Analytica Chimica Acta 432 (2001) 303–310

Digestion procedures for the determination of antimony and

arsenic in small amounts of peat samples by hydride
generation–atomic absorption spectrometry
Michael Krachler a , William Shotyk b , Hendrik Emons a,∗
a Research Centre Juelich, Institute of Applied Physical Chemistry, D-52425 Juelich, Germany
b Geological Institute, University of Berne, Berne, Switzerland

Received 29 June 2000; received in revised form 16 November 2000; accepted 5 December 2000

Abstract
Closed-pressurised and open vessel digestion procedures for the mineralisation of small amounts (∼100 mg) of peat
samples have been developed and evaluated. The two trace elements As and Sb were quantified in the diluted digests by flow
injection–hydride generation–atomic absorption spectrometry (FI–HG–AAS). Optimisation of the analytical procedures was
carried out with two bulk peat materials one of which was prepared as internal reference material. Both peat specimens were
additionally characterised by instrumental neutron activation analysis with respect to their concentrations of As and Sb. Good
agreement between instrumental neutron activation analysis (INAA) results and concentrations determined by HG–AAS were
obtained. The use of adequate reference materials during the course of all experiments guaranteed precise and accurate results.
Various acid mixtures with and without hydrofluoric acid were tested, because preliminary experiments revealed that HF in
the digestion mixture leads to the formation of the gaseous AsF5 resulting in diminished recoveries of As when open vessel
digestion procedures are employed. Avoiding HF for mineralisation of peat led to low recoveries for Sb because distinct
amounts of Sb are associated with silicates. Closed-pressurised vessel digestion proved to be less effective compared to
open vessel mineralisation. For successful quantification of both elements, two digestion procedures are needed, one without
HF for As and another one with HF to liberate Sb from the silicates. The optimised open vessel digestion procedure was
applied to the determination of ancient peat samples dating back to 9300 calendar years before present. Concentrations of
both elements showed a broad spread with values ranging from 18 to 1500 and 300 to 5700 ng g−1 for Sb and As, respectively.
© 2001 Elsevier Science B.V. All rights reserved.
Keywords: Antimony; Arsenic; Peat; Digestion; Atomic absorption spectrometry; Hydride generation

1. Introduction precise analytical data that may serve as a basis for

There is a rapidly increasing interest in the use of
peat bogs as archives of atmospheric metal deposi-
tion [1–4]. However, a prerequisite for accurate and
∗ Corresponding author. Tel.: +49-24-61-61-29-14;
fax: +49-24-61-61-24-93.
E-mail address: h.emons@fz-juelich.de (H. Emons).
a meaningful reconstruction of atmospheric metal
depositions, is the employment of reliable analyti-
cal procedures for trace element analysis. Currently,
no reference material with certified trace element
concentrations representing a peat matrix is com-
mercially available. Therefore, the development of a
suitable peat reference material, as at present under-
taken in the EUROPEAT Project [5], will contribute

0003-2670/01/$ – see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 0 0 3 - 2 6 7 0 ( 0 0 ) 0 1 3 6 4 - 7
304 M. Krachler et al. / Analytica Chimica Acta 432 (2001) 303–310
to an improvement in the credibility of analytical
results.
In particular such a peat reference material can dis-
tinctly support the development of suitable digestion
procedures of this difficult-to-digest matrix. Although
many mineralisation procedures for plant materials
exist, methods for the dissolution of peat samples are
scarce [6]. Peat materials are well known to contain
very resistant organic matter with different chemical
composition and siliceous inorganic materials from
organic dust. Therefore, digestion procedures de-
signed for plant matrices cannot necessarily also be
applied to peat because of the much higher demands
on the destructive power obligatory for peat.
While distinct information of human perturbations
of global cycles of Cd, Cu, Hg, Pb, and Zn is available
[7,8], much less is known about the effect of human ac-
tivity on emissions of arsenic and antimony. In the past
instrumental neutron activation analysis (INAA) has
been applied to the determination of As and Sb in peat
[2,4]. However, the determination of As by INAA is
hampered by bromine always present in peat samples.
Because of the frequently low concentration of Sb in
peat INAA has to be used close to its detection limit.
This holds especially true if only small amounts (0.5 g
or less) of peat samples are available for repetitive
analysis. Flow injection–hydride generation–atomic
absorption spectrometry (FI–HG–AAS) proved to be
well suited for the determination of trace concentra-
tions of As and Sb in small amounts of environmental
samples providing detection limits in the low pg g−1
range [9–12]. For a quantification of As and Sb by
HG–AAS, the powdered peat has to be converted into
a homogenous solution. Our previous studies revealed
that a considerable amount of Sb is bound to silicates
in plant materials [9]. Consequently, hydrofluoric acid
has to be used in the digestion mixture to destroy the
silicates. However, another recent study [12] showed
that concentrations of As determined in various plant
materials after application of a HF-based mineralisa-
tion procedure in open vessels were distinctly lower
than certified values of As. Moreover, we found that
digestion without HF yielded adequate recovery of
As [12]. The formation of the gaseous AsF5 most
probably leads to the diminished results for As when
HF is used in an open vessel digestion procedure.
Closed-pressurised digestion procedures may help to
overcome this particular problem.
In continuation of our research on As and Sb in
biota [9–13], this paper focuses on the following is-
sues: (1) the preparation of an internal peat reference
material for As and Sb, (2) the comparison of diges-
tion efficiencies of open vessel and closed-pressurised
vessel mineralisation procedures using HF and avoid-
ing HF in the acid mixture, (3) investigations of
potential losses of As in closed-pressurised vessel pro-
cedures using HF and behaviour of the glass surface of
the quartz tube atomiser when hydrides are generated
from digestion solutions containing HF, (4) the deter-
mination of As and Sb in two bulk peat materials that
have been additionally characterised by INAA with
respect to As and Sb, and (5) analysis of both elements
in selected ancient peat samples by FI–HG–AAS.
2. Experimental
2.1. Instrumentation
Samples were mineralised in closed-pressurised
digestion vessels made from PTFE (30 ml) fixed in
stainless steel jackets (home-made) on a hot plate or
in vessels made from glassy carbon (20 ml, Perkin-
Elmer, Norwalk, CT, USA) in an aluminium heat-
ing block (Gebrüder Liebisch, Bielefeld, Germany).
A flow injection system (FIAS 400, Perkin-Elmer),
equipped with an autosampler (AS 90, Perkin-Elmer)
was coupled to an atomic absorption spectrometer
(AAS 4100, Perkin-Elmer) for the quantification of
As and Sb in the digests [9,12].
2.2. Reagents and standards
For the preparation of all solutions Milli-Q water
(Millipore, Milford, MA, USA) was used. Acids for
mineralisations were sulphuric acid (96%, Suprapur® ,
Merck, Darmstadt, Germany), hydrofluoric acid
(40%, Suprapur® , Merck), perchloric acid (70%,
Suprapur® , Merck), and nitric acid (65%, analyti-
cal grade, Merck). For the flow injection system the
carrier solution was prepared from hydrochloric acid
(32%, Riedel-de Haen, Seelze, Germany). NaBH4
solutions were prepared daily by dissolving appropri-
ate amounts of powdered NaBH4 (analytical-reagent
grade, Riedel-de Haen) in 0.04% (w/v) NaOH (30%,
Suprapur® , Merck). Sb(V) and As(V) were reduced
 M. Krachler et al. / Analytica Chimica Acta 432 (2001) 303–310
to Sb(III) and As(III), respectively, with aqueous so-
lutions containing 30% (w/v) KI (Suprapur® , Merck)
and 5% (w/v) ascorbic acid (analytical grade, Merck).
Calibration solutions (0.1–2 ␮g l−1 ) for As and
Sb were prepared daily by diluting aliquots of stock
standard solutions containing 1000 mg SbCl3 l−1 in
5 mol l−1 HCl (Merck) or 1000 mg As2 O5 in water
(prepared from Titrisol® ampoules, Merck) to the
appropriate concentrations with 10% HCl.
2.3. Samples and preparation of an internal peat
reference material
Two bulk peat samples (Peat 1 and 2) with dif-
ferent chemical matrix characteristics (ash content,
concentration of elements) were employed for the de-
velopment of adequate digestion procedures for small
amounts of peat. Peat 1 consists of a fen peat from the
Holland Marsh, Ont., Canada. This material (sample
code 1878P) was dried, milled, homogenised, split
and bottled in 1982 by the Ontario Geological Sur-
vey and has been made available by the Geoscience
Laboratories, Sudbury, Ont., Canada.
Peat 2 was considered to serve as internal reference
material and was prepared from a peat core collected
at Schöpfenwaldmoor, near Interlaken, Switzerland.
The core was cut 50 cm below the “surface” (top
of the core) and the remaining material below this
depth (ca. 50 cm × 10 cm × 10 cm) was considered
for the following preparation of an internal reference
material. The entire fresh material (3.774 kg; 87.5%
water) was subjected to cryogenic milling at the En-
vironmental Specimen Bank at the Research Centre
Juelich before the powder was freeze-dried. About
160 aliquots containing approximately 3 g each of the
dry peat were poured into 20 ml high performance
glass vialsTM (Packard® , Canberra Industries, Meri-
Table 1
Characteristics of selected peat samples drilled at Etang de la Gruère, northwestern Switzerland
Sample ID Sample depth (cm)
2f12 30–33
2f13 33–36
2f14 36–39
2p11 200–210
2p44 530–540
a Calendar years before present.
305
den, CT, USA). Each bottle was closed with a screw
cap and was additionally sealed in a polyethylene
bag. The humidity content of the dry powder, as de-
termined on aliquots of the material by a moisture
analyser (LP16, Mettler-Toledo, Greifensee, Switzer-
land), was 5.1 and 9.0% for Peat 1 and 2, respectively.
The collection and preparation of the peat samples
analysed in this study has been described in detail pre-
viously [3]. Briefly, two cores were collected from peat
bogs at Etang de la Gruère in northwestern Switzer-
land. A stainless steel peat profile sampler was used to
remove a monolith from the peatland, wrapped in plas-
tic and then in aluminium foil, and brought directly
into the laboratory. The cores were immediately cut
into 3 cm slices, were dried at 105◦ C in PTFE bowls,
and subsequently macerated in a centrifugal mill
equipped with a Ti rotor and a 0.25 mm sieve. All sam-
ple handling and preparation was carried using clean
laboratory techniques [14]. Selected characteristics of
the analysed peat samples are juxtaposed in Table 1.
2.4. Method development
2.4.1. Closed-pressurised digestion
Aliquots (∼100 mg) of samples were weighed
to 0.1 mg into each of the PTFE digestion vessels.
After addition of 2 ml nitric acid and 0.1 ml perchloric
acid to the powders, the vessels were gently shaken
to mix the contents, sealed with the PTFE cap and
placed and fixed in the heating block. Also minerali-
sations were carried out using the above acid mixture
plus 0.5 ml hydrofluoric acid. The closed-pressurised
digestion vessels were heated on a hot plate at a tem-
perature of 180◦ C for 5 h and allowed to reach am-
bient temperature again (all overnight). The resulting
solution in the digestion vessels were quantitatively
transferred into graduated 15 ml polyethylene tubes
Ash content (%) Age date Reference
4.6 1879 ± 11 [2]
8.6 1843 ± 25 [2]
7.2 240 ± 20 [6]
1.5 >3000 BPa [6]
14.9 >9300 BPa [15]
306 M. Krachler et al. / Analytica Chimica Acta 432 (2001) 303–310

(Falcon, Becton Dickinson, Lincoln Park, NJ, USA) Table 2

and subsequently diluted to a final volume of 10 ml Operating conditions for the hydride generation–atomic absorption
spectrometer for the determination of antimony and arsenic
with 10% (w/v) hydrochloric acid.
Blank solutions were prepared by application of the Hydride generation
NaBH4 solution concentration 0.3% (w/v) stabilised
entire digestion procedure to reagent solutions con-
with 0.04% (w/v)
taining no sample. NaOH
NaBH4 solution flow rate 5 ml min−1
2.4.2. Open vessel acid digestion HCl solution concentration 10% (w/v)
Aliquots (∼100 mg) of the powdered materials, HCl solution flow rate 9 ml min−1
Carrier gas flow rate Argon, 50 ml min−1
weighed to 0.1 mg, were transferred into vessels made
Sample loop 500 ␮l
from glassy carbon and were subsequently placed in
Atomic absorption spectrometer
the aluminium heating block. Samples were digested
Antimony
with 3 ml of nitric acid, 0.5 ml of sulphuric acid and Wavelength 217.6 nm
0.3 ml of perchloric acid with a heating program Slit 0.2 nm
increasing the temperature stepwise from ambient Lamp current (HCL)a 20 mA
temperature up to 310◦ C [9]. Quartz tube atomiser temperature 770◦ C
As the resulting solutions always contained a pre- Arsenic
cipitate of silicates additionally 0.5 ml of hydrofluo- Wavelength 193.7 nm
Slit 2 nm
ric acid were added into the digestion vessels. Details
Lamp current (EDL)b 380 mA
have been reported earlier [9]. After reaching room Quartz tube atomiser temperature 900◦ C
temperature again, the completely clear, homogenous a HCL: hollow cathode lamp.
solutions in the digestion vessels were quantitatively b EDL: electrodeless discharge lamp.
transferred into 10 ml calibrated flasks and filled to the
mark with 10% HCl. 2.5.2. Determination of antimony and arsenic
Concentrations of As and Sb in the digests were
2.5. Procedures quantified by FI–HG–AAS according to our analyti-
cal procedure reported previously [9,12]. Detailed op-
2.5.1. Digestion procedure for the mineralisation of erating conditions of the entire analytical set-up are
peat samples summarised in Table 2.
Aliquots of ∼100 mg of peat samples were weighed
to 0.1 mg into the digestion vessel made from glassy 2.6. Quality control
carbon. For the determination of Sb, 3 ml of nitric
acid and 0.5 ml of hydrofluoric acid were added to The two above mentioned bulk materials (Peat 1
the powders and vessels were gently shaken to mix and 2) were characterised by instrumental neutron
the contents. The solutions were allowed to stand activation analysis (Actlabs, Activation Laboratories
overnight in a fume hood before next morning 0.3 ml Ltd., Ancaster, Ont., Canada) and by FI–HG–AAS in
of hydrochloric acid and 0.5 ml sulphuric acid were our laboratory with respect to concentrations of As
pipetted into the digestion vessels. These mixtures and Sb. These internal reference materials were used
were heated up to 310◦ C within about 2 h as reported for method developments and were analysed with
earlier [9]. After reaching room temperature again every batch of peat samples. Additionally, the plant
the resulting solutions were quantitatively transferred reference material GBW 07604 Poplar Leaves from
into graduated 15 ml polyethylene tubes (Falcon, the Institute of Geophysical and Geochemical Explo-
Becton Dickinson, Lincoln Park, NJ, USA) and sub- ration, Langfang, The People’s Republic of China,
sequently diluted to a final volume of 10 ml with was analysed during the establishment of concentra-
10% (w/v) hydrochloric acid. The identical digestion tions of As and Sb in the two internal peat reference
procedure without using HF in the digestion mix- materials. Experimental concentrations of As and Sb
ture was employed for the subsequent determination in this certified reference material were always within
of As. the uncertainty range indicated by the manufacturer.
 M. Krachler et al. / Analytica Chimica Acta 432 (2001) 303–310 307

2.7. Statistical data treatment
All analytical results were subjected to statistical
data treatment. The two-sided Student’s t-test for un-
paired samples was employed to investigate statistical
differences between results of As and Sb obtained
by HG–AAS after open and closed vessel digestion
procedures, respectively. A P-value of <0.05 was
considered as significant.
3. Results and discussion
3.1. Open vessel acid digestion
Attempts to employ the open vessel digestion pro-
cedure using nitric, perchloric, hydrofluoric and sul-
phuric acids developed for plant materials [9,11,12]
failed to produce correct results for Peat 1. However,
this peat material consists of a quite difficult-to-digest
matrix (∼22% ash, compare with Table 1) which is
not entirely representative for a conventional peat ma-
trix, but represents a worst case scenario. If accurate
and precise results for As and Sb can be obtained by
applying a particular digestion procedure prior to an
adequate analytical determination, this mineralisation
will work with any peat samples.
To arrive at conditions suitable to successfully di-
gest this peat material, the amount of sample to be
mineralised was reduced from about 250 to 100 mg.
This reduction of sample weight was also necessary
because only a limited amount (0.2–0.5 g) of peat
samples was available for repetitive mineralisations
and for the subsequent quantification of As and Sb
in the digests by HG–AAS. Additionally, digestions
of peat were carried out with and without addition of
hydrofluoric acid. These experiments with HF were
undertaken to evaluate the potential loss of As due to
the formation of the volatile AsF5 during the mineral-
isation of peat in open vessels, as observed previously
for various plant matrices [12]. Diminished results of
up to 40% were found for As in plant samples when
HF was used for the destruction of silicates [12].
The effect of HF on the As concentration found in
the two peat materials was detectable, but much less
pronounced (Table 3) than for plant materials. This

Table 3
Comparison of concentrations (ng g−1 ) of As and Sb in the two internal peat reference materials and in GBW 07604 Poplar Leaves
determined by HG–AAS after application of different digestion procedures
Open vessel Na Closed-pressurised vessel Na

Peat 1
Antimony With HF 292 ± 12b,c 10 41 ± 7c 4
Without HF 255 ± 25b 10 207 ± 15 8
Arsenicd With HF 9.00 ± 0.33b,c 16 2.52 ± 0.14c 4
Without HF 9.68 ± 0.38b 11 8.39 ± 0.28 8
Peat 2
Antimony With HF 72 ± 5b,c 12 7 ± 1c 4
Without HF 68 ± 4b 12 49 ± 5 8
Arsenic With HF 465 ± 22b,c 16 72 ± 4c 4
Without HF 482 ± 23b 16 256 ± 7 8
GBW 07604 Poplar Leaves
Antimony With HF 48 ± 3b,c 10 <1c 4
Without HF 43 ± 3b 10 32 ± 3 8
Certified value 45 ± 5
Arsenic With HF 315 ± 19b,c 15 147 ± 11c 4
Without HF 375 ± 15 15 387 ± 17 8
Certified value 370 ± 60
a Number of sub-samples analysed.
b Significant difference (P < 0.05) between open vessel and closed-pressurised vessel digestion.
c Significant difference (P < 0.05) between digestions with and without HF.
d Concentrations in ␮g g−1 .
308 M. Krachler et al. / Analytica Chimica Acta 432 (2001) 303–310
Table 4
Comparison of concentrations (␮g g−1 ) of As and Sb in the two
internal peat reference materials as determined by instrumental
neutron activation analysis (INAA) and by the optimised open
vessel/HG–AAS procedure
HG–AAS Na INAA
Peat 1
Antimony 0.287 ± 0.017 26 0.296 ± 0.023
Arsenic 9.82 ± 0.37 31 7.5 ± 1.2
Peat 2
Antimony 0.070 ± 0.005 23 0.082 ± 0.005
Arsenic 0.469 ± 0.022 21 0.61 ± 0.02
a Number of sub-samples analysed.
effect of diminished As concentrations after digestion
with HF was matrix-dependent and did not correlate
with the amount of silicates present in the sample
matrix. Applying the above open vessel digestion
approach with HF, results for As coincided well with
certified value for Poplar Leaves (Table 3). However,
experimental values for As obtained by INAA differed
distinctly from the As concentrations determined by
HG–AAS (Table 4). Fortunately, the preliminary re-
sults of the statistical evaluation of the interlaboratory
trial (EUROPEAT Project [5]) dealing with the de-
termination of selected trace elements in Peat 1 are
available to us. The results for As (8.9 ± 0.75 ␮g g−1 )
and Sb (0.34 ± 0.05 ␮g g−1 ), determined in this
peat sample by various institutions and analytical
methods, are in excellent agreement with our values
(Table 4).
As a distinct amount of Sb is always present within
the silicates, the use of HF in the digestion mixture
is always compulsory for the accurate determination
of Sb in silicate-containing matrices. The higher the
amount of silicates in the material digested the higher
was the difference between the — much too low —
experimental and certified Sb concentrations. During
the experiments it was observed that the shape of
the Sb signal from the atomic absorption spectrom-
eter served as an excellent indicator for monitoring
the quality of digestion solutions with respect to
residual silicates containing Sb. Normally, one ab-
sorbance peak for Sb was observed. In cases where
Sb-containing silicates (although almost non visible
very small particles) were present in the analyte so-
lution, two Sb peaks occurred in the measurement
window as depicted in Fig. 1. The main Sb peak was
Na
15
15
5
5
Fig. 1. Absorbance signals of Sb from the FI–HG–AAS set-up for
different qualities of digestion solutions. Signal obtained after suc-
cessful mineralisation of a peat samples yielding in a homogenous
solution without any residues (full line); signals from a solution
containing remaining silicates associated with Sb (dotted line).
shifted to later times thereby sometimes slightly mov-
ing out of the measurement window, whereas a small
peak was noticed at the time “normal” signals were
detected (Fig. 1). For example double peaks occurred
when diluted digests of Peat 1 mineralised without HF
were analysed for Sb. The occurrence of two peaks
can be attributed to the presence of two Sb species
present in the analyte solution. The first minor signal
represents Sb in ionic form because its signal is timely
overlaps with that of aqueous standard solutions of
Sb(III). Antimony associated with silicates is charac-
terised by the second major peak. This indicates that
the amount of HF used for the mineralisation of sam-
ples was not sufficient and needs to be increased. Ap-
proximately 10% lower results for Sb were obtained
when no HF was employed for the digestion of the in-
vestigated samples (Table 3), obviously depending on
the silicate content of the particular sample. However,
in all that cases also distinct amounts of silicates were
visible on the bottom of the sample tubes. Minerali-
sations of Peat 1 and 2 as well as of the reference ma-
terial Poplar Leaves with HF in the digestion mixture
yielded good agreement with certified or INAA values
(Tables 3 and 4).
 M. Krachler et al. / Analytica Chimica Acta 432 (2001) 303–310
3.2. Closed-pressurised vessel digestion
After reaching room temperature again, the closed-
pressurised digestion vessels were left overnight with
their lids open to release nitrous gases from the vessels.
Generally, when the reduction solution (30% KI + 5%
ascorbic acid) is added to the digestion solutions, the
latter turns slightly yellow because of a redox reac-
tion (oxidation of iodide to elemental iodine followed
by reduction to iodide again) [9]. However, after some
minutes the colour disappears again yielding a stable
AAS-signal after 2 min when the open vessel diges-
tion procedure is employed [9]. Digestion solutions
from the closed-pressurised digestion system needed
a longer time, i.e. approximately 30 min to discolour
again.
Mineralisation experiments carried out without HF
left visible amounts of silicates in the diluted diges-
tion solutions, however, not severely affecting the
quantification of As. Good agreement between ex-
perimental concentrations of As and certified values
could be achieved for Poplar Leaves (Table 3). On the
contrary, for the two peat materials distinctly lower
As values than those obtained from measurements
of open vessel digestion solutions were obtained
(Table 3). Moreover, the amount of silicates in the sam-
ple tubes remaining after mineralisation without HF
was considerably higher when the closed-pressurised
digestion procedure was employed. As expected, also
concentrations of Sb were lower than they should
be (Table 3) and distinctly lower than Sb results
obtained from open vessel digestion. For example,
concentrations of Sb in Peat 2 amounted to 49 ± 5
and 68 ± 4 ng g−1 when closed-pressurised and open
vessel digestion without HF containing acid mixtures
were used. After open vessel digestion with adequate
amounts of HF concentrations of Sb were found to
be 72 ± 5 ng g−1 in Peat 2 (Table 3). These facts
indicate that the closed-pressurised digestion proce-
dure does not provide sufficiently harsh conditions to
completely oxidise the difficult-to-digest peat matri-
ces. Because of the limited temperature stability of
the PTFE digestion vessels, the temperature was not
increased above 180◦ C during the closed-pressurised
mineralisation procedure. When the open vessel di-
gestion procedure was employed the temperature
of the heating block was continuously increased to
310◦ C, obviously leading to a better digestion quality.
309
However, it should be noted that microwave-assisted
acid digestion of peat in closed vessels resulted in
correct data for lead [6]. Therefore, the quality of
digestion procedures in closed vessels depends also
on the mode of energy supply and has to be checked
individually for each analyte and matrix of interest.
The use of HF in the acid mixture during closed-
pressurised mineralisation of peat samples led to less
remaining silicates in the digestion solutions com-
pared to mineralisations without HF. However, results
for both concentrations of As and of Sb of Peat 1 and
2 as well as of Poplar Leaves were unacceptably low
(Table 3). Whether these low concentrations are due
to a non sufficient reduction of the pentavalent Sb and
As to their corresponding trivalent oxidation states or
the HF containing digestion solutions influence the
performance of the glassy gas/liquid separator or if HF
vapours potentially reaching the quartz tube atomiser
may alter its glass surface was not further elucidated in
detail. However, the latter two arguments were tested
by analysing standard solutions of both elements
again after measurement of a sequence of HF contain-
ing analyte solutions. These repetitive measurements
of calibration solutions containing no HF revealed no
distinct differences to previous measurements.
3.3. Determination of As and Sb in selected peat
samples
The optimal open vessel/HG–AAS procedure was
applied to the determination of As (acid mixture with-
out HF) and Sb (acid mixture with HF) in the selected
peat samples indicated in Table 1. The ash content of
these peat samples varies from 1.5 to 14.9% and con-
sists mainly of quartz and aluminosilicates supplied to
the bog from windblown soil dust [2]. The variation in
ash content is mainly a reflection of the changing rates
of peat accumulation [2]. Due to the limited amount
of samples available for this study, only a total of four
digestions (two with HF for the determination of Sb,
and two without HF for As) involving each ∼100 mg
of peat could be performed. The analytical results of
the two independent digestions have been always in
good agreement indicating an adequate homogeneity
of the samples and a good reproducibility of the entire
analytical process (Table 5). Moreover, peat samples
digested with HF have been also analysed for ar-
senic. As the difference between data for the analysis
310 M. Krachler et al. / Analytica Chimica Acta 432 (2001) 303–310
Table 5
Concentrations (␮g g−1 ) of As and Sb in the selected peat samples
indicated in Table 1 as determined by HG–AASa
Sample ID As Sb
2f12 5.42/5.44 1.43/1.42
2f13 3.78/3.70 0.63/0.65
2f14 2.49/2.45 0.459/0.463
2p11 0.293/0.294 0.017/0.019
2p44 1.81/1.81 0.181/0.179
a Each number represents the average of three repetitive mea-
surements of the digestion solution. Relative standard deviations
of these measurements are normally less than 2%. A total of two
independent digestions were performed.
of digestion solutions that have been treated with or
without HF is not larger than approximately 10% for
peat samples, two additional “indicative” results (not
included in Table 5) helped to check the reliability of
the digestion/HG–AAS procedure. These “indicative”
results were always slightly lower (2–10%) than the
expected values. Concentrations of both elements in
samples of different years showed a broad time de-
pendent range with values ranging from 18 to 1500
and 300 to 5700 ng g−1 for Sb and As, respectively
(Table 5). For further retrospective geochemical stud-
ies, we will analyse the entire two peat cores for As
and Sb, as it has been carried out for other elements
previously [1–4].
4. Conclusions
For the accurate and precise determination of As
in digests of plant and peat matrices by HG–AAS,
hydrofluoric acid in the digestion mixture has to be
avoided. As is not bound to silicates and thus the
applied mineralisation procedure does not need to
completely destroy the silicates for the determination
of As. Concentrations of Sb in the above matrices can
only be determined successfully when Sb is liberated
from the silicates by the use of adequate amounts of
HF in the digestion mixture. Therefore, two digestions
— one with HF for the determination of Sb, the other
without HF for the determination of As — are needed
for the determination of As and Sb in peat and other
silicate containing matrices by HG–AAS.
Acknowledgements
The authors gratefully acknowledge the co-operation
of F. Backhaus, N. Commerscheidt and W. Wilms
in the preparation of the internal reference material
and the work of the analytical ESB team Jülich for
characterising this material. M.K. thanks the Euro-
pean Community who financially supported this study
through the Research Program TMR, EU contract no.
FMBICT982889.
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