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 / low resolution
> 1:140000 1:10000

4. Detector ⇒ CCD array detector/ single spot

detector (PMT)
5. Software ⇒ Aspect CS/ 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
- Status symbol! UNIQUE!
- Image of the customers -
contrAA 700
- Global Players
Flame and Graphite Furnace AA
- But also scientific image:
publications, research, projects...
2. AAS with 1 Lamp only!
Replacement of
HR-CS AAS
up to 60 different HCL´s
BGC lamp (deuterium lamp) 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

10
Radiance [W / cm sr nm]

Ag
1
Pb
2

0 .1
Au A
Zn B
As C
0 .0 1

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 1800
Xenon lamp contrAA 2100 - 2200
3. The total Flexibility!
Flexibel and simple in one system!

No limitation of elements
Minimum interferences
No limitations of lines
Simple to operate

Molecular bands and

Non metals (S,P...)
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:

Gd 407.870 nm 0.25 - 1.0 mg/ mL Gd

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 Degreasing by 5 3.58 ± 0.30 0.9

324.619 nm boiling (A)
2 3.51 ± 0.12 0.8

1 3.59 ± 0.07 1.4

Degreasing by 5 5.61 ± 0.29 0.9

electricity (B)
2 5.46 ± 0.13 2.4

1 4.92 ± 0.07 0.8

(A) (B)
Availability of molecular bands
Determination of S in wine

wine 1+
1 2000 ppm S
C0 (g/L) 0,355
CS- band at 258,054 nm
C2H2/ N2O - flame R2 0,9993
NWG (g/L) 0,071
Availability of molecular bands
Determination of S in wine

sample DF S- conc. RSD

[mg/L] [%]

Angelo Cremaschi 2003 Cabernet 1,043 155 9,2

Merlot (13,5% Vol.)
Domaine de Gazel 2000 Minervois 1,043 165 7,6
(12,0% Vol.)
Cabernet Sauvignon 2004 Récolte 1,043 148 11
(12,0% Vol.)
Señorio del Aguila 1998 Reserva 1,043 288 11
(13,0% Vol.)

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 Cu Pb Fe Ni Zn
sample 1
sample 2

Schema ändern-sieht Varian zu ähnlich!!
sample 3
… LS AAS

Tai schickt Idee!!!!

calibration Cu Pb Fe Ni Zn
sample 1
sample 2
sample 3
… CS AAS

Sequential multi element analysis

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 Fe 4-12 mg/L K 1000-3000 mg/L

Mg 10-40 mg/L Na 5-20 mg/L Pb 1-5 mg/L

Element spectrum

Fe
Ca Cu

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 reference pixels

sequential simultaneous

thermal emission Lamp modulation reference pixels

sequential simultaneous

unspecific absorption BG correction, sequential reference pixels

(D2 lamp, reference spectrum
Zeeman effect, reverse simultaneous
line method)
 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

Fe
Ni
sample
Ni: 232,003 nm
Fe: 232,036 nm
Ni 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 sample
5,0 mg/L Fe

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

Cu 244,164 nm
dilution:
factor 200 + 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 More spectral information
Ni: 324,846 nm 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 Time and wavelength
absorbance 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
Speed
combined with

Less interferences
Flexibility

Robustness
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