEST !!! 2. AAS with 1 Lamp only! 3. The total Flexibility! Flexibel and simple in one system! 4. Fastness! Immediately ready to measure! 5. Applications with complex sample matrix! 6. New dimension of information 7. Only Alternative to ICP 8. Method of choice for direct solid sampling AAS

1. SIMPLY THE BEST !!! The most innovative and state-of-the-art instrument in field of AAS -

Prestige

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Status symbol! UNIQUE!

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Image of the customers -

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Global Players

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But also scientific image: publications, research, projects...

contrAA 700 Flame and Graphite Furnace AA

2. AAS with 1 Lamp only! Replacement of up to 60 different HCL´s BGC lamp (deuterium lamp)

HR-CS AAS

Xenon short arc lamp as continuum radiator

No lamp adjustment No loss of energy with second light source No loss of time regarding heating time of the lamp No problems with aging of the lamp (line broadening, sensitivity loss...) ready for measuring: - each element on - each wavelength

Comparison of intensity of different light sources 100

Ag 1

Pb

2

Radiance [W / cm sr nm]

10

0 .1

0 .0 1

Au As

A B C

Zn Pb Cd

1 E -3 200

250

300

350

400

W a v e le n g t h [ n m ] Source: „High-resolution continuum source AAS“ Welz,Becker-Roß,Florek,Heitmann

A Xenon-short arc lamp, XBO 301, 300 W, (GLE Berlin), „Hot - Spot“ - Mode B Xenon lamp, L 2479, 300 W, (HAMAMATSU), diffuse mode C D2 - Lamp, MDO 620, 30 W, (HERAEUS)

Lamp Cost A Line source AAS needs a Deuterium Lamp and for each element a hollow cathode lamp For some elements (e. g. As, Se ) most manufacturer recommend EDL`s or Superlamps The contrAA needs only one lamp for background correction and all elements Customer price comparison in EURO contrAA

Line Source AAS

HCL (average)

350

D2 Lamp

550

Superlamp

940

Power supply for superlamp Xenon lamp contrAA

1800 2100 - 2200

3. The total Flexibility! Flexibel and simple in one system!

No limitation of elements No limitations of lines Molecular bands and Non metals (S,P...)

Minimum interferences Simple to operate

Continuum source – provides more flexibility All absorption and molecular lines are available independent of:
seldom or rare requested analysed elements


exit window of HCL (UV or VIS permeable) Cu - HCL ⇒ 217,9 nm, W - HCL ⇒ 255,1 nm
element interferences do not disturb the line selection
atomic absorption using element lines or molecular bands possible

analytical purpose decides element and line selection

Continuum source – provides more flexibility

LS AAS

 use of most sensitive line BUT:
Sometimes not the best SNR
Non linear calibration curve

HR-CS AAS

 no limitations in line choice
Use of less sensitive secundary lines
No problems with interferences

Continuum source – provides more flexibility Xenon lamp is covered in a safety lamp box

⇒ provides emission spectrum of the complete AAS relevant spectral range (190 – 900 nm)

all absorption lines are available independent if seldom or rare requested elements

more flexibility…independent line choice Gd in organic matrix as main component

Problem:
Extremly seldom, no standard application
High concentrated samples
No high concentrated standards available
No lamp available

more flexibility…independent line choice Gd in organic matrix - all absorption lines are available

Standard calibration: 0.25 - 1.0 mg/ mL Gd


Gd 407.870 nm
Gd 368.4 nm

all absorption lines are available independent if seldom or rare requested elements

Continuum source – provides more flexibility Molecular bands for additional analytical use
determination of phosphorus using PO – molecular bands (e.g. 246,40 nm, 247,62 nm, 247,78 nm, 324,62 nm, 327,04 nm)
determination of sulfur using CS – molecular bands (e.g. 257,59 nm, 258,06 nm)
determination of fluorine using AlF - molecular bands (e.g. 227,47 nm)
determination of chlorine using AlCl or GaCl - molecular bands (e.g. 261,44 nm, 249,06 nm)

absorption and molecular lines for analytical use

Availability of molecular bands Determination of P flame in defatting solvent PO- band at 324,619 nm C2H2/ air - flame 0,5 g/L P

1-7 g/L P in C2H2/ air 7 pixel c0 = 0,29 g/L LOD = 22 mg/L

Availability of molecular bands Determination of P flame in defatting solvent Element

Sample

DF

Concentration [g/L]

RSD [%]

P 324.619 nm

Degreasing by boiling (A)

5

3.58 ± 0.30

0.9

2

3.51 ± 0.12

0.8

1

3.59 ± 0.07

1.4

5

5.61 ± 0.29

0.9

2

5.46 ± 0.13

2.4

1

4.92 ± 0.07

0.8

Degreasing by electricity (B)

(A)

(B)

Availability of molecular bands Determination of S in wine

wine 1+ 1 2000 ppm S CS- band at 258,054 nm C2H2/ N2O - flame

C0 (g/L)

0,355

R2

0,9993

NWG (g/L)

0,071

Availability of molecular bands Determination of S in wine sample

DF

S- conc. [mg/L]

RSD [%]

Angelo Cremaschi 2003 Cabernet Merlot (13,5% Vol.)

1,043

155

9,2

Domaine de Gazel 2000 Minervois (12,0% Vol.)

1,043

165

7,6

Cabernet Sauvignon 2004 Récolte (12,0% Vol.)

1,043

148

11

Señorio del Aguila 1998 Reserva (13,0% Vol.)

1,043

288

11

Molecular bands could be used for determination of elements which are normally not detectable with atomic absorption

Simple….because it is a well known and well described method!

New technique but not new! Described methods(cookbook) are useable. Comparable with other systems and results. Simple analysis Well known accessories

4. Fastness Of measurement real sequential multi element analysis Of method development and parameter optimization you can see what you do! Immediately ready to measure!

No delay time with flushing and rinsing the system No delay with preheating time of lamps

Real Multielement Analysis

Single element method calibration sample 1 sample 2 sample 3 …

Cu

Pb

Fe

Ni

Zn


Schema ändern-sieht Varian zu ähnlich!!

LS AAS
Tai schickt Idee!!!!

calibration sample 1 sample 2 sample 3 …

Cu

Pb

Fe

Sequential multi element analysis

Ni

Zn

CS AAS

Determination of 7 elements in high concentrated sugar solution Sample is used for fermentation purposes, dark brown very viscose solution Problems of a LS AAS user
Elements to be analyzed, Ca, Mg, Na, K, Cu, Fe and Pb
Elements are present in very different concentration ranges
High sugar concentration leads to clogging of the burner head
Elements require different sample preparation
Analysis very time consuming

All problems can be solved using CS AAS

Sample preparation LS AAS Sample stock solution: 0.5 g sample + 2 mL HCl dilution up to 100 mL Ca: 2 mL stock solution dilute with 0.1% KCl up to 50 mL K:

0.5 mL stock solution dilute with 0.1% LaCl3 up to 100 mL

Mg: 2 mL stock solution dilute with 0.1% LaCl3 up to 50 mL Fe: 10 mL stock solution dilute with 0.2% CaCl2 up to 50 mL Na: 0.5 g sample + 2 mL HCl dilute with 0.1% KCl up to 50 mL Pb: 0.5 g sample + 1 mL HCl dilute with 0.1% HNO3 up to 50 mL Cu: 5.0 g sample + 2 mL HCl diluted up to 100 mL (Solution X) 10 mL solution X diluted with 1% HNO3 up to 50 mL

Sample preparation CS AAS Uniform sample preparation for all elements 1.5 g sample + 5 mL HCl diluted with 0.2% LaCl3 to 100 mL

Method parameter

Alternative wave lengths match to different element concentrations. Some wave lengths are not available with standard HCLs.

Method parameter

Different numbers of detectors (pixels) match to the element concentrations.

Multi element calibration

Ca 40-150 mg/L

Cu 0.25-1 mg/L

Mg 10-40 mg/L

Fe 4-12 mg/L

Na 5-20 mg/L

K 1000-3000 mg/L

Pb 1-5 mg/L

Element spectrum

Ca

Cu

Fe

K

Mg

Na

Multi element results Element

Concentration mg/kg

RSD %

Ca

4205 ± 38

1.2

Mg

1126 ± 18

0.4

K

74880 ± 288

0.2

Na

182 ± 6

0.7

Fe

179 ± 4

1.1

Cu

8.9 ± 0.1

0.4

Pb

0.82 ± 0.07

4.2

Startup Time The contrAA is ready to run samples within 5 minutes after the flame is ignited


Very fast analytical results
Very low cost for gas The ICP is ready to run samples 40 to 60 minutes after the plasma is ignited


It takes at least 40 minutes before you get the first analytical results
The argon gas consumption is between 1200 and 1800 liter before you start your analysis

5. Complicated applications_samples with complex matrizes Real samples – matrix effects, interferences,

Spectral information Graphite furnace - LS AAS

LS AAS – Visible is the Absorption vs. time within the small emission spectral range from the line source

In case of a spectral interference, we can see only the result, but not the reason – therefore an optimization of parameters to avoid the spectral interferences is difficult. Bernhard Welz, Departamento de Química, Universidade Federal de Santa Catarina, Florianópolis – SC, Brasil

Spectral information Graphite furnace - LS AAS HR-CS AAS – there is a 3th Dimension, it means we can see much more in the background

 We are able to see the reason for the spectral interferences

We can eliminate the spectral interferences

 And we have better possibilities to correct the spectral interferences

Bernhard Welz, Departamento de Química, Universidade Federal de Santa Catarina, Florianópolis – SC, Brasil

Background correction par excellance (1. correction of broad-band effects)

before BB correction

after BB correction

wavelength: 276.787 nm; sample: 10 µl i.e. 0.1 mg PACS-2 marine sediment SRM (NRC Canada); pyrolysis: 300°C; atomization: 1650°C; resolution ≈ 2 pm per pixel

Background correction par excellance (2. correction of molecular background)

before least-squares correction

“true” analyte signal

wavelength: 276.787 nm; sample: 10 µl i.e. 0.1 mg PACS-2 marine sediment SRM (NRC Canada); pyrolysis: 300°C; atomization: 1650°C; resolution ≈ 2 pm per pixel

Corrections applied to AAS Source of Error

Correction LS- AAS

Correction CS- AAS

lamp drift

optical double beam sequential

reference pixels simultaneous

thermal emission

Lamp modulation sequential

reference pixels simultaneous

unspecific absorption

BG correction, sequential (D2 lamp, Zeeman effect, reverse line method)

reference pixels reference spectrum simultaneous

Background correction / Signal generation What should be corrected ? 

structured background spektral interferences with other atom lines moleculare absorptions



broad-band background streyligth from particels thermal emission



instrumental influences Intensity drift of light source thermal drift detector failer

Effects are directly readable -

Structured background Intensity drift Continuous weakening Emission

Background Correction - simultaneously - no loss of analysis time - spectral resolution

Monochromator – minimization of spectral interferences Determination of Ni in grass flour

sample

Ni

Fe

Ni

Ni: 232,003 nm Fe: 232,036 nm Ni: 232,140 nm Warum misst man einmal mehr und manchmal weniger Bei diesen Störungen???

spectral band wide: 1,95 pm/ pixel spectral vicinity: 0,39 nm

Monochromator – minimization of spectral interferences Determination of Ni in grass flour

standard 0,4 mg/L Ni 5,0 mg/L Fe

Ni: 232,003 nm Fe: 232,036 nm Ni: 232,140 nm

sample


spectral interferences become visible but do not disturb the accuracy
background correction error with D2

Monochromator – freedom of line choice Determination of Cu, Ni, Fe in galvanic bath expected concentration: (r = 1,2 kg/L)

Cu 30 – 40 g/Kg Ni 2 g/Kg Fe 10 g/kg

Line selection defined by analytical task

dilution: factor 200

+

Cu 244,164 nm Ni 231,234 nm Fe 303,739 nm

Monochromator – minimization of spectral interferences Determination of Cu in Ni- galvanic bath

absorption CS AAS: 0,089 Abs absorption LS AAS: 0,057 Abs D2 – overcorrection: error -36%

spectral band wide: 2,1 pm/ pixel spectral vicinity: 0,11 nm Cu: 324,754 nm Ni: 324,846 nm

More spectral information about complex or unknown sample

6. New dimension of information 3dimensional information/Spectra Information about the line vicinity

New dimension of information content More information than LS AAS

- Easy method development - Results easy to evaluate - Improves accuracy

Int. wave length spectra

Abs. wave length spectra 2D

Abs. wave length spectra 3D

Detector – provides more information UV- sensitive linear array detector (CCD) instead of:
exit slit for LS AAS
photomultiplier tube (PMT) „Back Thinned” CCD chip
High quantum efficiency
High UV-sensitivity
588 pixel
each pixel as an individual detector

New detector technology for AAS guarantees best signal to noise ratio and more information content

Detector – provides more information Hydride technique - advanced information content for transient signals As signal – 1 µg/L continuous hydride mode

As


easy error detection
improves accuracy
eaier method development As Sample cup became empty

⇒ Air molecular absorption Time resolved absorbance

Time and wavelength resolved absorbance

7. Cost effective and only alternative to ICP Costs – Time – Manpower – Experience!

No argon neccessary Higher purchasing and maintance costs Better experience necessary Higher service requirements

Installation and Uptime It takes 2 to 3 hours to install a Flame AAS! It takes 2 to 3 days to install an ICP-OES!

Uptime ( time between service calls) is much higher for an AAS instrument Compare the maintance costs ICP – AAS!

HR-CS AAS: Bridging the gap between AAS and ICP AAS

ICP


Simplicity
Less interferences

combined with


Robustness


Speed
Flexibility
Information


Low operation cost HR-CS AAS

10. Method of choice for direct solid sampling AAS Strongest background correction No influence of Magnetic field Improved solid sampler

Key Application contrAA Agriculture – soil extracts Electroplating solutions Clinical samples Analysis of precious metal solutions Trace elements in Metals


As,Se in Cu or Co
Al in steel Wear metals in oil Foodstuff Additives in oil Etc.

Flame AAS – Renaissance instead of phase out model! Simpler method development with HR-CS AAS


no element specific HCL
no different current and slit conditions
background correction always available
no limitation in line selection
robustness and simplicity of AAS
third dimension of information

Thanks for your Attention