Atomic Absorption Spectroscopy (AAS)
FST-401
Dr. Imran Pasha
Associate Professor
NIFSAT 1
Atomic Absorption Spectroscopy (AAS)
AAS was developed in the 1950’s by Dr. Alan Walsh of the CSIRO Division of Chemical Physics
It uses the narrow atomic absorbance lines to uniquely identify and measure the
concentrations of atoms in a sample that may contain a complex mixture
Each element is measured separately by a hollow cathode lamp that uses the same element to
produce emission lines with its own unique wavelengths. In this way one element can be
singled out of many
The hollow cathode lamp works like a cathode ray tube
An electrical discharge is used to ionize gaseous atoms (+ve), which then impact onto a metal cathode (-ve).
The metal is vaporised and electronically excited, and hence emits its characteristic wavelengths when it
returns to its ground state
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Atomic Absorption Spectroscopy (AAS)…
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Atomic Absorption Spectroscopy (AAS)…
Samples for AAS analysis must be vaporized and atomized, so that they are not present as
molecules or strongly interacting with other atoms or molecules, as these affect the
electronic energy levels and hence the transition wavelengths
This is achieved in two ways
1. Flame
◦ Flame atomization heats the sample to ~1000°C, which can vapourise solutions. Flame atomizers
typically use a vacuum aspirator to suck solution with the element to be analyzed into a slit flame
(~5cm long)
2. Graphite Furnace
◦ A graphite furnace can work with solid or liquid samples, and smaller volumes than a flame. They
also provide a better controlled environment. E.g. the furnace can be oxygen-free to prevent
oxidation of the element of interest
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Conti…
Cylindrical shape of the cathode gives direction to emerging beam, and helps re-
deposit sputtered atoms back on cathode
Monochromator
◦ Isolates particular spectral line & eliminates stray radiation e.g., emissions from inert gas in lamp
Modulation
◦ Of light beam upstream of flame (by rotating chopper) allows detector to reject emission
generated within flame
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Conti…
AAS is used quantitatively, to measure the concentration of one or more
elements using the appropriate lamp
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Hollow Cathode Lamp
Absorption in the flame is by vapor phase atoms, giving line spectra in this case absorption
lines
A continuous spectrum light source, even with high quality monochromator cannot achieve
sufficiently narrow band pass width for absorption line spectra
Use special lamps, each emitting line spectrum matched to the line spectrum of the analyte
atoms in the flame. The type of lamp is a hollow cathode lamp
At high voltage, ions of He or Ar gas form at anode and bombard cathode
SPUTTERING occurs - atoms dislodged from the surface and produce an atomic cloud. Some
sputtered atoms are in excited state and emit their characteristic line spectrum as they revert
to the ground state
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Hollow Cathode Lamp…
window
Ar Ar
Ar
- Ar+
Ar
Ar
+
anode
Cathode
(made of metal to be measured)
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Hollow Cathode Lamps Uncoded Multi-Element
• Lamp is QA/QC tested for maximum
lifetime
• Low noise,
• Optimum stability
• These solid-cathode Uni-element
coded lamps
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Hollow Cathode Lamps Coded Multi-Element
• Lamp is QA/QC tested for maximum
lifetime
• Low noise
• Optimum stability
• These solid-cathode multi-element
coded lamps feature unique
combinations of compatible
elements that extend the
versatility of any AA spectrometer
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Trace Analysis of Elements by AAS
The concentration of an element in a sample can be determined from its
absorbance by comparing with one or more standard solutions
This uses Beer-Lambert Law, that absorbance, A, is directly proportional to the
optical path length, l and concentration, c.
A =ε cl
A slit flame is used to define
and the optical path length
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Experimental Aspects of AAS
Metallic elements (Ca & Mg) in clinical labs
Heavy metal pollutants ( Pb, Hg, Cu etc) in environmental labs
Strong metalcomplexes (not easily decomposed to atoms in the flame) low result e.g.,
◦ Ca interference by phosphate, overcome by adding lanthanum chloride (LaCl3) to samples (&
standards & blank). La3+ ions are a RELEASING AGENT for Ca
◦ Phosphate ions trapped as more stable lanthanum phosphate complexes; calcium released as
free Ca2+ ions - more easily reduced to atoms in the flame.
Flame is most common but not the only way of forming atomic vapor of an element to make use
of its absorption.
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Applications of AAS
1. Flame AAS is routinely used to determine the concentrations of metals in
particular in various water environments, and whether these exceed safe
levels
◦ e.g. The US Environmental Protection Agency limits lead in drinking
water to a maximum of 15 parts per billion (ppb)
1 part per million (ppm) = 1 mg/kg
ppb = 1 mg/1000kg
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Applications of AAS…
2. AAS can be used to in studies of toxicity, again particularly for heavy
metals
◦ Heavy metals like mercury, arsenic, lead, and chromium are not easily stored
within the body, so they accumulate in the hair and fingernails
◦ These can be prepared for flame AAS analysis by digestion in concentrated acid,
or combusted in an oven
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