PRINCIPLES, INTRUMENTATION AND
APPLICATIONS OF AAS & ICP
Atomic Absorption Spectrometry
(AAS)
• The Atomic Absorption Spectrometry is a
well-established technique for metal
determination, being the instrumental method
of choice for aqueous samples in geochemical
laboratories between the mid-1960s and
mid-1980s.
• The AAS is applicable to the analysis of a wide
range of samples from geochemistry studies
following dissolution or preparation of slurries.
PRINCIPLE OF AAS
• Based on the measurement of resonance
radiant energy absorbed by unexcited (ground
state) free atoms in a sample cell
• The population of the free atoms (i.e. the
concentration) is directly proportional to the
degree of the absorption.
PRINCIPLE OF AAS
• The AAS operate in such a way that a light
beam consisting of the emission spectrum of
the element of interest is passed through an
absorption cell containing the sample in an
atomised state.
PRINCIPLE OF AAS
• The Analyte atoms in the cell, by absorbing
light at their characteristics wavelengths and
re-emitting in random directions, cause a net
attenuation in the beam spectrum in
proportion to their abundance.
PRINCIPLE OF AAS
• The optimum analyte line in the beam
spectrum is isolated by a monochromator and
detector and the absorbance (the degree of
attenuation at that wavelength) is measured.
PRINCIPLES CONTD:
• relationship of the degree of absorption
(absorbance) to concentration is somewhat
very similar to that of the classical
Beer-Lambert’s law which applies to
colorimetric analysis.
• However, unlike the case in the uv-visible
molecular absorption spectrophotometric
system, the sample cell environment in AAS is
complex and not easily subject to the
Beer-Lambert’s law
PRINCIPLES CONTD:
A more accurate relationship for the AAS system is as follows:
Where
k is the absorption coefficient
e = charge of the electron,
m = mass of the electron, and c = the speed of light,
N is the number of free absorbing atoms in the light path and
f is the oscillator strength of the absorption line.
PRINCIPLES CONTD:
• only variables are N, the total number of atoms in
light path, and f the oscillator strength.
• relationship between them and the total amount
of light absorbed is a basis for quantitative
analysis.
• degree of absorption for each element and each
absorption line depends on the oscillator strength
which is a direct measure of how strongly each
atom will absorb at that wavelength.
INSTRUMENTATION:
(single-beam flame AAS)
▪ Ref: Diagram previous slide
– A = SOURCE OF RADIATION
– B = FLAME
– C = MONOCHROMATOR
– D = DETECTOR
– E= AMPLIFIER
– F = READOUT DEVICE
SOURCE LAMP:
• Commonest used is the Hollow Cathode Lamp
• Alternatives for a variety of purposes include:
• Vapour discharge lamps
• Electrodeless discharge lamps
• Lasers, etc
FLAME IN AAS contd:
• Usual oxidant is air, but nitrous oxide is often
used to produce hotter flames
• Usual fuel is acetylene
• Hence most common flames are
• Air-acetylene (c. 2300oC)
• Nitrous oxide-acetylene (c. 2700-3000oC)
• Other flame types for special needs include
air/hydrogen, argon/hydrogen, etc
BURNERS IN AAS
• May also be classified as either premix or total
combustion types. Premix most stable and
commonly used.
• Burners are specific for various gas mixtures:
– Air-acetylene burner
– Nitrous oxide-acetylene burner
• Configurations prevent “strike-back” and
“blow-out”.
NEBULISER-SPRAY CHAMBER
• Liquid samples are sucked into the nebuliser
through suction created by oxidant passage
through one arm of the nebuliser.
• Nebuliser breaks the solution up into very tiny
droplets and select a very small portion of
right size for passage through spray chamber
into burner.
• Nebuliser incorporates a system of baffles ffor
breaking sample into droplets/aerosols.
NEBULISER-SPRAY CHAMBER contd:
• In the spray chamber, oxidant, fuel and sample
aerosol are mixed together, and then sprayed
into the burner chamber for ignition fo give
the premix flame.
• Only about 10% of mass of sample intake
reaches the flame.
• Rest is discarded down the drain as waste.
WHAT HAPPENS TO SAMPLE IN FLAME
• Sample solution of a typical salt, MX, is first
desolvated by the heat energy of flame to give
solid sample – MX(s)
• Solid sample is then vapourised – MX(g)
• The vapourised salt is then disssociated into
M(g) and X(g) in the free ground state.
• This gaseous free ground state, M(g) is the
state in which the metal analyte participates in
absorption of resonance radiation in AAS
WHAT HAPPENS TO SAMPLE IN FLAME
contd:
• If the flame is sufficiently energetic, the
ground state atoms may ionise - -> M+
• The ionisation process is not desirable as it
consitutes an interference. The ionised atom is
incapable of absorbing the resonance
radiation at the set wavelength.
THE MONOCHROMATOR
• This serves as a spectral selection device
• In most AAS equipment this is a diffraction grating
capable of diffracting incident radiations and
selecting only the right/required one for passage
unto the detector
• Radiations emanating from the flame include:
– The resonance radiation from source (incident or
transmitted after absorption)
– Flame background emissions
– Lamp inert gas line emissions
• The monochromator ensures only resonance line
radiation passes through to detector
DETECTOR
• Most often a photomultiplier tube
• This converts the radiant energy from the
source into electrical signals of magnitude that
is proportional to the intensity of the radiation
reaching the detector.
• Usually then passed for amplification in the
amplifier.
READOUT
• The device presents the signal in a readable form
• This has undergo progressive development from
analogue to digital to microprocessor controlled
readouts
• Modern devices use software to interface
between the hardware equipment and a visual
display terminal, usually a computer – which
serves for inputing the operational information as
well as reading the results of analysis.
INTERFERENCES IN AAS
• Background Interference
• Physical Interference
• Chemical interference
• Matrix Interference
• Ionisation interference (for light metals)
CALIBRATION IN AAS
• Normal calibration methods
• Standard Addition method
Inductively – coupled plasma – Atomic Emission
Spectrometry/Optical Emission/Mass Spectrometry
There are three essential components in an
ICP-AES/OES/MS. The source unit (the ICP torch), the
spectrometer, and the computer.
ICP – AES/OES/MS is now established as one of the most
widely used techniques of elemental analysis.
Inductively – coupled plasma – Atomic Emission
Spectrometry/Optical Emission/Mass
Spectrometry
•The source unit provides the energy to generate the
emission spectral lines.
• The spectrometer separates and resolves these lines and
measure their signal strength.
•The computer enable the analyst to convert the signal into
numerical measurement of het analytic elements.
Inductively – coupled plasma – Atomic Emission
Spectrometry/Optical Emission/Mass Spectrometry
•The range of elements that can be determined in
geological samples by ICP-AES is considerable.
•All of the 10 major elements (Si, Al, Mg, Fe, Ca,
Na, K, Ti, P and Mn) normally determined can be
measured, in addition to most of the common trace
elements.
Inductively – coupled plasma – Atomic Emission
Spectrometry/Optical Emission/Mass Spectrometry
•One of the main reasons for the success and widespread acceptance
of ICP-AES is its ease of use.
•it is straight forward to install and set-up and routine elemental
analysis for a whole suit of element is easily accomplished.
•Modern ICP instruments can generate 20-60 element analysis for a
prepared sample in approximately 1 minute with more than 200
samples being analysed in a typical working day.
