Spectrochimica Acta Part B 57 (2002) 1277–1289

Analytical procedures for the determination of selected trace

elements in peat and plant samples by inductively coupled plasma
mass spectrometry
Michael Krachlera,*, Carola Mohlb, Hendrik Emonsb, William Shotyka
a
Institute of Environmental Geochemistry, University of Heidelberg, Heidelberg, Germany
b
Institute of Phytospheric Research, Research Centre Juelich, Juelich, Germany

Received 19 March 2002; accepted 21 June 2002

Abstract

A simple, robust and reliable analytical procedure for the determination of 15 elements, namely Ca, V, Cr, Mn,
Co, Ni, Cu, Zn, Rb, Ag, Cd, Ba, Tl, Th and U in peat and plant materials by inductively coupled plasma-quadrupole
mass spectrometry (ICP-QMS) was developed. Powdered sample aliquots of approximately 220 mg were dissolved
with various acid mixtures in a microwave heated high-pressure autoclave capable to digest 40 samples simultaneously.
The selection of appropriate amounts of digestion acids (nitric acid, hydrofluoric acid or tetrafluoroboric acid) was
crucial to obtain accurate results. The optimized acid mixture for digestion of plant and peat samples consisted of 3
ml HNO3 and 0.1 ml HBF4. An ultrasonic nebulizer with an additional membrane desolvation unit was found
beneficial for the determination of Co, Ni, Ag, Tl, Th and U, allowing to aspirate a dry sample aerosol into the ICP-
QMS. A pneumatic cross flow nebulizer served as sample introduction device for the other elements. Internal
standardization was achieved with 103 Rh for all elements, except for Th whose ICP-QMS signals were corrected by
103
Rh and 185Re. Quality control was ascertained by analysis of the certified plant reference material GBW 07602
Bush Branches and Leaves. In almost all cases HNO3 alone could not fully liberate the analytes of interest from the
peat or plant matrix, probably because of the silicates present. After adding small amounts (0.05–0.1 ml) of either
HF or HBF4 to the digestion mixture, concentrations quantified by ICP-QMS generally increased significantly, in the
case of Rb up to 80%. Further increasing the volumes of HF or HBF4 in turn, resulted in a loss of recoveries of
almost all elements, some of which amounted to approximately 60%. The successful analytical procedures were
applied to the determination of two bulk peat materials. In general, good agreement between the found concentrations
and results from an inter-laboratory trial or from instrumental neutron activation data were obtained, underpinning the
suitability of the developed analytical approach.
䊚 2002 Elsevier Science B.V. All rights reserved.

Keywords: Peat; Plant; Autoclave; Digestion; ICP-QMS; Ultrasonic nebulization; Trace elements

*Corresponding author. Tel.: q49-62-21-54-48-48; fax: q49-62-21-54-49-56; http:yywww.uni-heidelberg.deyinstituteyfak15y

ugcyi02ymkrachlerykrachler.htm.
E-mail address: krachler@ugc.uni-heidelberg.de (M. Krachler).
0584-8547/02/$ - see front matter 䊚 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 5 8 4 - 8 5 4 7 Ž 0 2 . 0 0 0 6 8 - X
1278 M. Krachler et al. / Spectrochimica Acta Part B 57 (2002) 1277–1289
1. Introduction
There is a growing interest in the use of plants
as bioindicators and peat bogs as archives of
atmospheric metal deposition w1–7x. However,
accurate and precise analytical data are needed to
provide reconstructions of atmospheric metal dep-
osition rates. Thus, reliable analytical procedures
for trace element analyses are a critical step in any
such study.
Most of the analytical techniques for the deter-
mination of trace elements require solid samples
to be dissolved. At present, this digestion is com-
monly achieved by heating the samples with acids
in open or closed vessels, increasingly by means
of microwave irradiation at present. Besides plant-
derived organic material, which is comparatively
easy to digest, peat consists of an inorganic (main-
ly mineral) fraction, predominantly derived from
atmospheric soil dust. This mixture with largely
variable contents makes peat a difficult-to-digest
matrix.
Open vessel microwave-assisted digestion sys-
tems were found to be less suited for this purpose
because they require distinctly larger volumes of
digestion reagents than closed pressurized disso-
lution procedures, resulting in elevated blank levels
and increased method detection limits w8x. More-
over, open vessel digestion is more prone to sample
contamination as well as to potential loss of
volatile compounds during heating and is generally
slower than closed vessel digestion. Digestion of
70-mg aliquots of moss samples, for example, was
carried out in an open vessel microwave-assisted
digestor using 8 ml HNO3 and 5 ml of each
H2O2 and HF, all of which were evaporated to
dryness w9x. As this digestion system works
sequentially, the digestion of only one sample
requires approximately the same time as needed
for the dissolution of 10–12 samples in closed
pressurized vessels in a conventional laboratory
microwave oven w8,9x.
Simply employing a closed pressurized digestion
system without optimizing the acid mixture and
the heating program of the microwave oven, how-
ever, will also not provide accurate and precise
results. Buchmann et al. w10x, for example, digest-
ed 0.5 g of pine needles with 15 ml HNO3 for 45
min at 630 W in a closed microwave-assisted
digestion system and subsequently failed to find
the certified concentrations of selected trace ele-
ments in these digests. Moreover, this approach
has two major drawbacks: first, the unnecessarily
high-acid concentration in the digestion solutions
required an extremely high-dilution factor of 5500
to be applied to minimize matrix effects of the
subsequent ICP-MS measurements; second, ele-
ments bound to the silicate fraction of the plant
samples were not fully released from the matrix
resulting in too low recoveries for selected ele-
ments such as Ce and La. Although the addition
of H2O2 to the digestion mixture will certainly
increase the oxidation power of HNO3 during
digestion and enhance the attack of organic matter,
H2O2 cannot dissolve siliceous material present in
the sample, thus still leading to diminished results
w11,12x. Especially critical in this respect is the
accurate determination of the rare earth elements
(REE), which are hosted in the silicate fraction of
plant and peat samples w13x. Most of the concen-
trations of REE reported for the reference material
SRM 1575 pine needles in Ref. w14x are distinctly
lower than indicative values given for this refer-
ence material, and this is most probably because
the authors failed to attack the silicate fraction
which hosts these elements.
Hydrofluoric acid is normally used in the acid
mixture to dissolve silicates which are present in
the samples. However, many elements such as Ca
and REE form insoluble fluorides that easily pre-
cipitate and result in poor recoveries of these
elements w13x. Boric acid (H3BO3) is often added
to digestion mixtures containing HF to complex
‘excess’ fluoride that has not been consumed
during digestion w15,16x to avoid precipitation of
fluorides. However, addition of H3BO3 introduces
a heavy borate matrix to the analyte solution
leading to additional analytical problems and thus
should be avoided. In a previous study w13x we
could show that small amounts of HF dramatically
improve recoveries of REE from peat and plant
matrices, but, however, an excess of fluoride in
the digestion solutions rapidly leads to low recov-
eries. Feng et al. w17x demonstrated that 0.5 g of
plant and grain standard materials can be success-
fully digested with 5 ml HNO3 and 0.1 ml HF.
 M. Krachler et al. / Spectrochimica Acta Part B 57 (2002) 1277–1289
Under their given experimental conditions this
amount of HF probably destroys the silicates pres-
ent in the samples and yet is low enough to avoid
precipitation of metal fluorides. However, as the
amount of silicates in environmental samples may
vary by a wide margin, this empirical approach is
of limited value.
The present study was undertaken to elucidate
the potential of tetrafluoroboric acid (HBF4) as
addition to the digestion mixture, eventually com-
bining the positive effects of HF and H3BO3 while
preventing their respective drawbacks. For the
determination of the 15 elements selected (Ca, V,
Cr, Mn, Co, Ni, Cu, Zn, Rb, Ag, Cd, Ba, Tl, Th
and U) in peat and plant materials by inductively
coupled plasma-quadrupole mass spectrometry
(ICP-QMS), an ultrasonic nebulizer (USN) with
membrane desolvation was evaluated for those
elements that are present at low concentration
levels or whose ICP-QMS determination is known
to be hampered by the occurrence of spectral
interferences.
2. Experimental
2.1. Instrumentation
Powdered peat and plant samples were dissolved
in PTFE digestion vessels (20 ml) placed in a
microwave-assisted high-pressure autoclave
(ultraCLAVE II, MLS, Leutkirch, Germany).
ICP-QMS measurements were carried out with
an ELAN 5000 (Perkin Elmer-Sciex) equipped
with an autosampler (AS 90, Perkin-Elmer) and a
cross flow (CF) nebulizer or an USN with
membrane desolvation (U-6000 ATq, Cetac Tech-
nologies, Omaha, NE). Gas flows and the position
of the torch were adjusted to obtain lowest possible
oxide formation rates for Ce and Ba and maximum
count rates for 103Rh. Using the USN, typical
ratios obtained for CeOyCe and BaOyBa were
approximately 0.07 and 0.02%, respectively. For
pneumatic nebulization with the CF nebulizer, the
oxide formation rates were higher by about one
order of magnitude. Optimized operating condi-
tions for the ICP-QMS are summarized in Table
1.
1279
2.2. Reagents and standards
For the preparation of all solutions, high-purity
water (18.2 MV cm) from a MilliQ-system (Mil-
lipore, Milford, MA) was used. Nitric acid (65%,
analytical-reagent grade, Merck, Darmstadt, Ger-
many) was further purified by sub-boiling distil-
lation (MLS). Other reagents for digestions were
hydrofluoric acid (40%, Suprapur䉸, Merck) or
tetrafluoroboric acid solution (HBF4, ;50%, pur-
um, Fluka, Buchs, Switzerland) as well as hydro-
gen peroxide (30%, Baker analyzed, J.T. Baker,
Deventer, Holland).
Calibration solutions for ICP-QMS were pre-
pared daily by adequate dilution with 0.42
mol ly1 high-purity nitric acid of two multi-ele-
ment stock standard solution (ICP Multi Element
Standard VI in 1 mol ly1 nitric acid, Merck and
SPEX, Metuchen, NJ, 5% nitric acid) containing
10 mg ly1 of each element, except for Ca and Zn
whose concentrations were 100- and 10-times
higher. To correct for instrumental drifts and plas-
ma fluctuations, all analyte solutions were spiked
with a rhodium and rhenium standard solution
(SPEX) to a final concentration of 5 or 50
mg ly1 of each element for USN-ICP-QMS and
CF-ICP-QMS, respectively. Dilution factors ranged
from approximately 200 for CF to 400 for USN.
2.3. Peat samples
Two bulk peat samples (Peat 1q2) with differ-
ent chemical matrix characteristics (botanical com-
position, degree of humification, ash content,
concentrations of major elements and trace ele-
ments) were employed for the development of
adequate peat digestion procedures. Peat 1 consists
of a fen peat from the Holland Marsh, Ont.,
Canada. This material (sample code OGS 1878P)
was dried, milled, homogenized, split and bottled
in 1982 by the Ontario Geological Survey and has
been made available by the Geoscience Laborato-
ries, Sudbury, Ont.
Peat 2 was considered to serve as internal
reference material in future studies and was pre-
¨
pared from a peat core collected at Schopfenwald-
moor, near Interlaken, Switzerland. The material
was subjected to cryogenic milling at the Environ-
 1280
M. Krachler et al. / Spectrochimica Acta Part B 57 (2002) 1277–1289
Table 1
Operating conditions for the quadrupole ICP-QMS

Instrument ELAN 5000 (Perkin-Elmer, Norwalk, CT)

Forward power 1200 W
Cones Nickel
Plasma gas 15.0 l miny1
Nebulizer gas ;1.0 l miny1, daily optimized to obtain maximum 103Rh signal intensity and minimum oxide formation rates
Auxiliary gas ;0.8 l miny1, daily optimized to obtain maximum 103Rh signal intensity and minimum oxide formation rates
Data acquisition Peak hoping mode, 50 sweepsyreading, 1 readingyreplicate, 3 replicates, dwell time 20 ms for all isotopes except 40 ms for Ag and Tl
Nebulizer 1 Cross flow, Scott-type spray chamber
Sample uptake ;1 ml miny1
Nebulizer 2 U-6000 ATq (Cetac Technologies)
Sample uptake ;2 ml miny1
Sweep gas (argon) ;2.85 l miny1 (depending on the condition of the membrane)
Heating temperature 140 8C
Desolvation temperature 140 8C
Cooling temperature 2 8C
 M. Krachler et al. / Spectrochimica Acta Part B 57 (2002) 1277–1289
Fig. 1. Temperatureypressureymicrowave power profile obtained during the digestion of plant and peat samples in the microwave
autoclave.
mental Specimen Bank at the Research Centre
Juelich before the powder was freeze-dried, split
and bottled in 1999. Details can be found else-
where w13,18,19x.
2.4. Closed vessel acid digestion in the microwave
autoclave
Sample aliquots (approximately 220 mg) were
weighed to 0.1 mg into PTFE vessels. The acid
mixtures contained 3–5 ml HNO3 with varying
amounts of HF and HBF4 ranging from 0.05 to 1
ml. Up to 40 samples can be digested simultane-
ously under identical experimental conditions in
the microwave autoclave. A starting pressure of
50 bar (with Ar) was applied to the reaction
chamber. Vessels were then heated in the micro-
wave autoclave for 76 min, increasing the temper-
ature up to 240 8C; during this phase the pressure
in the reaction chamber reached approximately
110 bar. The heating program consisted of the
following steps: room temperature to 60 8C in 9
1281
min; 60–125 8C in 25 min; 125–160 8C in 10
min; 160–240 8C in 12 min; holding 240 8C for
20 min (Fig. 1). After cooling for approximately
35 min well below the boiling point of the acid
mixture at atmospheric pressure, the reaction
chamber was opened. All digestion solutions of
peat samples contained a slight precipitate even
under optimized experimental conditions. Howev-
er, absolutely colorless digestion solutions were
obtained which indicates efficient destruction of
the organic matter. The contents of the digestion
vessels were quantitatively transferred into gradu-
ated 15 ml polypropylene tubes (Falcon䉸, Becton
Dickinson, Meylan Cedex, France) and filled to
the mark with high-purity water.
2.5. Quality control
A peat reference material with certified elemen-
tal concentrations is currently not available. There-
fore, a plant reference material with certified or
recommended elemental concentrations (GBW
1282 M. Krachler et al. / Spectrochimica Acta Part B 57 (2002) 1277–1289
07602 Bush Branches and Leaves, Institute of
Geophysical and Geochemical Exploration, Lang-
fang, China) was analyzed with every batch of
samples to ensure the accuracy of the applied
analytical procedures. Peat 1 was additionally char-
acterized by instrumental neutron activation anal-
ysis (INAA) for selected elements in a commercial
laboratory (ACTLABS, Activation Laboratories
Ltd, Ancaster, Ont., Canada). Moreover, elemental
concentrations from an inter-laboratory trial of Peat
1 were available to evaluate the accuracy of the
results obtained in this study.
All peat samples and the certified reference
material were used as bottled. Results were cor-
rected for the moisture content in the powders as
determined on 200 mg-aliquots of each material
by an electronic moisture analyzer (MA 100 H,
¨
Sartorius, Gottingen, Germany) w20x.
3. Results and discussion
Our previous studies w13,18x showed that the
digestion procedure, more precisely, the composi-
tion of the acid mixture, has a dominant influence
on the results obtained when determining trace
elements in digestion solutions of plant and peat
samples. REE easily form insoluble fluorides dur-
ing digestion with acid mixtures containing HF or
HBF4, resulting in poor recoveries of these ele-
ments w13x. Therefore, we extended our investi-
gations to other elements, aiming at developing a
robust, reliable and reproducible analytical proce-
dure for the determination of environmentally rel-
evant elements in plant and peat matrices, based
on the dissolution of the powered samples in a
microwave heated high-pressure autoclave; this is
followed by the quantification of selected elements
in these diluted digests by ICP-QMS utilizing
either conventional pneumatic or USN.
3.1. Digestion in the microwave autoclave
The innovative software of the microwave auto-
clave allows the user to select a desired heating
profile instead of power cycles, i.e. various power
steps, to achieve heating of the contents of the
digestion vessels. The heating algorithm automat-
ically adjusts the microwave power to follow the
selected heating profile (Section 2), the tempera-
ture of which is controlled by a sensor (Fig. 1).
This feature makes the digestion procedure inde-
pendent of the mass andyor number of samples
digested. In contrast, earlier microwave devices
utilized microwave power steps (onyoff cycles of
the magnetron) to heat the sampleyacid mixtures
w8x. In these previous versions of laboratory micro-
wave ovens, the microwave energy applied to a
particular vessel was obviously dependent on the
number of vessels placed in the microwave oven,
on sample mass and volumes of acids employed
w8x. When necessary, the software of the micro-
wave autoclave additionally allows on-line tem-
perature and pressure control by regulation of the
microwave power output.
Fig. 1 displays a typical temperatureypressurey
microwave power profile obtained during the
digestion of forty 220 mg aliquots of powdered
peat and plant samples with 3 ml HNO3 and 0.1
ml HBF4. Initially, the temperature of the acid
mixture in the digestion vessels was gently raised
to 125 8C within 34 min. At that point of the
digestion most of the organic material was readily
oxidized. Although a higher heating rate is possi-
ble, we preferred a moderate increase of the
temperature to avoid the production of foam, which
in turn, could potentially cause cross-contamina-
tion of the samples. In the second part of the
digestion procedure the temperature was continu-
ously increased to 240 8C for obtaining clear
digestion solutions. During this phase of the diges-
tion, the starting pressure of 50 bar exponentially
increased to approximately 110 bar (Fig. 1). The
microwave power that is needed to follow the pre-
selected heating profile is increased with increasing
temperature and ranged from approximately 100
to 1000 W. However, the maximum power of the
magnetron was only needed during the last minutes
before reaching the selected maximum temperature
of 240 8C and rapidly fell to about only 400 W
for holding this temperature. After 76 min, the
microwave power was completely turned off and
both temperature and pressure exponentially
decreased approaching their initial values approx-
imately 1 h later.
In comparison to other digestion devices, the
microwave autoclave provides several superior fea-
 M. Krachler et al. / Spectrochimica Acta Part B 57 (2002) 1277–1289
tures: The high-sample throughput of 40 samples
per run increases productivity. Samples are digest-
ed in ‘quasi-open’ vessels in a pressurized metal
reaction chamber. Therefore, only the maximum
heating temperature limits the lifetime of the ves-
sels and not additionally the pressure, which is the
case with conventional microwave digestion ves-
sels (pressurized digestion bombs). Moreover,
samples are digested under identical experimental
conditions, serving reproducibility and compara-
bility of the subsequent trace element measure-
ments. Another advantage of the microwave
autoclave is the fact that H2O2—which is used to
re-oxidize nitrous gases produced during digestion
to HNO3 again, thereby reducing the pressure
inside the reaction chamber—is not directly added
into each digestion vessel (as is common practice
in conventional microwave digestion procedures),
but can be added in a PTFE vessel which is placed
inside the reaction chamber. In this way H2O2 is
distilled into the digestion vessels avoiding direct
contact of the native H2O2 with the samples.
Therefore, analytical grade H2O2 can be used
instead of high-purity H2O2, thereby avoiding a
considerable expense.
Like other autoclaves employed for sample
digestion, e.g. high-pressure asher (HPA), the
microwave autoclave can be heated to 300 8C and
a pressure of 200 bar. Because microwave energy
is directed at the sampleyacid mixtures in the
microwave autoclave, samples are efficiently heat-
ed to the desired temperatures, speeding up the
dissolution reactions. The reaction chamber of the
microwave autoclave, in turn, is cooled by a chiller
which normally keeps the metal reaction chamber
at temperatures below 50 8C, reducing the cooling
times required to bring digestion solutions well
below their boiling point at atmospheric pressure
(Fig. 1).
3.2. Selection of nebulizers and internal standards
The selection of appropriate internal standards
(IS) is of utmost importance, especially when
high-efficiency nebulizers such as an USN are
employed w13,16x. The elements rhodium and rhe-
nium were tested for this purpose. Commonly, the
high-aerosol yield of USN improves detection
1283
limits by about one order of magnitude: this is a
distinct advantage for elements expected at low
concentrations (Ag, Cd, Tl, Th, U). Additionally,
many polyatomic interferences that may hamper
the reliable determination of a particular element
can be reduced to a negligible extent: this feature
is attractive for elements such as Co and Ni whose
ICP-QMS signals are known to overlap with pol-
yatomic species originating from the matrix and
the plasma gas (mainly CaO and ArOH) in a
quadrupole mass analyzer.
Based on the agreement between found concen-
trations and certified values for trace elements in
the reference material GBW 07602 Bush Branches
and Leaves, 103Rh was selected as IS to normalize
the ICP-MS signals of all elements. The ICP-QMS
signal response of Th was very similar to that of
most of the REE determined in a previous study
w13x. Thus, as reported earlier for the REE w13x,
the ICP-MS signals for Th were therefore corrected
by both Rh and Re.
As noted earlier, USN may be helpful to deter-
mine some critical elements, although some sub-
stantial discrepancies between measured and
certified values remained. For example, concentra-
tions of Co determined in the digests of the
reference material GBW 07602 Bush Branches
and Leaves were distinctly higher than the certified
value (Table 2), the reasons of which will be
outlined in detail below. Perfect agreement
between experimental Cd concentrations
(0.145"0.008 mg gy1) and the certified value of
0.14"0.01 mg gy1 was obtained for this reference
material using the USN. Employing the CF nebu-
lizer, cadmium concentrations determined in iden-
tical digestion solutions were distinctly higher
(0.204"0.008 mg gy1). To explain this discrep-
ancy, two additional environmental reference mate-
rials (BCR No. 62 Trace Elements in Olive Leaves
and CTA-VTL-2 Virginia Tobacco Leaves, Insti-
tute of Nuclear Chemistry and Technology, War-
szawa, Poland) with certified Cd concentrations
were analyzed using the CF nebulizer. Concentra-
tions of Cd determined in the digests of these
reference materials by ICP-QMS agreed well with
their corresponding certified values. Similarly, con-
centrations of Cd determined with USN-ICP-QMS
were approximately 25% lower than the values
1284 M. Krachler et al. / Spectrochimica Acta Part B 57 (2002) 1277–1289

Table 2 tionally determined Cu in this reference material

Comparison of experimental and certified concentrations by inductively coupled plasma-atomic emission
(mean"S.D., mg gy1) in the reference material GBW 07602
Bush Branches and Leaves spectrometry (ICP-AES) and found similar results
(4.42"0.19 mg gy1, Ns2) as established by ICP-
Isotope Nebulizerb Found Certified QMS (Table 2). Again the above mentioned cer-
for ICP-QMS (Ns15) tified reference materials were analyzed yielding,
43
Caa CF 2.14"0.14 2.22"0.07 however, variable agreement between found and
51
V CF 2.39"0.14 2.4"0.2 certified Cu concentrations. For the reference
52
Cr CF 2.27"0.18 2.3"0.2 material BCR No. 52 Trace Elements in Olive
55
Mn CF 57.9"3.0 58"3 Leaves found Cu values were approximately 15%
59
Co USN 0.591"0.048 0.39"0.03
60
Ni USN 2.12"0.32 1.7"0.3 below the target concentration, whereas the found
65
Cuc CF 4.63"0.38 5.2"0.3 and certified concentration (18.2"0.9 mg gy1) in
66
Zn CF 20.0"1.0 20.6"1.0 CTA-VTL-2 Virginia Tobacco Leaves (17.6"0.6
85
Rb
107
CF 3.95"0.12 4.2"0.2 mg gy1, Ns4) overlapped.
Ag USN 0.029"0.007 0.027"0.005 The concentration ranges of all other elements
114
Cdc CF 0.204"0.008 0.14"0.01
114
Cdc USN 0.145"0.008 0.14"0.01 determined in the reference material Bush Branch-
137
Ba CF 19.9"0.6 19"2 es and Leaves overlap with the values (most of
205
Tl USN 0.016"0.002 (;0.01)d them certified) provided by the manufacturer
232
238
Th USN 0.370"0.027 0.37"0.02 (Table 2).
U USN 0.117"0.006 (0.11)d
a
Concentration in mg gy1. 3.3. Influence of HF and HBF4
b
CF, cross flow nebulizer; USN, ultrasonic nebulizer.
c
See text. Our previous studies on the determination of
d
Indicative values only.
REE in plant and peat matrices clearly revealed
that the volume of HF or HBF4 added to the
obtained with the CF nebulizer. Repetitive prepa- digestion mixture is a dominant factor for obtain-
ration and analyses of procedural blank solutions ing correct results w13x. The tolerance to ‘excess
revealed stable Cd levels that were at least 20- fluoride’ was shown to be much higher in the case
times lower than actual Cd concentrations deter- of HBF4. Considering this aspect and various other
mined in any reference material. Therefore, we advantages, in the present study HBF4 was strongly
assume that (i) by the use of the USN Cd can be preferred over HF which is commonly added to
lost through its membrane desolvation unit leading dissolve siliceous matter present in plant and peat
to diminished results and (ii) the higher Cd value samples in the present study. In fact, it was
obtained with the CF nebulizer from digests of eventually decided to avoid HF altogether.
GBW 07602 Bush Branches and Leaves is correct. Although the reaction mechanism of HBF4 with
This implies that the certified Cd value is too low. silicates is quite complex and not fully elucidated,
Careful studies of the whole sample pretreatment it is assumed that HBF4 hydrolyses to Fy, BF3OH
revealed that contamination of the reference mate- and BF2(OH)2 in aqueous solution, thus liberating
rial GBW 07602 Bush Branches and Leaves with fluoride for the conversion of silicates in the
Cd in the laboratory can be most probably exclud- samples to gaseous SiF4.
ed. The analysis of two different bottles of this Therefore, we investigated only the influence of
material (an used bottle and an original, previously various volumes (0, 0.05, 0.1, 0.2, 0.5 and 1 ml)
unopened one) yielded—within the expected ana- of HBF4 added to 3 ml HNO3 used to dissolve
lytical uncertainty of 4%—identical Cd results. 250 mg aliquots of Peat 1 in the microwave
Results obtained for Cu in the reference material autoclave. Peat 1 which is approximately 22% ash
GBW 07602 Bush Branches and Leaves by CF- by weight, contains a distinctly higher amount of
ICP-QMS were approximately 10% lower than the silicates (experienced visibly) compared to the
corresponding certified concentration. We addi- other two matrices investigated in this study.
 M. Krachler et al. / Spectrochimica Acta Part B 57 (2002) 1277–1289 1285

Therefore, we chose Peat 1 to elucidate the influ-

ence of various amounts of silicate-dissolving
HBF4 with this peat material. For this investiga-
tion, elements in the digestion solutions were
determined by ICP-QMS using a CF nebulizer
because the USN contains quartz components that
are not resistant to the attack of fluorides. At least
two replicate digestions were carried out for each
acid mixture. The signal intensities of the ICP-
QMS measurements were normalized to sample
mass and IS count rate. Results of the analysis of
digestion solutions obtained after digestion with 3
ml nitric acid alone were set to 100% and all other
concentrations of each element were plotted rela-
tive to this first data point (Fig. 2a and b). As
clearly shown in Fig. 2, the added amount of
HBF4, which caused no matrix effects, distinctly
influences the final result.
Generally, addition of small volumes of HBF4
increased the measured concentrations indicating
an association of the investigated elements with
the silicate fraction of peat. Only concentrations
of cadmium were gradually decreasing with
increasing volumes of HBF4 (Fig. 2a). This
decrease, however, amounted to ‘only’ 10% when
the maximum volume of 1 ml HBF4 was added to
the digestion mixture. The relative increases of
concentrations of the other elements varied
between approximately 10% for Ag, Cu and Zn
(Fig. 2a) and approximately 80% for Rb (Fig.
2b), when the digestion mixture contained 0.05 ml Fig. 2. Dependence of the results for selected trace elements
on the composition of the digestion mixture (HNO3yHBF4 ) as
HBF4. The concentrations of most elements determined in digestion solutions of Peat 1 by ICP-QMS. (a)
remained fairly constant upon further addition of Ag, Cd, Cu, Ni, Tl, U, V and Zn; (b) Ba, Rb and Th.
HBF4, although either a slight decrease or increase
was observed for some elemental concentrations.
As documented in Fig. 2a, chromium shows a ICP-QMS. Comparison of the results obtained for
different behavior, so does Th and Rb (Fig. 2b). Ca and Mn with certified or accepted values in
Interestingly, the patterns observed for Th and Rb the reference material GBW 07602 Bush Branches
are very similar to those observed for the fraction- and Leaves showed good agreement, underpinning
ation of REE caused by higher volumes of HBF4 the suitability of the applied analytical approach
as elucidated in a previous study w13x. for the reliable quantification of both elements
Calcium and Mn are not included in this initial (Table 2). Signal intensities of the mono-isotopic
59
study because their high concentrations in Peat 1 Co increased dramatically with increasing vol-
caused detector overflow in ICP-QMS. Conse- umes of HBF4 in the digestion mixture. Blank
quently, sample mass of digested aliquots of Peat levels of Co, however, remained constant. The
1 were decreased by 20% for further analyses, formation of the polyatomic species 40Ca19F is
thereby avoiding signals for the 2 elements to most probably the reason for this observed effect
exceed the detector capabilities of the employed which can be reduced by employing an USN. The
1286 M. Krachler et al. / Spectrochimica Acta Part B 57 (2002) 1277–1289

Table 3
Concentrations (mean"S.D., mg gy1) of the 15 investigated elements in Peat 1, as determined by various analytical approaches

Isotope Present study HotplateyICP-QMSb Europeatd INAAe

for ICP-QMS (Ns14) (Ns15) (Ns15)
43
Caa 43.1"2.3 –c 40"2 41"7
51
V 11.0"0.3 –c 9.8"0.6 –c
52
Cr 9.87"0.54 9.19"0.54 8.3"0.8 8.9"2.6
55
Mn 247"15 253"5 230"15 –c
59
Co 2.09"0.21 1.76"0.03 1.80"0.12 1.9"0.4
60
Ni 6.56"0.57 6.28"0.17 6.0"0.6 –c
65
Cu 190"6 204"2 202"9 –c
66
Zn 40.3"1.8 46.8"1.5 43"3 40.9"7.1
85
Rb 7.1"0.8 –c 7.5"1.2 6.3"1.6
107
Ag 0.31"0.05 –c 0.42"0.08 –c
114
Cd 0.503"0.017 0.53"0.01 0.53"0.03 –c
137
Ba 126"4 132"1 127"5 129"28
205
Tl 0.076"0.004 –c –c –c
232
Th 0.55"0.08 –c 0.79"0.01f 0.8"0.2
238
U 1.22"0.07 –c 1.13"0.08f 1.3"0.3
a
Concentration in mg gy1.
b
Analytical procedure routinely applied at the Research Centre Juelich based on closed pressurized digestion on a hotplate for 5
h at 180 8C followed by ICP-QMS.
c
Not determined.
d
Mean"95% confidence interval. Data displayed include the results of at least four independent analytical approaches based on
different physical principles.
e
Instrumental neutron activation analysis.
f
One analytical method only.

same holds true for the occurrence of 43Ca16O
species that plagues the reliable determination of
Co by ICP-QMS. Elevated results for Co in the
reference material GBW 07602 Bush Branches
and Leaves might have its rationale in the above
mentioned aspects, although results for Co
obtained for Peat 1 agreed very well with the
accepted concentrations derived from the Europeat
Project w21x and from INAA (Table 3).
The above experiments show that digestion
using an acid mixture containing 3 ml HNO3 and
0.1 ml HBF4 is a good compromise to obtain
reliable results for all elements investigated in this
study. Therefore, this digestion procedure was
applied to the dissolution of all samples.
3.4. Results for peat samples
Table 3 summarizes the concentrations of the
15 elements determined in Peat 1 by the developed
microwave autoclaveyICP-QMS procedure in this
study. Results for these elements obtained by
INAA, an inter-laboratory trial (Europeat project
w21x) and by an analytical procedure routinely
applied in the Research Centre Juelich (home-
made closed pressurized digestion procedure on a
hotplate at 180 8C for 5 h followed by ICP-QMS)
are included in this Table for a comparison. Gen-
erally, individual results for a particular element
from the various analytical techniques based on
different physical principles compare well to each
other (Table 3). Concentrations of V determined
in this study were somewhat higher than the results
of the Europeat project. Besides using the CF
nebulizer, V has been additionally determined
employing the USN, reducing the potential 35Cl16O
interference hampering the reliable determination
of V by orders of magnitude. Results obtained by
USN-ICP-MS and CF-ICP-MS were identical and
analytical problems of a 35Cl16O polyatomic inter-
ference on the 51V signal can therefore be exclud-
ed. The high-destruction power of the developed
digestion procedure might release all V present in
the peat samples, thereby yielding the reported
 M. Krachler et al. / Spectrochimica Acta Part B 57 (2002) 1277–1289 1287

Table 4
Influence of the composition of the digestion mixture on the analytical results (mean"S.D., mg gy1) in Peat 2 as obtained by the
microwave autoclaveyICP-QMS procedure

Isotope 3 ml HNO3 3 ml HNO3q 3 ml HNO3q ICP-AES or

for ICP-QMS (Ns8) 0.1 ml HF 0.1 ml HBF4 ICP-QMSb
(Ns8) (Ns8) (Ns4)
43
Caa 1.67"0.08 1.64"0.09 2.66"0.24 2.83"0.04
51
V 3.28"0.09 3.39"0.18 3.79"0.13 4.0"0.2
52
Cr 3.62"0.54 4.06"0.39 4.84"0.13 5.24"0.73
55
Mn 4.25"0.66 4.04"0.16 4.61"0.24 4.4"0.1
59
Co 0.46"0.06 0.46"0.05 0.46"0.05 –c
60
Ni 2.15"0.35 2.20"0.26 2.45"0.35 –c
65
Cu 2.37"0.14 2.28"0.19 2.43"0.16 2.87"0.05
2.74"0.28d
66
Zn 4.47"0.23 4.98"0.44 4.67"0.21 4.78"0.23d
85
Rb 1.77"0.06 1.80"0.06 2.12"0.09 –c
107
Ag 0.007"0.002 0.007"0.001 0.007"0.001 –c
114
Cd 0.074"0.009 0.077"0.005 0.071"0.004 0.078"0.002d
137
Ba 18.3"0.3 21.8"0.6 21.4"0.6 22.7"0.4
205
Tl 0.013"0.001 0.015"0.02 0.015"0.01 0.019"0.002d
232
Th 0.303"0.016 0.221"0.043 0.371"0.015 –c
238
U 0.075"0.002 0.134"0.007 0.122"0.003 –c
a
Concentration in mg gy1.
b
Analytical procedures routinely applied at the Research Centre Juelich by well-qualified operators based on closed pressurized
digestion on a hotplate for 5 h at 180 8C followed by either ICP-QMS or ICP-AES, respectively.
c
Not determined.
d
Determined by ICP-QMS.

higher V results. It should be noted that results
from INAA generally had the highest standard
deviations.
Experiments carried out to study the influence
of the acid mixture on the recovery of the elements
under investigation in Peat 2 are summarized in
Table 4. For selected elements additional results
from ICP-AES (closed, pressurized digestion: 200
mg sampleq2 ml HNO3q200 ml HF for 5 h at
180 8C) or ICP-QMS (closed, pressurized diges-
tion: 200 mg sampleq2 ml HNO3 for 90 min at
300 8C) measurements in Peat 2 were available
and are included for comparison with the results
obtained in the present study. For Ca, V, Cr, Rb
and Th the highest concentrations were determined
in digests containing 0.1 ml HBF4. Concentrations
of Ba determined in Peat 2 were statistically non-
distinguishable in digestion solutions containing
either 0.1 ml HF or 0.1 ml HBF4, but were
distinctly higher than results of the analysis of
digestion solutions with nitric acid alone. A similar
result was obtained for uranium, which requires
HF or HBF4 in the digestion mixture to achieve
good recoveries. In fact, an increase of approxi-
mately 70% of the uranium concentrations in HF-
or HBF4-containing digestion solutions was found,
compared to digests containing HNO3 alone. Inter-
estingly, the aforementioned effects strongly vary
with the composition of the peat matrix. When
comparing uranium results for digestion solutions
of HNO3 alone and of HNO3 y0.1 ml HBF4, the
increase of uranium concentrations amounted to
approximately 15 and 63% for Peat 1 and 2,
respectively. In contrast, concentrations of Ba
increased by approximately 70 and 16% for Peat
1 and Peat 2, respectively, in digestion solutions
containing small amounts of HF or HBF4. These
findings indicate that Ba and U are bound to
different fractions of peat, both of which, however,
partly consist of silicates.
For Co, Zn, Ag, Cd and Tl in Peat 2, no
significant differences were obtained from the
determination of these elements in solutions of the
three different digestion procedures listed in Table
1288 M. Krachler et al. / Spectrochimica Acta Part B 57 (2002) 1277–1289
4. A strong negative effect caused by the presence
of fluorides in the digests was observed for thori-
um. As already documented in Fig. 2, concentra-
tions of Th quantified in digestion solutions of
Peat 1 containing 1 ml HBF4 were only approxi-
mately 45% relative to HNO3 digests. This nega-
tive impact of fluoride in the digestion solution on
the Th results is already evident for very small
amounts of HBF4 (Fig. 2). In the case of HF in
the solutions, this situation even worsens as dem-
onstrated in Table 4 for Peat 2. Approximately
40% less Th concentrations was found when Peat
2 was digested with 3 ml nitric acid and 0.1 ml
HF compared to HNO3 alone. However, adding
0.1 ml HBF4 to the digestion mixture increased
Th concentrations by more than 20% relative to
digestion solutions containing only HNO3 (Table
4). Additionally, the determination of Th by ICP-
MS is hampered by the occurrence of a distinct
memory effect which can easily yield inaccurate
results when samples with high and low Th con-
centrations are measured alternatively. This Th
memory effect has been also observed by other
authors w16,22x and originates from the tendency
of an unidentified thorium compound to volatilize
from the spray-chamber walls w22x. Therefore, it
is of utmost importance to measure blank solutions
before standards or digested sample solutions. As
concentrations of Th in the investigated samples
were quite comparable, the described memory
effect did not cause any analytical problems in
this study.
4. Conclusions
The microwave autoclave employed for disso-
lution of plant and peat samples in the present
study provides an efficient tool for sample diges-
tion. Nitric acid alone cannot completely liberate
all elements from the peat or plant matrix probably
because much of the inventory of many elements
is hosted in the silicate fraction ultimately derived
from rock weathering. Addition of fluoride (via
HF or HBF4) to the digestion mixture efficiently
destroys siliceous material but has to be carefully
selected to avoid diminished results for some
elements. Dissolution of 200–250 mg aliquots of
powdered peat or plant samples with 3 ml HNO3
and 0.1 ml HBF4 at a temperature of 240 8C is
recommended.
Careful selection of appropriate IS allows the
reliable determination of trace elements in the
digestion solutions of peat and plant samples by
ICP-QMS. Although the use of an USN helps to
reduce polyatomic interferences significantly, the
determination Co which is prone to spectral inter-
ferences by CaO, ArF and CaF, remains critical.
The use of a sector field ICP-MS would substan-
tially improve the determination of Co. Elements
such as Cd are removed through the membrane
desolvation of the USN and therefore have to be
determined employing a CF nebulizer.
The developed analytical procedure allows the
reliable determination of 15 elements in plant and
difficult-to-digest peat matrices including peat with
high ash (Peat 1: approximately 22%) and high
concentrations of matrix components (Peat 1 con-
tains 4% Ca, 0.8% Fe, 0.3% K and 0.3% Na) by
ICP-QMS. This new procedure is a powerful tool
for biomonitoring and geochemical studies and
will be subsequently applied to the determination
of these elements in age-dated ombrotrophic peat
bogs to reconstruct the changing rates of atmos-
pheric deposition of the elements investigated and
to relate these to Holocene climate change and
anthropogenic emissions.
Acknowledgments
Financial support to M.K. from the Forschung-
spool of the University of Heidelberg (Project:
‘Trace element analyses of geological archives:
sediments, peat, and ice’) and to C.M. from the
Deutsche Forschungsgemeinschaft DFG (EM 51y
3-1) are gratefully acknowledged.
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