Atomic Absorption Spectrometry

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Current Status of Direct Solid Sampling for Electrothermal Atomic

Absorption Spectrometry—A Critical Review of the Development between
1995 and 2005
Maria Goreti R. Valea; Nédio Oleszczuka; Walter N. L. dos Santosb
a
Instituto de Química, Universidade Federal do Rio Grande do Sul, Porto Alegre, RS, Brazil b Campus
Prof. Soane Nazaré de Andrade, Universidade Estadual de Santa Cruz, Rodovia Ilhéus-Itabuna, BA,
Brazil
To cite this Article Vale, Maria Goreti R. , Oleszczuk, Nédio and Santos, Walter N. L. dos(2006) 'Current Status of Direct
Solid Sampling for Electrothermal Atomic Absorption Spectrometry—A Critical Review of the Development between
1995 and 2005', Applied Spectroscopy Reviews, 41: 4, 377 — 400
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Applied Spectroscopy Reviews, 41: 377–400, 2006
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DOI: 10.1080/05704920600726167
Current Status of Direct Solid Sampling

for Electrothermal Atomic Absorption
Spectrometry—A Critical Review of the
Development between 1995 and 2005
Downloaded By: [PERI - Tanzania] At: 09:39 22 March 2011
Maria Goreti R. Vale and Nédio Oleszczuk

Instituto de Quı́mica, Universidade Federal do Rio Grande do Sul,
Porto Alegre, RS, Brazil
Walter N. L. dos Santos

Universidade Estadual de Santa Cruz, Campus Prof. Soane Nazaré de
Andrade, Rodovia Ilhéus-Itabuna, BA, Brazil
Abstract: The literature about direct solid sampling (SS) and slurry sampling atomic
absorption spectrometry (AAS) over the past decade has been surveyed critically. It
became apparent that a very significant change had occurred, particularly in the
relation between the two major techniques used for that purpose. In the 1990s, slurry
sampling was typically considered the technique of choice, combining the significant
advantages of the solid and the liquid sampling methods, at least in part because of
the availability of a commercial accessory for automatic slurry sampling. The
situation is completely inverted now, as the above accessory has been discontinued
and rugged and reliable accessories for direct SS became available. Direct SS electro-
thermal (ET) AAS has been shown to provide the best limits of detection because of the
absence of any dilution and a minimal risk of contamination. Calibration against
aqueous standards appears to be feasible after careful program optimization. The
absence of any significant sample handling makes SS ET AAS ideally suited for fast
screening analyses. The introduction of high-resolution continuum source AAS
appears to open additional attractive features for SS ET AAS because of the signifi-
cantly simplified optimization of furnace programs and the visibility of the spectral
environment, which makes it easy to avoid spectral interferences. New calibration
Received 12 December 2005, Accepted 1 February 2006

Address correspondence to Maria Goreti R. Vale, Instituto de Quı́mica, Universi-
dade Federal do Rio Grande do Sul, Av. Bento Gonçalves, 9500, 91501-970,
Porto Alegre, RS, Brazil. E-mail: mgrvale@iq.ufrgs.br
377
378 M. G. R. Vale, N. Oleszczuk, and W. N. L. dos Santos
strategies make a “dilution” of samples unnecessary, which used to be one of the major
limitations of SS ET AAS. Finally, direct SS analysis is an important contribution to
clean chemistry, as practically no reagents are used.
Keywords: Solid sampling, slurry sampling, electrothermal atomic absorption spec-

trometry, high-resolution continuum source atomic absorption spectrometry, clean
chemistry
INTRODUCTION
The atomic absorption spectrometry (AAS), as it has been proposed for chemical
analysis by Walsh in 1955 (1) was intended for solution analysis, using a
pneumatic nebulizer; a spray chamber, where the sample aerosol was mixed
with the oxidant and fuel gas; and a laminar flame for atomization. The use of
solutions for chemical analysis undoubtedly has a number of distinct advantages.
Solutions are easy to handle with conventional laboratory equipment, they can
readily be diluted to bring the analyte concentration within the optimum
working range, and the addition of buffers, releasers, and other reagents is
straightforward. The introduction of solutions into all kinds of atomizers can
easily be automated, and to bring a sample into solution is obviously the most
efficient way of homogenization, resulting in excellent repeatability and
precision. However, sample preparation for solution analysis is usually labor
intensive and time consuming, and it is the major source of errors (2), mostly
due to analyte loss and/or contamination. Sample digestion might also
include health hazards for the laboratory personnel, and it usually produces a
lot of corrosive and/or toxic waste. Last but not least, any digestion or dissol-
ution is inevitably associated with a dilution of the analyte content, making
solution analysis not necessarily suitable for determination of the lowest trace
concentrations. Direct solid sample analysis has therefore always been investi-
gated as an alternative in order to avoid the above limitations.
Two of the three sample introduction and atomization techniques
routinely used in AAS, i.e., the flame technique and chemical vapor generation
(CVG) are not particularly suited for solid sample analysis for different
reasons. Conventional nebulizers can handle suspended solids only in excep-
tional cases without a high risk of clogging, and the flames used in AAS are
only capable of vaporizing extremely small particles, as the time available
for atomization is of the order of a few milliseconds, and the temperatures
are only between 2250 and 27008C. The few successful attempts for the
analysis of slurries (3 – 5) or the direct analysis of solid samples (6 – 9) using
flame atomization require specially designed accessories that are not commer-
cially available, limiting these approaches to research.
The application of slurry sampling has been tried for both CVG AAS
techniques, the cold vapor (CV) generation of mercury (10, 11) and hydride
generation (HG) AAS (12 –14), and more recently also with inductively
Direct Solid Sampling—A Review 379
coupled plasma optical emission spectrometric (ICP OES) and mass spectro-
metric (ICP-MS) detection (15 –19). However, at least for mercury, it has been
shown that complete extraction of the analyte into the liquid phase is a pre-
requirement for CV AAS from slurries; i.e., this cannot really be considered
solid sample analysis. An additional problem arises for HG AAS, as it is
well known that for Group V elements (As, Sb, Bi) the oxidation state þ5
reacts much slower and results in lower sensitivity than the oxidation state
þ3, and for the Group VI elements (Se, Te) only the oxidation state þ4 is
forming a hydride. In addition, most of the hydride forming elements are
often present in biological and environmental materials as stable organic
compounds, which do not form hydrides, and require harsh digestion con-
ditions to be converted to the inorganic form. All this is obviously a source
of error in slurry sampling CVG techniques, as no pre-reduction or harsh
digestion is involved in solid sample analysis. These techniques will

therefore no longer be considered here.
This means that there remains electrothermal (ET) AAS with graphite
furnace (GF) atomization as the only technique to be considered for solid
sample analysis with AAS. Direct solid sample analysis was actually the
first application reported for ET AAS (20) back in 1957, when L’vov put a
“pinch of NaCl” into a graphite furnace that was standing unused in a corner
of his laboratory and watched how the radiation of a sodium lamp, passing
through the furnace, disappeared upon heating the furnace. Solid sampling
(SS) analysis has been used ever since in ET AAS (21), as graphite furnaces
allow a relatively easy introduction of solid samples, and the atomization
times are some three orders of magnitude longer than in typical flames,
making possible complete vaporization and atomization of even relatively
large amounts of sample. However, in spite of the obvious advantages of
direct SS analysis, which are a significantly reduced sample preparation time
and hence a faster analysis; higher accuracy, as errors due to analyte loss
and/or contamination are dramatically reduced; higher sensitivity due to the
absence of any dilution; and the absence of any corrosive or toxic waste, the
method has not been really accepted until the end of the 20th century. The
major arguments against direct SS analysis using ET AAS have been (a) the
difficulty of handling and introducing the small sample mass, although a
wide variety of tools has been developed for that purpose (22); (b) the difficulty
of calibrating, which usually requires solid standards of similar composition
and analyte content compared to the samples to be analyzed; (c) the limited
linear working range of AAS and the difficulty of diluting solid samples;
and (d) the high imprecision of the results due to the inhomogeneity of
natural samples, which requires a large number of repetitive determinations.
Slurry sampling ET AAS, in contrast to direct solid sampling, has been
accepted much earlier as an alternative technique for sample introduction,
mostly because of the availability of a commercial autosampler, the USS-
100 (Perkin Elmer) for that technique (23). It therefore appears worthwhile
to compare these two approaches regarding their pros and cons.
SLURRY VS. SOLID SAMPLING ET AAS
The book of Kurfürst (22) summarizes the literature about solid and slurry
sampling up to the mid 90s, and Cal-Prieto et al. (24) published a review of
the literature about slurry sampling for ET AAS from 1990 to 2000, so that
only the most important aspects and recent development have to be considered
here. The breakthrough of slurry sampling ET AAS clearly came with the
introduction of the above-mentioned commercial equipment (23) that was
based on extensive research work done by Miller-Ihli (25), and which
consisted of a modified furnace autosampler, in which the slurries were hom-
ogenized by an ultrasonic probe immediately before their transfer to the
graphite tube. In a review article about solid sampling in ET AAS, which
covers the literature up to 1990, Bendicho and de Loos-Vollebregt (26)
came to the conclusion that “the slurry technique gives better analytical per-
formance than direct solid sampling”. This judgment was based on the facts
that (a) the slurry concentration can be easily changed so that the analyte con-
centration falls into the analytically useful range of the calibration graph; (b)
chemical modification is easier to perform in the slurry technique, because of
more effective contact between the sample particles and the modifier, and (c)
slurry introduction can be easily automated, hence combining the significant
advantages of the solid and liquid sampling methods. This latter sentence
has ever since been repeated in almost all publications about slurry
sampling without considering potential progress in the field of SS that
might relativize this statement.
One of the major problems of the slurry technique, which has already
been recognized by Bendicho and de Loos-Vollebregt (26), is the stabilization
of the slurries during the time until they are finally introduced into the graphite
atomizer. Although various techniques have been proposed for homogeniz-
ation of slurries, including the ultrasonic probe that is used in the USS-100,
particle size distribution, specific gravity of the sample, sampling depth, and
other factors were found to have an influence on the accuracy of the results
(27). Several authors have been investigating problems associated with
grinding time, particle size, and sedimentation errors (28 –31), and a
particle size ,37 mm appears to be necessary to obtain accurate results, at
least in the case of high-density materials. In contrast to sedimentation,
flotage of light and finely ground material, such as biological samples or
coal, on the surface has also been reported as a potential problem, which
requires the addition of a surfactant, such as Triton X-100 (30).
Another very important factor in slurry analysis is the quantity of analyte
that is extracted into the liquid phase, i.e., solubilized, during slurry prepara-
tion, which depends on the analyte, the matrix, the liquid phase, and the slurry
preparation conditions, and which can be between 0 and 100% (32 – 34).
Analytes are usually much more easily extracted from biological than
from inorganic materials, and 100% extraction of Cd, Cu, Mn, and Pb has
for example been reported using 1 mol L21 nitric acid and ultrasonic
agitation (35). Usually, a high extraction rate is considered advantageous, so

that various authors have been using very high acid concentrations, including
concentrated hydrofluoric acid for slurry preparation of environmental
samples, such as fly ash, soil, and sediment (36 – 40), which obviously
results in a similar corrosive waste problem as with conventional sample
digestion. Cal-Prieto et al. (34) developed an analytical scheme for the deter-
mination of antimony in geological materials using slurry sampling ET AAS,
an element, for which the extraction rate to the liquid phase was negligible.
They found that the normalized absorbance remained constant up to a
sample mass of 50 mg mL21, which corresponds to a sample mass of 1 mg
in a 20-mL aliquot injected into the furnace. This corresponds to a typical
sample mass used also for direct SS, as will be discussed later. Normally,
however, significantly smaller sample aliquots are used for slurry sampling.
The same authors (34) also determined the minimum number of particles
that should be introduced into the graphite tube in order to ensure the repre-
sentativeness of the aliquot for the sample to be analyzed, and they
concluded that a minimum of 50 particles have to be introduced. This deter-
mines the limits of the dilution that can be applied in order to determine
higher analyte concentrations. This limit, similar to other problems such as
sedimentation, obviously depends on the quantity of analyte extracted to the
liquid phase, and disappears in the case of 100% extraction. Miller-Ihli (32)
has therefore introduced the term “representative sample mass”, which
takes analyte extraction into consideration. On the other hand, analyte extrac-
tion can also become a source of errors, as has been shown by Maia et al. (41)
for the determination of Tl in marine sediment samples. Due to the presence of
co-extracted chloride in the aqueous phase, extracted and added thallium was
lost at pyrolysis temperatures above 4008C as volatile TlCl, whereas the non-
extracted thallium was stable up to 9008C. Although the determination was
made with ICP-MS in this case, the reactions in the graphite furnace are
obviously independent of the detection system. This potentially different
behavior of the analyte in the liquid and in the solid phase has to be taken
into account as potential source of error particularly in cases where the
analyte addition technique is used to correct for differences in sensitivity
between the slurry and calibration solutions (34, 38). All these problems of
sedimentation, extraction and distribution of the analyte between two
phases are obviously non-existent in the case of direct SS analysis.
DIRECT SOLID SAMPLING ANALYSIS USING LINE SOURCE

ET AAS
The situation regarding the commercial availability of equipment for slurry

and direct SS has changed completely within the last decade. Firstly, there
has been the ongoing effort of Krivan and co-workers at the Department of
Analytical Chemistry and Maximum Purification at the University of Ulm,
Germany, to improve existing equipment for direct SS analysis (42, 43). The
accessory he developed, which included a pair of tweezers for the reproduci-
ble introduction of a graphite platform containing the solid sample into the
graphite tube has been further tested (44, 45) and introduced as a commercial
device in the late 1990s. Nowadays, the second generation of this solid
sampling accessory is available both in a rugged and inexpensive manual,
as well as in a fully automatic version, as shown in Figures 1a and 1b. In
the automatic version, the graphite platform with the solid sample is trans-
ferred first to an integrated micro-balance, and then into the graphite tube,
and the software automatically calculates the integrated absorbance normal-
ized for a sample mass of 1 mg. The second event was the discontinuation
of the USS-100, the only commercially available autosampler for slurry
sampling, which obviously completely inverted the situation comparing
slurry and direct SS ET AAS, and also the conclusion, at which Bendicho
and de Loos-Vollebregt (26) had arrived some 15 years ago. It is therefore
time to reconsider the relation between the two approaches based on recent
research and advances in that field.
Figure 1. Accessories for direct SS ET AAS; (a) manual system SSA 5, consisting of
a pre-adjusted pair of tweezers for reproducible insertion of the SS platform; (b) SS
autosampler SSA 62 for automatic transfer of up to 62 SS platforms to a microbalance
and into the graphite furnace (by courtesy of Analytik Jena AG, Jena, Germany).
(continued)
Figure 1. Continued.
Table 1 gives an overview over a number of representative publications in

the field of direct SS ET AAS over the last decade, as the earlier literature is
fully covered in the book of Kurfürst (22). The survey shows that a great
number of elements have been determined in a wide variety of organic and
inorganic matrices, including high-purity metals and metal oxides and
plastic materials. Even natural waters have been analyzed, co-precipitating
Cr with Pd/8-quinolonol/tannic acid (46) or As with Ni –ammonium pyrroli-
dine dithiocarbamate complex (47), analyzing the precipitate directly in order
to avoid dilution and potential errors in the dissolution step. One of the
most important contributions in the field of direct SS analysis undoubtedly
came from Krivan and co-workers (42, 43, 48 – 52) who showed in an
impressive number of publications that SS ET AAS, at least in the analysis
of high-purity materials, always gave the best limits of detection (LOD),
even compared to much more sophisticated techniques, such as neutron
activation analysis (NAA), ICP-MS, isotope dilution mass spectrometry
(IDMS), and others.
The advantage of direct SS ET AAS is most obvious for materials that are
very difficult to be brought into solution and for elements that are kind of
omnipresent, and hence most susceptible to contamination. Friese and
Krivan (43) determined seven trace elements in high-purity tantalum
powders using a sample mass up to 60 mg and aqueous standards for
384
Table 1. Selected publications about direct solid sampling ET AAS using LS AAS, covering the period 1995– 2005
Background
Analyte Matrix correction Calibration Modifier LODa Remarks Reference
Bi, Pb, Se, Nickel-based alloys Zeeman-effect Aqueous Ni n.a.b Single-alloy chips (58)
Te, Tl standards
Cr Biological samples n.a. Addition None n.a. Comparison of (64)
calibration calibration
Cu, K, Mg, Mn, Molybdenum metal, Deuterium Aqueous None 0.06 –0.5 ng g21 Up to 80-mg sample (48)
M. G. R. Vale, N. Oleszczuk, and W. N. L. dos Santos

Na, Zn molybdenum silicide standards 0.5 –4.5 ng g21 introduced
Cd Kidney, liver Zeeman-effect Aqueous None n.a. Wet animal tissue (62)
standards
Cd, Cr, Mn, Pb Biological samples Deuterium Aqueous Pd (Cd only) n.a. Trace element (63)
standards distributions
Cu, Fe, Mn, Na, Zn High-purity tantalum Zeeman-effect Aqueous None 0.1 –27 ng g21 Up to 40-mg sample (42)
powder standards introduced
Cu, Fe, K, Mn, Na, High-purity tantalum Deuterium Aqueous None 0.02 –4 ng g21 Transversely heated (43)
Zn powder standards atomizer
Ca, Co, Cr, Cu, Fe, High-purity tungsten Deuterium Aqueous None 0.01 –4 ng g21 Up to 100-mg sample (49)
K, Mg, Mn, Na, standards introduced
Ni, Zn
Co, Cr, Cu, Fe, K, High-purity aluminium Deuterium Aqueous None 0.25 –25 ng g21 (83)
Mg, Mn, Ni, Zn oxide standards
Al, As, Ca, Co, Cr, High-purity titanium Deuterium Aqueous Carbon 0.02 –30 ng g21 Single pieces of (50)
Cu, Fe, K, Mg, standards powder metal; up to 30-mg
Mn, Na, Ni, Pb, sample introduced
Sn, Zn
Sb PVC Deuterium Aqueous Pd n.a. Screening method (59)
standards
Direct Solid Sampling—A Review

As, Cd, Co, Cr, Barytes Deuterium Solid HNO3 (for n.a. (45)
Ni, Pb, V standards Cr, Ni, V)
Cd, Sn Sewage sludge PVC Deuterium Aqueous Pd or PO4 n.a. (60)
standards
Ca, Co, Cr, Cu, Fe, High-purity tungsten Deuterium Aqueous H2 gas during 0.07 –2 ng g21 Up to 70 mg sample (51)
K, Mg, Mn, Na, trioxide and tungsten standards pyrolysis 0.01 –1.7 ng g21 introduced
Ni, Zn blue oxide
Cr Natural waters Deuterium Aqueous None 20 ng L21 Coprecipitation with (46)
standards Pd/8-quinolinol/
tannic acid
Cu, Pb Sewage sludge Deuterium Aqueous None n.a. Gas flow during (54)
standards atomization
P Plastic materials Deuterium Aqueous Pd þ ascorbic 2.5 mg g21 (61)
standards acid
Si Niobium, titanium, Deuterium Aqueous CH4 gas 10 ng g21 3 – 15 mg sample (52)
zirconium oxides standards during introduced
pyrolysis
Cd, Cu, Pb Mineral coal Deuterium Solid Ru 3 – 40 ng g21 Permanent modifier (71)
standards permanent for solid sampling
Tl River and marine Zeeman-effect Aqueous Ru perm. þ 20 ng g21 Permanent modifier (69)
sediments standards NH4NO3 for solid sampling
Hg Environmental Deuterium Aqueous Pd permanent 200 ng g21 KMnO4 added to (72)
materials standards stabilize Hg in
aqueous solutions
As Sediment Deuterium Aqueous None 440 ng g21 Residues from leach- (84)
standards ing processes
385
(continued )
386
Table 1. Continued
Background
Analyte Matrix correction Calibration Modifier LODa Remarks Reference
Fe Rice plants Deuterium Aqueous None 0.14 ng at Micro samples (85)

standards 302.1 nm
Co, Zn Vitamin complex, Deuterium Aqueous None Co: 0.5 mg g21 Gas flow during ato- (55)
agricultural soil standards Zn: 4 mg g21 mization 307.6 nm

line for Zn
As(III), As(V) Sea water Deuterium Aqueous None 20 ng L21 Co-precipitation with (47)
standards Ni-PDC complex
Si Polyamide Deuterium Aqueous Pt 0.1 mg g21 (75)
standards
Cr Milk powder, lobster n.a. Aqueous None 2 ng g21 LOD better than with (86)
hepatopancreas, standards SS-ETV-ICP-MS
polyethylene,
sewage sludge
Mn Vitamin-mineral Deuterium Aqueous None n.a. Comparison of cali- (65)
tablets standards bration techniques
P Food samples Deuterium Aqueous Pd þ Ca 18 ng (87)
standards
Cu, Zn Bovine liver Zeeman-effect Aqueous Zn: W þ Rh Cu: 1.6 ng Zn: Cu: 216.5 nm Zn: (56)
standards 1.3 ng 307.6 nm Micro-
homogeneity study
a
LOD ¼ limit of detection.
b
n.a. ¼ not available.
calibration with detection limits of 4.0, 0.16, and 0.02 ng g21 for Fe, Na, and
Zn; i.e., elements that are known to be extremely sensitive to contamination.
Doc̆ekal and Krivan (48) reported similar detection limits for the same
elements in high-purity molybdenum metal and molybdenum silicide
powders. Huang and Krivan (52) determined silicon, another element that is
extremely susceptible to contamination, in niobium, titanium, and
zirconium oxides with a detection limit around 10 ng g21, again using
aqueous standards for calibration. The most decisive contribution to this
success obviously came from the fact that no reagents at all were used, or
reagents that did not contribute any blank signal. Hornung and Krivan
(49, 51) for example used hydrogen as alternate gas in the pyrolysis stage
for the analysis of high-purity tungsten, tungsten trioxide and tungsten blue
oxide, Huang and Krivan (52) used methane for the analysis of niobium
pentoxide, and Krivan and Huang (50) used high-purity carbon powder in
the determination of 15 elements in high-purity titanium.
One of the arguments in favor of slurry sampling was that the slurry
concentration can easily be changed so that the analyte concentration falls
into the analytically useful range of the calibration graph (26). This is true
as long as the analyte is 100% extracted into the liquid phase; if this is not
the case, slurry sampling is subject to the same limitations as SS ET AAS
due to natural inhomogeneity of the small subsamples used, which is not
always improved by reducing particle size (53). It has been well established
that a minimum number of particles is required for a subsample to be
representative for the laboratory sample, independent of the technique used
for the analysis (34). Anyway, there are other means available to reduce
sensitivity in ET AAS that might be more appropriate than a dilution, such
as the use of a gas flow during atomization (54, 55), the use of alternate,
less sensitive analytical lines (55, 56), or the use of the three-field Zeeman-
effect (56), a technique that has recently become available commercially
(57). On the other hand, SS ET AAS is much less affected by the particle
size, as sedimentation, etc., obviously do not have to be considered, and
even relatively large pieces may be analyzed, such as metal chips (50, 58),
pieces of plastic materials (59 – 61), or wet tissue samples (62, 63). Finally,
while the maximum sample mass that can be introduced into the graphite
furnace by slurry sampling is around 1 mg (34), an almost two orders of
magnitude greater sample mass has been introduced by Krivan et al.
(48, 49, 51) for SS ET AAS to improve sensitivity and LOD.
Another topic that has been discussed quite controversially in SS ET AAS
is calibration, and it has been stated repeatedly that accurate results could only
be obtained using solid standards, i.e., certified reference materials (CRM).
Kurfürst (22), for example, writes in his book: “If a CRM is available
whose matrix composition and analyte content match that of the sample,
ideal analytical conditions are fulfilled”—a situation that can rarely be met
in real life. Several authors have compared the three possible basic calibration
techniques for SS ET AAS, (a) calibration using solid CRM, (b) the analyte
addition technique, and (c) the standard calibration technique with aqueous
standards (64 – 67), and the errors associated with these calibration techniques.
Calibration using one or more solid CRM, besides being expensive and not
applicable for routine analysis, was found to contribute significantly to
imprecision, as the uncertainty of the certified value is fully introduced into
the calibration (66, 67). The analyte addition technique is particularly cumber-
some to apply in SS ET AAS, as it is impossible to reproducibly insert the
same sample mass into the graphite furnace. The analyte addition technique
hence requires a three-dimensional approach, the Generalized Standard
Additions Method (GSAM), which takes into consideration the added
analyte mass, the response and the sample mass (68). Besides being labor
intensive, as a large number of measurements is necessary to arrive at reason-
ably reliable results, the latter still exhibit rather high uncertainty. However,
this problem appears to be kind of academic when Table 1 is consulted, as

in essentially all of the manuscripts, with only two exceptions, the standard
calibration technique with aqueous standards has been used successfully.
This means that interference-free determination could be attained after
careful optimization of the analytical conditions. This might include a pre-
treatment of the sampling platform with the refractory matrix, as in the case
of the high-purity materials investigated by Krivan et al. (24, 43, 48 –52)
and/or the use of a proper modifier (50 –52, 61, 69).
Yet another argument that has been brought up in favor of slurry sampling
was that chemical modification is easier to perform, because of more effective
contact between the sample particles and the modifier (26). However, this
effective contact is not necessary for analyte stabilization, as the analyte
becomes mobile well before its atomization, and can be efficiently trapped
even if it is not been in contact with the modifier (see Maia et al. (70) and
the references therein). The fact that analytes can be stabilized by a
permanent modifier even when they are introduced as a solid sample was for
the first time demonstrated in 2001 for the determination of Cd and Pb in
mineral coal, using Ru as permanent modifier (71). This principle has
been confirmed later also for the determination of Tl in river and marine
sediments (69), for Hg in environmental reference materials (72), and for
Cd in coal using Ir as permanent modifier (73). In the case of mercury determi-
nation, it could actually be shown that analyte stabilization by a permanent
modifier is much more efficient for solid samples than for aqueous standards,
which are obviously in much closer contact with the modifier than a solid
sample (72).
Last but not least, it has to be mentioned that SS ET AAS is offering a few
unique possibilities that are not available with any solution or slurry
technique. Firstly, there is the possibility for a very fast screening, essentially
without any sample preparation, in cases where only outliers have to be
detected that will be investigated more carefully later using other techniques.
This possibility has been theoretically evaluated by Belarra et al. (74) using
information theory. These authors found that the median can be used to
better effect than the mean value as the former is less affected by the presence
of outliers. The minimum number of measurements that need to be carried out
to guarantee a recall of over 0.95 in a screening method ranges from 5 to 20,
involving between 15 min and 1 h of work. Lücker and Schuierer (62) inves-
tigated the sources of error in direct SS ET AAS analysis of fresh animal tissue
for screening purposes and found that manual working time and the necessity
of operator presence were reduced by at least 80% compared to conventional
digestion procedures. Belarra and co-workers investigated the determination
of antimony in polyvinylchloride (59), of phosphorus in polyethyleneter-
ephthalate (PET) and polypropylene (61), and of silicon in polyamide (75)
also for screening purposes, and claimed a high sample throughput, a
precision better than 10%, and low detection limits as the main advantages.
Secondly, SS ET AAS can be used to determine the homogeneity and
micro-homogeneity of CRM and other materials (53, 56) and to detect

potential outliers (74). Nomura et al. (56) found for a bovine liver sample
that both the drying and the grinding process had an influence on micro-hom-
ogeneity, which in addition was different for different elements. Belarra et al.
(53) also found that lack of homogeneity of the small subsamples used in SS
ET AAS is the major source of high RSD values, which is not always
improved by reducing particle size. Thirdly, there is the possibility of deter-
mining trace element distributions in extremely little samples, such as hair
segments, tissue biopsy samples or plant segments, as has been shown by
Štupar and Dolinšek (63).
HIGH-RESOLUTION CONTINUUM SOURCE ET AAS
The state of the art of high-resolution continuum source AAS (HR-CS AAS) is
fully described in a recent book of Welz et al. (76). Although this technique is
currently commercially available only with flame atomization, it appears to be
more than appropriate to discuss its potential for SS ET AAS in this context, as
there are already a number of results available that have been obtained with
prototype equipment. The general layout of this system, which is based on
preliminary work of Heitmann et al. (77) is shown schematically in
Figure 2. It consists of a specially developed xenon short arc lamp,
operating in a hot-spot mode for maximum emission intensity in the far UV
range, a high-resolution double monochromator with a spectral bandwidth
per pixel of 1.6 pm at 200 nm, and a charge-coupled-device (CCD) array
detector with full vertical binning. As only an intermediate, but no exit slit
is used, a segment of about 0.4 nm of the highly resolved spectrum is
reaching the detector and registered simultaneously by 200 pixels of the
detector, all of which act as independent detectors.
One of the features of this new concept is that the spectral environment of
the analytical line becomes visible at high resolution, as is shown in Figure 3
for the example of Tl in marine sediment CRM. While continuous background
Figure 2. Instrumental concept for HR-CS AAS (from Welz et al. (82)).
absorption is eliminated automatically, as any of the 200 pixels can be used for
correcting spectrally continuous events, spectrally discontinuous absorption,
such as atomic absorption of concomitants and molecular absorption
with rotational fine structure, become visible. Obviously, any atomic or
molecular absorption that is not within the very small spectral window used
to measure analyte absorption does not cause any spectral interference. ET
AAS in addition offers the possibility to separate analyte and molecular
absorption in time by optimizing the temperature program.
Using all these possibilities, Welz et al. (78) succeeded in determining Tl
in marine sediment samples without any modifier and calibration against
aqueous standards, just by optimizing the temperature program, as shown in
Table 2. Using conventional LS AAS with deuterium background correction
and calibration against solid CRM it was not possible to arrive at consistent
results, even with very sophisticated modifier combinations (69). When the
same determination was carried out using LS AAS with Zeeman-effect back-
ground correction, an extremely careful selection of chemical modifiers was
still necessary, and only a combination of Ru as permanent modifier and the
addition of a solution of ammonium nitrate on top of the solid sample
resulted in accurate values (69). This actually appeared like a clear indication
that the problem originally encountered with deuterium background correction
was a combination of spectral interference (which could be eliminated Zeeman-
effect background correction) and non-spectral interference (which could only
be overcome with a carefully selected combination of modifiers). However, the
fact that the same determination could finally be carried out without any
modifier and calibration against aqueous standards using HR-CS AAS (78)
clearly showed that the interference still encountered with Zeeman-effect back-
ground correction must obviously have been of spectral origin, because
otherwise it would have appeared as well with the former system.
Figure 3. Atomic and molecular absorption signals observed during the atomization
of a marine sediment sample in the vicinity of the Tl resonance line at 276.787 nm
using SS HR-CS ET AAS (from Welz et al. (78)).
The concept was later extended to the determination of Tl in mineral coal

and the only condition that had to be met was a pyrolysis temperature higher
than 6008C in order to avoid excessive continuous background absorption
due to radiation scattering at volatilized particles. Using a pyrolysis tempera-
ture of 7008C, this problem was solved, and no modifier was required for
the determination of Tl in coal (79). Cadmium could be determined in coal
under the same conditions, i.e., using a pyrolysis temperature of 7008C,
which, however, required a chemical modifier to stabilize Cd, and Ir as
permanent modifier was found optimum for that purpose (73). It is interesting
to note that the same determination of Cd in coal, using the same equipment,
but slurry instead of direct SS ET AAS could not be carried out satisfactorily,
as the maximum applicable pyrolysis temperature in this case was only 6008C
(80). This appears to be the first case where under otherwise identical analytical
conditions, the direct SS ET AAS method succeeded, whereas the slurry
method failed. Another application has been the determination of Co in a
variety of biological materials, which also did not require any modifier and
could be carried out against aqueous standards after program optimization (81).
It has to be mentioned that HR-CS AAS, in addition to the above features,
has the advantage that, due to the use of a high-intensity continuum source, all
392
Table 2. Determination of thallium in marine sediment reference materials (CRM) using direct solid sampling ET AAS and three different
instrumental concepts: Deuterium background correction with calibration against a solid CRM (from Vale et al. (69)), Zeeman-effect background
correction with calibration against aqueous standards (from Welz et al. (78)) and HR-CS AAS with calibration against aqueous standards (from
Vale et al.(78))
D2 correction Zeeman-effect background correction HR-CS AAS

Reference ETV-ICP- Ru/ Ru/
CRM valuea MSb NH4NO3c Withoutd NH4NO3e NH4NO3c Withoutd
BCSS-1 (0.6) — 0.36 + 0.03 — — 0.59 + 0.04 0.51 + 0.04

HISS-1 (0.06) 0.055 + 0.004 0.04 + 0.01 0.02 + 0.002 0.03 + 0.003 0.05 + 0.003 0.054 + 0.01
MESS-1 (0.7) — 0.42 + 0.05 — — 0.70 + 0.02 0.57 + 0.01
MESS-2 (0.98) 0.99 + 0.04 0.87 + 0.03 0.19 + 0.01 0.72 + 0.01 1.07 + 0.03 0.98 + 0.02
MESS-3 0.90 + 0.06 — 0.85 + 0.10 — — 1.08 + 0.07 0.93 + 0.04
PACS-2 (0.6) 0.52 + 0.02 0.21 + 0.06 0.12 + 0.03 0.22 + 0.04 0.58 + 0.02 0.50 + 0.01
SRM 1646a (,0.5) – 0.10 + 0.02 — — 0.20 + 0.02 0.20 + 0.02
a
Values in brackets are not certified.
b
Values taken from Maia et al. (41).
c
400 mg Ru as permanent modifier þ 20 mL of 5% w/v NH4NO3 added to the solid sample.
d
Without use of a modifier.
e
Twenty microliters of 5% w/v NH4NO3 added to the solid sample.
All values are in mg g21, and average and standard deviation of n ¼ 3.
analytical lines are available without any compromise regarding the signal-to-
noise ratio; i.e., there are no more “weak lines.” Another possibility offered by
this technique is that in addition to the usual evaluation of the line center using
1– 3 pixels, there is the possibility to evaluate the absorbance at the line wings
only in order to reduce the sensitivity and expand the linear dynamic range to
some five orders of magnitude. This appears to be particularly important for
SS ET AAS to reduce the sensitivity in cases where no secondary line of
appropriate sensitivity is available, such as in the case of Cd or Zn. It is of
particular importance that this extension of the working range does not
require a new measurement, as a whole set of calibration curves can be estab-
lished simultaneously. All these possibilities obviously have yet to be explored,
but the expectations for this excitingly new technique are high for good reasons.
CONCLUSION
Direct SS ET AAS has matured significantly during the past decade, and with
proper accessories for sample introduction being available it can be con-
sidered a rugged technique ready for routine application. A relative standard
deviation (RSD) of the order of 10%, as it is typical for this technique due
to the naturally inhomogeneous distribution of trace elements in the relatively
small subsamples, should not be considered a major limitation. In the opinion
of the present authors a 10% RSD of an accurate result is much more accep-
table than a 1% RSD of a result that is affected by systematic errors due to
analyte loss or contamination during sample preparation. Direct SS ET
AAS is not affected by problems such as sedimentation or partial leaching
of the analyte, and particle size is much less critical than in slurry sampling.
It is fast, offers the lowest LOD, and has a significant contribution to clean
chemistry. HR-CS AAS is expected to further enhance the attractiveness of
SS ET AAS, making it even simpler to use and more flexible in its application.
ACKNOWLEDGEMENT
The authors are grateful to Conselho Nacional de Desenvolvimento Cientı́fico

e Tecnológico (CNPq) for financial support. M. G. R. Vale and W. N. L. dos
Santos have scholarships from CNP.
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Applied Spectroscopy Reviews

Current Status of Direct Solid Sampling for Electrothermal Atomic

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Current Status of Direct Solid Sampling

Maria Goreti R. Vale and Nédio Oleszczuk

Walter N. L. dos Santos

Received 12 December 2005, Accepted 1 February 2006

Keywords: Solid sampling, slurry sampling, electrothermal atomic absorption spec-

digestion is involved in solid sample analysis. These techniques will

SLURRY VS. SOLID SAMPLING ET AAS

agitation (35). Usually, a high extraction rate is considered advantageous, so

DIRECT SOLID SAMPLING ANALYSIS USING LINE SOURCE

The situation regarding the commercial availability of equipment for slurry

Table 1 gives an overview over a number of representative publications in

M. G. R. Vale, N. Oleszczuk, and W. N. L. dos Santos

Direct Solid Sampling—A Review

Fe Rice plants Deuterium Aqueous None 0.14 ng at Micro samples (85)

M. G. R. Vale, N. Oleszczuk, and W. N. L. dos Santos

this problem appears to be kind of academic when Table 1 is consulted, as

micro-homogeneity of CRM and other materials (53, 56) and to detect

HIGH-RESOLUTION CONTINUUM SOURCE ET AAS

The concept was later extended to the determination of Tl in mineral coal

D2 correction Zeeman-effect background correction HR-CS AAS

M. G. R. Vale, N. Oleszczuk, and W. N. L. dos Santos

BCSS-1 (0.6) — 0.36 + 0.03 — — 0.59 + 0.04 0.51 + 0.04

The authors are grateful to Conselho Nacional de Desenvolvimento Cientı́fico

1. Walsh, A. (1955) The application of atomic absorption spectra to chemical

3. López-Garcı́a, I., Ortiz-Sobejano, F., and Hernández-Córdoba, M. (1991) Use of

52 (4): 437– 443.

tungsten blue oxide. Spectrochim. Acta B, 54 (8): 1177– 1191.

65. Coşkun, N. and Akman, S. (2004) Direct determination of manganese in

thallium in marine sediment reference materials using high-resolution

spectrometry for the direct determination of Cr in various materials using solution-

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