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Efficiency of oxidation in wet digestion procedures and influence from


the residual organic carbon content on selected techniques for
determination of trace elements{

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M. Wasilewska,a W. Goessler,b M. Zischka,c B. Maichinc and G. Knapp*c


a

Blachownia Institute of Heavy Organic Synthesis, ul. Energetykow 9, 47-225 KedzierzynKozle, Poland
b
Institute of Chemistry, Analytical Chemistry, Karl-Franzens-University, Universitatsplatz 1,
A-8010 Graz, Austria
c
Institute for Analytical Chemistry, Micro- and Radiochemistry, Graz University of
Technology, Technikerstrasse 4, A-8010 Graz, Austria
Received 17th January 2002, Accepted 22nd April 2002
First published as an Advance Article on the web 23rd May 2002
The efficiency of oxidation in wet digestion procedures for organic materials can be of great importance for the
quality of the analytical data of various measurement techniques. Four items of commercial equipment for
pressurised sample digestion were compared and it could be shown that the residual carbon content achieved
only depends on the temperature of the digestion solution and not on the equipment, if the digestion time is
long enough to reach the steady state. The consumption of nitric acid during the digestion procedure was
investigated. This is important to consider, because the signal response of instrumental element determination
can be influenced by the acid concentration of the sample solution. The relation between sample amount,
maximum digestion temperature and residual carbon content in a closed vessel digestion system was depicted
and the influence of incomplete oxidation of organic sample matrix on the determination of As and Se by
means of axial ICP-OES was investigated.

Introduction
Many powerful methods for the determination of trace
elements in solid samples, such as AAS, ICP-OES, ICP-MS
and voltammetry, require sample decomposition in most cases.
In this context it is important to know the relevant factors for
the complete decomposition of organic matrices, particularly
to know about the interferences resulting from the residual
carbon content after incomplete sample decomposition, in
order to obtain data of highest possible reliability and least
possible measurement uncertainty. However, it is often the
sample decomposition in particular which affects the accuracy
and repeatability of the entire analytical procedure. While
systematic errors like contamination and volatilisation play
only a subordinate role when pressurised sample decomposition in closed systems is applied, insufficient oxidation of
organic compounds can affect the subsequent instrumental
determination to a considerable degree.
Pressurized wet digestion is a state-of-the-art procedure for
sample decomposition before the analysis of trace elements.
Pure nitric acid, the reagent recommended for most of the
high performance measuring devices, can be applied to digestion of organic materials due to its elevated boiling point in
a pressurized system. Standard errors like contamination and
losses of volatile analytes can be reduced significantly. The
oxidation efficiency of a digestion method has to be checked by
measuring the residual organic carbon content (TOCtotal
organic carbon) in digestion residues, because it often happens
that completely clear and colourless solutions are obtained but
their carbon content is still high. Those residual organic compounds can be more or less interfering in subsequent measuring
methods. Wurfels et al.1,2 described extremely strong impacts
from organic compounds in the elemental determination by
{Presented at the 2002 Winter Conference on Plasma Spectrochemistry, Scottsdale, AZ, USA, January 612, 2002.

DOI: 10.1039/b200644h

means of inverse voltammetry. He showed that a digestion


temperature of about 300 uC is necessary for pressurized
sample digestion with pure nitric acid to obtain a digestion
solution with less than 0.1% carbon. Otherwise, trace elements
cannot be determined with inverse voltammetry.
Not only inverse voltammetry but also other instrumental
analytical techniques, such as AAS, ICP-OES and ICP-MS,
can be interfered to a certain degree by dissolved organic
compounds. Organic oxidation products can act as surfactants
and the efficiency of pneumatic nebulizers can be changed. By
applying internal standardization or standard addition correct
analytical results can be obtained in such cases. The determination of hydride-forming elements like As and Se needs
a complete oxidation of the organic compounds of these elements; otherwise, the optical background in graphite furnace
AAS and ICP-OES can rise and polyatomic ions in ICP-MS
interfere with the determination of some isotopes.3

Experimental
Reagents
Nitric acid (69.5%) and hydrochloric acid (37.5%) pro analysis
reagent grade, and KOH (0.1 M), cellulose and nicotinic acid
were obtained from Merck (Darmstadt, Germany). Nitric acid
was purified in-house by sub-boiling distillation using a quartz
still. Standard solutions for As, Cd, Co, Cr, Cu, Fe, Hg, Mn,
Ni, Pb, Se, Sr, V and Zn were prepared from 1000 mg L21 (2%
HNO3) standard solutions (SPEX Plasma Standard, SPEX,
Metuchen, NJ, USA). Solutions were made up with distilled,
deionised (18 MV) water (Barnstead Nanopure, Dubuque, IA,
USA). The certified reference materials CRM 151 (Skimmed
Milk) and CRM 422 (Cod Muscle) were obtained from the
European Commission Joint Research Centre, Institute for
Reference Materials and Measurements (IRMM) (B-2440
Geel, Belgium), and CRM TORT 2 (Lobster Hepatopancreas)
J. Anal. At. Spectrom., 2002, 17, 11211125

This journal is # The Royal Society of Chemistry 2002

1121

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was obtained from the National Research Council Canada,


Ottawa, Canada. The mobile phases for chromatography of
organic arsenic compounds were prepared with NH4H2PO4
and pyridine obtained from Merck (Darmstadt, Germany):
anion exchange, 20 mM NH4H2PO4 at pH 6.0; cation
exchange, 20 mM aqueous pyridine at pH 2.6.

Table 1 Digestion programs for four different decomposition procedures


Digestion
system

Applied
vessel

Pressure/
bar

HPA

35 ml,
quartz

100

Multiwave

50 ml,
quartz

75

MLS Ethos
1600

100 ml,
TFM

30

MLS
ultraCLAVE2

20 ml,
TFM

60

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Instrumentation
A Multiwave pressurized microwave digestion device, equipped
with 50 mL quartz vessels, for 75 bar working pressure and a
High Pressure Asher HPA high temperature digestion device
with 70 mL quartz vessels for 140 bar digestion pressure were
used (Anton Paar GmbH, Graz, Austria, and PerkinElmer,
Norwalk, CT, USA). Also used were an MLS Ethos 1600
pressurized digestion device with 100 mL TFM vessels and
an MLS ultraCLAVE 2 microwave digestion device for high
pressurehigh temperature sample digestion, equipped with
30 mL TFM-vessels (MLS, Leutkirch, Germany). A Shimadzu
TOC-5050 total organic carbon analyser (Shimadzu GmbH
Europe, Duisburg, Germany) was used for the determination
of the residual organic carbon content. Determination of
elements were carried out by ICP-OES (Optima 3000XL),
GFAAS (AAnalyst 800) and ICP-MS (PE-SCIEX ELAN 6100
ICP-DRCMS), all from PerkinElmer. Separation and determination of organic arsenic compounds were carried out by
ion chromatography with HPLC (Series 1100) from HewlettPackard, Supelcosil LC-SCX cation-exchange column, Hamilton
PRP-X100 anion-exchange column and VG PQ2 Turbo Plus
ICP-MS equipped with a hydraulic high pressure nebulizer as
detector.
Part AOxidation capability of different decomposition
techniques
The oxidation capability of nitric acid depends strongly on the
digestion temperature. The increased pressure is needed just to
raise the boiling point of nitric acid. To show the temperature
dependency of the oxidation capability of nitric acid and the
influence of the applied digestion equipment, CRM TORT 2
was digested at various temperatures by means of four different
pieces of digestion equipment:
$ HPA (High Pressure Asher): Pressurized wet digestion in
closed quartz vessels with conductive heating;
$ Multiwave: Pressurized microwave-assisted wet digestion
in closed quartz vessels;
$ MLS Ethos 1600: Pressurized microwave-assisted wet
digestion in closed Teflon vessels;
$ MLS ultraCLAVE 2: Pressurized microwave-assisted wet
digestion in open vessels.
Digestion methods. For all the four investigated digestion
techniques a portion of 200 0.1 mg each of TORT 2 was
digested with 5 mL HNO3. Conditions of digestion are
presented in Table 1.
The certified reference material TORT 2 was chosen because
of its content of organic compounds which need a high
oxidation potential to be oxidised. Some of those compounds
cannot be oxidised with nitric acid at temperatures below
300 uC, even after a long digestion time.1,2 The digestion time
for each of the digestion techniques used was optimised. The
reduction of the optimised digestion time of 30% gave a

Digestion program
Step 1ramp20 min
(to digestion temp.)
Step 2hold60 min
(digestion temp.)
Step 3cooling30 min
Step 1ramp10 min
(to digestion temp.)
Step 2hold30 min
(digestion temp.)
Step 3cooling15 min
Step 12 min (85 uC)
Step 25 min (145 uC)
Step 33 min (200 uC)
Step 430 min
(digestion temp.)
Step 5cooling
Step 1ramp15 min
(to digestion temp.)
Step 2hold30 min
(digestion temp.)
Step 3cooling30 min

significant increase in the TOC value. On the other hand,


extension of the digestion time did not result in any reduction
of the residual carbon content.
Comparison of the oxidation capability. Oxidation efficiency
for the sample by means of four different digestion systems
at different temperatures was checked by determination of
residual organic carbon content (TOC) in % of the initial
weight (TORT 2 about 50% carbon). The obtained results are
presented in Table 2.
These results clearly indicate that the oxidation efficiency
is almost independent of the digestion equipment applied. With
the ultraCLAVE 2 digestion temperatures up to 300 uC are
possible but were not investigated in this study due to the use of
Teflon vessels. Sample digestion with Ethos 1600 showed
somewhat higher TOC values at lower temperatures. Probably
the temperature measurement was not quite correct in this
range. The HPA and ultraCLAVE 2 systems are the only pressurized digestion systems which enable digestion temperatures
w300 uC. Digestion times with ultraCLAVE 2 are shorter due
to the microwave heating applied.
Part BNitric acid consumption versus oxidation efficiency
It can be assumed that the consumption of nitric acid depends
strongly on the oxidation efficiency. Corresponding TOC
values and nitric acid consumption figures were determined to
find out this dependence.
Analytical procedure. Cellulose and nicotinic acid, 0.4 g
each, were digested with 4 mL of nitric acid by means of the
Multiwave. The ramp time up to the digestion temperature was
10 min, the hold time 25 min. The digestion temperatures were
150 uC and 200 uC. The digestion solutions were diluted to
40.0 mL with distilled water. The remaining nitric acid was
determined by titration with 0.1 M KOH. The digested

Table 2 Oxidation efficiency of four digestion systems at different temperatures (200 mg TORT 2; 5 mL nitric acid 69.5%)
Temperature/uC

200

HPA TOC (%) (n ~ 3)


Multiwave TOC (%) (n ~ 5)
Ethos 1600 TOC (%) (n ~ 5)
UltraCLAVE 2 TOC (%) (n ~ 6)

8.3
5.8
10.6
7.5

1122

220

0.6
1.0
1.0
0.5

3.6
3.5
6.3
3.6

J. Anal. At. Spectrom., 2002, 17, 11211125

0.2
0.4
0.7
0.4

240

250

260

280

300

2.1 0.5
2.0 0.4

2.0 0.4

1.6 0.5
1.6 0.5

1.2 0.2

1.1 0.4

0.4 0.1

v0.1

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Table 3 Nitric acid consumption in comparison with the digestion


temperature and oxidation efficiency (0.4 g cellulose; 0.4 g nicotinic
acid; 4 mL nitric acid 69.5%)
Remaining nitric acid (%) and TOC (%) after sample decomposition
(n ~ 3)

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Temperature/
uC
4 mL HNO3
Blank
digestion
Cellulose
Nicotinic
acid

150

200

Nitric acid

TOC

Nitric acid

100
98.5 0.2

0
0

100
94.8 0.7

74.8 2.4
98.4 0.6

0.3 0.1
99.0 1.0

67.1 0.4
94.4 0.3

TOC
0
0
0.3 0.1
98.0 1.0

solutions were compared with 4 mL of the original nitric acid.


For the calculation of the residual organic carbon (TOC), the
carbon contents of cellulose and nicotinic acid were considered
to be 44.4% and 58.5%, respectively.
Results. The results in Table 3 show that the consumption
of nitric acid corresponds with the oxidation efficiency. The
higher the digestion temperature, the more of the organic
sample is oxidised and the lower is the concentration of the
remaining nitric acid. In this particular case the influence of the
digestion temperature on the digestion efficiency is not obvious,
because cellulose is easy to oxidise and is therefore completely
oxidised even at 150 uC. The somewhat lower concentration of
nitric acid at 200 uC results from the degradation of nitric acid
at elevated temperature, as shown with the blank digestion.
Nicotinic acid, on the other hand, is such a tough compound
that it cannot be oxidised, even at 200 uC. Therefore the nitric
acid concentration is about the same as with the blank
digestion.
A varying nitric acid consumption leads to different acid
concentrations of the digestion solution and had to be considered because the signal response of some measurement
techniques is influenced by the concentration of nitric acid.46
Part COxidation efficiency for various organic materials
Various organic materials were decomposed and the digestion
efficiency was determined as the TOC value. In a closed wet
digestion system, the maximum possible digestion temperature
and therefore the oxidation efficiency decreases with increasing
sample mass.
The pressure in a closed digestion vessel consists primarily of
the partial pressures of CO2, HNO3 and NOx (eqn. 1).
ptotal ~ pCO2 1 pHNO3 1 pNOx

(1)

pCO2 corresponds to the sample mass and pHNO3 primarily to


the digestion temperature. The maximum possible pressure
depends on the digestion equipment. The conclusion of this
equation is that at a constant digestion pressure, the temperature increases with decreasing sample mass.
Analytical procedure. The organic materials were digested
with 4 mL of nitric acid in 50 mL quartz vessels at 75 bar by
means of the Multiwave. A two-step program was used:
1. Ramp within 5 min up to 75 bar working pressure;
2. Hold within 30 min at the working pressure of 75 bar.
Results. Fig. 1 shows the digestion of 0.31.2 g of milk
powder. The digestion temperature dropped from about 240 uC
to 150 uC with increasing sample mass. With decreasing
digestion temperature the residual carbon content increased.
Table 4 shows the residual carbon content (TOC) after
decomposition of various materials at 75 bar. The temperatures

Fig. 1 Correlation between sample mass, digestion temperature and


residual carbon content at constant digestion pressure of 75 bar.
(Multiwave: pressure 75 bar; digestion time 35 min. Sample matrix:
milk powder; 4 mL nitric acid 69.5%.)
Table 4 Oxidation efficiency for different various sample materials
(Multiwave; pressure 75 bar; temperatures 220250 uC; digestion time
35 min; 4 mL nitric acid 69.5%)
Sample material
NBS 1566a (oyster tissue)
TORT 2 (lobster hepatopancreas)
TORT 2 (lobster hepatopancreas)
Bovine liver
Bovine liver
Pumpkin seed
Liver pate
Milk powder
Wheat flour
CRM 414 (plankton)
NBS 1547 (peach tree leaves)
CRM 278 (mussel tissue)
CRM 422 (cod muscle)
Bisphenol A (H5C6C(CH2)2C6H5)
Bisphenol A (H5C6C(CH2)2C6H5)
Adipic acid (HOOC(CH2)4COOH)
Adipic acid (HOOC(CH2)4COOH)

Sample
mass/g
0.4
0.4
0.2
0.4
0.2
0.2
0.2
0.2
0.4
0.4
0.4
0.2
0.2
0.08
0.2
0.06
0.2

TOC (%)
(n ~ 3)
1.7 0.3
4.4 0.2
1.9 0.1
3.2 0.4
1.6 0.3
2.0 0.2
0.3 0.03
0.5 0.02
0.8 0.03
0.8 0.2
1.8 0.1
4.0 0.5
3.2 0.2
v0.1
v0.1
v0.1
v0.1

varied between 220 uC and 250 uC, depending on the material


and the corresponding sample mass (eqn. 1). The oxidation
efficiency of a given closed vessel digestion system can be
improved simply by reduction of the sample weight, always
supposing that the detection power of the subsequent measurement allows it. To obtain TOC values in the tenths of a
percent range also for tough organic substances, temperatures
between 250 and 300 uC are necessary.
Part DOxidation of organic arsenic compounds in marine
samples
The determination of As in marine samples with the hydride
generation technique requires a complete oxidation of the
organic arsenic compounds, because not all of them give the
same signal response compared with arsenous acid solutions
usually employed for calibration.7 Decomposition of TORT-2
with nitric acid at various temperatures and determination of
the remaining anionic species (arsenous acid [As(III)], arsenic
acid [As(V)], methylarsonic acid [MA], dimethylarsinic acid
[DMA]) and cationic species (arsenobetaine [AB], trimethylarsine oxide [TMAO], arsenocholine [AC] and tetramethylarsonium ion [TETRA]) by means of ion-chromatography
coupled to ICP-MS show the importance of high temperature
digestion at 300 uC with nitric acid.
J. Anal. At. Spectrom., 2002, 17, 11211125

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Analytical procedure. 0.2 g of TORT 2 was digested with 4 ml


of nitric acid at 220, 240, 260, 280 and 300 uC by means of
HPA. A two-step digestion program was used:
1. Ramp within 20 min from 20 uC to the digestion
temperature;
2. Hold within 90 min at the digestion temperature.
For the ion chromatographic separation of the digestion
residues, the acidic solutions were evaporated to dryness and
re-dissolved in 4 ml of distilled water. The chromatographic
separation of the anions was carried out on a PRP-X100 anionexchange column, and of the cations on a cation exchange
column LC-SCX, both from Hamilton.

Results. The residual organic carbon content after sample


digestion is shown in Table 2. Oxidation of organic arsenic
compounds to arsenate versus the digestion temperature is
given in Table 5.
Fig. 2 shows the chromatograms of the anionic arsenic
species after digestion of TORT 2 at 220, 260 and 300. The
signal at y90 s accounts for trimethylarsine oxide, at y120 s
Table 5 Oxidation of organic arsenic compounds to arsenate in TORT
2 at increasing decomposition temperatures (HPA; 0.2 g TORT 2; 4 mL
nitric acid 69.5%; digestion time 110 min)
Digestion temperature/uC

Arsenate (%)

220
240
260
280
300

16
22
43
91
97
Fig. 3 HPLC-HHPN-ICP-MS chromatograms of a TORT 2 sample
digested at 220, 260 and 300 uC (column: Supelcosil LC-SCX cationexchange column operated at 30 uC; mobile phase: 20 mM aqueous
pyridine at pH 2.6; injection: 100 mL).

for dimethylarsinic acid and at y310 s for arsenic acid. With


increasing temperatures the signals of the organic arsenic
species are decreasing whereas the signal of arsenic acid
increases. At 300 uC only arsenic acid can be seen in the
chromatogram. The determined total arsenic content corresponds to the certified value.
Fig. 3 shows the chromatograms of TORT 2 digests at 220,
260 and 300 uC. Going from the left to the right, there are
arsenic acid, dimethylarsinic acid and trimethylarsine oxide,
respectively. With the increasing temperature, the peaks of
the organic arsenic species disappear and only arsenic acid is
present at 300 uC.
These results show why As determination in biological
materials with hydride techniques can be completely wrong,
when the organic samples are digested by means of most of the
commercially available digestion equipment that does not
allow temperatures up to 300 uC.
Part EInfluence of remaining organic compounds on ICP-OES
with axial configuration and on a quadrupole ICP-MS with a
dynamic reaction cell
Spiked nicotinic acid samples and certified reference materials
were digested using methods of different oxidation capability.
The digests with various concentration of organic compounds
were analysed by means of the Optima 3000 XL and the ELAN
6100 DRC. The analytical results show the influence of
elevated TOC values.
Fig. 2 HPLC-HHPN-ICP-MS chromatograms of a TORT 2 sample
digested at 220, 260 and 300 uC (column: Hamilton PRP-X100 anionexchange column operated at 40 uC; mobile phase: 20 mM NH4H2PO4
at pH 6.0; injection: 100 mL).

1124

J. Anal. At. Spectrom., 2002, 17, 11211125

Digestion procedure. 0.2 g samples of nicotinic acid spiked


with arsenic (1.5 mg g21) and selenium (2.5 mg g21) were
digested with 3 ml nitric acid (65%) at 180, 220 and 250 uC by
means of the Multiwave.

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Table 6 Measurement of As and Se after digestion of nicotinic acid at


various temperatures by means of an axial viewing ICP-OES (Optima
3000 XL; shear gas, air 30 L min21; auxiliary gas, Ar 0.8 L min21;
carrier gas, 0.6 L min21; cross flow nebulizer; solution delivery,
1.4 mL min21; As 188.979 nm; Se 196.026 nm; As content, 1.5 mg g21;
Se content, 2.5 mg g21; the TOC value is the residual organic carbon
content in % of the original carbon content)
Digestion
temperature/uC

As/mg g21

Se/mg g21

TOC (%)

180
220
250

0.9 0.06
1.2 0.10
1.5 0.09

4.1 0.15
4.0 0.20
3.0 0.40

97 3
85 5
41 8

Table 7 Interference from residual organic carbon on the determination of Se in cod muscle digests by means of an axial viewing ICP-OES
and Zeeman GFAAS
Se concentration/mg g21
Certified value

Axially ICP-OES

Zeeman GFAAS

1.63 0.07

2.62 0.08

1.75 0.13

0.5 g samples of CRM 422 (cod muscle) were digested with


4 ml nitric acid and 0.2 ml hydrochloric acid by means of the
Multiwave at (a) 180 uC and (b) 250 uC, respectively.
0.2 g samples of SRM TORT 2 were digested with 5 mL of
nitric acid and 0.2 mL of hydrochloric acid at 200 and 280 uC,
respectively, by means of the HPA. The addition of small
amounts of hydrochloric acid prevents losses of Fe by adsorption of Fe(OH)3 at the surface of the quartz vessels.
Results. ICP-OES measurement by means of the Optima
3000 XL. Table 6 lists the results of the measurements along
with the corresponding TOC values for the digestion solutions.
The results show that the theoretical value is approached, and
can be achieved with decreasing TOC content. However, it
should be kept in mind that the element concentrations given
are close to the detection limit. Analysis in nicotinic acid with
ten times the analyte concentration no longer shows this
relationship to the residual carbon content.
The digests of the cod muscle samples showed TOC values of
(a) 0.8 0.1% and (b) 11 2% (n ~ 3). As, Cd, Cu, Fe, Hg,
Mn, Se and Zn were measured in these digests by means of the
Optima 3000 XL. All obtained results were within the certified
region. Only Se in the digestion solutions (b) was strongly
interfered by the remaining organic compounds. Table 7 shows
the Se concentration after measurement with ICP-OES and
Zeeman GFAAS.

ICP-MS measurement by means of the ELAN 6100


DRC. TORT 2 was digested at various temperatures and the
corresponding TOC values were shown in Table 2. As, Cd,
Co, Cr, Cu, Fe, Mn, Ni, Pb, Se, Sr, V and Zn were measured
in samples with about 8% TOC (digestion temperature 200 uC)
and with v1 % TOC (digestion temperature 280 uC) by means
of ICP-MS. No interference from the residual carbon content
could be observed.

Conclusion
The investigations described here show that for complete
oxidation of organic compounds with nitric acid the digestion
temperature should be raised up to 300 uC. The influence of the
digestion equipment is negligible if the digestion time employed
is long enough to reach the steady state. Sample digestion with
nitric acid between 220 and 250 uC (most commercial equipment is able to fulfil this prerequisite) leads to residual carbon
contents in the low percentage range. Some of the instrumental
measurement techniques can be interfered by remaining
organic compounds. Voltammetry is strongly interfered and
needs a complete oxidation of the organic matrix. Hydride
technique in combination with AAS, ICP-OES and ICP-MS
can be interfered depending on the remaining organic compounds. This paper shows that even ICP-OES can be interfered
under certain circumstances. We observed interferences at the
measurement of As and Se in the region of the detection limits
by means of the Optima 3000 XL. The same digestion residues
measured with a JobinYvon JY 701 showed no interferences.8 Such interferences seem to depend on the ICP-OES
equipment used. Also, the varying consumption of nitric acid
during the digestion procedure must be considered due to the
possible influence on the signal response.

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2 M. Wurfels, LABO, 1989, 3, 7.
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