long-lived radio-isotopes of the elements to be analy- Hieftje GM and Norman LA (1992) Plasma source mass
sed are added as internal standards, e.g. the use of spectrometry. International Journal of Mass Spectro-
111Cd in the analysis of 114Cd. In addition, ICP-MS metry and Ion Processes 118/119: 519573.
can be extremely useful in speciation. In this respect, Iribarne JV and Thomson BA (1976) On the evaporation
of small ions from charged droplets. Journal of
there is a growing interest in the use of ICP-MS
Chemical Physics 64: 2287 and (1979) Field induced
directly coupled to LC or capillary electrophoresis for ion evaporation from liquid surfaces at atmospheric
speciation and analysis of elements of toxicological pressure. Journal of Chemical Physics 71: 4451.
interest, like As, Se, Pb and Hg. Knewstubb PF and Sugden TM (1958) Mass-spectrometric
See also: Chemical Ionization in Mass Spectrome- observation of ions in flames. Nature 181: 474475.
try; Chromatography-MS, Methods; Cosmochemical Knewstubb PF and Sugden TM (1958) Mass-spectrometric
Applications Using Mass Spectrometry; Inductively observation of ions in hydrocarbon flames. Nature
181: 1261.
Coupled Plasma Mass Spectrometry, Methods; Inor-
Meek JM and Craggs JD (1978) Electrical Breakdown of
ganic Chemistry, Applications of Mass Spectrometry.
Gases. Chichester: Wiley.
Meng CK, Mann M and Fenn JB (1988) Proceedings of
Further reading the 36th ASMS Conference on Mass Spectrometry and
Allied Topics, June 510, San Francisco, CA,
Bruins AP, Covey TR and Henion JD (1987) Ion spray pp. 771772.
interface for combined liquid chromatography/atmo- Niessen WMA (1998) Liquid Chromatography Mass
spheric pressure ionization mass spectrometry. Analyti- Specctrometry, 2nd edn. New York: Marcel Dekker.
cal Chemistry 59: 26422646. Niessen WMA (1998) Advances in instrumentation in liq-
Carroll DI, Dzidic I, Horning EC and Stillwell RN (1981) uid chromatography mass spectrometry and related
Atmospheric pressure ionization mass spectrometry. liquid-introduction techniques. Journal of Chromatog-
Applied Spectroscopic Review 17: 337406. raphy A 794: 407435.
Chowdhury SK, Katta V and Chait BT (1990) An elec- Vela NP, Olson LK and Caruso JA, Elemental speciation
trospray-ionization mass spectrometer with new fea- with plasma mass spectrometry. Analytical Chemistry
tures. Rapid Communications of Mass Spectrometry 65: 585A597A.
4: 8187. Yamashita M and Fenn JB (1984) Electrospray ion source.
Cole RB (ed) (1997) Electrospray Ionization Mass Spec- Another variation on the free-jet theme. Journal of
trometry. Chichester, UK: Wiley. Physical Chemistry 88: 44514459.
Fenn JB, Mann M, Meng CK, Wong SF and Whitehouse Yamashita M and Fenn JB (1984) Negative ion production
CM (1989) Electrospray ionization for mass spectro- with the electrospray ion source. Journal of Physical
metry of large biomolecules. Science 246: 6471. Chemistry 88: 46714675.
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
Figure 1 Schematic representation of a hollow-cathode lamp.
that may be emitted by the atom cell and then detect- From Ebdon L (1998) Introduction to Analytical Atomic
ed. Thus, much of the instrumentation used for elec- Spectrometry. Reproduced by permission of John Wiley & Sons
trothermal and flame absorption spectroscopy is Limited.
identical. Both techniques require a similar light
source, background correction system, line isolation
device (monochromator or polychromator), detector intense than the microwave-excited ones, but are still
(photomultiplier or charge coupled device) and read- 5100 times more intense than a standard hollow-
out system. Each of these components is discussed cathode lamp. In the electrodeless discharge lamp, a
below, together with details of the individual atom bulb contains the element of interest (or one of its
cells (flame and the electrothermal atomizer) and salts) in an argon atmosphere. The radiofrequency
sample introduction systems. energy ionizes the argon and 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 better signal-to-noise ratio
Light source
than hollow-cathode lamps and have a longer useful
The fundamental requirement of the light source lifetime. A schematic diagram of an electrodeless dis-
is to provide a narrow line profile with little charge lamp is shown in Figure 2.
background. It should also have a stable and repro-
ducible output with sufficient intensity to ensure that Background correction systems
a high signal-to-noise ratio is obtained. Two basic
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 three
ionized by an electric current and these ions are then main automatic methods are the deuterium or hy-
attracted by the cathode. The inert gas ions bombard drogen lamp, the Zeeman effect, and SmithHieftje
the cathode and in so doing excite the metal ions background correction. The deuterium lamp
coated on it. It is this excitation of the metal that produces a continuum of radiation, some of which
produces the emission of radiation with wavelengths will be absorbed by molecular species within the
characteristic of the analyte. Hollow-cathode lamps atom cell. The amount of atomic absorption ob-
are available for most metallic elements. A schematic served using the deuterium lamp is negligible and
diagram of a hollow-cathode lamp is shown in hence the atomic absorption signal is obtained by
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 lamps lamp is of most value at wavelengths in the UV re-
may be excited using either microwave energy (al- gion (< 350 nm). The Zeeman effect background
though these tend to be less stable) or radiofrequency correction system is more versatile. It relies on a
energy. The radiofrequency-excited lamps are less strong magnetic field operating at approximately
26 ATOMIC ABSORPTION, METHODS AND INSTRUMENTATION
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 5060 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. This
component is at the normal analyte wavelength; the is because the reference beam does not pass through
components are typically 0.01 nm (depending on the atom cell. Despite this, double-beam instruments
the strength of the magnetic field) either side of the can compensate for source drift and for warm-up
component and hence lie outside the atomic absorp- and source noise.
tion profile. Background can be corrected by sub-
tracting the absorbance with the magnetic field on,
from the signal with the magnet off. It should be Line isolation devices
noted that this is a simplified description of the To ensure that only light of a wavelength specific to
process, as different elements have different splitting the analyte of interest is being measured, a line
patterns and the magnetic field may be applied longi- isolation device is required. Until recently, the line
tudinally or transversely, which may also produce isolation device used for atomic absorption was a
different splitting patterns.
When utilizing the SmithHieftje 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.
monochromator. There are numerous types of A monochromator enables only one wavelength to
monochromator, but modern instruments typically be interrogated at any instant; this was something of
use one of three designs: Ebert, CzernyTurner or a weakness of atomic absorption spectroscopy. New
Littrow configuration. These are shown schematical- technology, however, has enabled the development
ly in Figure 4. of multielement spectrometers that use a bank of
Light of all wavelengths enters the monochroma- between 4 and 6 hollow-cathode lamps and an
tor through an entrance slit and is then split into spe- echelle-style polychromator employing orders of 100
cific wavelengths using either a prism, or more or more and are thus capable of considerable disper-
commonly, a diffraction grating. By altering the sion. In addition, such instruments have no exit slit
position of this dispersing element, light of only the and so a huge number of wavelengths may be focused
desired wavelength passes through the exit slit to the onto an array detector such as a charge-coupled
detector. Since the method of atomic absorption is so device. A schematic diagram of such an instrument is
specific, very highly resolving monochromators are shown in Figure 5. Research continues into produc-
not required. Thus, the focal length of an atomic ing a continuum light source that would enable 30
absorption monochromator is often 0.25 or 0.5 m 40 analytes to be determined simultaneously.
compared with a minimum of 0.75 m required for
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. CsSb, NaKSbCs or GaAs), 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
then measured at the anode and the resulting current Instrument control and output devices
is proportional to the radiation reaching the PMT.
As described previously, a number of different Manual controls and dials have slowly disappeared,
materials may be used to coat the photocathode in with the large majority of modern instruments being
the PMT, and each has a different response curve. controlled by computer. In addition to controlling
Some, for example the CsSb tube, have very little the instrumental parameters, the computer may be
sensitivity above 600 nm, but others, for example used to program autosamplers, save experimental
GaAs, may be used up to almost 900 nm. The parameters and data, calibrate with known stand-
response profiles of some commonly used photomul- ards, plot calibration curves, use scale expansion
tipliers are shown in Figure 6. facilities (if necessary) and produce statistical data
Conventional spectrometers use a detector that is from the results. A continuous graphics mode ena-
capable of measuring only one signal. Multielement bles the signal to be monitored over a period of
instruments use state-of-the-art diode arrays or time. This is especially useful when flow injection,
charge-coupled devices that can measure numerous chromatography or hydride-generation transients
spatially separated signals and can therefore simulta- are to be detected and integrated. Older instrumenta-
neously determine the signals arising from a bank of tion relied on a chart recorder for the same purpose.
hollow-cathode lamps. A charge-coupled device may
be considered to be similar to an electronic photo- Sample introduction and atom cells
graphic plate. The device consists of several hundred
linear photodetector arrays on a silicon chip with For flame systems, the sample is introduced via a
dimensions of typically 13 18 mm. The line isola- nebulizer and spray chamber assembly. Sample is
tion device (often an echelle grating) separates the drawn up the intake capillary by the Venturi effect.
analytical wavelengths and these may then be The liquid sample column comes into contact with
detected on different regions of the array. A detailed the fast moving flame gases and is shattered into
description of how the array works is beyond the small droplets. In many systems it is further smashed
scope of this text. into still smaller droplets by an impact 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 (8590% 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 airacety-
lene burner. This provides a flame that is at approxi-
mately 2300C (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. Chromium, for instance, gives better
sensitivity in a reducing flame, whereas for magne-
Figure 6 Response curves for several commercial photomulti-
plier tubes. From Ebdon L (1998) Introduction to Analytical sium it is better to use a lean, oxidizing flame.
Atomic Spectrometry. Reproduced by permission of John Wiley Different areas of the flame have different tem-
& Sons Limited. peratures and different chemical properties. The
ATOMIC ABSORPTION, METHODS AND INSTRUMENTATION 29
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 interme-
mum sensitivity is achieved. diate temperature to remove as much of the concom-
Although an airacetylene flame is sufficient for the itant matrix and potential interferences as possible
atomization of the majority of analytes, it is not suf- without losing any analyte); and then atomized at a
ficiently hot or reducing to atomize analytes that form high temperature. During the atomization stage, the
refractory oxides (e.g. Al, Mo, Si and Ti). For analytes atoms leave the graphite surface and enter the light
such as these a nitrous oxideacetylene flame of beam, where they absorb the incident radiation. The
length 5 cm is used. This flame is hotter (2900C) and ashing and atomizing temperatures used will depend
contains typically 2.53 times as much fuel as the air on the analyte of interest; for example, some ana-
acetylene flame. Other flame types, e.g. airpropane lytes such as lead are relatively volatile and so cannot
and airhydrogen also exist, although they are less be ashed at temperatures above 450C, otherwise
commonly used. The airhydrogen flame (2200C) is volatile salts such as chlorides will be lost. Other an-
almost invisible and has the advantage of being trans- alytes, for example, magnesium, are less volatile and
parent at lower wavelengths offering improved noise can be ashed at temperatures close to 1000C with-
characteristics for elements such as lead or tin at out analyte loss. Such elements require a much
around 220 nm. The inhomogeneity of flame chemis- higher atomization temperature. The sensitivity of
try and the need for burner height optimization hold electrothermal atomization AAS is greater than for
true for all flame types. flame AAS because the atoms are formed within the
One common modification to a flame cell is to confines of a tube and hence spend longer in the light
place a quartz tube on the burner head so that the beam. Also, since the sample is placed within the
light beam passes through the length of the tube. atom cell, 100% of it is available for analysis com-
This method is especially useful when using sample pared with the 1015% available in flame systems.
introduction by hydride generation or by gas chro- A comparison of characteristic concentrations (con-
matography. The tube is heated either by a flame or centration that gives an absorbance of 0.0044) ob-
electrically using a wire winding. The analyte, which tained for flame and electrothermal techniques for
enters the tube via a hole or slit cut into the side, is many analytes is shown in Table 1. It must be
atomized within the tube. The atoms then leave the stressed that the figures for ETAAS will depend
tube but, because of their retention in the tube, critically on the injection volume and so values tend
spend longer in the light beam than in normal flame to be given in absolute terms (i.e. a weight).
systems. An increase in sensitivity is therefore Overall, the Massmann design of electrothermal
obtained. Another small modification of this system atomizer in which the tube is heated from either end
is that, instead of a quartz tube, a quartz T-piece is still the most common (Figure 7B), but more
may be used. However, the function is the same. recently transversely heated tubes have been devel-
Electrothermal atom cells have changed radically oped (Figure 7A). The longitudinally heated tubes
since their inception in the late 1950s. The majority have a temperature gradient along the tube, with the
of electrothermal devices have been based on graph- central portion being several hundred degrees hotter
ite tubes that are heated electrically (resistively) from than the ends. This can lead to condensation of
either end. Modifications such as the West Rod analyte at the cooler ends and subsequent re-
Atomizer (a carbon filament) were also devised but atomization from the hot graphite surface. Several
were later abandoned. Tubes and filaments made atomization peaks may therefore result. The trans-
from highly refractory metals such as tungsten and versely heated tubes do not have a temperature gra-
tantalum have also been made, but they tend to dient and therefore do not suffer from this problem.
become brittle and distorted after extended use and
have poor resistance to some acids. Their use contin- Interferences
ues, however, in some laboratories that need to deter-
mine carbide-forming elements. For example, silicon Flame techniques are regarded as being relatively free
reacts with the graphite tube to form silicon carbide, from interferences, but some distinct classes of
which is both very refractory and very stable. The interference do exist. These include a few spectral
silicon is therefore not atomized and is lost analyti- interferences (e.g. Eu at 324.753 nm on Cu at
cally. Use of a metal vaporizer prevents this. 324.754 nm), ionization interferences and chemical
30 ATOMIC ABSORPTION, METHODS AND INSTRUMENTATION
Electrothermal
Analyte Flame AAS (g L1) AAS (pg)
Ag 30 5
Al 300 30
As 800 a,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 Figure 7 Electrothermal tubes available commercially: (A)
Rb 30 10 transversely heated graphite atomizer (THGA), (B) longitudinally
Sb 300 60 heated Massmann atomizer. From Ebdon L (1998) Introduction
to Analytical Atomic Spectrometry. Reproduced by permission
Se 350a,4b 45
of John Wiley & Sons Limited.
Si 1 500 120
Sn 400 100
Sr 40 4 ionized (and lost analytically) and hence serious over-
Te 300 50 estimates of the true concentration will be obtained.
Ti 1 400 70 This type of interference may be overcome by adding
Tl 300 50 an excess of easily ionized element to all standards
U 110 000 40 000 and samples.
V 750 42 Chemical interferences may exist in several differ-
Yb 700 3 ent forms:
Zn 10 1
a
Formation of less volatile compounds, e.g. when
Under normal flame conditions.
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 contains chlorides.
large amounts of an easily ionized element. The Occlusion into refractory compounds. Small
presence of large concentrations of easily ionized ele- amounts of analyte may become trapped in a
ments will lead to a large concentration of electrons refractory substance and hence not be atomized
in the flame. These electrons prevent the ionization of efficiently.
the analyte and hence lead to higher atomic absorp- Occlusion into volatile compounds. Some com-
tion signals. If the easily ionized element is not pounds sublime explosively and hence atomization
present in the standards, the analyte may be partially may be enhanced.
ATOMIC ABSORPTION, METHODS AND INSTRUMENTATION 31
Most of these interferences may be overcome by concept. Other interferences, e.g. formation of car-
using a hotter flame (e.g. nitrous oxideacetylene); 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 Numerous methods have been described for use with
effects, chemical interferences (loss of analyte as a AAS, but the majority require the sample to be in a
volatile salt, carbide formation, condensation and liquid form. Some ETAAS systems allow the analysis
recombination), background absorption (smoke), of solids directly (e.g. by weighing small amounts
and physical interferences such as those resulting onto sampling boats that may be slotted into special-
from placing the sample on a different part of the ized tubes), but usually, if solids are to be analysed,
tube. The stabilized temperature platform furnace acid decomposition methods are required. An alter-
(STPF) concept has gone a long way to eliminating native is the analysis of slurries, using finely ground
the problem. The concept is that a matrix modifier material (< 10 m) dispersed in a solvent. Manual
is required for interference-free determinations. This agitation of the slurry ensures homogeneity of the
is a material that either decreases the volatility of the sample, enabling a representative aliquot to be intro-
analyte, enabling higher ash temperatures to be duced. Some autosamplers come equipped with an
achieved and hence boiling away more interference ultrasonic agitator that will perform the same task.
(a common example is a mix of palladium and mag- This method of analysis is frequently used in ETAAS.
nesium nitrates) or increases the volatility of the If samples containing high dissolved (or sus-
matrix (for example, the introduction of air burns pended) solids are to be analysed by FAAS, a flow
away many interferences leaving the analytes in the injection technique (in which discrete aliquots of
atomizer). The matrix modifier may be placed in the sample are introduced) may be used. This has also
autosampler, and added to all samples and stan- been referred to as gulp sampling. This prevents
dards. Other requirements for the STPF concept salting up of the nebulizer and blockage of the burner
include a rapid heating rate during atomization, inte- slot, which are obviously undesirable effects that
grated signals (rather than peak height), a powerful have an adverse effect on sensitivity and signal stabil-
background correction system (e.g. Zeeman), fast ity. Flow injection techniques may also be used to
electronics to measure the transient signal, and iso- preconcentrate analytes. If the sample flows through
thermal operation. Isothermal operation means that a column containing an ion-exchange resin, the ana-
the analyte is vaporized from the graphite surface lytes will be retained. Elution with a small volume of
into hot gas. In normal electrothermal AAS, the ana- acid may yield very high preconcentration factors.
lyte leaves the hot tube wall and enters the cooler gas This technique has been used for both FAAS and,
phase. Under these circumstances it may recombine more recently, for ETAAS, yielding limits of detec-
with some other species to form a compound and tion far superior to those achieved under normal con-
thus be lost analytically. To overcome this, platforms ditions. A typical flow injection manifold suitable for
that are only loosely in contact with the tube walls this type of application is shown in Figure 8.
have been developed. The analytes in this case are A more traditional method of preconcentration is
atomized not by the resistively heated graphite tube solvent extraction. Flame AAS may be used as a
but by the surrounding gas. The transversely heated detector for analytes in organic solvents (sensitivity
tubes described earlier have a platform as an integral
part of the tube. A modification to this 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 Figure 8 Typical flow injection manifold for matrix analyte pre-
work now utilize the advantages of the STPF concentration or matrix elimination.
32 ATOMIC ABSORPTION, METHODS AND INSTRUMENTATION
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, Se, expert operators. If increased sensitivity is required,
Sn and Te, although other vapours, e.g. Hg or alky- the analyst has the option of preconcentrating the
lated Cd, may also be determined. This technique analyte using one of a number of methods prior to
improves the sensitivity of the analysis substantially. introduction to flame AAS, or alternatively may use
Since the sample is in the gas phase, the sample electrothermal AAS. The latter technique, however,
transport efficiency is close to 100%. The hydrides does require more experience if reliable results are to
atomize readily in the flame, although this approach be obtained.
is usually used in conjunction with a quartz T-piece A potential disadvantage of using atomic absorp-
in the atom cell. Methods have been developed that tion is that in the past instruments have been capable
trap the hydrides on the surface of a graphite tube of determining only one analyte at a time. Modern
for use with ETAAS. This leads to preconcentration instrumentation has improved this number to as
and further improvements in detection limit. many as six, although it must be stressed that com-
Chromatography has been coupled to AAS to promise conditions (e.g. in ETAAS temperature pro-
effect speciation analysis. Here different chemical grams) must be used. This may lead to a decrease in
forms of an analyte are separated (either by high- overall sensitivity compared with single-element
performance liquid chromatography or, if they are determinations. However, the ongoing development
sufficiently volatile, by gas chromatography) prior to of multielement AAS will certainly boost the use of
introduction to the atomic absorption instrument. this already popular and versatile technique.
Gas chromatography is usually coupled directly with
See also: Atomic Absorption, Theory; Atomic Fluo-
a T-piece interface arrangement, but HPLC coup-
rescence, Methods and Instrumentation; Atomic
lings introduce the sample through the conventional
Spectroscopy, Historical Perspective; Light Sources
nebulizer/spray chamber assembly. A small postcol-
and Optics.
umn air bleed may be necessary to compensate for
the differences in flow rate between the chromato-
graph (12 mL min1) and the uptake rate of the
nebulizer (510 mL min1). Chromatography is not Further reading
frequently coupled with ETAAS because the atom
Dedina J and Tsalev DL (1995) Hydride Generation
cell is not well suited to continuous monitoring.
Atomic Absorption Spectrometry. Chichester: Wiley.
The limited linear range offered by the AAS tech- Ebdon L, Evans EH, Fisher A and Hill SJ (1998) An Intro-
nique may be partially overcome by using alternative, duction to Analytical Atomic Spectrometry. Chichester:
less sensitive lines. This is a useful technique that Wiley.
avoids the requirement to dilute samples. Care must Harnly JM (1996) Instrumentation for simultaneous
be taken, however, to ensure that viscosity effects do multielement atomic absorption spectrometry with
not cause a difference in nebulization efficiency graphite furnace atomization. Fresenius Journal of Ana-
between samples and standards. Alternatively, burner lytical Chemistry 355: 501509.
head rotation may be used. This shortens the path in Haswell SJ (ed) (1991) Atomic Absorption Spectrometry,
the flame through which the light beam travels and Theory, Design and Applications, Analytical Spectros-
copy Library. Amsterdam: Elsevier.
hence decreases sensitivity. However, there is often an
Hill SJ, Dawson JB, Price WJ, Shuttler IL, Smith CMM
increase in noise as a result of using this approach.
and Tyson JF (1998) Atomic spectrometry update
advances in atomic absorption and fluorescence spec-
Conclusions trometry and related techniques. Journal of Analytical
Atomic Spectrometry 13: 131R170R.
The sensitivity offered by the various techniques Vandecasteele C and Block CB (1993) Modern Methods
utilizing AAS for the determination of metals and for Trace Element Determination. Chichester: Wiley.
ATOMIC ABSORPTION, THEORY 33
Atomic absorption spectroscopy (AAS) is a technique provide complete atomization of the element irrespec-
for quantitative determination of metals and metal- tive of the sample matrix producing a well-defined
loids by conversion of a sample to atomic vapour and and reproducible absorption layer of the analyte
measurement of absorption at a wavelength specific atoms. Excitation processes, however, should be
to the element of interest. Owing to high sensitivity minimal so that analyte and background emission
and selectivity, the technique is widely used for fun- noise is small. For achieving the best detection limits,
damental studies in physics and physical chemistry: the analyte vapour should not be highly diluted by the
measurements of oscillator strengths, diffusion coef- atomizer gas. Various types of electric discharges,
ficients of gas phase species, partial pressure of laser radiation, electron bombardment and induc-
vapours, rate constants of homogeneous and hetero- tively coupled plasmas were tested as atomizers.
geneous reactions, etc. The widest application of Although not ideal, high-temperature flames and elec-
AAS, however, is in analytical chemistry. Nowadays trothermal atomizers have gained acceptance as the
it is one of the most popular techniques for trace most common technique of atom production in AAS.
analysis of over 65 elements in practically all types of
Flame atomization
samples (environmental, biological, industrial, etc.).
The vast majority of substances to be analysed by The longest practiced technique for converting a
AAS are in the condensed phase. At the same time, sample into atoms is the spraying of a sample solu-
atomic absorption, like any other atomic spectrome- tion into a combustion flame. The most popular
try technique, can only detect free atoms that are in flames used in AAS are the airC2H2 flame providing
the gas phase. Thus, as analyte initially present in so- a maximum temperature of about 2500 K and the
lution at a concentration c(liq) must first be trans- N2OC2H2 flame with a maximum temperature ex-
ferred into the gas phase via the atomization process ceeding 3000 K. Atomization occurs because of the
to produce N(g) free atoms in an atomizer volume. high enthalpy and temperature of the flame, and
The analyte atoms are then detected by absorption through chemical effects. Owing the generation of
of radiation from a primary source at a wavelength cyanogen radicals, which are known to be an effi-
characteristic of the element resulting in an absorp- cient scavenger for oxygen, the nitrous oxide-acety-
tion signal, A. Thus, the general scheme of AAS can lene flame provides not only a hotter but also a more
be presented as follows: reducing environment for atom production: the lack
of oxygen moves equilibria such as MeO o Me + O
to the right. Therefore a N2OC2H2 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.
The primary goal of the theory of AAS is to establish Atom production in flames is an extremely com-
the relationship between the measured analytical sig- plex process consisting of many stages and involving
nal, atomic absorbance, A, and the analyte concen- numerous sides processes. A quantitative theory of
tration, c, in the sample. Theoretical description of analyte atomization in flames is absent. Qualitative-
the two stages involves entirely different sciences: ly, the process can be described as follows: the solu-
theory of atomization is based on thermodynamics, tion droplets sprayed into the flame are first dried,
kinetics and molecular physics, while description of the resulting solid microparticles become molten and
absorbances is based on optics and spectroscopy. vaporize or thermally decompose to produce gaseous
Below, the two stages will be considered separately. molecules that are finally dissociated into free atoms.
The atoms may further be excited and ionized and
form new compounds. These processes are depend-
Atom production
ent upon the temperature and the reducing power of
In the first step of an AA determination the element of the flame and occur within a few milliseconds the
interest must be atomized. The ideal atomizer would time required by the sample to pass through the
34 ATOMIC ABSORPTION, THEORY
flame. The processes taking place in flames are volatilization of matrix components that are purged
shown in more detail in Figure 1. from the atomizer by a flow of inert gas); (iii) analyte
atomization (15003000 K achieved rapidly at a
Electrothermal atomization heating rate of about 2000 K s1). A major difference
of electrothermal atomization from atomization in
In the majority of cases this occurs in a small graph-
flames is that some matrix components are removed
ite tube where the sample to be analysed is intro-
at the pyrolysis step and the atomization takes place
duced via a small aperture in the upper tube wall.
within a confined geometry in an inert gas atmos-
Metals such as tantalum or tungsten are also used to
phere. During atomization, the purge gas flow is
construct electrothermal atomizers as well as non-
shut off so that analyte atoms remain in the probing
tubular geometry for the atomizer (graphite cups,
beam as long as possible.
rods, filaments, etc.). After a 550 L droplet of the
The number of analyte atoms in the atomizer vol-
sample solution has been deposited into the graphite
ume N(t), generated during the atomization stage is
furnace, it is heated resistively through a series of
described by the convolution:
preprogrammed temperature stages to provide: (i)
drying of the droplet to evaporate the solvent
( 370 K for about 30 s); (ii) thermal pretreatment
(pyrolysis) to remove volatiles without loss of ana-
lyte (6001500 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.
ATOMIC ABSORPTION, THEORY 35
Table 2 Selected relative detection limits (g L1) 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
aDetection 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, THEORY 37
AAS because the analyte concentration is small. How- of the absorption profile is used for computations:
ever, Lorentz broadening, which involves collisions Z = (/D)2 . Within about 1% accuracy, the
between analyte atoms and foreign species (Ar atoms FWHM of the Voigt profile can be estimated from
in electrothermal atomizers) called perturbers, are the following empirical equation:
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:
relationship A = f(N) is called the concentration Here, b and h are the width and the height of the
curve and its description is one of the primary goals monochromator entrance slit, l is the length of the
of theoretical AAS. absorbing layer; the limits of O* to O* are the spec-
The phenomenon of radiation absorption had tral bandwidth isolated by the monochromator. It
already been studied quantitatively early in the 18th was assumed that radiation attenuation occurs only
century, mainly on liquids and crystals. The investi- because of atomic absorption, i.e. H(O) = 0. The
gations resulted in the BeerLambert law relating the absorption coefficient, k(O;x,y,z), depends on the
radiant flux, )tr, transmitted through an absorbing number density of absorbing atoms in the ground
layer to the optical properties of the layer. In modern state, no (cm3), and the spectral profile, k(O), of the
formulation, the law applied to a spatially uniform absorption line, and is presented as:
absorbing layer of length l and a uniform parallel
probing beam is written as follows:
Chang SB and Chakrabarti CL (1985) Factors affecting Mitchell ACG and Zemansky MW (1961) Resonance
atomization in graphite furnace atomic absorption Radiation and Excited Atoms. Cambridge: Cambridge
spectrometry. Progress in Analytical Atomic University Press.
Spectroscopy 8: 83191. Slavin W (1991) Graphite Furnace AAS A Source Book,
Ebdon L (1982) An Introduction to Atomic Absorption 2nd edn. Norwalk, CT: Perkin-Elmer Corporation.
Spectroscopy. London: Heyden. Styris DL and Redfield DA (1993) Perspectives on mecha-
Haswell SJ (Ed.) (1991) Atomic Absorption Spectrometry. nisms of electrothermal atomization. Spectrochimica
Amsterdam: Elsevier. Acta Reviews 15: 71123.
Holcombe JA and Rayson GD (1983) Analyte distribution Welz B (1985) Atomic Absorption Spectrometry, 2nd edn.
and reactions within a graphite furnace atomizer. Weinheim: VCH.
Progress in Analytical Atomic Spectroscopy 6: 225251. Winefordner JD (ed) (1976) Spectroscopic Methods for
Lvov BV (1970) Atomic Absorption Spectrochemical Elements. New York: Wiley-Interscience.
Analysis. London: Adam Hilger.
Atomic emission spectroscopy is one of the most use- microwave plasmas (CMP). Glow discharges are
ful and commonly used techniques for analyses of utilized for direct solids analyses, but will not be dis-
metals and nonmetals providing rapid, sensitive cussed here. An analytical plasma is a high-energy,
results for analytes in a wide variety of sample matri- slightly ionized gas (about 0.01 to 0.1% ionized).
ces. Elements in a sample are excited during their
residence in an analytical plasma, and the light emit- Inductively coupled plasmas
ted from these excited atoms and ions is then The most commonly used ion source for plasma spec-
collected, separated and detected to produce an emis- trometry, the ICP, is produced by flowing an inert
sion spectrum. The instrumental components which gas, typically argon, through a water-cooled induc-
comprise an atomic emission system include (1) an tion coil which has a high-frequency field (typically
excitation source, (2) a spectrometer, (3) a detector, 27 MHz) running through it (Figure 1). The alter-
and (4) some form of signal and data processing. The nating current in the coil has associated with it a
methods discussed will include (1) sample introduc- changing magnetic field, which induces a changing
tion, (2) line selection, and (3) spectral interferences electric field. The flowing gas is seeded with electrons
and correction techniques. by means of a Tesla coil. These electrons undergo
acceleration by the electric field, and gain the energy
Atomic emission sources necessary to excite and ionize the gaseous atoms by
collision. This produces the plasma, self-sustaining as
The atomic emission source provides for sample long as the RF and gas flows continue.
vaporization, dissociation, and excitation. The ideal Sample particles entering the plasma undergo de-
excitation source will allow the excitation of all lines solvation, dissociation, atomization, and excitation.
of interest for the elements in the sample, and do this The ICP has sufficiently long residence times and
reproducibly over enough time to encompass full ele- high enough temperatures so that the sample solvent
mental excitation. Excitation sources include but are is completely vaporized, and the analyte reduced to
not limited to (1) inductively coupled plasma (ICP), free atoms, which undergo excitation. This
(2) direct current plasmas (DCP), (3) microwave excitation results in the emission of light at specific
induced plasmas (MIP), and (4) capacitively coupled frequencies for elements in the sample, which is