An atomic-absorption speotrophotometer and its application to the

analysis of sohxtions

AI&~&--The con&u&ion of an &to~c-absorption s~eetruphotomet~r is described and its

performance is illustrated by resulbs obtained in applying the instrument;to the analysis of
solutions. The sample is sprayed into 8 flame and the absorption by the Xrttterof an atomic
reson~nu~line of the element to be estimated is measured, the apparatus being so arranged
that the absorption measurement in ind.ependentof any radiation err&tad by the flame. The
results confirm that, in contrast with the emission method, the sensitivity of the absorption
rn~t~~)~is independent of the excit~t~~~ potential of the spectral line used.

Ix 8 pm&u;3 paper [E] it wft;s shown, from a ~ons~d~rat~~~ of the ~he~~et~~a~

factors governing the relatio~lship between atomic absorption and atomic concen-
tration, that atomio absorption spectra provide a promising method of chemical
analysis with vital advantages over emission methods, particularly from the
viewpoint of absolute analysis, This paper describes an atomic ebsorption speetro-
photometer [2, 31 which has been constructed to test the practioal possibilities
of this method of analysis and to investigate some of the factors involved in
recording atomic absorptiorl ~~~~~~~rnents* The design adopted has been
determined to a large extent by the items of equipment, such as monochromators,
atomizers, etc., which were readily available for these experiments. Whilst this
apparatus has proved admirably suited for testing the prk~5ple uf the atomic
a~s~~~~~~~ method, it wiIf be apparent %hat it fs possible to use simpler and more
inexpensive forms of apparat‘us for varioius ana~~~~~a~problems.
There are two main fetltures in the design of the atcrmic absorption spectro-
photomater. In the first place, since it is practically impossible to design an
instrument which wil$ accurately record the profiles of atomic absorption lines
having half-widths of the order of 0.01 A, the approach adopted has been to
construct a series of light sources which emit atomic spectra of the various elements
under oonditions favouring tbs production of sharp lines having half-widths
of the same order, or less than, those of the ~o~es~ndil~g adsorption lines. The
absorption by the sample of these lines, which will usually bo resonance lines,
is a function of the profilea of the emission line of the source and the absorption
fine of the sample. Z the former can be considered as being inkitefy narrow
smeared to the absorpt~o~~ line, & measure of the peak abso~t~~n is obtained.
The second feature of the design is &he provision of compensation for the spectrum
 BARBARA 3. RUSSELL, J. P. SHELTON, tend A. WALSH

emitted by the sample. This is necessary, since the atomized sample will generally
emit at precisely the same w~velen~h as that at which the absorption measure-
ment is made.
The general arrangement of the apparatus is shown in Fig. 1. The operation
of the apparatus shown in Fig. 1 is as follows. The source emits a sharp atomic-
line spectrum of the element to be estimated and this emitted radiation is modu-
lated before it passes through the atomized sample. The monochromator isolates
a given spectrum line, which then falls on a photo-electric detector. The output
from the latter is passed to an amplifier tuned to the same frequency as the
modulator so that only the signal due to radiation from the source is amplified:
any radiation emitted by the atomized sample is not modulated and thus produces

Amplifier

Monochromotor

Fig. 1. Schematic diagram illustrating the principle of the

atomic absorption spectrophotometer.

no signal at the output of the amplifier. After recti~cation, the amplified signal
is passed to a recorder which indicates the signal with and without the absorbing
sample in the radiation path. Alternatively, a ratio recorder can be used in
conjunction with a double-beam method, so that per cent absorption is recorded
directly. The various components are shown in Figs. 2 and 3, and are discussed
below.
In Fig. 2 the console on the right contains (reading from bottom to top):
regulated power-supply for the hollow-cathode tubes which were used as atomic
line sources; Speedomax recorder converted to ratio recording; and a twin-channel
homodyne amplifier. The close-up of the optical system (Fig. 3) shows, reading
from right to left: hollow-cathode tube; beam splitter; twin-frequency modulator
and sector controlling the synchronous rectifiers; condensing lenses; atomizer
and burner; beam combiner; photo-mult~iplier; and monochromator.

(b) Atomic line source

Since the atomic line source used must not exhibit erratic fluctuations in
intensity, which would preclude accurate absorption measurements, it is not
possible to use any electrical discharge operating in an open atomsphere. Apart
from instability, such sources would also be unsatisfactory, since the lines would
be too broad and the resonance lines would certainly show some self-reversal,
Some form of enclosed discharge is essenGa1, and there are three main possibilities:
laboratory discharge lamps similar to the Wotan spectral lamps supplied by

318
 Fig. 2. Photograph of t&3 atomicd3s5rption 6~eetr5photometer.

Fig. 3. Photograph of the optical @y&em of the atomic absorption spectrophotometer

 An atomic-absorption spectrophotometer and its application to the analysis of solutions

Osram; high-frequency electrodeless discharge lamps; and hollow-cathode tubes.

Of the Wotan lamps, those containing sodium, potassium, thallium, rubidium,
and caesium are probably more convenient sources for these elements than any
other type of discharge. It is essential, however, to under-run the lamps, since
at the recommended operating currents the resonance lines exhibit self-reversal

Wavelength-

Fig. 4. Contour of Cd-3888-line 8, emitted by

Wotan lamp at recommended current.

and thus reduce the sensitivity of the absorption method. This is illustrated in
Fig. 4 which shows a microphotometer tracing of an echelle spectrum of the
2288-A line emitted by a Cd Wotan lamp operating at the recommended current.
Similarly, instead of operating the sodium lamp at a recommended current of
I.3 amp, it is necessary to decrease the current to 0.8 amp to remove self-reversal,
and although the manufacturers warn that such under-running may harm the
tube, we have not yet damaged any bulb. Whilst the zinc and cadmium lamps,
provided with silica envelopes to transmit the resonance lines at 2138 A and
2288 A respectively, may also be used as sources, they are not so satisfactory,
since even when they are under-run the lines are not nearly so narrow as those
provided by hollow-cathode tubes, and consequently the sensitivity of detection
is not so high. This type of lamp is, of course, limited to a restricted range of
elements having a low boiling-point.
High-frequency electrodeless discharge lamps of the type developed by
MEGGERS and WESTFALL [4] and others [5] would suffice for elements having
low boiling-points or which form volatile halides, but they require an expensive
power-pack, and our experience is that their light-output is not so constant as
that from hollow-cathode lamps.
The most suitable source for a wide range of elements is the hollow-cathode

319
 BARBARA J. RUSSELL, J. P. SHELTON, and A. WALSH

Glass
silica window

Fig. 5. Diagram of hollow-cathode tube with separate getter assembly.

Glossor
silica window

-Graded seal
or wax joint

Zirconium

Aa$
-Pyrex

Fig. 6. Diagram of hollow-cathode tube in which the getter and the anode are combined.

320
 An atomic-absorption spectrophotometer and its application to the analysis of solutions

discharge tube. Our early experiments involved the use of a closed gas-circulating
system, of the type described by TOLANSKY [6], for purification of the rare gas
filler. However, following the success of DIEKE [7, 81 and his co-workers in making
sealed-off iron hollow-cathode tubes, we have abandoned the gas-circulating system
and all our hollow-cathode tubes are of the sealed-off variety. Whereas these
workers used activated uranium as a getter and state that this is much more
effective than other methods of purification of rare gases, we have adopted the
suggestion of Dr. A. L. G. REES and made sealed-off tubes using zirconium as
a getter. Our general experience has been that the preparation of sealed-off
tubes presents little difficulty, and that any standard gettering technique is
satisfactory, provided the tube and electrode assembly is thoroughly outgassed
before sealing off the tube. Early forms of tube employed an electrode assembly
and a separate getter arrangement similar to that shown in Fig. 5. The anode
is made of nickel and the electrode assembly outgassed by induction heating
or by running the discharge in argon at currents up to 150 mA, according to
the material of the cathode. After several fillings and evacuations of the tube,
the latter is filled with spectroscopically pure argon and sealed. The getter,
consisting of zirconium wire, is then fired by passage of an electrical current
or by induction heating. Many of these tubes are now two years old and are
quite satisfactory, including some in which the quartz window is sealed on with
black wax.
Whilst the above design of hollow-cathode tube has proved quite satisfactory,
we believe the design given in Fig. 6 is preferable, although this design has only
been in use for a short time and in this respect cannot be regarded as having
been so fully tested as the original models. To date, however, all tubes of this
new design have been entirely satisfactory.
The basis of the design is to make the anode of zirconium (or tantalum) strip,
and this getter is fired simply by reversing the polarity of the discharge or by
induction heating. In this fashion it is possible to dispense with the separate
getter and the construction of the tube then becomes extremely simple.
The cathode may be open at both ends or have one end sealed with a plug
of t,he metal whose spectrum is required. For low melting-point metals such as
cadmium and lead, it is sufficient to place a pellet of the metal in the cathode,
which can be made of any suitable metal, but preferably one such as aluminium,
which has a simple spectrum. The tube is then used in a vertical position.
Operating currents for the tubes vary from 5 to 100 mA, and should be as small
as possible consistent with a satisfactory signal/noise ratio. This is particularly
essential for tubes of the low-melting-point metals, which, even at current as
low as 10 mA, produce sufficient vapour to cause appreciable resonance broadening.
The tubes are operated from a regulated d.c. supply giving 600 V and currents
up to 150 mA.

(c) #prayer
Our work to date has been restricted to the analysis of solutions, and these
have been atomized by spraying into the air supply of a Meker burner operating
on air and coal-gas. The sprayer is similar to that used in early types of

391
 BAIZBARA J. RUSSELL, J. P. SEEELTON, and A. WALSH

Perkin-Elmer flame photometers and the flame has a diameter of 2 cm at the base.
A rate of flow of 1850 c.c./min of gas and 8200 c.c./min of air was found to provide
a convenient flame. The consumption of solution is then 0.2-0.3 c.o./min. This
type of flame is suitable for many elements, but it is not hot enough to atomize
elements such as aluminum, silicon, and hafnium, which form refractory com-
pounds, and these are not decomposed in the flame.
It may be noted that if the flame is strongly emitting, then it is important
that it be placed before the monochromator so that the emitted light is dispersed
before falling on the detector. Otherwise, although the emitted light will give
no resultant d.c. signal, it will give rise to noise which will lower the accuracy
of the absorption measurement.

(d) &.?onochromator
The required resonance line has been isolated from all other lines by means
of a Beckman monochromator which is mounted so that the entrance slit is
horizontal, The resolution is adequate for many elements, but for those such
as iron and nickel, which have complex spectra, a slightly higher dispersion is
desirable to facilitate isolation of the desired line. If lines other than the resonance
line are transmitted by the monochromator, there will obviously be a loss in
sensitivity, since only a portion of the signal will be attenuated by passage of
the beam through the flame. For many analyses the monochromator can be
replaced by an appropriate filter, or by an a~angement similar to that used by
ALKIGMADEand MILATZ [9] for the analysis of sodium.

(e) Detector
The detector in the ultra-violet and visible is a RCA. IP28 photomultiplier
tube operated from a regulated supply. A sodium salicylate film deposited on
the window of the photomultiplier permits satisfactory recording of lines below
2500 a down to the zinc line at 2138 A. For caesium and rubidium with resonance
lines in the near infrared a red-sensitive IP22 photomultiplier tube has been
used.

(f) AmpZijZer
It was originally assumed that some form of double-beam method would
be necessary in order to compensate for variations in the light output from the
hollow-cathode tubes. It has been found, however, that when the tubes are
operated from stabilized supplies, the light output is highly stable and single-
beam operation is perfectly satisfactory, provided t,he photomultiplier also is
operated from a regulated supply. consequently, double-beam working is not
essential but is valuable if rapid analysis is required, and obviates the necessity
for regulated supplies.
We have followed OBERLEY’S [IO] method of phase discrimination in which
the sample signal is chopped at frequency f (in our case 93 c/s) and the reference
signal at frequency 2f (186 c/s), the 8.0. signals being amplified and then rectified
by synchronous rectifiers operating at the co~esponding frequencies. Rectifi-
cation is controlled by interrupting the light falling on a photo-cell using the

322
 An atomic-qbsorption spectrophotomneterand its application to the analysis of solutions

rotating sector shown in Fig. 3. The ratio of the two d.c. signals is then measured
on a Speedomax Type-G recorder which has been converted to ratio recording.
This measurement is quite satisfactory provided that the amplifier or dynode
voltage is adjusted so that the d.c. signal from the reference beam is approximately
10 mV.
Whilst this method of double-beam operation has proved very satisfactory,
it is not claimed that it is better than other well-known methods for this purpose.
The selection of this particular method ‘was determined by the fact that it is
wished to use the same system in a double-pass ozone spectrophotometer, for
which this two-frequency method has decided advantages over other methods.
It may be noted that in one respect the design of double-beam systems for use
in atomic-absorptiofi spectrophotometers is much simpler than when recording
spectra using a, source which emits a continuous spectrum, since with atomic
spectra the spectral slit-width of the monochromator is greater than the line-
width and thus matching of the two beams in the monochromator is not nearly
so important.

2. Application of the atomic absorption spectrophotometer

to the analysis of solutions
Ia) Comparison of peak absorption with oscillator strength
The work to date has been restricted to solutions, and no attempt has been
made to develop the method for application to any specific analytical problem.
The main aim of the work has been to investigate some of the factors involved
in the recording of atomic absorption measurements in terms of peak absorption
and to assess the possibilities of absolute analysis. We have therefore confined
most of our investigations to those elements for which the oscillator strengths
of the resonance lines are known. In this connection it may be noted that measure-
ment or calculation of oscillator strengths is by no means simple and the values
obtained are therefore not highly accurate, as witnessed by the discrepancies
between the results of various workers.
To test the absorption method we have taken measurements on aqueous
solutions containing salts of different elements and compared the peak absorption
measurements with the known oscillator strengths (see equation 8, ref. 1). By
using the oscillator strength of the strongest resonance line of copper as the
reference, the oscillator strengths of the resonance lines of other elements have
been determined from the measurements of peak absorption. The results of
this comparison are shown in Table 1, in which the oscillator strengths, expressed
as f-values, indicate the extent to which the atom, for the line concerned, behaves
as a classical oscillator for which f = 1.
It will be seen that the agreement between these values and those obtained
by other methods, whilst by no means perfect, is extremely encouraging. It
means that if the instrument is calibrated for one element, then it is also approxi-
mately calibrated for the other elements listed. In this respect we believe that
the absorption method, even in its present form, represents a significant advance
on any emission method.

323
 BARBARA J. RL-SSELL. J. P. SHELTON, and A. Waum

Table 1. Relative f-values measured on atomic absorption spectrophotometer

I
Resonance f I f
line , (preview work) / (atomic absorption)

-__. _ _..... __..-__ I

_ _._ ..___-.. __

Cu.3247 0.62 O-62

x$3-2852 1.74 1.8
Na-5890 I 0.70 1.0
K-7865 0.64 0.5
Cd-2288 1.20 2.8
TI-2769 0.20 0.15
211-2138 - 1.9
Ag-3280 - 1.3
Au-2428 - 0.8
3%3720 .013 0.01
Xi-3415 0.02 0.04
Cr.4254 0.08 0.01

At this stage in the development of the absorption method there are various
reasons why perfect correlation between our measurements of peak absorption
and oscillator strength is not to be expected. In the first place, the unjustifiable
assumption has been made that the shape of the absorption line is the Doppler
contour, whereas it is known that, there will be a pressure-broadening width,
of the order of the Doppler width, and this broadening will be different for the
lines of the various elements. Similarly, t.he widths of the lines emitted by the
hollow-cathode lamps are not known, and it is necessary to establish that this
width is negligible compared to the width of the absorption line. Fortunately,
it is possible to obtain some indication whether this is so by making absorption
measurements with the hollow-cathode t,ube operating at different currents.
For high-melting-point metals such as iron, chromium, and nickel, the peak
absorption is sensibly independent of the tube current, and this suggests that
the emitted line must be much narrower than the absorption line. For low-
melting-point metals such as cadmium and zinc, on the ot.her hand, the absorption
varies rapidly wibh current. This is shown in Fig. 7, which gives calibration
curves for cadmium wit.h the hollow cathode operated at various currents. It
will be seen that at lower currents t,here is a marked increase in absorption, which
must, be due to a decrease in the width of the line emitted. It would, of course,
be quite possible to extrapolate the resu1t.s to zero current, and this may prove
desirable in absolute ana.lysis. It may also be not.ed that in those cases where
the absorption varies rapidly with current in the light source, it is important
to operate the source from a well-regulated supply.

(b) Sensitivily
The limit of sensitivity of the method depends on various factors such as
the oscillator strength of the line involved, the intensity of the line emitted by
the source, and the spectral slit-width required to isolate the required line.

324
 An atomic-absorption spectrophotometer and its application to the analysis of solutions

I
--

Concentmticn p.p.m.

Fig. 7. Calibration curves for cadmium for different currents in the hollow-cathode tube.

-Rb(W)V3A

;; ‘3” ;t A

-Fd30 f?lA
50 60 70 80 90 1C 3
Concentration p.p.m.

Fig. 8. Cnlibration ~UI‘VRRfor various clcmcnts.

325
 B.QU%ARA J. RTBSELL, 3. P. Saa~mx, and A. WAWH

~nse~uently, it is diB3cult to give any pxweiseSgures for sensitivity. fzowewx,

in T&k 2 we given OUT~~~~~~~~~~which it is believed are ~onse~ati~e, for the
elements studied. Those marked with an asterisk indicate that Usram lemps
were used as source. For all other elements the sources were hollow-eath~e
tubes. The calibr&ion curves are shown in Fig 8. These curves are linear over
a limited concentration range. The tail-off is presumably clue to pressure-
broadening.
Table 2. Limits af detaction

Possibly thtJmost interesting result is the confirmation of the expected result

that elements suoh as zinc and cadmium, with resonance lines in the extreme
ultra-violet, have the same order of sensitivity as sodium with its resoaanoe
line at the long-wave end of the visible spectrum. This is in marked contrast
to emission spectra, where the limit of detection depends critically on the excite-
tion energy of the Grst resonance level. Thus in emission, zinc, for example,
has a much lower sensitivity than sodium. This is because a flame is not hot
enough to excite an appreciable proportion of zinc atoms, In absorption, on
the other hand, where we are concerned only with the atoms in the ground state,
this is of no o~~s~~uen~e~ and in this respect the absorption measu~rn~~t is
independent of the wave~en~h of the resonance line. There is, of course, a much
smaller effect due to the variation in the Doppler width of the absorption line.
It may be noted that the sensitivity for rubidium and caesium is not nearly
so high as for sodium. This is due to the faot that the resonance lines emitted
by the rubidium and eaesium lamps are self-reversed at the lowest current (1 A)
which can be ueod in order to obtain a satisfactory signal-noise ratio.
The sensitivities quoted in Table 2 are for a! single passage of the radiation
through the flame. It is possible to achieve higher sensitivities by multiple
traversals. For example, using a J. II. White system to give twelve traversals,

326
 An atomic-absorption spectrophotometer and its application t.o the analysis of solutions

we have obtained an increase in sensitivity of approximately tenfold. The effect

of increasing pathlength on sensitivity is shown by the iron calibration curves
in Fig. 9.

Concentrotior wm.
Fig. 9. Calibration curves using multiple traversals of the flame.

(c) Limitations
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.
For example, highly oxidizable elements such as aluminium, silicon, hafnium,
etc. are not atomized in the air-coal-gas flame used in this work and t,hus are
not detectable in absorption. Similarly, many other elements will not bc com-
pletely atomized, thus decreasing the sensitivity and providing a serious obstacle
to accurate absolute analysis. In this respect the cyanogen-oxygen flame, having
a temperature of about 46OO”C, which has recently been applied by BAKER and
VALLEE [l l] to emission methods, may prove to be extremely valuable. This
problem of complete atomization of the sample seems to us to be the outstanding
problem at the present time.

Acknowledgement-We are grateful to Mr. W. C. JOXES for the construction of all

hollow-cathode tubes used in this work.

References
l] WALSH A. Spectrochim. Acta 1955 7 108.
j2] Handbook of Third Exhibition of Institute of Phy8ic8 Melbourne, March 1954.
31 Patent Specific&ions: Australia, Provisional Spec. 12041/1953; Complete 23041/53;
Great Britain 33,068/54; USA 469,221; France 679,886; Cormany Cl0276 IXb/421;
Holland 192,460; Italy 82/322; Sweden 10436/64.

327
 BARBARA J. RUSSELL,J. P. SHELTON,and A. WALSH

[4]MEGCERS W.F.and WESTFALL F. O.J. Res.Nat. Bur.Stundards 195044 447.

[5]ZELIKOFFM., WYCKOFF P.H., ASCHENBRANDL.M.,andLoo~~sR. S.J.Opt.Soc.Amer.
195242 818.
[6]TOLANSKY S.High Resolution Spectroscopy 1947Methuen,London.
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328