e.

Atomic absorption spectrometry

Atomic absorption spectrometry (AAS) is an atoms there is in the vapour, the more radiation is
analytical technique that measures the concentrations absorbed. The amount of light absorbed is
of elements. Atomic absorption is so sensitive that it proportional to the number of lead atoms. A
can measure down to parts per billion of a gram (µg calibration curve is constructed by running several
dm–3) in a sample. The technique makes use of the samples of known lead concentration under the same
wavelengths of light specifically absorbed by an conditions as the unknown. The amount the standard
element. They correspond to the energies needed to absorbs is compared with the calibration curve and
promote electrons from one energy level to another, this enables the calculation of the lead concentration
higher, energy level. in the unknown sample.
Atomic absorption spectrometry has many uses in Consequently an atomic absorption spectrometer
different areas of chemistry. needs the following three components: a light source;
Clinical analysis. Analysing metals in biological a sample cell to produce gaseous atoms; and a means
fluids such as blood and urine. of measuring the specific light absorbed.
Environmental analysis. Monitoring our
environment – eg finding out the levels of various The light source
elements in rivers, seawater, drinking water, air, petrol The common source of light is a ‘hollow cathode
and drinks such as wine, beer and fruit drinks. lamp’ (Fig. 1). This contains a tungsten anode and a
Pharmaceuticals. In some pharmaceutical cylindrical hollow cathode made of the element to be
manufacturing processes, minute quantities of a determined. These are sealed in a glass tube filled
catalyst used in the process (usually a metal) are with an inert gas – eg neon or argon – at a pressure of
sometimes present in the final product. By using
AAS the amount of catalyst present can be
determined.
Industry. Many raw materials are examined and
AAS is widely used to check that the major elements
are present and that toxic impurities are lower than
specified – eg in concrete, where calcium is a major
constituent, the lead level should be low because it is
toxic.
Mining. By using AAS the amount of metals such as
gold in rocks can be determined to see whether it is
worth mining the rocks to extract the gold.
Figure 1
How it works
Atoms of different elements absorb characteristic between 1 Nm–2 and 5 Nm–2. The ionisation of some
wavelengths of light. Analysing a sample to see if it gas atoms occurs by applying a potential difference of
contains a particular element means using light from about 300–400 V between the anode and the cathode.
that element. For example with lead, a lamp These gaseous ions bombard the cathode and eject
containing lead emits light from excited lead atoms metal atoms from the cathode in a process called
that produce the right mix of wavelengths to be sputtering. Some sputtered atoms are in excited states
absorbed by any lead atoms from the sample. In and emit radiation characteristic of the metal as they
AAS, the sample is atomised – ie converted into fall back to the ground state – eg
ground state free atoms in the vapour state – and a Pb* → Pb + h ν (Fig. 2). The shape of the cathode
beam of electromagnetic radiation emitted from concentrates the radiation into a beam which passes
excited lead atoms is passed through the vaporised through a quartz window, and the shape of the lamp is
sample. Some of the radiation is absorbed by the lead such that most of the sputtered atoms are redeposited
atoms in the sample. The greater the number of on the cathode.

1. Ionisation 2. Sputtering 3. Excitation 4. Emission

M° M* M*
+ + + +
- Ne° Ne+ - - M° Ne+ - M° Light
Ne+

Figure 2

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Sample Cell

Source Monochromator Detector Meter

Chopper
Flame
(or furnace)

Figure 3

A typical atomic absorption instrument holds several constant monitoring between the reference beam and the light
lamps each for a different element. The lamps are housed source. To ensure that the spectrum does not suffer from loss
in a rotating turret so that the correct lamp can be quickly of sensitivity, the beam splitter is designed so that as high a
selected. proportion as possible of the energy of the lamp beam passes
through the sample.
The optical system and detector
A monochromator is used to select the specific wavelength
of light – ie spectral line – which is absorbed by the Atomisation of the sample
sample, and to exclude other wavelengths. The selection of Two systems are commonly used to produce atoms from the
the specific light allows the determination of the selected sample. Aspiration involves sucking a solution of the sample
element in the presence of others. The light selected by the into a flame; and electrothermal atomisation is where a drop
of sample is placed into a graphite tube that is then heated
monochromator is directed onto a detector that is typically electrically.
a photomultiplier tube. This produces an electrical signal
proportional to the light intensity.(Fig. 3) Some instruments have both atomisation systems but share
one set of lamps. Once the appropriate lamp has been selected,
Double beam spectrometers it is pointed towards one or other atomisation system.
Modern spectrometers incorporate a beam splitter so that
one part of the beam passes through the sample cell and the
other is the reference (Fig. 4). The intensity of the light Flame aspiration
source may not stay constant during an analysis. If only a Figure 5 shows a typical burner and spray chamber. Ethyne/
single beam is used to pass through the atom cell, a blank air (giving a flame with a temperature of 2200–2400 °C) or
reading containing no analyte (substance to be analysed) ethyne/dinitrogen oxide (2600–2800 °C) are often used. A
would have to be taken first, setting the absorbance at zero. flexible capillary tube connects the solution to the nebuliser.
If the intensity of the source changes by the time the sample At the tip of the capillary, the solution is ‘nebulised’ – ie
is put in place, the measurement will be inaccurate. In the broken into small drops. The larger drops fall out and drain
double beam instrument there is a off while smaller ones vaporise in the flame. Only ca 1% of
the sample is nebulised.

Reference beam

Sample beam

Source Beam splitter Monochromator Detector Readout

Electronics
Sample cell
Beam recombiner

Figure 4

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Sample hole

Flow spoiler

Mixing chamber
with burner head

Nebuliser
Impact bead Light

End cap

Figure 5 Figure 6
Electrothermal atomisation
of the original sample. Figure 7 shows a flame
Figure 6 shows a hollow graphite tube with a
atomic absorption spectrometer with an autosampler
platform. 25 µl of sample (ca 1/100th of a raindrop) is
and flow injection accessory.
placed through the sample hole and onto the platform
When making reference solutions of the element
from an automated micropipette and sample changer.
under analysis, for calibration, the chemical
The tube is heated electrically by passing a current
environment of the sample should be matched as
through it in a pre-programmed series of steps. The
closely as possible – ie the analyte should be in the
details will vary with the sample but typically they
same compound and the same solvent. Teflon
might be 30–40 seconds at 150 °C to evaporate the
containers may be used when analysing very dilute
solvent, 30 seconds at 600 °C to drive off any volatile
solutions because elements such as lead are sometimes
organic material and char the sample to ash, and with a
leached out of glass vessels and can affect the results.
very fast heating rate (ca 1500 °C s-1) to 2000–2500 °C
for 5–10 seconds to vaporise and atomise elements
(including the element being analysed). Finally Background absorption
heating the tube to a still higher temperature It is possible that other atoms or molecules apart from
those of the element being determined will absorb or
– ca 2700 °C – cleans it ready for the next sample.
scatter some radiation from the light source. These
During this heating cycle the graphite tube is flushed
species could include unvaporised solvent droplets, or
with argon gas to prevent the tube burning away. In
electrothermal atomisation almost 100% of the compounds of the matrix (chemical species, such as
sample is atomised. This makes the technique much anions, that tend to accompany the metals being
more sensitive than flame AAS. analysed) that are not removed completely. This
means that there is a background absorption as well as
Sample preparation that of the sample.
Sample preparation is often simple, and the chemical One way of measuring and correcting this
form of the element is usually unimportant. This is background absorption is to use two light sources, one
because atomisation converts the sample into free of which is the hollow cathode lamp appropriate to the
atoms irrespective of its initial state. The sample is element being measured. The second light source is a
weighed and made into a solution by suitable dilution. deuterium lamp.
Elements in biological fluids such as urine and blood The deuterium lamp produces broad band
are often measured simply after a dilution radiation, not specific spectral lines as with a hollow

Figure 7

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cathode lamp. By alternating the measurements of the two light sources generally at 50 –100 Hz the total
absorption (absorption due to analyte atoms plus background) is measured with the specific light from the hollow
cathode lamp and the background absorption is measured with the light from the deuterium lamp. Subtracting the
background from the total absorption gives the absorption arising from only analyte atoms.

Calibration
A calibration curve is used to determine the unknown concentration of an element eg lead in a solution.

The instrument is calibrated using several solutions of known concentrations. A calibration curve is produced
which is continually rescaled as more concentrated solutions are used the more concentrated solutions absorb
more radiation up to a certain absorbance. The calibration curve shows the concentration against the amount of
radiation absorbed (Fig. 8(a)).
The sample solution is fed into the instrument and the unknown concentration of the element eg lead is then
displayed on the calibration curve
(Fig. 8(b)).
Absorbance

Absorbance

Concentration Concentration

Figure 8(a) Figure 8(b)