ATOMIC ABSORPTION, METHODS AND INSTRUMENTATION 1

long-lived radio-isotopes of the elements to be Hieftje GM and Norman LA (1992) Plasma source mass
analy- sed are added as internal standards, e.g. the spectrometry. Imtermatiomal Jomrmal of Mass
use of 111Cd in the analysis of 114Cd. In addition, Spectro- metry amd Iom Processes 118/119: 519–
ICP-MS can be extremely useful in speciation. In 57S.
this respect, there is a growing interest in the use of Iribarne JV and Thomson BA (1976) On the evaporation
ICP-MS directly coupled to LC or capillary of small ions from charged droplets. Jomrmal of
electrophoresis for speciation and analysis of CSemical PSysics 64: 2287 and (1979) Field induced
elements of toxicological interest, like As, Se, Pb ion evaporation from liquid surfaces at atmospheric
pressure. Jomrmal of CSemical PSysics 71: 4451.
and Hg.
Knewstubb PF and Sugden TM (1958) Mass-
See also: Chemical Ionization in Mass Spectrome- spectrometric observation of ions in flames. Natmre
try; Chromatography-MS, Methods; Cosmochemical 181: 474–475.
Applications Using Mass Spectrometry; Inductively Knewstubb PF and Sugden TM (1958) Mass-
Coupled Plasma Mass Spectrometry, Methods; Inor- spectrometric observation of ions in hydrocarbon
ganic Chemistry, Applications of Mass Spectrometry. flames. Natmre 181: 1261.
Meek JM and Craggs JD (1978) Electrical Breaddomm of
Gases. Chichester: Wiley.
Further reading Meng CK, Mann M and Fenn JB (1988) Proceedimgs of
tSe -6tS ASMS Comferemce om Mass Spectrometry amd
Bruins AP, Covey TR and Henion JD (1987) Ion spray Allied Topics, June 5–10, San Francisco, CA,
interface for combined liquid chromatography/atmo- pp. 771–772.
spheric pressure ionization mass spectrometry. Niessen WMA (1998) Liqmid CSromatograpSy – Mass
Amalyti- cal CSemistry 59: 2642–2646. Specctrometry, 2nd edn. New York: Marcel Dekker.
Carroll DI, Dzidic I, Horning EC and Stillwell RN (1981) Niessen WMA (1998) Advances in instrumentation in liq-
Atmospheric pressure ionization mass spectrometry. uid chromatography – mass spectrometry and related
Applied Spectroscopic Reviem 17: SS7–406. liquid-introduction techniques. Jomrmal of CSromatog-
Chowdhury SK, Katta V and Chait BT (1990) An elec- rapSy A 794: 407–4S5.
trospray-ionization mass spectrometer with new fea- Vela NP, Olson LK and Caruso JA, Elemental speciation
tures. Rapid Commmmicatioms of Mass Spectrometry with plasma mass spectrometry. Amalytical CSemistry
4: 81–87. 65: 585A–597A.
Cole RB (ed) (1997) Electrospray Iomiçatiom Mass Spec- Yamashita M and Fenn JB (1984) Electrospray ion
trometry. Chichester, UK: Wiley. source. Another variation on the free-jet theme.
Fenn JB, Mann M, Meng CK, Wong SF and Whitehouse Jomrmal of PSysical CSemistry 88: 4451–4459.
CM (1989) Electrospray ionization for mass spectro- Yamashita M and Fenn JB (1984) Negative ion
metry of large biomolecules. Sciemce 246: 64–71. production with the electrospray ion source. Jomrmal
of PSysical CSemistry 88: 4671–4675.

Atomic Absorption, Methods and Instrumentation

Steve J Hill and Andy S Fisher, University of ATOMIC SPECTROSCOPY
Plymouth, UK
Methods & Instrumentation
Copyright © 1999 Academic Press

Introduction (i) the flame and (ii) electrothermal heating of a

sam- ple cell. It is generally acknowledged that if
Atomic absorption spectroscopy has become one of sufficient analyte is present in the sample, then it
the most frequently used tools in analytical chemis- should be de- termined using a flame technique
try. This is because for the determination of most because this has the added advantages of being
metals and metalloids the technique offers sufficient rapid (assuming only a few elements need be
sensitivity for many applications and is relatively in- determined) and, in com- parison with alternative
terference free. There are two basic atom cells (a techniques, very simple to use. Electrothermal
means of turning the sample, usually a liquid, into atomic absorption spectroscopy (ETAAS) requires
free atoms) used in atomic absorption more operator skill and is less rapid, but yields
spectroscopy: substantially superior limits of
detection when compared with flame atomic absorp-
tion spectroscopy (FAAS). This section describes
some of the methods and instrumentation that have
been developed for both flame and electrothermal
techniques of atomic absorption spectroscopy.

Instrumentation
The basic principle of both FAAS and ETAAS is that
sample is introduced into the atom cell, where it is
desolvated and then atomized. The analyte atoms
so formed then quantitatively absorb light in a way
that is proportional to the concentration of the atoms
of the analyte in the cell. The light, which is at a
specific wavelength, is then isolated from other
wavelengths that may be emitted by the atom cell Figure 1 Schematic representation of a hollow-cathode lamp.
and then detect- ed. Thus, much of the From Ebdon L (1998) Introduction to Analytical Atomic
Spectrometry. Reproduced by permission of John Wiley & Sons
instrumentation used for elec- trothermal and flame Limited.
absorption spectroscopy is identical. Both
techniques require a similar light source,
background correction system, line isolation device intense than the microwave-excited ones, but are
(monochromator or polychromator), detector still 5–100 times more intense than a standard
(photomultiplier or charge coupled device) and hollow- cathode lamp. In the electrodeless
read- out system. Each of these components is discharge lamp, a bulb contains the element of
discussed below, together with details of the interest (or one of its salts) in an argon atmosphere.
individual atom cells (flame and the electrothermal The radiofrequency energy ionizes the argon and
atomizer) and sample introduction systems. this in turn excites the analyte element, causing it to
produce its characteris- tic spectrum. For analytes
such as arsenic and seleni- um, these lamps give a
Light source better signal-to-noise ratio than hollow-cathode
lamps and have a longer useful lifetime. A
The fundamental requirement of the light source schematic diagram of an electrodeless dis- charge
is to provide a narrow line profile with little lamp is shown in Figure 2.
background. It should also have a stable and repro-
ducible output with sufficient intensity to ensure that
a high signal-to-noise ratio is obtained. Two basic Background correction systems
types of light source are used for atomic absorption,
There are basically three types of automatic back-
of which the hollow-cathode lamp (HCL) is the
ground correction system available for atomic ab-
more commonly used. This is a lamp in which the
sorption, although manual methods such as the use
cathode is coated with the analyte metal of interest.
of nearby non-atomic absorbing lines to estimate
Within the lamp, inert filler gas (neon or argon) is
background absorbance may also be used. The
ionized by an electric current and these ions are
three main automatic methods are the deuterium or
then attracted by the cathode. The inert gas ions
hy- drogen lamp, the Zeeman effect, and Smith–
bombard the cathode and in so doing excite the
Hieftje background correction. The deuterium lamp
metal ions coated on it. It is this excitation of the
produces a continuum of radiation, some of which
metal that produces the emission of radiation with
will be absorbed by molecular species within the
wavelengths characteristic of the analyte. Hollow-
atom cell. The amount of atomic absorption ob-
cathode lamps are available for most metallic
served using the deuterium lamp is negligible and
elements. A schematic diagram of a hollow-cathode
hence the atomic absorption signal is obtained by
lamp is shown in Figure 1.
subtracting the absorbance from the continuum
Electrodeless discharge lamps are used less fre-
lamp from the total analyte absorbance from the
quently than the hollow-cathode lamps except for
hollow cathode lamp. The deuterium or hydrogen
analytes such as arsenic and selenium. These
lamp is of most value at wavelengths in the UV re-
lamps may be excited using either microwave
gion ( S50 nm). The Zeeman effect background
energy (al- though these tend to be less stable) or
correction system is more versatile. It relies on a
radiofrequency energy. The radiofrequency-excited
strong magnetic field operating at approximately
lamps are less
Figure 2 Electrodeless discharge lamp. From Ebdon L (1998) Introduction to Analytical Atomic Spectrometry. Reproduced by
permission of John Wiley & Sons Limited.

1 T and 50–60 Hz, placed either around the light more complex and offers far fewer advantages for
source or, more commonly, around the atom cell to atomic absorption when compared with double-
split the signal into a number of components. The  beam spectrometers in molecular spectroscopy.
component is at the normal analyte wavelength; the This is because the reference beam does not pass
 components are typically 0.01 nm (depending on through the atom cell. Despite this, double-beam
the strength of the magnetic field) either side of the instruments can compensate for source drift and for
 component and hence lie outside the atomic warm-up and source noise.
absorp- tion profile. Background can be corrected
by sub- tracting the absorbance with the magnetic
field ‘on', from the signal with the magnet ‘off'. It Line isolation devices
should be noted that this is a simplified description
To ensure that only light of a wavelength specific to
of the process, as different elements have different
the analyte of interest is being measured, a line
splitting patterns and the magnetic field may be
isolation device is required. Until recently, the line
applied longi- tudinally or transversely, which may
isolation device used for atomic absorption was a
also produce different splitting patterns.
When utilizing the Smith–Hieftje system, the hol-
low-cathode lamp is boosted periodically to a much
higher current, causing the lamp to ‘self-absorb'. In
this state no atomic absorption occurs in the atom
cell but the molecular absorption still remains. Back-
ground correction is achieved automatically by sub-
tracting the signal obtained at high current from that
obtained using the normal current. The process is
particularly efficient at removing interferences such
as that caused by phosphate or selenium
determina- tions, although the high currents used
may shorten the lifetime of the lamp. In modern
instruments, modulation of the source is achieved
electronically. This enables discrimination between
absorption and emission signals. Previously, a
rotating sector, often referred to as a ‘chopper',
placed between the source and the atom cell was
used.

Single-beam and double-beam

instruments
The vast majority of instruments used for atomic ab- Figure 3 Schematics of (A) single-beam and (B) double-beam
sorption measurements have a single-beam spectrometers. From Ebdon L (1998) Introduction to Analytical
Atomic Spectrometry. Reproduced by permission of John Wiley
configu- ration, using the optical layout shown in & Sons Limited.
Figure 3A. The double-beam arrangement (Figure
3B) is far
monochromator. There are numerous types of A monochromator enables only one wavelength
monochromator, but modern instruments typically to be interrogated at any instant; this was something
use one of three designs: Ebert, Czerny–Turner or of a weakness of atomic absorption spectroscopy.
Littrow configuration. These are shown schematical- New technology, however, has enabled the
ly in Figure 4. development of multielement spectrometers that
Light of all wavelengths enters the monochroma- use a bank of between 4 and 6 hollow-cathode
tor through an entrance slit and is then split into lamps and an echelle-style polychromator
spe- cific wavelengths using either a prism, or more employing orders of 100 or more and are thus
commonly, a diffraction grating. By altering the capable of considerable disper- sion. In addition,
position of this dispersing element, light of only the such instruments have no exit slit and so a huge
desired wavelength passes through the exit slit to number of wavelengths may be focused onto an
the detector. Since the method of atomic absorption array detector such as a charge-coupled device. A
is so specific, very highly resolving monochromators schematic diagram of such an instrument is shown
are not required. Thus, the focal length of an atomic in Figure 5. Research continues into produc- ing a
absorption monochromator is often 0.25 or 0.5 m continuum light source that would enable S0– 40
compared with a minimum of 0.75 m required for analytes to be determined simultaneously.
conventional optical emission spectroscopy.

Detection systems
Traditionally, detection of the light isolated by the
monochromator has been accomplished using a
photomultiplier tube (PMT). Several configurations
exist, e.g. end-on and side-on, and the construction
may be of different materials, to increase the
efficien- cy at different wavelengths; but basically
they all work in a similar way. Light enters the
multiplier through a quartz window and impacts with
a photo- cathode that is usually made from one of a
number of alloys (e.g. Cs–Sb, Na–K–Sb–Cs or Ga–
As), which then emits electrons. These electrons
are then accel- erated down a series of dynodes,
each being at a more positive potential than the
previous one. As the electrons impact with
successive dynodes, further electrons are ejected
and hence a cascade effect occurs. In this way a
single photon may cause the ejection of 106
electrons. The number of electrons is

Figure 4 Schematics of different monochromator types: (A)

Ebert, (B) Czerny–Turner, (C) Littrow. From Ebdon L (1998)
Introduction to Analytical Atomic Spectrometry. Reproduced by
permission of John Wiley & Sons Limited. Figure 5 Echelle-based polychromator.
then measured at the anode and the resulting
Instrument control and output devices
current is proportional to the radiation reaching the
PMT. Manual controls and dials have slowly disappeared,
As described previously, a number of different with the large majority of modern instruments being
materials may be used to coat the photocathode in controlled by computer. In addition to controlling
the PMT, and each has a different response curve. the instrumental parameters, the computer may be
Some, for example the Cs–Sb tube, have very little used to program autosamplers, save experimental
sensitivity above 600 nm, but others, for example parameters and data, calibrate with known stand-
Ga–As, may be used up to almost 900 nm. The ards, plot calibration curves, use scale expansion
response profiles of some commonly used facilities (if necessary) and produce statistical data
photomul- tipliers are shown in Figure 6. from the results. A continuous graphics mode ena-
Conventional spectrometers use a detector that is bles the signal to be monitored over a period of
capable of measuring only one signal. Multielement time. This is especially useful when flow injection,
instruments use state-of-the-art diode arrays or chromatography or hydride-generation transients
charge-coupled devices that can measure are to be detected and integrated. Older
numerous spatially separated signals and can instrumenta- tion relied on a chart recorder for the
therefore simulta- neously determine the signals same purpose.
arising from a bank of hollow-cathode lamps. A
charge-coupled device may be considered to be
similar to an electronic photo- graphic plate. The Sample introduction and atom cells
device consists of several hundred linear
For flame systems, the sample is introduced via a
photodetector arrays on a silicon chip with
nebulizer and spray chamber assembly. Sample is
dimensions of typically 1S  18 mm. The line isola-
drawn up the intake capillary by the Venturi effect.
tion device (often an echelle grating) separates the The liquid sample column comes into contact with
analytical wavelengths and these may then be the fast moving flame gases and is shattered into
detected on different regions of the array. A detailed small droplets. In many systems it is further
description of how the array works is beyond the smashed into still smaller droplets by an impact
scope of this text. bead. The flame gases then carry the aerosol (the
nebular) through a spray chamber containing a
series of baf- fles or flow spoilers. These act as a
droplet size filter, passing the larger droplets to
waste (85–90% of the sample) and allowing the
finer droplets to be trans- ported to the flame. For
electrothermal atomizers, the sample is placed into
the atom cell either using a hand-held micropipette
or by an autosampler. Since most instruments are
supplied with an autosampler and the precision
associated with their use is superi- or to that of the
micropipette, most laboratories make use of this
method of sample introduction.
As described previously, there are two basic
types of atom cell; flame and electrothermal tube,
but both can have numerous modifications. The
flame cell most commonly used is the 10 cm length
air–acety- lene burner. This provides a flame that is
at approxi- mately 2S00C (although the actual
temperature will depend on the fuel/air ratio). The
flame may be used in a fuel-lean mode, which
produces a hot, oxidizing blue flame; in a fuel-rich
mode, which produces a cooler, reducing yellow
flame; or in a stoichiometric mode whose properties
are between the two. Differ- ent analytes give
different sensitivities depending on the flame type.
Figure 6 Response curves for several commercial photomulti- Chromium, for instance, gives better sensitivity in a
plier tubes. From Ebdon L (1998) Introduction to Analytical reducing flame, whereas for magne- sium it is better
Atomic Spectrometry. Reproduced by permission of John Wiley to use a lean, oxidizing flame.
& Sons Limited. Different areas of the flame have different tem-
peratures and different chemical properties. The
efficiency of atomization of analytes will therefore In electrothermal atomization the sample is intro-
depend critically on the area within the flame. duced into the tube, which is then heated in a series
Hence, it is important that the light beam from the of steps at increasing temperature. The sample is
HCL passes through the region of the flame where dried at a temperature just above the boiling point of
atomization is optimal. Optimization of the burner the solvent (but not so hot as to cause frothing and
height is therefore necessary to ensure that maxi- spitting of the sample); ashed (charred at an
mum sensitivity is achieved. interme- diate temperature to remove as much of
Although an air–acetylene flame is sufficient for the concom- itant matrix and potential interferences
the atomization of the majority of analytes, it is not as possible without losing any analyte); and then
suf- ficiently hot or reducing to atomize analytes that atomized at a high temperature. During the
form refractory oxides (e.g. Al, Mo, Si and Ti). For atomization stage, the atoms leave the graphite
analytes such as these a nitrous oxide–acetylene surface and enter the light beam, where they absorb
flame of length 5 cm is used. This flame is hotter the incident radiation. The ashing and atomizing
(2900C) and contains typically 2.5–S times as temperatures used will depend on the analyte of
much fuel as the air– acetylene flame. Other flame interest; for example, some ana- lytes such as lead
types, e.g. air–propane and air–hydrogen also exist, are relatively volatile and so cannot
although they are less commonly used. The air– be ashed at temperatures above 450C, otherwise
hydrogen flame (2200C) is almost invisible and has volatile salts such as chlorides will be lost. Other
the advantage of being trans- parent at lower an-
wavelengths offering improved noise characteristics alytes, for example, magnesium, are less volatile
for elements such as lead or tin at around 220 nm. and can be ashed at temperatures close to 1000 C
The inhomogeneity of flame chemis- try and the with-
need for burner height optimization hold true for all out analyte loss. Such elements require a much
flame types. higher atomization temperature. The sensitivity of
One common modification to a flame cell is to electrothermal atomization AAS is greater than for
place a quartz tube on the burner head so that the flame AAS because the atoms are formed within the
light beam passes through the length of the tube. confines of a tube and hence spend longer in the
This method is especially useful when using sample light beam. Also, since the sample is placed within
introduction by hydride generation or by gas chro- the atom cell, 100% of it is available for analysis
matography. The tube is heated either by a flame or com- pared with the 10–15% available in flame
electrically using a wire winding. The analyte, which systems. A comparison of characteristic
enters the tube via a hole or slit cut into the side, is concentrations (con- centration that gives an
atomized within the tube. The atoms then leave the absorbance of 0.0044) ob- tained for flame and
tube but, because of their retention in the tube, electrothermal techniques for many analytes is
spend longer in the light beam than in normal flame shown in †able 1. It must be stressed that the
systems. An increase in sensitivity is therefore figures for ETAAS will depend critically on the
obtained. Another small modification of this system injection volume and so values tend to be given in
is that, instead of a quartz tube, a quartz T-piece absolute terms (i.e. a weight).
may be used. However, the function is the same. Overall, the Massmann design of electrothermal
Electrothermal atom cells have changed radically atomizer in which the tube is heated from either end
since their inception in the late 1950s. The majority is still the most common (Figure 7B), but more
of electrothermal devices have been based on recently transversely heated tubes have been
graph- ite tubes that are heated electrically devel- oped (Figure 7A). The longitudinally heated
(resistively) from either end. Modifications such as tubes have a temperature gradient along the tube,
the West Rod Atomizer (a carbon filament) were with the central portion being several hundred
also devised but were later abandoned. Tubes and degrees hotter than the ends. This can lead to
filaments made from highly refractory metals such condensation of analyte at the cooler ends and
as tungsten and tantalum have also been made, but subsequent re- atomization from the hot graphite
they tend to become brittle and distorted after surface. Several atomization peaks may therefore
extended use and have poor resistance to some result. The trans- versely heated tubes do not have
acids. Their use contin- ues, however, in some a temperature gra- dient and therefore do not suffer
laboratories that need to deter- mine carbide- from this problem.
forming elements. For example, silicon reacts with
the graphite tube to form silicon carbide, which is Interferences
both very refractory and very stable. The silicon is
therefore not atomized and is lost analyti- cally. Use Flame techniques are regarded as being relatively
of a metal vaporizer prevents this. free from interferences, but some distinct classes of
interference do exist. These include a few spectral
interferences (e.g. Eu at S24.75S nm on Cu at
S24.754 nm), ionization interferences and chemical
Table 1 Comparison of characteristic concentrations for flame
and electrothermal AAS
Electrothermal
Analyte Flame AAS (g L–1) AAS (pg)
Ag 30 5
Al 300 30
As 800a,5b 42
Au 100 18
B 8 500 600
Ba 200 15
Be 16 2.5
Bi 200 67
Ca 13 1
Cd 11 1
Co 50 17
Cr 50 7
Cs 40 10
Cu 40 17
Fe 45 12
Ge 1 300 25
Hg 2 200a,0.1b 220
K 10 2
La 48 000 7 400
Mg 3 0.4
Mn 20 6
Mo 280 12
Ni 50 20
Pb 100 30
Rb 30 10 Figure 7 Electrothermal tubes available commercially: (A)
transversely heated graphite atomizer (THGA), (B) longitudinally
Sb 300 60
heated Massmann atomizer. From Ebdon L (1998) Introduction
Se 350a,4b 45 to Analytical Atomic Spectrometry. Reproduced by permission
Si 1 500 120 of John Wiley & Sons Limited.
Sn 400 100
Sr 40 4
ionized (and lost analytically) and hence serious
Te 300 50
over- estimates of the true concentration will be
Ti 1 400 70
obtained. This type of interference may be
Tl 300 50
overcome by adding an excess of easily ionized
U 110 000 40 000
element to all standards and samples.
V 750 42
Chemical interferences may exist in several differ-
Yb 700 3
ent forms:
Zn 10 1
a
Under normal flame conditions. • Formation of less volatile compounds, e.g. when
b
With vapour generation. phosphate is present during the determination of
calcium. Calcium phosphate is refractory and
hence atomization will be retarded in comparison
interferences. Ionization interference is a vapour-
with calcium in the standards.
phase interference (in the past often termed cation
• Formation of more volatile compounds, e.g.
enhancement) that occurs when the sample
chlorides.
contains large amounts of an easily ionized
• Occlusion into refractory compounds. Small
element. The presence of large concentrations of
amounts of analyte may become trapped in a
easily ionized ele- ments will lead to a large
refractory substance and hence not be atomized
concentration of electrons in the flame. These
efficiently.
electrons prevent the ionization of the analyte and
• Occlusion into volatile compounds. Some com-
hence lead to higher atomic absorp- tion signals. If
pounds sublime explosively and hence
the easily ionized element is not present in the
atomization may be enhanced.
standards, the analyte may be partially
Most of these interferences may be overcome by concept. Other interferences, e.g. formation of car-
using a hotter flame (e.g. nitrous oxide–acetylene); bides, may be partially overcome by treating the at-
by adding a chelating reagent, e.g. EDTA, to com- omizer with a carbide-forming element, for example
plex preferentially with the analyte; by adding a by soaking in tantalum solution. The principle is
releasing agent, e.g. lanthanum, that will combine that the tantalum occupies the active sites on the
preferentially with phosphate; or by optimizing the surface, thereby preventing the analyte from form-
flame conditions and viewing height. ing a carbide.
Electrothermal AAS was renowned for being
highly prone to interferences. However, modern
methods and instrumentation have decreased this Methods
problem substantially. Interferences include memory
effects, chemical interferences (loss of analyte as a Numerous methods have been described for use
volatile salt, carbide formation, condensation and with AAS, but the majority require the sample to be
recombination), background absorption (smoke), in a liquid form. Some ETAAS systems allow the
and physical interferences such as those resulting analysis of solids directly (e.g. by weighing small
from placing the sample on a different part of the amounts onto sampling boats that may be slotted
tube. The stabilized temperature platform furnace into special- ized tubes), but usually, if solids are to
(STPF) concept has gone a long way to eliminating be analysed, acid decomposition methods are
the problem. The concept is that a ‘matrix modifier' required. An alter- native is the analysis of slurries,
is required for interference-free determinations. This using finely ground material ( 10 m) dispersed in
is a material that either decreases the volatility of a solvent. Manual agitation of the slurry ensures
the analyte, enabling higher ash temperatures to be homogeneity of the sample, enabling a
achieved and hence boiling away more interference representative aliquot to be intro- duced. Some
(a common example is a mix of palladium and mag- autosamplers come equipped with an ultrasonic
nesium nitrates) or increases the volatility of the agitator that will perform the same task. This method
matrix (for example, the introduction of air ‘burns of analysis is frequently used in ETAAS. If samples
away' many interferences leaving the analytes in containing high dissolved (or sus- pended) solids
the atomizer). The matrix modifier may be placed in are to be analysed by FAAS, a flow injection
the autosampler, and added to all samples and technique (in which discrete aliquots of sample are
stan- dards. Other requirements for the STPF introduced) may be used. This has also been
concept include a rapid heating rate during referred to as ‘gulp sampling'. This prevents salting
atomization, inte- grated signals (rather than peak up of the nebulizer and blockage of the burner slot,
height), a powerful background correction system which are obviously undesirable effects that have an
(e.g. Zeeman), fast electronics to measure the adverse effect on sensitivity and signal stabil- ity.
transient signal, and iso- thermal operation. Flow injection techniques may also be used to
Isothermal operation means that the analyte is preconcentrate analytes. If the sample flows through
vaporized from the graphite surface into hot gas. In a column containing an ion-exchange resin, the ana-
normal electrothermal AAS, the ana- lyte leaves the lytes will be retained. Elution with a small volume of
hot tube wall and enters the cooler gas phase. acid may yield very high preconcentration factors.
Under these circumstances it may recombine with This technique has been used for both FAAS and,
some other species to form a compound and thus more recently, for ETAAS, yielding limits of detec-
be lost analytically. To overcome this, platforms that tion far superior to those achieved under normal
are only loosely in contact with the tube walls have con- ditions. A typical flow injection manifold
been developed. The analytes in this case are suitable for
atomized not by the resistively heated graphite tube this type of application is shown in Figure 8.
but by the surrounding gas. The transversely heated A more traditional method of preconcentration is
tubes described earlier have a platform as an solvent extraction. Flame AAS may be used as a
integral part of the tube. A modification to this detector for analytes in organic solvents (sensitivity
technique, called probe atomization, has also been
developed. Here the sample is placed on a probe
and is then dried and ashed in the normal way. The
probe is then removed from the tube, which is
heated to the atomization temperature. The probe is
then re-intro- duced into the hot environment.
Most analytical techniques for use with furnace
work now utilize the advantages of the STPF
Figure 8 Typical flow injection manifold for matrix analyte pre-
concentration or matrix elimination.
may even be improved because of improved nebuli- metalloids is often sufficient for many applications.
zation efficiency), but occasional blocking of the Direct aspiration of samples in solution into a flame
burner slot by carbon may occur. This may be atomic absorption instrument provides the analyst
removed by gentle rubbing with a noncombustible with rapid acquisition of data with good precision.
material (such as a spatula). Organic solvents may The technique is remarkably free from interferences
also be introduced to ETAAS, but the ‘dry'-stage and those that do exist may usually be overcome by
temperature has to be modified to prevent sample judicious choice of operating conditions. The instru-
loss by spitting. mentation involved is relatively simple and, for flame
Hydride generation is a common method for the work, analyses may easily be performed by non-
detection of metalloids such as As, Bi, Ge, Pb, Sb, expert operators. If increased sensitivity is required,
Se, Sn and Te, although other vapours, e.g. Hg or the analyst has the option of preconcentrating the
alky- lated Cd, may also be determined. This analyte using one of a number of methods prior to
technique improves the sensitivity of the analysis introduction to flame AAS, or alternatively may use
substantially. Since the sample is in the gas phase, electrothermal AAS. The latter technique, however,
the sample transport efficiency is close to 100%. does require more experience if reliable results are
The hydrides atomize readily in the flame, although to be obtained.
this approach is usually used in conjunction with a A potential disadvantage of using atomic absorp-
quartz T-piece in the atom cell. Methods have been tion is that in the past instruments have been
developed that trap the hydrides on the surface of a capable of determining only one analyte at a time.
graphite tube for use with ETAAS. This leads to Modern instrumentation has improved this number
preconcentration and further improvements in to as many as six, although it must be stressed that
detection limit. com- promise conditions (e.g. in ETAAS
Chromatography has been coupled to AAS to temperature pro- grams) must be used. This may
effect speciation analysis. Here different chemical lead to a decrease in overall sensitivity compared
forms of an analyte are separated (either by high- with single-element determinations. However, the
performance liquid chromatography or, if they are ongoing development of multielement AAS will
sufficiently volatile, by gas chromatography) prior to certainly boost the use of this already popular and
introduction to the atomic absorption instrument. versatile technique.
Gas chromatography is usually coupled directly with
a T-piece interface arrangement, but HPLC coup- See also: Atomic Absorption, Theory; Atomic Fluo-
lings introduce the sample through the conventional rescence, Methods and Instrumentation; Atomic
nebulizer/spray chamber assembly. A small postcol- Spectroscopy, Historical Perspective; Light Sources
umn air bleed may be necessary to compensate for and Optics.
the differences in flow rate between the chromato-
graph (1–2 mL min1) and the uptake rate of the
nebulizer (5–10 mL min1). Chromatography is not Further reading
frequently coupled with ETAAS because the atom
cell is not well suited to continuous monitoring. Dedina J and Tsalev DL (1995) Hydride Gemeratiom
The limited linear range offered by the AAS tech- Atomic Absorptiom Spectrometry. Chichester: Wiley.
Ebdon L, Evans EH, Fisher A and Hill SJ (1998) Am
nique may be partially overcome by using
Imtro- dmctiom to Amalytical Atomic Spectrometry.
alternative, less sensitive lines. This is a useful
Chichester: Wiley.
technique that avoids the requirement to dilute Harnly JM (1996) Instrumentation for simultaneous
samples. Care must be taken, however, to ensure multielement atomic absorption spectrometry with
that viscosity effects do not cause a difference in graphite furnace atomization. Fresemims Jomrmal of
nebulization efficiency between samples and Ama- lytical CSemistry 355: 501–509.
standards. Alternatively, burner head rotation may Haswell SJ (ed) (1991) Atomic Absorptiom Spectrometry,
be used. This shortens the path in the flame through TSeory, Desigm amd Applicatioms, Analytical
which the light beam travels and hence decreases Spectros- copy Library. Amsterdam: Elsevier.
sensitivity. However, there is often an increase in Hill SJ, Dawson JB, Price WJ, Shuttler IL, Smith CMM
noise as a result of using this approach. and Tyson JF (1998) Atomic spectrometry update —
advances in atomic absorption and fluorescence spec-
trometry and related techniques. Jomrmal of Amalytical
Conclusions Atomic Spectrometry 13: 1S1R–170R.
Vandecasteele C and Block CB (199S) Moderm MetSods
The sensitivity offered by the various techniques for Trace Elememt Determimatiom. Chichester: Wiley.
utilizing AAS for the determination of metals and
 ATOMIC ABSORPTION, THEORY 33

Atomic Absorption, Theory

Albert Kh Gilmutdinov, Kazan State University,
Russia ATOMIC SPECTROSCOPY
Copyright © 1999 Academic Press Theory

Atomic absorption spectroscopy (AAS) is a provide complete atomization of the element

technique for quantitative determination of metals irrespec- tive of the sample matrix producing a
and metal- loids by conversion of a sample to well-defined and reproducible absorption layer of
atomic vapour and the analyte
measurement of absorption at a wavelength atomizer would
specific to the element of interest. Owing to high
sensitivity and selectivity, the technique is widely
used for fun- damental studies in physics and
physical chemistry: measurements of oscillator
strengths, diffusion coef- ficients of gas phase
species, partial pressure of vapours, rate constants
of homogeneous and hetero- geneous reactions,
etc. The widest application of AAS, however, is in
analytical chemistry. Nowadays it is one of the
most popular techniques for trace analysis of over
65 elements in practically all types of samples
(environmental, biological, industrial, etc.).
The vast majority of substances to be analysed
by AAS are in the condensed phase. At the same
time, atomic absorption, like any other atomic
spectrome- try technique, can only detect free
atoms that are in the gas phase. Thus, as analyte
initially present in so- lution at a concentration
c(liq) must first be trans- ferred into the gas phase
via the atomization process to produce N(g) free
atoms in an atomizer volume. The analyte atoms
are then detected by absorption of radiation from
a primary source at a wavelength characteristic of
the element resulting in an absorp- tion signal, A.
Thus, the general scheme of AAS can be presented
as follows:

The primary goal of the theory of AAS is to

establish the relationship between the measured
analytical sig- nal, atomic absorbance, A, and the
analyte concen- tration, c, in the sample.
Theoretical description of the two stages involves
entirely different sciences: theory of atomization
is based on thermodynamics, kinetics and
molecular physics, while description of
absorbances is based on optics and spectroscopy.
Below, the two stages will be considered
separately.

Atom production
In the first step of an AA determination the
element of interest must be atomized. The ideal
34 ATOMIC ABSORPTION, THEORY
atoms. Excitation processes, however, should be
minimal so that analyte and background emission
noise is small. For achieving the best detection
limits, the analyte vapour should not be highly
diluted by the atomizer gas. Various types of
electric discharges, laser radiation, electron
bombardment and induc- tively coupled plasmas
were tested as atomizers. Although not ideal, high-
temperature flames and elec- trothermal atomizers
have gained acceptance as the most common
technique of atom production in AAS.
Flame atomization
The longest practiced technique for converting a
sample into atoms is the spraying of a sample
solu- tion into a combustion flame. The most
popular flames used in AAS are the air–C 2H2 flame
providing a maximum temperature of about 2500
K and the N2O–C2H2 flame with a maximum
temperature ex-
ceeding S000 K. Atomization occurs because of the
high enthalpy and temperature of the flame, and
through chemical effects. Owing the generation
of cyanogen radicals, which are known to be an
effi- cient scavenger for oxygen, the nitrous
oxide-acety- lene flame provides not only a
hotter but also a more reducing environment for
atom production: the lack
of oxygen moves equilibria such as MeO = Me 
O
to the right. Therefore a N2O–C2H2 flame provides
greater atomization efficiencies and thus better
de-
tection limits for refractory elements, such as Al,
Ta Ti, Zr, Si, V and the rare earths.
Atom production in flames is an extremely com-
plex process consisting of many stages and
involving numerous sides processes. A
quantitative theory of analyte atomization in
flames is absent. Qualitative- ly, the process can
be described as follows: the solu- tion droplets
sprayed into the flame are first dried, the
resulting solid microparticles become molten and
vaporize or thermally decompose to produce
gaseous molecules that are finally dissociated
into free atoms. The atoms may further be
excited and ionized and form new compounds.
These processes are depend- ent upon the
temperature and the reducing power of the flame
and occur within a few milliseconds – the time
required by the sample to pass through the
flame. The processes taking place in flames are
volatilization of matrix components that are
shown in more detail in Figure 1.
purged from the atomizer by a flow of inert gas);
(iii) analyte atomization (1500–S000 K achieved
Electrothermal atomization
rapidly at a heating rate of about 2000 K s–1). A
In the majority of cases this occurs in a small major difference of electrothermal atomization
graph- ite tube where the sample to be analysed is from atomization in flames is that some matrix
intro- duced via a small aperture in the upper tube components are removed at the pyrolysis step and
wall. Metals such as tantalum or tungsten are also the atomization takes place within a confined
used to construct electrothermal atomizers as well geometry in an inert gas atmos- phere. During
as non- tubular geometry for the atomizer atomization, the purge gas flow is shut off so that
(graphite cups, rods, filaments, etc.). After a 5–50 analyte atoms remain in the probing beam as long
L droplet of the sample solution has been as possible.
deposited into the graphite furnace, it is heated The number of analyte atoms in the atomizer
resistively through a series of preprogrammed vol- ume N(t), generated during the atomization
temperature stages to provide: (i) drying of the stage is described by the convolution:
droplet to evaporate the solvent ( S70 K for
about S0 s); (ii) thermal pretreatment (pyrolysis)
to remove volatiles without loss of ana- lyte (600–
1500 K for 45 s) (this allows selective

Figure 1 Schematic representation of the processes taking place in a flame. The bold arrows show the pathways for analyte atom
production and thin arrows show side processes. Reproduced with permission from Welz B (1985) Atomic Absorption Spectrometry,
2nd edn, p. 167. Weinheim: VCH.
Here tSe smpply fmmctiom S(t), gives the rate
(atoms s1) of the primary generation of analyte
atoms from the deposited sample, whereas tSe
removal fmmctiom, R(t,t) characterizes the
subsequent transfer of the vaporized atoms in the
atomizer volume. In the sim- plest case of
vaporization of a monolayer of atoms from the
atomizer surface the supply function is given as:

where N0 is the total number of atoms in the

depos- ited sample,  and E are the frequency Figure 2 Supply function S(t ) of silver atoms computed for the
factor and the activation energy of the change in the atomizer temperature T(t ) (E  280 kJ mol1, U 
vaporization process, respec- tively, R is the gas 1013 s1); the change in the total number of silver atoms within
constant and T(t) is the time- dependent atomizer the atomizer volume N(t ).
temperature. A typical example of the supply
function in electrothermal AAS is given in Figure 2.
with the diffusion removal function is given in
The removal function R(t,t) gives the probability
Figure 2.
of an analyte atom, vaporized at the time, t, to be
The actual atom production and dissipation pro-
present in the atomizer volume at a later instant, t
cesses in electrothermal atomizer are much more
> t. Early in time, the probability is equal to unity
complex than that described above. In many cases
and decreases with increasing time because of loss
the analyte is atomized as a result of a set of
processes. Generally, the loss proc- esses include
multi- stage processes taking place simultaneously.
concentration and thermodiffusion, and
The ba- sic processes that occur with analyte in a
convection. The knowledge of the removal func-
graphite furnace are shown schematically in Figure
tion allows calculation of the mean residence
time, r, of analyte in the atomizer volume. This 3 and list- ed in †able 1. The last column of the
Table shows the elements for which the respective
parameter is defined as r  R(t) dt and gives the
processes have been documented.
life-time of evaporated atoms in the atomizer
In addition to the above widely used atomization
volume. When the analyte loss is governed only by
techniques, mention must also be made of ‘the hy-
concentration diffu- sion through the tube ends,
dride generation technique'. The method is based
the residence time can be estimated by the
on conversion of a hydride forming element (As,
following relationship:
Bi, Ge, Sb, Se, Sn, Te) in an acidified sample to
volatile hy- dride and transport of the released
hydride to an atomizer (hydrogen diffuse flame,
graphite furnace, heated quartz tube) where they
are atomized to give free analyte atoms. Sodium
where L is the tube length, a is the linear borohydride is almost ex- clusively used as an
dimension of the area occupied by the sample on agent for conversion of analyte to hydride:
the atomizer surface, D is the analyte diffusion
coefficient. Typi- cally, the analyte residence time
in tube graphite atomizers is a few tenths of a
second, which is about 100 times longer than in a
flame. The long residence time, along with the
where El, is the element of interest and m may or
high degree of analyte atomiza- tion caused by the
may not equal m. The advantage of sample
reducing environment, leads to a 10- to 1000-fold
volatilization as a gaseous hydride lies in the
increase in graphite furnace sensi- tivity compared
analyte's preconcen- tration and separation from
with flame AAS.
the sample matrix. This results in an enhanced
The typical change in the total number of
sensitivity and in a significant
analyte atoms, N(t), in the tube electrothermal
atomizer obtained by convolution [1] of the supply
function
Table 1 Selection of processes involving analyte in graphite
tube atomizers
Ref. in
Processa Figure 3 Elements
Me (s,l)  Me (g) 1 Ag, Au, Co, Cu,
Ni, Pb, Pd
MeO (s,l)  Me (g) 1 Al, Cd, In, Pb
MeO (s,l) + C(s)  Me (g) 1 Mn, Mg
Me C (s,l)  Me (g) 1 Al, Ba, Ca, Cu, Figure 3 Schematic representation of the basic physical and
Mo, Sr, V chemical processes taking place in a tube electrothermal atom-
MeOH (s,l)  Me (g) 1 Rb izer. Solid arrows denote pathways of free analyte atoms, dotted
MeO (s,l)  MeO (g) 1 Al, As, Ga, In, Tl arrows show the pathways of the analytes that are bound into
Me (s,l)  Me2 (g) 1 Se, Co molecules. Primary generation of the analyte vapour from the
site of sample deposition as an atomic (1) or a molecular (1)
Me (ad)  Me (g) 3 As, Cu
species. Irreversible loss of analyte from the furnace through its
Me (g)  Me (s,l) 4 Ag, Au, Cu, Mg, ends (2) and through the sample dosing hole (2) by diffusion
Mn, Pd and convection. Physical adsorption/desorption at the graphite
Me (g) + O (g)  MeO (g) 5 Al, Si, Sn sur- face (3). Gas phase condensation (4) at the cooler parts of
MeO (g)  Me (g) 5 Al, As, Cd, Ga, the atomizer. Gas phase reactions (5) that bind free analyte
In, Mn, Pb, Zn atoms into stable molecules or those (5) that increase the
free atom
MeO (g) + C(s)  6 Al, Ga, In, Tl density. Heterogeneous reactions of analyte vapour with the
Me (g) + CO atomizer walls: includes both production (6) and loss (6) of free
Me (g) + C(s)  MeC (g) 6 Al atoms at the furnace wall.
a
s, l, g, ad stand for solid, liquid, gaseous and adsorbed
species, respectively.
by substances in the solution that reduce the
efficiency of hydride generation.
reduction of interferences during atomization. The Relative detection limits achieved by the
main disadvantages of the method are described atomization techniques are presented in
interferences †able 2.

Table 2 Selected relative detection limits (g L–) for different atomization techniquesa
Element Flame AA GF AA Hydride AA Element Flame AA GF AA Hydride AA
Ag 1.5 0.02 Mn 1.5 0.035
Al 45 0.1 Mo 45 0.08
As 150 0.2 0.03 Na 0.3 0.02
Au 9 0.15 Ni 6 0.3
B 1000 20 P 75 000 130
Ba 15 0.35 Pb 15 0.06
Be 1.5 0.008 Pd 30 0.8
Bi 30 0.25 0.03 Pt 60 2
Ca 1.5 0.01 Rb 3 0.03
Cd 0.8 0.008 Ru 100 1
Co 9 0.15 Sb 45 0.15 0.045
Cr 3 0.03 Se 100 0.3 0.03
Cu 1.5 0.1 Sn 150 0.2 0.03
Fe 5 0.1 Sr 3 0.025
Ge 300 10 1 Te 30 0.4 0.03
Hg 300 0.6 0.009 Ti 75 0.35
Ir 900 3 Tl 15 0.15
K 3 0.008 V 60 0.1
Li 0.8 0.06 Zn 1.5 0.1
Mg 0.15 0.004
a
Detection limits are based on 98% confidence level (3 standard deviations). The values for the graphite furnace technique are re-
ferred to sample aliquots of 50 L.
Adapted with permission from The Guide to Techniques and Applications of Atomic Spectroscopy (1997) p 5. Norwalk, CT, USA:
Perkin-Elmer.
Atomic absorption effect, interatomic collisions and hyperfine
splitting. Other types of broadening (natural
AAS is based on the interaction of the probing
broadening, Stark broadening, etc.) are negligible.
radia- tion beam from a primary source with gas
The Doppler broadening originates from the
phase ana- lyte atoms. Two different types of
thermal agitation of emitting and absorbing atoms
primary source are used in AAS: line sources
that results in a Gaus- sian-shaped spectral line
emitting narrow spectral lines of the element to be
(curve G in Figure 5). The full width, D, at one-
analysed and a continuum source (normally high-
half of the maximum intensity (FWHM) of the
pressure xenon arc lamp) that produces radiation
Doppler-broadened atomic line is given by:
from below 180 nm to over 800 nm. In principle,
the continuum source is best suited for AAS. It has
a unique capability for multi- element
determinations, and provides extended ana- lytical
range and inherent background correction.
However, the lack of intensity found below 280 nm
still limits the use of the source in research where D is in cm1,  in nm, T in K and M in
laborato- ries. In conventional AAS, the line g mol1. The width is inversely proportional to
radiation of the element of interest is generated in the wavelength of the transition, to the square
a hollow cathode lamp (HCL) or an electrodeless root of the absolute temperature, T, and to the
discharge lamp (EDL). The spectral profile, J(λ), of reciprocal of the square root of the molecular
the analytical line emitted by the source interacts weight of the analyte,
with the absorption profile, d(λ), of the analyte M. The absorption line widths predicted from this
atoms in the atomizer (Figure 4). It is seen that equation range from 1 pm to 10 pm for flame and
radiation absorption is strongly dependent on the electrothermal atomizers. The Doppler widths of
shape and relative posi- tion of the two spectral the lines emitted by HCLs and EDLs are 2–S times
profiles. In order to describe quantitatively lower than those for absorption profiles in
absorption, both emission and absorp- tion profiles atomizers.
must first be well defined. The second major broadening mechanism in AAS
is collision or pressure broadening which originates
Emission and absorption line profiles from deactivation of the excited state due to
inter- atomic collisions. There are two types of
Three major broadening mechanisms determine collisions. Collisions between two analyte atoms
emission and absorption profiles in AAS: the lead to resonance broadening which is negligible in
Doppler analytical

Figure 5 Normalized theoretical Gaussian (G), Lorentzian (L)

and Voigt (V) line profiles versus dimensionless frequency. The
FWHMs and areas of the Gaussian and Lorentzian peaks are
Figure 4 Schematic diagram of the emission J(λ) and absorp- equal; the Voigt profile is the convolution of the (G) and (L)
tion k(λ) spectral profiles typical in AAS. profiles.
AAS because the analyte concentration is small.
of the absorption profile is used for computations:
How- ever, Lorentz broadening, which involves
m = (/D)2 . Within about 1% accuracy,
collisions between analyte atoms and foreign
the FWHM of the Voigt profile can be estimated
species (Ar atoms in electrothermal atomizers)
from the following empirical equation:
called perturbers, are significant. Compared to a
Doppler spectral profile, the Lorentzian profile is
broader, has a lower peak height and is
described by a Lorentzian function f(curve L in
Figure 5) with the FWHM given by:

Finally, the third broadening mechanism is hyper-

fine splitting which is caused by isotope shifts and
nuclear spin splitting. Generally a spectral line
con- sists of m hyperfine components with relative
intensi- ties, bj, ( bi = 1) that are located at a
Here Np is the number density of perturbers (cmS),
distance i
a is the collisional cross-section (cm2), MA and Mp is from the component with the minimum frequency.
the molecular weight (g mol1) of the analyte and Each component is Doppler and collision
the per- turbers, respectively. The collision width broadened and described by the Voigt function [6].
predicted by Equation [5] for absorption profiles is
Thus in the general case the emission J() and
about the same order of magnitude as the Doppler
line width (1–10 pm). The UL values for lines absorption d() profiles are presented as follows:
emitted by the HCLs and EDLs are much lower
than those for the
absorption profiles in atomizers because of low
pres- sure in the primary sources. Therefore this
part of the broadening is normally neglected in the
sources. However, at high optical densities of an
absorbing layer when the wings of the emission
line play an important role, the Lorentzian
component in the broadening of the emission line
where  is the ratio of the Doppler width of the
is also becoming important. In addition to
emission line to the Doppler width of the
broadening the lines, colli- sions also cause a small
absorption line. The equation takes into account
shift in the line centre (towards the longer
that the emis- sion profile, J(), is approximately
wavelengths in an Ar environ- ment) and an
1/ times nar- rower than the absorption profile,
asymmetry in the far line wings. The shift is
proportional to the collision width and theory d(), in the scale of dimensionless frequency 
and that the absorp- tion profile, is pressure-
predicts a value of 2.76 for the width-to-shift ratio
shifted relative to the emis- sion profile to a value
(it is shown schematically in Figure 4).
S. For many analytical lines used in AAS the
The total spectral profile of an atomic line is
given hyperfine splitting is greater than Doppler and
by the convolution of the Gaussian profile (due to pressure broadening and determines the total
Doppler broadening) and the Lorentzian profile FWHM.
(due to pressure broadening). The result is the In graphite furnace AAS, the damping constant,
Voigt function (curve V in Figure 5), H(,a): a, varies from 0.17 (Be resonance line, 2S4.9 nm)
to
S.27 (Cs, 852.1 nm) for absorption lines and its val-
ue for emission lines, ae, in the primary sources
var- ies from 0.01 to 0.05. A relatively small value
of the
a-parameter means that the emission profile is pri-
marily determined by the Doppler broadening.
where a  (L/D) is the damping constant
determining the shape of the Voigt profile: as the Figure 6 shows the emission and absorption spec-
damping constant increases, the profile broadens tral profiles of the lead 28S.S nm resonance line
and its peak height decreases. In the extreme computed for the conditions of graphite furnace
cases of a  0 and a  , the Voigt function goes to AAS using Equation [8]. The line consists of five
the purely Gaussian function and purely Lorentzian hyper- fine components that are clearly seen in
function, respectively. Normally, a dimensionless the emission profile. Because of higher
frequency, m normalized by the Doppler width D temperature and much higher pressure, the
absorption profile is wider and shifted towards the
longer wavelengths.
Calibration curve shapes where J(λ) is a function describing the spectral
composition of the radiation.
It has been demonstrated that in AAS the atomiza-
tion efficiency is close to 100% for the majority of
elements in aqueous solutions. Assuming complete
atomization, the shape of calibration curves in AAS
is determined by the dependence of detected
atomic absorbance on the number of absorbing
atoms. The

relationship A  f(N) is called the comcemtratiom

cmrve and its description is one of the primary
goals of theoretical AAS.
The phenomenon of radiation absorption had
already been studied quantitatively early in the
18th century, mainly on liquids and crystals. The
investi- gations resulted in the Beer–Lambert law
relating the
radiant flux, Фtr, transmitted through an absorbing
layer to the optical properties of the layer. In
modern
formulation, the law applied to a spatially uniform
absorbing layer of length l and a uniform parallel
probing beam is written as follows:

where Ф0(λ) is the incident radiant flux incident at

a wavelength λ, µ(λ) is a wavelength-dependent
attenu- ation coefficient which is the sum of
absorption, d(λ), and scattering, г(λ),
coefficients: µ(λ)  d(λ)  г(λ). Curve Jtr(λ) in
Figure 6 shows the spec- tral profile of the lead
28S.S nm resonance line that is transmitted
through a uniform layer of S  1012 cm2 lead
atoms. It was assumed that the spatially uniform
incident radiation with the spectral profile J(λ) is
absorbed by the absorption profile d(λ), without
scattering, following Equation [9]. Generally, a
non-uniform radiation with intensity
distribution J(x,y) over the beam cross section is
used to probe a non-uniform layer of absorbing
spe- cies with the number density m(x,y,ç). With
non-uni- form probing beams, a radiant flux
passing through a surface S within a spectral
bandwidth {λ*, λ*} is expressed in terms of
intensities as follows:
 Absorbance, A, which is the analytical signal in
AAS, is defined as the logarithm of the ratio of
the incident radiant flux, 0, to the radiant flux,
tr, that is transmitted through the absorbing
layer of the ana- lyte atoms. Using the Beer–
Lambert law [9] for expressing the transmitted
radiant flux, the general relationship for the
absorbance recorded by an AA spectrometer can
be expressed as follows:

Here, b and S are the width and the height of the

monochromator entrance slit, l is the length of
the absorbing layer; the limits of λ* to λ* are the
spec- tral bandwidth isolated by the
monochromator. It was assumed that radiation
attenuation occurs only because of atomic
absorption, i.e. г(λ) = 0. The absorption
coefficient, d(λ;x,y,ç), depends on the number
density of absorbing atoms in the ground state,
mo (cmS), and the spectral profile, d(λ), of the
absorption line, and is presented as:

Figure 6 Emission J(λ ) and absorption k(λ) spectral profiles of

the 283.3 nm lead resonance line computed for the conditions
of graphite furnace AAS (ae = 0.01, a = 1.24; T = 2100 K). Jtr(λ)
is the emission profile that is transmitted through a uniform
layer of 3  1012 cm2 lead atoms.
Here e and m are the charge and mass of the
electron, respectively, c is the velocity of light, f is
the oscillator strength of the spectral transition,
D is the Doppler width of the absorption line. The
coefficient c(λ, T) denotes the combination of
values that depend only on the spectral features of
the analysis lines.
The general relationship [10] is simplified signifi-
cantly if the following assumptions are made: (i)
ra- dial distributions of the probing beam and the
analyte atoms are uniform, i.e. J(x,y)  const,
m(x,y,ç)  m(ç); (ii) the atomizer is spatially
isother- mal, i.e. T(x,y,ç)  const and (iii) the
emission line is a single and infinitely narrow line
at λ0 so that it is described by Dirac's delta-
function: J(λ)  J0 (λλ0). Substitution of these
simplifications into Equation [10] gives:

Figure 7 The evolution of the 283.3 nm lead concentration

curve as the spectral and spatial features are successively taken
into account. Emission line is: single and infinitely narrow (1),
where c(λ0,T) is a constant for given transition and single and broadened (2); all the spectral features of the line are
for a given temperature, N(cm–2) = m(ç)dç is taken into account including hyperfine splitting and the pressure
shift (3); (4) as (3) plus absorbing layer is assumed to be non-
the number of absorbing atoms per unit cross-
uniform in the radial cross section with the analyte number
sectional area along the radiation beam; in the density at the atomizer bottom 4 times greater than that in the
case of uniform analyte distributions, this value is upper part of the absorbing layer.
proportional to the total number of analyte atoms
in the atomizer. Thus, if the above assumptions
are valid, the record- ed absorbance is The effect of spectral features of the analysis line
proportional to the total number of absorbing and spatial nonuniformities of the absorbing layer
atoms in the atomizer and the concentra- tion is il- lustrated in Figure 7. Curve 2 is the lead
curve A  f(N) is a straight line. This is a basis for concentra- tion curve when the resonance line is
AAS to be an analytical technique, because the assumed to be a single but broadened one;
recorded signal, A, is directly proportional to the accounting for all the spectral features of the
un- known number, N, of analyte atoms. Such a emission and absorption pro- files, including
concen- tration curve computed for the case of a hyperfine structure and pressure shift, results in
lead resonance line is presented by curve 1 in curve S. It can be seen that broadening of the
Figure 7. analysis line lead to a bending of the concentra-
The actual situation, however, differs tion curve and decreasing of its slope, the major
substantially from that presented by simple effect being the hyperfine broadening. Additional
Equation [12]. It fol- lows from general ac- counting for the fact that the analyte is
relationship [10] that absorbance is dependent on distributed nonuniformly in the atomizer cross
three groups of factors: (1) the spec- tral section leads to further curvature and a decrease
characteristics of the analysis line (dependence of in the slope of con- centration curve (curve 4).
J and d on λ); (2) the cross-sectional distribution of Figure 7 illustrates clear- ly the importance of the
intensity in the incident beam, J(x,y); and (S) spectral and spatial features in relationship [10].
spatial distribution of the analyte and temperature Recent research shows, how- ever, that these
within the atomizer (dependence of d on x,y,ç). undesirable dependencies can be avoided if
Thus detect- ed absorbance, A, depends not only transmitted intensities are measured with
on the number, N, of absorbing atoms but also on spectral, spatial and temporal resolutions. The
the spectral fea- tures of the analysis lines used to mmlti- dimemsiomal absorbance detected in such a
probe the absorb- ing layer and the spatial way is dependent only on the number of absorbing
distribution of analyte atoms and radiation atoms irrespective of their spatial distribution and
intensity in the probing beam: spectral features of the primary source.
Interferences
the additions curve is different from that of the
An interference effect is a change of the analytical calibration curve. For most systems, nonspectral
signal by the sample matrix as compared to the interferences in electrothermal AAS can be
reference standard, typically an acidified aqueous effective- ly eliminated by adding a proper matrix
solution. There are two types of interference in modifier (Pd-Mg(NOS)2 is the most common
spectrochemical analysis, spectral and momspectral. modifier) that
Spectral interference originates from incomplete delays analyte volatilization until the atomizer tem-
isolation of the radiation emitted or absorbed by perature is sufficiently high and steady for
the analyte from other radiation detected by the efficient atomization, and buffers the gas phase
spec- trometer. Any reasons other than specific composition.
atomic absorption that cause radiation attenuation
in equation [9] result in spectral interferences.
They arise from: absorption of radiation by
List of symbols
overlapping molecular bands or atomic lines of a  damping constant; ae  damping constant for
concomitants; scattering of source radiation by emission lines; a  the linear dimension of the area
nonvolatilized microparticles (smoke, salt occupied by the sample on the atomizer surface;
particles, condensed microdrops); foreign line A  absorbance; b  width of monochromator
absorption if the corre- sponding radiation happens entrance slit; c(liq)  concentration of analyte in
to be emitted by the radiation source, in addition solu- tion; c  velocity of light; D  analyte
to the analysis line, within the spectral bandwidth diffusion coefficient; e  charge of electron; E 
of the monochroma- tor. The first two sources of activation energy; f  oscillator strength; S 
spectral interferences are most common and height of mono- chromator entrance slit; J() 
described as background attenua- tion or spectral profile; d()  absorption profile; l 
background absorption. In general, they are more length of absorbing layer; L  tube length; m 
pronounced at shorter wavelengths. Most mass of electron; M  molecular weight of the
background attenuation can be distinguished from analyte; MA  molecular
the analyte absorption because the element only weight of analyte; Mp  molecular weight of perturb-
absorbs in the very narrow spectral region while ers; mo  number density of absorbing atoms in the
the background attenuation is less specific and ground state; N  number of analyte atoms;
extends over a considerably broader wavelength N(g)  number of free atoms in an atomizer
band. Instrumental methods of correction for volume; N0  total number of atoms in the
background attenuation effects include deposited sample;
compensation using a continuum source and the NP  number density of perturbers; N(t)  number
Zeeman effect. of analyte atoms in the atomizer volume; R  gas
For interferences other than spectral, the con- stant; R(t,t)  removal function; S(t) 
analyte itself is directly affected. The nonspectral supply func-
interferenc- es are best classified according to the tion; t  time analyte atom present in atomizer
stage at which the particular interference occurs, volume; t  time of vaporization; T  absolute
i.e. solute-volatil- ization and vapour-phase tem- perature; T(t)  time-dependent atomizer
interferences. A nonspec- tral interference is tempera- ture; α  ratio of the Doppler width of
found when the analyte exhibits a different the emission to the absorption line; D  width of
sensitivity in the presence of sample con- Doppler-broad- ened atomic line; L  width of
comitants as compared to the analyte in a Lorentzian-broad- ened atomic line; г(λ) 
reference solution. The difference in the signal scattering coefficient; λ  wavelength; λ 
may be due to: analyte loss during the thermal wavelength; (λ)  wavelength- dependent
pretreatment stage in the electrothermal attenuation coefficient;   frequency fac- tor; a 
atomizer: analyte reaction with concomitants in collisional cross section; r  mean residence time;
the condensed phase to form com- pounds that are   transmitted radiant flux; 0  incident radiant
atomized to a lesser extent, analyte ionization or flux; m  frequency (dimensionless).
change the degree of ionization caused by
See also: Atomic Absorption, Methods and
concomitants.
Instrumentation; Atomic Fluorescence, Methods and
Reactions of the analyte with the tube material
Instrumentation; Fluorescence and Emission Spec-
(graphite) or the purge gas are not normally
troscopy, Theory.
consid- ered to be interferences because they
influence the analyte in the sample and in the
standard to the same degree. A nonspectral
Further reading
interference is in many in- stances best detected
by the use of the analyte addi- tion technique. An Alkemade CThJ, Hollander T, Snelleman W and Zeegers
interference exists if the slope of PJTh (1982) Metal Yapomrs im Flames. Oxford:
Pergamon Press.
42 ATOMIC EMISSION, METHODS AND

Chang SB and Chakrabarti CL (1985) Factors affecting

Mitchell ACG and Zemansky MW (1961) Resomamce
atomization in graphite furnace atomic absorption
Radiatiom amd Excited Atoms. Cambridge: Cambridge
spectrometry. Progress im Amalytical Atomic
University Press.
Spectroscopy 8:8S–191.
Slavin W (1991) GrapSite Fmrmace AAS – A Somrce
Ebdon L (1982) Am Imtrodmctiom to Atomic Absorptiom
Bood, 2nd edn. Norwalk, CT: Perkin-Elmer
Spectroscopy. London: Heyden.
Corporation.
Haswell SJ (Ed.) (1991) Atomic Absorptiom Spectrometry.
Styris DL and Redfield DA (199S) Perspectives on mecha-
Amsterdam: Elsevier. nisms of electrothermal atomization. SpectrocSimica
Holcombe JA and Rayson GD (198S) Analyte distribution Acta Reviems 15: 71–12S.
and reactions within a graphite furnace atomizer. Welz B (1985) Atomic Absorptiom Spectrometry, 2nd edn.
Progress im Amalytical Atomic Spectroscopy 6: 225–251. Weinheim: VCH.
L'vov BV (1970) Atomic Absorptiom SpectrocSemical Winefordner JD (ed) (1976) Spectroscopic MetSods for
Amalysis. London: Adam Hilger. Elememts. New York: Wiley-Interscience.

Atomic Emission, Methods and Instrumentation

Sandra L Bonchin, Los Alamos National Laboratory,
NM, USA ATOMIC SPECTROSCOPY
Grace K Zoorob, Biosouth Research Laboratories, Methods & Instrumentation
Inc., Harahan, LA, USA
Joseph A Caruso, University of Cincinnati, OH, USA
Copyright © 1999 Academic Press

Atomic emission spectroscopy is one of the most microwave plasmas (CMP). Glow discharges are
use- ful and commonly used techniques for utilized for direct solids analyses, but will not be
analyses of metals and nonmetals providing rapid, dis- cussed here. An analytical plasma is a high-
sensitive results for analytes in a wide variety of energy, slightly ionized gas (about 0.01 to 0.1%
sample matri- ces. Elements in a sample are ionized).
excited during their residence in an analytical
plasma, and the light emit- ted from these excited Inductively coupled plasmas
atoms and ions is then collected, separated and
The most commonly used ion source for plasma
detected to produce an emis- sion spectrum. The
spec- trometry, the ICP, is produced by flowing an
instrumental components which comprise an
inert gas, typically argon, through a water-cooled
atomic emission system include (1) an excitation
induc- tion coil which has a high-frequency field
source, (2) a spectrometer, (S) a detector, and (4)
(typically 27 MHz) running through it (Figure 1).
some form of signal and data processing. The
The alter- nating current in the coil has associated
methods discussed will include (1) sample
with it a changing magnetic field, which induces a
introduc- tion, (2) line selection, and (S) spectral
changing electric field. The flowing gas is seeded
interferences and correction techniques.
with electrons by means of a Tesla coil. These
electrons undergo acceleration by the electric
Atomic emission sources field, and gain the energy necessary to excite and
ionize the gaseous atoms by collision. This
The atomic emission source provides for sample produces the plasma, self-sustaining as long as the
vaporization, dissociation, and excitation. The RF and gas flows continue.
ideal excitation source will allow the excitation of Sample particles entering the plasma undergo de-
all lines of interest for the elements in the sample, solvation, dissociation, atomization, and
and do this reproducibly over enough time to excitation. The ICP has sufficiently long residence
encompass full ele- mental excitation. Excitation times and high enough temperatures so that the
sources include but are not limited to (1) sample solvent is completely vaporized, and the
inductively coupled plasma (ICP), analyte reduced to free atoms, which undergo
(2) direct current plasmas (DCP), (S) microwave excitation. This excitation results in the emission
induced plasmas (MIP), and (4) capacitively of light at specific frequencies for elements in
coupled the sample, which is