AAS

Atomic Absorption Spectroscopy

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BACKGROUND

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Atomic absorption spectroscopy

Absorption of light to measure the concentration of gas-phase atoms Quantitative method of analysis that is applicable to many metals and a few nonmetals. Quantitative method for the determination of trace elements in various sample matrices

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Types of Atomic Absorption Techniques

Flame Atomic Absorption (FAAS) Air/acetylene flame as atomization cell 2360 K to 2600 K Solution samples Electrothermal atomic absorption (EAAS) Electrically heated graphite tube Consistent temperature profile Heated up to 3000 K Argon gas Better accuracy Less sample LOD to 100 ppb Solutions, slurries, solid samples
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Limit of Detection (LOD) for Elements using AAS

Li 2 0.1
Na 0.2 0.005

Be 1 0.02
Mg 0.3 0.004

Element Flame AA

Detection Limits (ng/mL) Graphite furnace AA

B 500 15

Ne

S Al 30 0.01 Si 100 0.1 P 40 000 30

Cl

Ar

K 3 0.1

Ca 0.5 0.01

Sc 40 -

Ti 70 0.5

V 50 0.2

Cr 3 0.01

Mn 2 0.0 1

Fe 5 0.2

Co 4 0.02

Ni 90 0.1

Cu 1 0.02

Zn 0.5 0.001

Ga 60 0.5

Ge 200 -

As 200 0.2

Se 250 0.5

Br

Kr

Rb 7 0.05

Sr 2 0.1

Y 200 _

Zr 1000 -

Nb 2000 0 -

Mo 20 0.02

Tc

Ru 60 1

Rh 4 -

Pd 10 0.3

Ag 2 0.005

Cd 0.4 0.003

In 40 1

Sn 30 0.2

Sb 0.08

Te 30 0.1

Xe

Cs 4 0.2

Ba 10 0.04

La 2000 -

Hf 2000 -

Ta 2000 -

W 1000 -

Re 600 -

Os 100 -

Ir 400 -

Pt 100 0.2

Au 10 0.1

Hg 150 2

Tl 20 0.1

Pb 10 0.05

Bi 40 0.1

Po

At

R n

Ce

Pr 6000 -

Nd 10

Pm

Sm 1000 -

Eu 20 0.5

Gd 2000 -

Tb 500 -

Dy 30 1

Ho 40 -

Er 30 2

Tm 900 -

Yb 4 -

Lu 300 -

Th

Pa

U 40 000

Np

Pu

Am

Cm

Bk

Cf

Es

Fm

Md

No

Lr

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Major Components of the System

Light Source
Nebulizer

Flame Apparatus
Detector

Data System

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Schematic of an atomic-absorption experiment

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Basic Parts of Atomic Absorption Spectrometer

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Sample Compartment

Light Source

Detector

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Light Source
Purpose:
Provide analytical light line for the element of interest
Provide constant and intense beam

Composition
Hallow-Cathode lamp Electrodeless Discharge Lamp Lasers AAS and Atomic Fuorescence

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A hollow cathode lamp for Aluminum (Al)

Inert gas at low pressure

Low electrical current 3 30 mA

Lamp whose cathode is composed of the element being measured. Each element requires a different lamp Glass window transparent to UV/Vis
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Light Path

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Aspirate liquid at a controlled rate

Forms fine aerosols Mix aerosol, fuel and oxidant

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ATOM CELL

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FLAME

Destroy any analyte ions and breakdown complexes Create atoms (the elemental form) of the element of interest Major variable that impact on number of excited atoms Sample holder

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FLAME

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Sample is vaporized in the flame.

Aspirator tube sucks the sample into the flame in the sample compartment.
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Graphite Tube

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Monochromator
Isolate analytical lines' photons passing through the flame
Remove scattered light of other wavelengths from the flame, so that only a narrow spectral line impinges on the PMT Allows only light not absorbed by sample to reached PMT

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Detector
Purpose Determines the intensity of photons of the analytical line exiting the monochromator. Composition PMT Solid State detector

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Photomultiplier Tube

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Matrix Modifier
Change the behavior of the analyte element or matrix in solution with respect to temperature Convert element to less volatile form
Increase the volatility of matrix

Samples
NICKEL NITRATE SOLUTION AMMONIUM PHOSPHATE SOLUTION

CALCIUM NITRATE SOLUTION

LANTHANUM NITRATE SOLUTION

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Quantitative analysis
Measure the absorbance of a series of solutions of known concentration. (Calibration Curve) Standards in duplicates Acid content of 1 10% Minimum of 5 known concentrations Use the method of standard additions, especially if the sample matrix is not well known.

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Use the calibration curve and the equation for the line to determine an unknown concentration based on its absorbance. Least Square Method

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Quantitative analysis

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Laboratory Precautions
1. Thoroughly clean glasswares 2. Use distilled or DI water 3. Use HNO3 instead of HCl to completely dissolve traces of organic compounds 4. Run DI/blank or dilute acid in between sample run 5. Use matrix modifier if needed 6. Observe start-up and shut down procedures strictly
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Applications
Lead in clinical and environmental samples GFAAS at > 1 ng/ml Field instrumentation Garment industry Forensics Arsenic in hair Gunshot residues; Ba, Sb, Pb Quality Control and pollution monitoring in food industry Residual catalyst, Cr, Ni, Fe, Cu in hydrogenated vegetable oil Presence of Pb and Sn in cans

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Least Square Method

Simplest form of linear regression Best linear fit through set of points

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Least Square Method

The least squares line method basically uses an equation f(x) = a + bx, So the equation for the least square line is

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Calculate for a and b

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CALIBRATION CURVE

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TIPS TO ENSURE LINEARITY

1. Sample dilution 2. Alternative wavelength with low absorptivity 3. Reduce path length by rotating the burner head

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INTERFERENCES
1. Spectral Interference : radiation overlapping that of the light source, Na/Mg, Fe/Co or Ni 2. Formation of compounds that do not dissociate in flame, Phospates of Ca and Sr 3. Ionization of analyte that reduces signal, Ba, Ca, Sr, Na, K 4. Matrix effects : surface tension and viscosity 5. Broadening of spectral line
Doppler effect Lorentz effect Quenching effect Self-absorption or self-reversal effect

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DOPPLER EFFECT
Due to atoms having different components of velocity along the line of observation. Atoms moving towards source absorb lower frequency light than atoms moving away

Broadening is about 10-3 to10-2 nm

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LORENTZ EFFECT
Due to concentration of foreign atoms in the environment of emitting or absorbing atoms
Magnitude of broadening varies with pressure of foreign gases and their properties Collision shortens lifetime of excited state

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QUENCHING EFFECT

Low pressure spectral source

Flame AAS Presence of foreign gas molecules with vibrational levels close to excited state of the resonance line

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Self-Absorption or Self-Reversal

Atoms of the same kind as emitting radiation absorb maximum radiation at center of line Maximal effect if the vapor absorbing radiation is cooler than emitting radiation

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