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Spectroehimica

Act&,
1982,
Tol.18,
pp.805to614.Pwgpamon
3%~ Ltd.PrintedInNorthern
Imlmd

A review of recent work in atomic absorption sp~~s~py*


J.E. ALLAN
Rukuhia Soil Research Station, Hamilton, New Zealand
(lie&&

15 November 1961)

IN the six years since WALSH


fir& suggested using atomic absorption spectra for
analytical purposes [l] interest in this new field has steadily grown, Over forty
papers, including two reviews [2, 31, have appeared-all
but five since the last
Australian Spectroscopy Conference two years ago. In this review I shall attempt
to give an account of the progress that has been made and the problems that have
been met, as revealed by these papers.
ANALYTICALMETHODS

More than half have been concerned with the establishment


of analytical
procedures for the determination
of various elements in solutions derived from
various materials. Thus rnug~~~urn has been determined in agricultural materials
[P-7], slags and cements [7], biological fluids [S-lo] and aluminium ahoys [ll];
calciua in agricultura1 materials [6, 121 and biological fluids [lo,13, 141; sodium
* Paper presented at the Australian Spectroscopy Conference Sydney, August 1961.
[l] A. Walsh, &$ectrochim.Acta 7, 108 (1955). The application of atomic absorption spectra to
chemical analysis.
[Z] D. J. ZfAwD, Ana&.& 85, 779 (1960). The application of atomic absorption to chemical
analysis-a review.
[3] J. W. ROBINSON, Anal. Chem. 32, 17A (1960). Atomic-absorption spectroscopy (A review).
[4] J. E. ALLAN, Andyst 88, 466 (1958). Atomic absorption spectrophotometry with special
reference to the determination of magnesium.
[5] D. J. Dave, Analyst 83,656 (1958). The determination of zinc and other elements in plants
by atomic-absorption specrtroscopy.
IS] D. J. DAVLD,Analyst 85,4Bfi (1960). The de~r~ation
of exchangeable sodium, potassium,
calcium and magnesium in soils by atomic-absorption spectrophotometry.
[7] W. LEITHE and A. HOFER, Mkrochim. Acto 268 (1961). The determination of magnesium
by atomic-absorption flame photometry.
[S] J. B. WILLIS, Nature 184, 186 (1959). The determination of magnesium in blood serum by
atomic-absorption speo&osoopy.
[Q] J. B. WJIUS, Speetrochim. Acta 16,273(1960). The determination of metals in blood serum
by ato~c-abso~tion
spectroscopy-IL
amnesic.
[IO] J. B. WILLIS, And. Chem. 38, 556 (1961).The determination of calcium and magnesium in
urine by atomic-absorption spectroscopy.
[lI] W. LEITHE and A. HOFER, Micrachinz. Acta 277 (1961). The determination of magnesium
in aluminium alloys by atomic-absorption flame photometry.
1121 D. J. DAVID, Analyat 84, 530 (1959). The determination of calcium in plant material by
atomic-absorption speatrophotomet~.
1131J. B. WILLIS, N&we
186,249 (1960). The dete~i~tion
of oalcium in blood serum by
atomic-absorption spectroscopy.
[143 J. B. Wmms, Spectrochim. Ada 16,259(1960). The determination of metals in blood serum
by atomic-absorption spectroscopy--I. Calcium.
605

606

J. E. ALLAN

and potmsiwn in soil leachates [6] and blood serum [15]; iron and manganese in
agricultural materials [16]; copper in agricultural materials [17], copper alloys [18]
and ores [19]; zinc in agricultural materials [5, 201 and metallurgical samples [21];
lead in copper alloys, steel [22], and gasoline [23]; silver in lead concentrates [24];
rnoZybdenum in fertilizers and steel [25]; and strolztium in plants [25]. Other
elements that have been studied include Ni, Co [26], Au, Pt, Pd and Rh [27].
In all these methods the technique used has been to spray the solutions into a
flame, and, with a hollow cathode lamp or a spectral discharge lamp as a source, to
measure the absorption by the atoms in the flame, at the wavelength of a particular line isolated by a monochromator.
Generally, the precision has been
good-coefficients
of variation of about 1 to 3 per cent being obtained where
stable lamps were used. The sensitivity has been adequate-sometimes
more than
adequate-for
the purpose of the particular method, and from the point of view
of simplicity and speed atomic absorption methods have been found to be superior
to most other methods. Interferences have been few but in some cases have had to
be overcome in order to obtain accurate results.
INTERFERENCEEFFECTS
As WALSH pointed out at the last Conference, interferences in spectroscopic
methods generally can be classified into three main groups: radiation, physical
and chemical.
(1) Radiation
interferences occur when the light emitted by one element
interferes with the measurement of the light emitted by another. In absorption
measurements,
there is no interference from emitted light when a modulated
[ 151 J. B. WILLIS,Spectrochim.Acta 16,551 (1960). The determinationof metals in blood serum
by atomic-absorption spectroscopy-III. Sodium and potassium.
[ 161 J. E. ALLAN,Spectrochinz.
Acta 15,800 (1959). The determinationof iron and manganeseby
.
atomic absorption.
[17] J. E. ALLAN, Spectrochim. Acta 17, 459 (1961). The determination of copper by atomicabsorption spectrophotometry.
[18] A. C. MENZIES,flpectrochim. Acta 106 (1957). Trends in automatic spectrochemicalanalysis.
[19] A. STRASHEIM,
F. W. E. SRELOWand L. R. P. BUTLER,J. S. African Chem. Inst. 18, 73
(1960). The determinationof copper by means of atomic-absorptionspectroscopy.
[20] J. E. ALLAN,Analyst 86,530 (1961). The determinationof zinc in agriculturalmaterials by
atomic-absorption spectroscopy.
[21] J. A. F. GIDLEYand J. T. JONES,Andy& 85, 249 (1960); 86, 271 (1961). (Note) The
determinationof zinc in metallurgicalmaterials by atomic-absorption spectrophotometry.
[22] W. T. ELE~ELL and J. A. F. GIDLEY,Anal. Chim. Acta 24,71 (1961). The determinationof
lead in copper-based alloys and steel by atomic-absorption spectroscopy.
[23] J. W. ROBINSON,Anal. Chim. Acta 24,451 (1960). The determinationof lead in gasolineby
atomic absorption spectroscopy.
[24] B. S. RA~LIN~, M. C. GREAVESand M. P. AMOS,Nature 188,137 (1960). The determination
of silver in lead concentratesby atomic-absorption spectroscopy.
[25] D. J. DAVID, Nature 187, 1109 (1960). Atomic-absorption spectrophotometricdetermination of molybdenum and strontium.
[26] J. E. FAN,
Nature 187, 1110 (1960). The determination of nickel and cobalt by atomic
absorption.
[27] R. LOCKYERand G. E. HAMES, Analyst 84, 385 (1959). Quantitative determination of
noble metals by atomic-absorptionspectroscopy.

A review of recent work in atomic absorption spectroscopy

607

and a detector arranged to respond only to the modulated signal is used [28].
With the simpler d.c. system of measurement however, emission from an airacetylene flame may be troublesome at wavelengths much above 3200 _k [17],
although at shorter wavelengths there is no problem [4,16,20,261.
(2) Physical interferences, where an atom is caused to gain or lose excitation
energy by collisions with the interfering atoms or molecules, do not have a measurable effect on absorption as the number of excited atoms is always a very small
fraction of the total number [I].
(3) Chemical interferences occur when, as a result of some chemical reaction,
the concentration
of atoms is altered.
As the total concentration
of atoms is
altered this type of interference affects both emission and absorption similarly.
In flames, the two chemical phenomena which commonly give rise to interferences, both in emission and absorption, are ionization and the formation of
involatile compounds.
Ionization
occurs to a measurable extent with elements having ionization
potentials of about 6 eV and lower, particularly when their concentration is low,
and results in a reduction in the number of atoms present, and hence in the absorption.
However, in the presence of an excess of a second easily ionizable
element, the ionization equilibrium is shifted in the direction of the neutral atoms
and the concentration
of neutral atoms and hence the absorption is increased.
This type of interference, which is minimized in cool flames, and which can be
overcome, either by using standards containing a similar concentration
of the
interfering element as the sample solutions, or by adding a large excess of the
interfering element to both solutions and standards, has been met with by WILLIS
[15] in the determination
of potassium in blood serum, where the large excess of
sodium enhances the potassium absorption.
The small enhancement of calcium by
sodium and potassium which occurs in the analysis of plants [12] and blood serum
[14]is also probably due to the repression of ionization.
Potassium however has
been reported not to interfere in the determination of sodium [29].
In the determination of the alkaline earth elements by both flame emission and
absorption, depression by phosphate, sulphate, silicate and aluminium is well established, and has been shown to be due to the formation of compounds which are
only slowly volatilized in the flame. This effect is generally greater in cool flames.
Magnesium absorption for example is depressed by aluminium, silicate, phosphate
and sulphate [7,301 in a coal gas flame, but usually not by the two latter in an
acetylene flame, although depression by phosphate and sulphate in this flame has
been reported by one worker [6].The depression of calcium is more serious and is
found in both type of flames, although to varying degrees by different workers [6,
12, 10, 141. Complete agreement between different laboratories is not to be
expected as the magnitude of the depression depends on a number of factors such
as the actual temperature of the flame used, the fineness of spray entering the
source

[28] BARBARAJ. RUSSELL,J. P. SHELTON


and A. WALSH. Spectrochim. Actu 8, 317 (1957). An
atomic-absorption spectrophotometer and its application to the analysis of solutions.
[29] J. W. ROBINSON,
Anal. Chim. Acta 23,458 (1960). The determimtion of sodium by atomicabsorption spectroscopy.
[30] A. C. MENZIES,Anal. Chem. 32, 898 (1960). A study of atomic-absorption spectroscopy.

J. E.

608

ALLAN

flame, the rise time of the particles in the flame and the height in the flame at
which the measurements are made. This type of interference so far appears to be
confined almost entirely to the alkaline earths, although the depression of zinc
absorption by silica has been noted [21].
Accurate results can be obtained by:
1. Removal of the offending element e.g. silica [7, 12, 211.
2. Addition of an excess of the offending element (if sensitivity considerations
permit).
3. Addition of an excess of a competing cation (e.g. Sr or La).
4. Addition of an excess of a competing anion (e.g. PO, depression does not
occur in presence of excess sulphate).
5. Addition of a complexing reagent to prevent the formation of the involatile
compound e.g. EDTA.
It has been found for example that magnesium can be determined in aluminium alloys by the addition of either calcium or sulphate to prevent interference
by Al [ 111, while in the determination of calcium, either strontium or lanthanum has
been used in the analysis of urine [lo] and soil extracts [6], EDTA in the analysis of
blood serum [14], and a mixture of magnesium and sulphuric acid in the analysis
of plants [12].
High salt concentration [17, 201 or high acid concentration [5, 16, 201 generally
results in reduced sprayer efficiency and hence low absorption readings, and it is
therefore necessary to ensure that samples and standards are sufficiently similar in
composition to avoid this effect, However, for the determination of molybdenum
in fertilisers and steels, DAVID [25] has successfully used the method of additions,
to obtain accurate results in the presence of strong interferences caused in part by
high salt concentration in the solution sprayed.
In this method known amounts of the element to be determined are added to
two aliquots of the sample solution and a third aliquot is diluted with water to the
same extent.
The three solutions are then analysed and from the results the
concentration
of the element in the original solution can readily be calculated,
provided that the relationship between absorption and concentration
is linear.
FLAMES
The flames most frequently used have been air-coal gas, air-propane
and
air-acetylene, generally with burners designed to give a long light path through the
flame. The commonly available burners for hot flames such as oxygen-hydrogen
and oxygen-acetylene
provide a flame of small dimensions so that sensitivity
suffers and the system of direct injection of the spray into the flame used with
these burners usually leads to increased anion interference [14]. Lead, however,
has been determined in gasoline with an oxy-hydrogen
flame with good sensitivity
[23], although for most elements the sensitivities obtained with this flame, and
with the hotter oxy-cyanogen
flame, have been low [31].
Some comparisons have been made between the three flames first mentioned
above, the temperatures of which increase in the order given. It appears that:
[31]

J. W.

ROBINSON,

spectroscopy.

hal.

Chem. 33, 1067 (1961).

Recent

advances

in atomic-absorption

A review

of recent work in atomic

absorption

spectroscopy

609

(a) For those elements which are completely volatilized and dissociated into
atoms in the flame, slightly more sensitive results are obtained in the cool coal-gas
flame (e.g. Cu [17] Zn Ni Co [32]. This cool flame is also preferable where ionization interferences are troublesome [ 151.
(b) For elements which are not completely volatilized or which suffer interference by the formation of involatile compounds, the hotter air-acetylene
flame
is preferable both from the point of view of sensitivity and freedom from interference, e.g. magnesium [7] and calcium [14].
(c) For elements which are not completely
dissociated into atoms the greatest
absorption is found in the region immediately above the blue cone, and the use of a
fuel-rich flame usually leads to increased dissociation and hence increased absorption.
The increased sensitivity obtained with a fuel-rich flame is of the order
of 20 to 30 per cent for potassium [15] and magnesium [4] but may be quite substantial as in the case of molybdenum
where about a hundred fold increase is
obtained [25]. There is not yet sufficient data to enable one to generalize about the
effect of flame temperature
on dissociation.
An increase in temperature
will
inevitably alter the composition of the flame gases and this may well result in less
dissociation of the metallic oxides and hydroxides.
More sensitive results for
example are obtained for potassium in a fuel-rich coal-gas flame than in a fuelrich acetylene flame [15].
Apart from the use of a flame the only other method so far described for
converting a sample into atoms is by means of a sputtering chamber [33]. Although not yet fully developed this method shows promise for metallic samples.

ABSORPTION LINES
Some attention has been paid to the determination of the strongest absorption
lines of those elements which have complex spectra in which the strongest line
is not immediately apparent. The spectra of Fe, Mn [16], Ni, Co, [26] and MO [25]
have been examined and the strongest lines established.
Investigations have also
been made of less sensitive lines and list of lines for Fe, Mn [ 161 and Cu [ 171 have
been published which enable analyses to be carried out over a wide concentration
range. In the analysis of blood serum which contains very much more sodium than
potassium, both these elements have been estimated in the same solution by using
the less sensitive Na doublet at 3303 A [15],
while in the analyses of fertilisers for
copper the less sensitive line at 2178 A has the advantage of requiring less dilution
of the sample and so reducing the risk of contamination [17].

ORGANIC SOLVENTS
However, a more usual analytical problem is how to increase sensitivity and
to that end the use of organic solvents has been investigated [31, 34-361 and has
[32]0. E.

CLINTON, X~ectrochim. Acta 16,985(1960).


A burner for atomic-absorption
spectrophotometry.
[33]B. M. GATEHOUSE and A. WALSH, Spect~ochim. Acta 16,602(1960).
Analysis of metallic
samples by atomic-absorption
spectroscopy.
[34]J. E. ALLAN, Spectrochim. A& 17, 467 (1961). The use of organic solvents in atomic
absorption spectrophotometry.

610

J.E.

ALLAi

been used in the routine determination of Cu in plants and soil extracts [17]. This
is a common technique in emission flame photometry and at the last conference it
was reported that about a five-fold gain in sensitivity could be obtained in absorption by spraying an organic rather than an aqueous solution.
This has been further investigated [34], and it has been found that:
(a) Where an organic solvent, miscible with water is added to an aqueous
solution gains in sensitivity of about 2-3-fold are obtained, depending on the
solvent and the atomizer, with exactly the same increase being obtained for
different eIements.
(b) When the element was extracted into an organic solvent immiscible with
water, and the organic solution sprayed, the sensitivity was increased from 3 to
I-fold, again depending on the solvent and the atomizer and being the same for
all elements tested.
This work was done with a pre-mixed air-acetylene flame and the spray from
the atomizer passed through a spray chamber before entering the flame, Under
these conditions it was established experimentally that the greater part of the
increase in sensitivity was accounted for by the increased amount of the solution
reaching the flame and that the small reduction in temperature which occurred
when organic solvents were used accounted for the remainder of the increase in
sensitivity.
With similar equipment to that used above, LOCKYERet al. [SS] have reported
increases in absorption of about l-5-3 with various organic-aqueous mixtures,
different increases being obtained with different elements. These differences
prevented the authors from suggesting a possible mechanism. It should be noted
that as the curve relating absorption with concentration is not straight it is not
valid to compare increases in absorption for different elements, and had these
workers compared sensitivities, or detection limits, it is possible they would have
obtained the same increase for different elements, except in the case of iron. For
iron in 50 per cent iso-propyl alcohol they reported a lo-fold increase in absorption
compared with 2-3-fold for other elements. This is a most surprising result and
we have not been able to confirm it.
ROBINSOX [36] has reported increases in nickel absorption obtained by spraying various organic solutions into an oxycyanogen flame. This writers discussion
of the possible mechanism is handicapped by a lack of experimental data, but he
appears to favour the idea that the increased sensitivity is due to a more complete
vaporization of the spray droplets in the flame. If the solutions were sprayed
directly into the flame, with no spray chamber-and this is not stated-then this
idea may have some merit,
In a recent paper, [31] the same author reports detection limits in aqueous and
organic solvents for a number of elements in both an oxy-hydrogen and an oxycyanogen flame. The increase in sensitivity obtained was not only very different
for different elements, but also for different lines of the same element, and even for
[35] R. LOCKYER,J. E. SCOTTand S. SLADE, Nccture 189, 830 (1961). Enehancement of atomic
absorption in flames by organic solvents.
[36j J. W. ROBINSON, And Chim.Acta28,479(1960). The effect of organicand aqueoussolvents
on flame photometric emission and atomic-absorption spectrowopy.

A review of recent work in atomic absorption spectroscopy

611

It would be difficult indeed to suggest a mechanism


to explain these results which must surely be due to some uncontrolled factor in
the experimental procedure.
lines in the same multiplet.

INSTRUMENTATION
In the field of instrumentation
a number of atomic absorption spectrophotometers have been described, in addition to the early work by RUSSELL et al. [28].
ALKEMADE and MILATZ [37] who independently
demonstrated
the possibility of
using atomic absorption
measurements for analytical purposes used a doublebeam system in which two light beams from the source lamp were chopped
alternately.
One beam passed through the flame, and the beams were then
recombined at the photomultiplier
and the a.c. signal due to the inequality of the
intensities of the two beams was measured with an amplifier and synchronous
galvanometer.
In the writers laboratory a medium quartz spectrograph, fitted with an exit
slit and photomultiplier
has been used [4]. The source lamp was unmodulated and
a simple d.c. system was used and proved adequate to about 3200 A. Above this
wavelength emission from the flame was likely to interfere [17].
The Hilger instrument [27] also uses an unmodulated light source and a d.c.
An optical system, consisting of two lenses, one before
system of measurement.
the flame which renders the light from the hollow cathode lamp parallel, and one
following the flame which focusses this beam of light into the slit of the monochromator, together with the use of a cool coal-gas flame minimizes, but does not
entirely eliminate, the effect of emission from the flame.
Box and WALSH [38] have described a simple single-beam instrument.
The
power supply delivers unsmoothed d.c. to the hollow cathode lamp, so that the
output from the lamp is modulated at 50 or 100 c/s. A simple a.c. amplifier, with
a meter output, follows the photomultiplier
and responds only to the a.c. component of the light passing through the monochromator,
and thus eliminates any
interference by the light emitted by the flame. This instrument, which has been
widely used by WILLIS, DAVID and others in work quoted in this review, is now
used extensively in Australia.
LEEN and ATWOOD, at the Pittsburgh
Conference this year described a
double-beam instrument, now manufactured by Perkin-Elmer [39]. Here again the
source is modulated.
The light beam is split, one beam passing through the flame.
The beams are then recombined to pass through the monochromator,
redivided
and detected by two photomultipliers.
After amplification in separate amplifiers
the outputs are compared electrically and the ratio may be read or recorded.
Somewhat greater precision is obtained with this instrument in the measurement
of low absorption than is usual with a single-beam system, particularly when the
recorder is used to average the results over about a minute.
[37] C. T. J. ACEESIADE and J. M. W. MILATZ, Appl. Sci. Res. 4B, 289 (1955); J. Opt. Sot. Am.
45, 583 (1955).
[38] G. F. Box and A. WALSH,Spectrochim. Actu 16, 255 (1900). A simple atom&absorption
spectrophotometer.
[39] Manufacturers literature Perkin-Elmer Corporation Norwalk, Connecticut, U.S.A.

J. E. ALLAN

612

A null-point atomic absorptiometer


has been described by MALMSTADT and
CHAMBERS [40]. Sample and standard are sprayed alternately and the standard
concentration
adjusted by titration until no difference in absorption from the
sample is obtained.
This system requires a stable source lamp and seems somewhat slow and cumbersome.
In some cases, errors in burette readings contributed
substantially
to the variability
but under the best conditions,
coefficients of
variation of between O-1 and 0.4 per cent were obtained which is somewhat better
than is usual.
MENZIES [30] has described a ratio system, whereby the intensities of two lines
emitted by the source, one of which is absorbed, and one of which is not, are
compared.
This has the obvious advantage of simplicity as no beam splitting
optical system is required. However, it was found that the ratio of the two lines
did not remain constant when the lamp intensity was varied as almost inevitably
the two lines had widely different excitation potentials.
Of the possible types of atomic absorption
spectrophotometry,
modulated
and unmodulated, single and double beam, it is apparent that a modulated doublebeam system has the greatest potential.
Unmodulated instruments are liable to
flame-emission interference particularly toward the higher wavelength and with
hotter flames, while single-beam instruments depend on the stability of the source
lamp so that the precision at low absorption may be limited.
The usefulness of long flames has been recognized [4] and burners designed to
give a long light path through the flame are now commonly used to obtain maximum sensitivity.
One such, made from cast aluminium alloy and providing a
1%cm flame with either air-coal gas or air-acetylene
has been described by
CLINTON
[32]. This burner is rotatable, so that a 12-fold range in sensitivity is
obtained and is water cooled to avoid the slow decrease in absorption which
occurred when the uncooled burner was used continuously for prolonged periods.
A stainless steel burner of similar construction has been described by WILLIS [15].
Another point of interest in instrumentation
is the use of scale expansion by
DAVID [25] to obtain increased sensitivity in the determination
of small amounts
of strontium.
The success of this device of course depends on the stability of the
hollow cathode lamp, and is by no means of universal application, and GIDLEY
and JONES [21] have in fact had to use an integrating circuit in order to obtain
sufficient precision with an unstable lamp.
As sources, hollow cathode lamps or spectral discharge lamps have been
universally used. Hollow cathode lamps are now available commercially
from
several sources, and their construction
and characteristics
have been described
[41, 421. Spectral discharge lamps have generally been used for the determination
of the alkali metals but for the determination of Na and K, WILLIS [15] has used
hollow cathode lamps having an aluminium cathode lined with Na or K nitrate.
[40] H. V. MALMSTADT and W. E. CHAMBERS. Anal. Chem. 32, 225 (1960). Precision null-point
atomic-absorption spectrochemical analysis.
[41] W. G. JONES and A. WALSH, Spectrochim. Acta 16,249 (1960). Hollow cathode dischargesthe construction and characteristics of sealed-off tubes for use as spectroscopic light sources.
[42] BARBARA J. RUSSELL and A WALSH, Spectrochim. Acta 15, 883 (1959). Resonance radiation

from a hollow cathode.

A review of recent work in atomic absorption spectroscopy

613

Various factors of instrumental


origin, capable of causing a reduction in
sensitivity, have been recognized.
Sensitivity is reduced if the width of the line
emitted by the source is too great compared with the width of the absorption line
in the flame. The width of source line can be minimized by running the lamp at as
low a current as is possible for stable operation [4, 281.
Sensitivity is also lost if, in the spectrum of the source lamp, there is an unabsorbed line sufficiently close to the absorption line to be incompletely resolved
If the interfering line is a rare gas line it may sometimes
by the monochromator.
be practicable to use another gas [41], otherwise higher resolving power is necessary
for maximum sensitivity.
Similarly, a serious reduction in sensitivity results from the presence of a continuum in the spectrum of the source lamp [16]. In this case the best line to background ratio is obtained by running the lamp at as high a current as possible and
by using narrow slits. The presence of a continuum is probably indicative of faulty
manufacturing technique and improvements in lamps from this point of view can
be expected in the future.
CoNCLUsIoNs

It is, I hope, apparent from this review that atomic absorption spectroscopy
has provided a rapid and reliable method for the determination of many elements
in a wide variety of materials, using equipment which, although a little more
complex than that required for flame photometry,
is much simpler and cheaper
than the conventional spectrographic instruments required for arc or spark emission methods. We may confidently expect its extension, in the immediate future,
to other elements known to give good sensitivity in the flame (e.g. Cd Cr) but which
have not yet been studied in detail.
We have some way to go however before all our problems are solved. Hollow
cathode lamps, improved
as regards stability, freedom from background
and
length of life are desirable and will undoubtedly
be available as manufacturing
techniques improve. Investigations into other possible types of narrow-line sources
may be profitable for some elements.
We may also expect efforts to be made to increase sensitivity, possibly by
improved double-beam methods to measure low absorptions more accurately, or
possibly by methods to increase the absorption such as longer light paths or more
eflicient sprayers, while extension of the method to regions below 2000 A would
enable the determination of a number of elements with strong absorption lines in
that region, but has obvious difficulties.
In 1956 RUSSEL, SHELTONand WALSH [SS] concluded their pioneer paper by saying at the present state of its development, by far the most serious difficulty in the
absorption method is due to the difficulty in atomizing various elements - * * - this
seems to us to be the outstanding problem at the present time.
It still is. In the
flames at present in use many elements exist in stable molecular compounds so that
the concentration of free atoms is reduced, often to negligible proportions.
For the
determination of many elements therefore atomic-absorption
spectroscopy cannot
yet be applied, while for others, only low sensitivity is obtained. I hope that in the
future a deeper knowledge of the chemistry of the stable compounds formed, and
of the reactions involved in their dissociation into atoms, may lead to the more

614

J.E.ALLAN

effective use of flames. It is likely, however, that alternatives to flames will be


necessary.
After all, although spraying a solution into a flame is a simple convenient and reproducible way of obtaining a cloud of atoms, the efficieimy is not
high, even for those elements which are completely atomized.
With the usual type of flame and sprayer, the sample is sprayed at the rate of
about 2 ml/min.
Of this, only about 0.1 ml is sufficiently finely divided to reach
the flame, and the remainder is held by the spray chamber and is lost. In the
process, this 0.1 ml is diluted with about 10 1. of air and fuel gas, and this volume
In other words, we tip 95 per cent of
expands to about 80 1. at flame temperature.
the sample down the drain and dilute the remainder nearly a million-fold before
making the actual absorption measurement-so
there is certainly room for improvement .
There does not seem to be any easy solution to this problem but we may expect
developments with sputtering chambers, possibly arcs or plasma jets, and possibly
furnaces.
The future of atomic absorption spectroscopy is undoubtedly promising-and
there is no doubt that there are enough challenging problems to make it interesting
as well.