Anal Bioanal Chem (2005) 381: 6971
DOI 10.1007/s00216-004-2891-8
TRENDS
Bernard Welz
High-resolution continuum source AAS:
the better way to perform atomic absorption spectrometry
Published online: 9 December 2004
Springer-Verlag 2004
The rst atomic absorption spectroscopes, designed by
Bunsen and Kirchho and a few others in the second
half of the nineteenth century, used a continuum source
since this was the only reliable light source available at
that time. This was undoubtedly also one of the main
reasons that optical emission spectroscopy (OES) was
preferred over atomic absorption spectroscopy (AAS)
during the rst half of the twentieth century, a period
when atomic spectroscopy was increasingly being used
for quantitative analysis. It is obviously much easier to
detect a weak emission signal in front of a dark back-
ground than a slight reduction in emission intensity over
a small spectral interval in front of a bright background.
For the same reason Walsh [1, 2] came to the conclusion
in 1952 that line sources (LS) with the sharpest possible
emission lines are required for measurements with AAS,
since a resolution of approximately 2 pm would be
necessary if a continuum source was to be used. This
conclusion resulted in half a century of LS AAS, with all
of its advantages and limitations.
However, the idea of using continuum sources (CS)
for AAS has never completely faded away, and in 1989
Hieftje [3] wrote ...for AAS to remain viable in the face
of strong competition from alternative techniques will
require novel instrumentation approaches. Among the
novel concepts that have been introduced are those
involving CS and high-resolution spectral-sorting de-
vices ... and entirely new detection approaches. Only a
decade later, the progress made in CS AAS caused
Harnly [4] to forecast the future appears bright for CS
AAS. Whereas previously, CS AAS was striving for
parity with LS AAS, it is now reasonable to state that it
is CS AAS, which is setting the standard. This forecast
was, at least in part, based on the pioneering article
B. Welz
Department of Chemistry,
Federal University of Santa Catarina (UFSC),
Florianopolis, SC, Brazil
E-mail: welz@qmc.ufsc.br, wbernard@matrix.com.br
published in 1996 by Heitmann et al. [5], in which the
entire concept of CS AAS was re-designed.
This breakthrough was possible only because the re-
search group working under Becker-Ross [6] systemati-
cally solved all of the problems that were associated with
this technique. Firstly, there was the notoriously weak
emission in the far UV below 250 nm from commer-
cially-available continuum radiation sources, such as
xenon arc lamps. This problem was solved by the
development of a xenon short-arc lamp that operates in
a hot-spot mode with a temperature of about 10,000 K,
which resulted in a signicantly higher radiation inten-
sity, particularly in the far UV. Secondly, a monochro-
mator had to be developed with a resolution >100,000
in order to provide a spectral bandwidth corresponding
to the half-width of atomic absorption lines. The very
compact design of the double monochromator, consist-
ing of a 300-mm prism pre-monochromator and a
400-mm echelle grating monochromator is shown sche-
matically in Fig. 1. Obviously, such a high-resolution
monochromator requires active wavelength stabiliza-
tion, which was accomplished via an internal neon lamp
that provides a precision better than 0.2 pm. Thirdly,
a linear CCD array with 512 pixels was chosen as the
detector, oering a whole series of new features.
This instrumental concept only really oers advan-
tages over LS AAS, as it eliminates most of its notorious
limitations.
First, as the instrument uses a CCD array with sev-
eral hundred pixels, each of which has an on-pixel
amplier, it is equipped with hundreds of independent
detectors (200 of which are typically used for analytical
purposes), which are all illuminated and read out
simultaneously. As only a few pixels are necessary to
measure atomic absorption, the rest of them are avail-
able for other purposes. The rst duty of these detectors
is to correct for all spectral events that occur simulta-
neously on all pixels, such as lamp icker noise and
changes in the transmission of the atomizer that are
independent of wavelength. This correction creates a
70

Fig. 1 Instrumental concept for

HR-CS AAS

kind of simultaneous double-beam system that results in possible, there is the option to store complete molecular
shot-noise-limited readout, so that the noise is inversely spectra in the software and subtract them from the
proportional to the square root of the integration time. measured spectrum using a least squares algorithm, so
Obviously, the system also corrects for any background that only the net atomic absorption signal is left. The
absorption that is continuous within the spectral win- eciency of this procedure has, for example, been
dow controlled by the detector. In addition, measure- demonstrated in the determination of arsenic and sele-
ment of atomic and background absorption is strictly nium in human urine [6], and of thallium in sediment
simultaneous so that even very high and rapidly samples [9].
changing background can be corrected without prob- Fourth, as a continuous radiation source is used in
lems [7]. HR-CS AAS, any line of the spectrum is available, and
Second, because of the much higher radiation inten- even molecular absorption lines can be used for
sity of the CS compared to conventional LS (at least 12 quantitative determination, as shown by Huang et al for
orders of magnitude), detection limits obtained with the determination of phosphorus at PO bands [10] and
HR-CS AAS are typically a factor of ve better than sulfur at CS bands using ame AAS. Many of these
those of LS AAS, whereby the improvement may vary rotational transitions have a half-width of only a few
from element to element. The sensitivity, which is in picometers, so they are of the same dimensions as atomic
AAS independent of the intensity of the radiation lines, making them highly suitable for HR-CS AAS
source, is essentially the same for both systems, and the
best sensitivity in HR-CS AAS is usually obtained when
three pixels are used for measurement, covering the line
core and the major part of the wings. On the other hand,
however, it is possible to reduce the sensitivity by using
the center pixel only, or pairs of pixels further away
from the center pixel, such as 2, 3, and so on to
measure the absorbance on the line wings only. In this
way several working curves of signicantly dierent
sensitivities can be established simultaneously, extending
the linear working range to 56 orders of magnitude.
Third, while in LS AAS only the absorbance (with
ame atomizers) or the absorbance over time (with
electrothermal atomizers) is measured, the CCD array
detector adds the wavelength as a third dimension in
HR-CS AAS, as shown in Fig. 2. This three-dimensional
imaging obviously enhances the information about the
spectral environment of the analytical line dramatically,
which is a particular advantage in the case of dynamic
signals, as they are produced in electrothermal atomiz-
ers. Potential spectral interferences due to other atomic
lines, and particularly due to electron excitation spectra
Fig. 2 Atomic and molecular absorption signals observed during
of diatomic molecules, which exhibit a pronounced ne the atomization of a marine sediment sample in the vicinity of the
structure, are now easily recognized and often avoided T1 resonance line at 276.787 nm using electrothermal atomization
by program optimization [8]. In cases where this is not and HR-CS AAS (from [9])

measurement. The authors reported detection limits in
the low milligram per liter range for both elements, and
a linear working range of more than three orders of
magnitude.
Finally, although simultaneous multi-element mea-
surement is not yet possible because of the limited
readout rates of currently-available CCD chips, partic-
ularly with the transient signals of electrothermal
atomizers, fast sequential measurements are possible
using ame atomizers. The double monochromator with
echelle grating in particular supports rapid wavelength
change, and the sequential approach has the clear
advantage that ame stoichiometry and observation
height can be adjusted automatically for each element,
avoiding compromised conditions, typical of the
simultaneous approach. The low noise level allows the
use of very short measurement times, making possible
the determination of at least 1015 elements per minute
under optimized conditions. This makes the system
compatible even with simultaneous ICP OES, at least for
a limited number of elements, as AAS burners do not
need any conditioning and washout time. This fast
sequential system obviously also allows the use of more
than one analytical line per element in order to increase
the working range, as well as the use of internal stan-
dards, making the time-consuming analyte addition
technique unnecessary.
It is obvious that HR-CS AAS will redene not only
AAS, but the entire atomic spectroscopy market, as it
71
combines the simplicity, ease of operation, relatively low
cost and freedom from the interferences found during
classical AAS with a number of features that have not
been available until now, or only with much more
sophisticated instrumentation. This is also only the
beginning of a new era, so we might expect a great deal
more with future instrumentation in this eld.
Acknowledgements The author is grateful to Coordenacao e
Aperfeicoamento de Pessoal de N vel Superior (CAPES) for a re-
search scholarship.
References
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(2004) Anal Chem (submitted)