WHAT IS ATOMIC ABSORPTION SPECTROSCOPY?

Atomic absorption spectroscopy (AAS) is the technique for determining the elemental

composition of an analyte by its electromagnetic or mass spectrum. It is a spectroanalytical
procedure for the quantitative determination of chemical elements using the absorption of optical
radiation (light) by free atoms in the gaseous state.

In analytical chemistry, the technique is used for determining the concentration of a particular
element (the analyte) in a sample to be analyzed. AAS can be used to determine over 70 different
elements in solution or directly in solid samples used
in pharmacology, biophysics and toxicology research.

WORKING PRINCIPLE

The technique makes use of absorption spectrometry to assess the concentration of an analyte in
a sample. It requires standards with known analyte content to establish the relation between the
measured absorbance and the analyte concentration and relies therefore on the Beer-Lambert
Law.

In short, the electrons of the atoms in the atomizer can be promoted to higher orbitals (excited
state) for a short period of time (nanoseconds) by absorbing a defined quantity of energy
(radiation of a given wavelength). This amount of energy, i.e., wavelength, is specific to a
particular electron transition in a particular element. In general, each wavelength corresponds to
only one element, and the width of an absorption line is only of the order of a few picometers
(pm), which gives the technique its elemental selectivity. The radiation flux without a sample
and with a sample in the atomizer is measured using a detector, and the ratio between the two
values (the absorbance) is converted to analyte concentration or mass using the Beer-Lambert
Law.

EXAMPLE OF INSTRUMENT

Atomic absorption spectroscopy uses the absorption of light to measure the concentration of gas-
phase atoms. Since samples are usually liquids or solids, the analyte atoms or ions must be
vaporized in a flame or graphite furnace. The atoms absorb ultraviolet or visible light and make
transitions to higher electronic energy levels. The analyte concentration is determined from the
amount of absorption. Applying the Beer-Lambert law directly in atomic absorption
spectroscopy is difficult due to variations in the atomization efficiency from the sample matrix,
and nonuniformity of concentration and path length of analyte atoms (in graphite furnace).
Concentration measurements are usually determined from a working curve after calibrating the
instrument with standards of known concentration.
 Atomic absorption spectrometer block diagram

Schematic of an atomic-absorption experiment

 Hollow cathode lamp (HCL) Monochromator

Flame atomizers Electrothermal atomizers

METHOD IN ANALYSIS OF DATA

  Detection limits

The detection limits achievable for individual elements are important in determining the
usefulness of an analytical technique for a given analytical problem. Without adequate detection-
limit capabilities, lengthy analyte concentration procedures may be required prior to analysis.

 Analytical working range

The analytical working range can be viewed as the concentration range over which quantitative
results can be obtained without having to recalibrate the system. Selecting a technique with an
analytical working range (and detection limits) based on the expected analyte concentrations
minimizes analysis times by allowing samples with varying analyte concentrations to be
analyzed together. A wide analytical working range can also reduce sample-handling
requirements, minimizing potential errors.

 Sample throughput
Sample throughput is the number of samples that can be analyzed or elements that can be
determined per unit of time. For most techniques, analyses performed at the limits of detection or
where the best precision is required will be more time-consuming than less demanding analyses.
Where these factors are not limiting, the number of elements to be determined per sample and
the analytical technique will determine the sample throughput.

• Flame AA – Provides relatively high sample throughput when analyzing a large number of
samples for a limited number of elements. A typical determination of a single element requires
only 3-10 seconds. However, Flame AA requires specific light sources and optical parameters
for each element to be determined and may require different flame gases for different elements.
As a result, even though it is frequently used for multi-element analysis, Flame AA is generally
considered to be a single-element technique.

• Graphite Furnace AA – As with Flame AA, GFAA is basically a single-element technique. Because of the
need to thermally program the system to remove solvent and matrix components prior to atomization,
GFAA has a relatively low sample throughput. A typical graphite-furnace determination normally
requires 2-3 minutes per element for each sample.

• ICP-OES – A true multi-element technique with exceptional sample throughput. ICP-OES systems
typically can determine more than 73 elements per minute in individual samples. Where only a few
elements are to be determined, however, ICP is limited by the time required for equilibration of the
plasma with each new sample, typically about 15-30 seconds.

• ICP-MS – Also a true multi-element technique with the same advantages and limitations of ICP-OES.
ICP-MS can typically determine more than 73 elements per minute in an individual sample, depending
on such factors as the concentration levels and required precision. Although ICP-MS has a wide working
range, the upper linear concentration range is generally less than that of ICP-OES systems and may
require that some samples be diluted.

 Costs
As they are less complex systems, instrumentation for single element atomic spectroscopy (Flame AA
and GFAA) is generally less costly than that for the multi-element techniques (ICP-OES and ICP-MS).
There can also be a considerable variation in cost among instrumentation for the same technique.
Instruments offering only basic features are generally less expensive than more versatile systems, which
frequently also offer a greater degree of automation. Figure 8 provides a comparison of typical
instrument price ranges for the major atomic spectroscopy techniques.

APPLICATION ATOMIC ABSORPTION SPECTROSCOPY

 Graphite furnace atomic absorption

WHAT IS GRAPHITE FURNACE ATOMIC ABSORPTION?

Graphite furnace atomic absorption spectrometry (GFAAS) also known as Electro thermal
Atomic Absorption spectrometry (ETAAS) is a type of spectrometry that uses a graphite-coated
furnace to vaporize the sample. Instead of employing the high temperature of a flame to bring
about the production of atoms from the sample and it is non-flame methods involving electrically
heated graphite tubes or rods.

WOKING PRINCIPLE OF GRAPHITE FURNACE ATOMIC ABSORPTION

• Aqueous samples should be acidified (typically with nitric acid, HNO3) to a pH of 2.0 or less.
Discoloration in a sample may indicate that metals are present in the sample. For example, a
greenish color may indicate high nickel content, or a bluish color may indicate a high copper
content. A good rule to follow is to analyze clear (relatively dilute) samples first, and then
analyze colored (relatively concentrated) samples. It may be necessary to dilute highly colored
samples before they are analyzed.

• After the instrument has warmed up and been calibrated, a small aliquot (usually less than 100
microliters (µL) and typically 20 µL) is placed, either manually or through an automated
sampler, into the opening in the graphite tube. •The graphite furnace is an electrothermal
atomizer system that can produce temperatures as high as 3,000°C. The heated graphite furnace
provides the thermal energy to break chemical bonds within the sample and produce free ground-
state atoms. Ground-state atoms then are capable of absorbing energy, in the form of light, and
are elevated to an excited state.

•The sample is vaporized in the heated graphite tube; the amount of light energy absorbed in the
vapour is proportional to atomic concentrations.

• The free atoms will absorb light at frequencies or wavelengths characteristic of the element of
interest .

• Within certain limits, the amount of light absorbed can be linearly correlated to the
concentration of analyte present.

ADVANTAGES OF GRAPHITE FURNACE ATOMIC ABSORPTION

  The detection limits for the graphite furnace fall in the ppb range for most elements

 Greater sensitivity and detection limits (hundred- or thousand fold improvements in the
detection limit compared with flame AAS) than other methods.

 Direct analysis of some types of liquid samples.

 Some solid samples do not require prior dissolution.

 Low spectral interference.

 Very small sample size (as low as 0.5µL)

SYSTEM COMPONENTS OF GRAPHITE FURNACE ATOMIC ABSORPTION

Graphite furnace atomic absorption spectrometry instruments have the following basic features:

1. A source of light (lamp) that emits resonance line radiation.

2. An atomization chamber (graphite tube) in which the sample is vaporized.

3. A monochromator for selecting only one of the characteristic wavelengths (visible or

ultraviolet) of the element of interest.

4. A detector, generally a photomultiplier tube (light detectors that are useful in low-intensity
applications), that measures the amount of absorption.

5. A signal processor-computer system (strip chart recorder, digital display, meter, or printer)