Atomic Absorption Spectroscopy —

Alan Walsh
Division of Chemical Physics
CSIRO
P.O. Box 160
Clayton, Vic, 3168, Australia

When Foil Miller invited me to I realize that anyone who reminis- tained in absorption and atomic spec-
participate in the Silver Anniversary ces is usually so decrepit that his tra in emission. The result of this
Symposium on Great Moments in memory is totally unreliable. I shall, musing was quite astonishing: there
Analytical Chemistry, he suggested therefore, try to avoid too many er- appeared to be no good reasons for
that I may care to indulge in some rors of fact by restricting my com- neglecting atomic absorption spectra;
personal reminiscences and com- ments largely to matters which are on the contrary, they appeared to
ments regarding the development and documented in reports of CSIRO, in offer many vital advantages over
present status of atomic absorption correspondence, or in publications. atomic emission spectra as far as
spectroscopy. I hope the ones I have My initial interest in atomic ab- spectrochemical analysis was con-
selected may illuminate, if not an- sorption spectroscopy was a result of cerned. There was the attraction that
swer, the problem posed by the title two interacting experiences: one of absorption is, at least for atomic va-
of my address. the spectrochemical analysis of met- pours produced thermally, virtually
als over the period 1939-46; the other independent of the temperature of
Presented at the Pittsburgh Conference on of molecular spectroscopy over the the atomic vapour and of excitation
Analytical Chemistry and Applied Spec- period from 1946-52. The interaction potential. In addition, atomic absorp-
troscopy, Cleveland, Ohio, March 6, 1974. occurred early in 1952, when I began tion methods offered the possibility of
Silver Anniversary Symposium on Great avoiding excitation interference,
Moments in Analytical Chemistry and to wonder why, as in my experience,
Applied Spectroscopy. molecular spectra were usually ob- which at that time was thought by
many to be responsible for some of
the interelement interference experi-
enced in emission spectroscopy when
using an electrical discharge as light
- 2 -
source. In addition, one could avoid
problems due to self-absorption and
self-reversal which often make it dif-
The purpose of this report .is to suggest a new technique for ficult to use the most sensitive lines
recording absorption spectra which offers many interesting possibilities. in emission spectroscopy.
The method is basically simple and is illustrated in the diagram below.
As far as possible experimental
problems were concerned, I was par-
ticularly fortunate in one respect. For
several years prior to these first
thoughts on atomic absorption, I had
been regularly using a commercial in-
frared spectrophotometer employing a
modulated light source and synchro-
nously tuned detection system. A fea-
ture of this arrangement is that any
radiation emitted by the sample pro-
duces no signal at the output of the
detection system. This experience
Assuming that the sample is vaporised by the usual methods, e . g. had no doubt prevented the forma-
flame, arc, or spark, then the emission spectrum is "removed" by means tion of any possible mental block as-
of the chopper principle . Thus, the absorption spectrum of the vapour sociated with absorption measure-
ments on luminous atomic vapours.
is measured by passing through it white light which is chopped. The
absorption spectrum and the emission spectrum are then scanned by a In an internal report for the period
February-March 1952,1 suggested
detector, the output from which is amplified by an amplifier tuned to that the same type of modulated sys-
the same frequency as the chopper. Thus the emission spectrum produces tem (Figure 1) should be considered
no output signal and only the absorption spectrum is recorded. for recording atomic absorption spec-
For analytical work it is proposed that the sample is dissolved, tra. The following extracts from that
report may be of interest:
and then vaporised in a Lundegardh flame . Such flames have a low
temperature (2000°K) compared to arcs or sparks (500CTKJ and have the
advantage that few atoms would be excited, the great majority being in
the ground state . Thus absorption will be restricted to a small number
Figure 1 . Extract from report for Feb-
ruary-March 1952

698 A • ANALYTICAL CHEMISTRY, VOL. 46, NO. 8, JULY 1974


Stagnant or Pregnant?
"Assuming that the sample is va-
porised by the usual methods, e.g.,
flame, arc, or spark, then the emis-
sion spectrum is 'removed' by means
of the chopper principle. Thus the
emission spectrum produces no out-
put signal and only the absorption
spectrum is recorded."
"For analytical work it is proposed
that the sample is dissolved and then
vaporised in a Lundegardh flame.
Such flames have a low temperature
(2000°K) compared to arcs and
sparks (5000°K) and have the advan-
tage that few atoms would be excited,
the great majority being in the
ground state. Thus absorption will be
restricted to a small number of tran-
sitions and a simple spectrum would
result. In addition, the method is ex-
pected to be sensitive since transi-
tions will be mainly confined to those
from the ground level to the first ex-
cited state."
At this stage I was thinking of elec-
trical discharges, as well as flames, as
a means of atomization. It will also
be apparent that initially I had not
appreciated the difficulties which
would be involved in recording atomic
absorption spectra when using a con-
tinuum source.
The next Bimonthly Report, for the
period April-May 1952, includes the
diagram shown in Figure 2 and de-
scribes our first experiment as follows:
"The sodium lamp was operated
from 50 cycles/sec. and thus had an
alternating output so that it was not
necessary to use a chopper. The D
lines from this lamp were isolated—
but not resolved from each other—by
means of a direct vision spectroscope
and their intensities were measured
by means of a photomultiplier tube,
the output from which was recorded
on a cathode ray oscillograph. Ampli-
fication of the signal was achieved by
the A.C. amplifiers in the oscillo-
graph. With the slit-width used the
signal gave full-scale deflection on the
oscillograph screen. A Meker flame
Figure 2. Extract from report for A p r i l -
May 1952
Report
was interposed between the sodium ysis. "Look," I said, "that's atomic
lamp and the entrance slit of the absorption." "So what?" was his
spectroscope. When a solution of so- reply, which was the precursor of
dium chloride was atomised into the many similar disinterested reactions
air supply of the flame the signal at to our atomic absorption project over
the oscillograph was reduced to zero. the next few years.
The principle of the method is there- My report for June-July 1952 dis-
fore established." cusses the problems of recording
In retrospect, such optimistic naiv- atomic absorption spectra of flames
ety is quite incredible. with a continuum source and con-
This simple experiment gave me a cludes that a resolution of about 0.02
great thrill, and I excitedly called in À would be required; this was well
John Willis, who at that time was beyond the best spectrometer avail-
working on infrared spectroscopy and able in our laboratory at that time.
was later to make important contri- The report concluded as follows:
butions to the development of atomic "One of the main difficulties is due
absorption methods of chemical anal- to the fact that the relations between
CHEMICAL PHYSICS SECTION
42nd Bimontly Report. April-May, 1952.
C.P. 1/14. Atomic Absorption Spectra
In the previous report the application of atomic absorption spectra
to spectrochemical analysis was suggested. The possibilities of this
approach have been explored and the results obtained to date are most
encouraging. In the preliminary work the apparatus shown below was used.
The sodium lamp was operated from 50 cycles/sec. and thus had
an alternating output so that it was not necessary to use a chopper.
The D lines from this lamp were isolated-but not resolved from each
other-by means of a direct vision spectroscope and their intensities
were measured by means of a photo-multiplier tube , the output from which
was recorded on a cathode ray oscillograph. Amplification of the signal
was achieved by the A. C . amplifiers in the oscillograph . With the slit-
width used the signal gave full-scale deflection on the oscillograph screen.
A Meker flame was interposed between the sodium lamp and the entrance slit
of the spectroscope. When a solution of sodium chloride was atomised into
the air supply of the flame the signal at the oscillograph was reduced to
zero. The principle of the method is therefore established. No attempt
ANALYTICAL CHEMISTRY, VOL. 46, NO. 8, JULY 1974 • 699 A

Figure 3. Schematic diagram of use of sharp line source
to measure peak absorption
absorption and concentration depend
on the resolution of the spectrograph,
and on whether one measures peak
absorption or total absorption as
given by the area under the absorp-
tion/wavelength curve."
At this juncture the possibilities of
measuring peak absorption were ob-
viously coming into consideration.
There is then a gap of four months
in my reports, owing to absence from
the laboratory on sick leave for much
of this period. The next report, for
the period December 1952-January
1953, refers to the poor sensitivity ob-
tained in the determination of copper
by use of a continuum source and a
monochromator obtained by placing a
slit and detector on the focal wave of
a Littrow spectrograph. The report
states:
"It is thought that this (poor sensi-
tivity) is due to the low resolution of
the Littrow spectrograph and to the
excessive amount of scattered light at
low wavelengths. It is hoped to over-
come this difficulty by using a hol-
low-cathode source (copper cathode)
as source. This will emit sharp lines
and a low resolution spectrometer
will then be sufficient. The first at-
tempts at producing hollow-cathode
sources have not been successful."
This use of a sharp line source to
measure peak absorption is illus-
trated schematically in Figure 3. In
this case, the function of the mono-
chromator is to isolate the required
line for measurement from all other
lines emitted by the source. The high
700 A • ANALYTICAL CHEMISTRY, VOL. 46, NO. 8, JULY 1974
resolution required for atomic absorp-
tion measurements is, in effect, pro-
vided by the sharp line source.
At this stage we had arrived at the
principle of the technique which, in
due course, became the generally ac-
cepted method of making the intensi-
ty measurements required in atomic
absorption methods of chemical anal-
ysis.
These early experiments, carried
out in collaboration with John P.
Shelton, were originally confined to
hollow-cathode lamps through which
argon was flowed by a closed circulat-
ing system. We did not commence
the development of sealed-off hollow-
cathode lamps until December 1953-
January 1954, when we first became
aware of the work of Dieke and Cross-
white (2), which had been published
in 1952.
The first person to express any in-
terest in the application of the tech-
nique we had developed was John
David, at the CSIRO Division of
Plant Industry in Canberra; and on
February 24th, 1953, he wrote to me a
letter which began as follows:
"I understand from several sources
that you have in mind a new tech-
nique of spectrochemical analysis in-
volving the measurement of the ab-
sorption by the analysis line of an el-
ement in a vaporized sample rather
than the measurement of its emission.
"I would very much appreciate any
information which you may have and
are prepared to give me regarding its
application to analysis for traces of
metallic and semi-metallic elements
in plant ash, soil, mineral or similar
samples."
My reply, dated 27th February
1953, was as follows:
"At the moment my work on atom-
ic absorption spectra is still in the
development stage and I cannot spec-
ify exactly what equipment will be
necessary, but I think it will include
the following items :-
(a) Monochromator having a reso-
lution of 1 À.
(b) Discharge tubes and gas-circu-
lating system.
(c) Flame burner assembly.
(d) Photomultiplier plus associated
power packs.
(e) Amplifiers having two homo-
dyne rectifiers on the output
side.
(f ) Ratio-meter, potentiometer or
ratio-recorder.
(g) One or two choppers.
"It is still too early to make any
definite claims for the method, but it
certainly offers most exciting possi-
bilities and will, I believe, prove par-
ticularly valuable in your work, pro-
vided the sample can be taken into
solution. It may prove possible to ex-
tend the method to solids.
"I should add that we are most
anxious not to divulge any informa-
tion to people overseas, so please re-
gard this letter as confidential."
In view of the almost complete lack
of interest in our work over the next
few years, this request for secrecy was
quite superfluous.
Later in 1953 I discussed possible
commercial exploitation of our ideas
with various instrument manufactur-
ers in the United States and England,
but the only person who viewed our
work with enthusiasm was A. C.
Menzies of Hilger and Watts Ltd.,
London; CSIRO arrived at a tentative
exclusive licence agreement with that
firm, based on the patent which we
lodged in November 1953.
The next significant event was the
first public exhibition of a working
atomic absorption spectrophotometer
(Figure 4). It was demonstrated in
March 1954 in Melbourne University
as part of an Exhibition of Scientific
Instruments, arranged by the Austra-
lian Branch of the (British) Institute
of Physics.
The apparent complexity of the in-
strument was due largely to its being
of the double-beam type, which in
our early experiments we regarded as
essential because of the poor stability
of many of our hollow-cathode lamps.
The viewer was possibly further con-
fused by the optical path being in op-
posite directions on the instrument
and on the explanatory diagram!
Whatever the reason, the instrument
aroused no interest whatsoever during
the three days it was on exhibition.
However, when Dr. Menzies visited
Melbourne shortly afterward to assess
its performance, he was sufficiently
impressed for his firm to decide to
produce, under licence to CSIRO, the
first commercial atomic absorption
spectrophotometer.
As soon as our final patent specifi-
cation was lodged on October 21, 1954
(3), I submitted to Spectrochimica
Acta my first paper (4), in which I
discussed the factors governing the
relationship between atomic absorp-
tion and atomic concentration, and
the experimental problems involved
in making atomic absorption mea-
surements. The paper was published
early in 1955, at about the same time
as the paper by Alkemade and Milatz
(5), who had independently arrived at
the atomic absorption method. Nei-
ther paper created any great impact,
and Alkemade and Milatz did not Figure 4. Photograph of atomic absorption spectrophotometer demonstrated
pursue their work further, possibly at Institute of Physics Exhibition, Melbourne, March 1954
because they regarded this method
merely as one for determining "all
metals usually to be determined by
flame photometry."
In 1956 and 1957 we published pa-
pers (6, 7) describing results obtained
with our instrument, but these papers
also created little interest. John Shel-
ton wrote to me from London on
March 5th, 1956, after giving a lec-
ture on our work to the Institute of
Physics, and reported that my first
paper had given the impression that
"the method was a scientific curiosity
rather than a practical analytical
method."
When I gave a series of lectures on
the subject at the Louisiana State
University Symposium in 1958, the
net result was that only one person,
Jim Robinson, was stimulated into
activity. He became a "hot gospeller"
and in due course played an impor- Figure 5. Photograph of simple atomic absorption spectrophotometer pro-
duced commercially in Australia
tant part in stirring up interest in the
United States.
The surprising thing is that the ap-
pearance in 1958 of the papers by
Allan (8) in New Zealand and David Australia. The necessary items were total staff of five. During the period
(9) in Canberra did not arouse any manufactured by three small com- 1958-62, some 30 Australian laborato-
sizable impact, even though they de- panies in Melbourne and then assem- ries were equipped by these "do it
scribed eminently successful appli- bled by the user, according to our in- yourself" units.
cations of the technique. structions. As it transpired, for the While knowledge of the technique
On the commercial side, Hilger and next few years the members of our re- spread rapidly throughout Australian
Watts had produced an instrument search group were increasingly in- industry, there was one memorable
which did not incorporate a modu- volved in supporting the commercial exception. I recall the technical direc-
lated source and therefore could not production in Australia of atomic ab- tor of one of our biggest mining com-
fully exploit the technique. Other in- sorption equipment. That a new type panies phoning CSIRO Head Office
strument manufacturers subsequently of Australian industry was eventually in the early 1960's and stating that he
perpetrated the same error. By 1958 created was, of course, cause for had just returned from South Africa
there was no sign of any instrument much satisfaction, but it was inevita- where they were using a brand new
manufacturer willing to produce the ble that there was a substantial re- instrument called an atomic absorp-
type of instrument which we thought duction in our research effort over a tion spectrophotometer. He wanted to
desirable. This was most curious period of several years. know if there was anyone in CSIRO
since by that time there was some in- Figure 5 shows a typical instrument who knew anything about it. Our
terest by other Australian laborato- produced in this manner, the elec- man in Head Office said he didn't
ries in possible applications of this tronic units having been produced to know but he would make inquiries!
technique. It was at this stage that our specifications by a firm in Mel- In this period there was also a
we decided to arrange for the produc- bourne called Techtron Appliances slightly increased interest by manu-
tion of appropriate equipment in Pty. Ltd., which at that time had a facturers in other countries. For me,

702 A • ANALYTICAL CHEMISTRY, VOL. 46, NO. 8, JULY 1974

 one of the "great moments" was in
1962 when I described to various
members of staff of the Perkin-Elmer
Corp. in Norwalk the impressive re-
sults which were being obtained by
the laboratories in Australia which
were by that time successfully using
the technique. It was during these
discussions that Chester Nimitz asked,
rather tersely: "If this goddam tech-
nique is as useful as you say it is, why
isn't it being used right here in the
United States?" My reply, which my
friends in Norwalk have never al-
lowed me to forget, was to the effect
that he would have to face up to the
fact that, in many ways, the United
States was an underdeveloped coun-
try! The Perkin-Elmer decision to
embark on a large-scale project relat-
ing to the production of atomic ab-
sorption equipment was made shortly
afterward. They were, in fact, guilty
of overreacting, as witnessed by their
subsequent claim that atomic absorp-
tion was "the greatest invention since
the bed."
It was also in 1962 that Techtron
decided to market a complete spec-
trophotometer. Initially, this incorpo-
rated an imported monochromator,
Australian production of an appropri-
ate monochromator being delayed
until 1965. By that time the ruling
engine constructed in the CSIRO Di-
vision of Chemical Physics was in full
operation and has since supplied all
the master gratings required by Tech-
tron. Other firms also were becoming
increasingly interested, and from that
time onward I do not think the tech-
nique has suffered any major setback.
In 1965 its future was virtually se-
cured by the development (down-
under) of the nitrous-oxide flame
which made the technique applicable
to more than 65 elements. I might
add that the development of this
flame by workers in atomic absorp-
tion spectroscopy was most altruistic,
since it put back on its feet emission
flame photometry which, at that
stage, appeared to be dying rapidly.
The recent remarkable growth in
the number of atomic absorption
spectrophotometers produced is
shown in Figure 6 and is indicative of
the increasingly widespread accep-
tance of atomic absorption methods.
In view of such growth, there would
appear to be little justification for de-
scribing the subject as having been
stagnant at any stage during the past
decade. But the growth in the num-
ber of applications has resulted main-
ly from fairly straightforward exten-
sions of a technique which originated
more than 20 years ago. I believe it is
no exaggeration to state that more
than 99.99% of all analyses are still
carried out by that original tech-
nique. In this respect the subject has
been stagnant over an extended peri-
704 A • ANALYTICAL CHEMISTRY, VOL. 46, NO. 8, JULY 1974
Figure 6. World sales
of atomic absorption
spectrophotometers
od. The situation is particularly de-
pressing in view of the well-known
limitations of existing flame methods,
of which the most serious was de-
scribed as follows in our first paper
(3) describing our spectrophotometer:
"By far the most serious difficulty
in the absorption method is due to
the difficulty in atomizing various el-
ements. This problem of complete at-
omization of the sample seems to us
to be the outstanding problem at the
present time."
As Allan (10) stated in his review of
the subject in 1962, "It still is."
In a review (11) I presented in that
same year, I pointed out that when a
flame is used some elements are only
partially atomized, "thus resulting in
loss in sensitivity and the possibility
of chemical interference due to varia-
tions of the degree of atomization of
one element with the concentration of
other elements, radicals or com-
pounds in the solution . . . . This type
of interference is present to the same
extent in emission and absorption
methods and is responsible for serious
limitations in flame methods."
Several years later, exactly the
same statement was being made, as if
it represented the disclosure of a new
fundamental truth regarding flame
spectroscopy.
It is not my intention to decry the
use of a flame as an atomizer, since it
is unlikely that any other method will
match its enormous range of applica-
tion, its speed of operation, or its re-
markable convenience. Nevertheless,
I remain convinced that the best
means of extending the range of ap-
plication of atomic absorption meth-
ods of analysis is by developing new
methods of atomization.
In some respects I imagine the
above remarks present a gloomy pic-
ture of the present state of atomic ab-
sorption spectroscopy. Fortunately,
there is a happier way of assessing
the situation, and I want to mention
briefly some aspects which lead me to
think that this stagnation is more il-
lusory than real. In the first place, so-
called flameless methods of atomiza-
tion, based on developments of the
L'vov furnance, have in the last two
years become of rapidly increasing
importance, and their full potentiali-
ties have by no means been fully ex-
ploited. They now provide a remark-
able ability to analyse extremely
small amounts of material, and their
importance, particularly in biochemi-
cal and clinical work, is already ap-
parent. The technique is still in its
infancy, and we can expect it to de-
velop rapidly over the next few years.
Of particular interest to me was the
paper presented at the Toronto Con-
ference last year in which Segar and
Gonzalez {13) described, I believe for
the first time, the coupling of a gas
chromatograph to the graphite cu-
vette of an atomic absorption spectro-
photometer. This combination may
well make even more ubiquitous the
remarkable techniques of chromatog-
raphy.
The recent development of im-
proved methods for the operation of
electrodeless lamps seems likely to
produce a new interest in the flame
fluorescence methods since, as was
first pointed out by Alkemade (14) and
demonstrated by Winefordner and MODULATED
Vickers (15), they have striking po- ATOMIC
tential advantages over atomic ab-
sorption spectroscopy. In this respect, SPECTRAL
it has always surprised me that work- LAMP
ers in flame fluorescence have, in
general, failed to exploit the fact that
the fluorescence phenomenon pro-
vides its own monochromator. In the
arrangement shown in Figure 7, for
example, if the illuminating source is
"pure," the only need to have any
wavelength selection is to avoid ex-
cessive noise owing to radiation from ATOMIC FLUORESCENCE
the atomic vapour.
I would also like to refer to our re-
cent work on the development of
atomic absorption and atomic fluo-
rescence methods for the direct anal- SYNCHRONOUS
ysis of solids (16, 17). The sample is DETECTION
made the cathode of a low-pressure SYSTEM
discharge, and the atomic vapour is
produced by cathodic sputtering. The
encouraging results obtained in the
analysis of low-alloy steels have re- OUTPUT
cently been published (17). In that SIGNAL
paper we reported the difficulties en-
countered when the method was ap-
plied to the analysis of aluminum- Figure 7. Schematic diagram of nondispersive atomic flame fluorescence
and zinc-base alloys. These difficul- spectrophotometer

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ties have now been overcome, a n d it
seems t h a t t h e sputtering technique
will be applicable t o t h e analysis of a
wide range of m e t a l s a n d alloys. It re­
m a i n s t o compare t h e performance
a n d range of these m e t h o d s with
those of other analytical techniques.
In t h e m e a n t i m e , I would not ex­
pect t h e scientific i n s t r u m e n t m a n u ­
facturers to be greatly interested in
the simple sputtering cell shown in
Figure 8.1 would, however, like t o
think t h a t some of t h e m are musing
on possible ways of embellishment t o
ensure t h a t any commercial version
will have a n impressive price tag.
We are now exploring t h e extension
of our work t o t h e v a c u u m ultraviolet
for t h e d e t e r m i n a t i o n of carbon,
phosphorus, a n d sulfur. W e also pro­
pose t o extend our experiments t o t h e
analysis of powders a n d solutions. W e
are increasingly conscious of t h e i m ­
p o r t a n t advantages of cathodic sput­ Figure 8. Photograph of atomic absorption spectrophotometer incorporating
tering over t h e r m a l m e t h o d s of a t o m - sputtering chamber for atomization of solid samples
ization in isotopic analysis. Finally, I
believe our recent work on cathodic
sputtering takes u s one step nearer
t h e goal I discussed in m y first paper
on atomic absorption spectroscopy,
the development of absolute methods
of spectrochemical analysis.
It would appear, therefore, t h a t t h e Alan Walsh is assistant chief of the ble, and inexpensive hollow-cathode
subject h a s not really been stagnant, Division of Chemical Physics, Com­ discharge lamps. He has published
b u t merely pregnant, a n d h a s now monwealth Scientific and Industrial over 60 papers in atomic, infrared,
given birth t o new offspring on which Research Organization (CSIRO), and Raman spectroscopy. Dr. Walsh
I t r u s t Bunsen a n d Kirchhoff will Melbourne, Australia. He received is currently interested in what he
look with approval a n d regard as wor­ his DSc from Manchester Univer­ considers the ultimate goal of spec-
thy descendants of their original sity in England. He is considered trochemical analysis, the develop­
brainchild. the "father" of atomic absorption ment of absolute methods. This inter­
spectroscopy and exhibited a com­ est has resulted in the development of
References plete apparatus for the technique in methods of atomization by using ca-
March 1954. His now classic paper thodic sputtering; and these, in turn,
(1) G. Dieke and H. M. Crosswhite, J. appeared in Spectrochimica Acta in have led to the development of reso­
Opt. Soc. Amer., 42, 433 (1952).
(2) Australian Patent Application 1955. He holds basic patents in Aus­ nance detection and selective modu­
23,041/53 (Nov. 17, 1953). tralia, the U.S., and other countries lation techniques. More recently, he
(3) Australian Patent Specification on atomic absorption spectroscopy, and his colleagues have adapted these
163,586 (Oct. 21, 1954). multiple monochromators, and im­ techniques to the development of
(4) A. Walsh, Spectrochim. Acta, 7, 108
(1955); Erratum, ibid., ρ 252. provements in grating monochroma­ atomic absorption and atomic fluo­
(5) C. T. J. Alkemade and J. M. W. Mi- tors. One of his major contributions rescence methods for the direct anal­
latz, Appl. Sci. Res., B4, 289 (1955). was the development of intense, sta- ysis of solid samples.
(6) J. P. Shelton and A. Walsh, Proc.
XVth Congress IUPAC, 2, TV-50, Lis­
bon, 1956.
(7) B. J. Russell, J. P. Shelton, and A.
Walsh, Spectrochim. Acta, 8, 317 (1957).
(8) J. E. Allan, Analyst, 83, 433 (1958).
(9) D.J.David, ibid., ρ 536.
(10) J. E. Allan, Spectrochim. Acta, 18,
605 (1962).
(11) A. Walsh, Proc. Xth Colloquium
Spectroscopicum Internationale, ρ 127,
Spartan Books, Washington, 1962.
(12) B. V. L'vov, Spectrochim. Acta, 17,
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(13) D. A. Segar and J. G. Gonzalez,
paper presented at Fourth International
Conference on Atomic Spectroscopy, To­
ronto, Canada, 1973.
(14) C. T. J. Alkemade, Proc. Xth Collo­
quium Spectroscopicum Internationale,
ρ 143, Spartan Books, Washington,
1962.
(15) J. D. Winefordner and T. J. Vickers,
Anal. Chem., 36, 161 (1964).
(16) Β. Μ. Gatehouse and A. Walsh,
Spectrochim. Acta, 16, 602 (I960).
(17) D. S. Gough, P. Hannaford, and A.
Walsh, ibid., B28, 197 (1973).

708 A • ANALYTICAL CHEMISTRY, VOL. 46, NO. 8, JULY 1974