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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
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
1121
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
Table 2 Oxidation efficiency of four digestion systems at different temperatures (200 mg TORT 2; 5 mL nitric acid 69.5%)
Temperature/uC
200
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
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
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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
(1)
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
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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).
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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
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.
References
1 M. Wurfels, E. Jackwerth and M. Stoeppler, Fresenius J. Anal.
Chem., 1987, 329, 459.
2 M. Wurfels, LABO, 1989, 3, 7.
3 T. Wondimu and W. Goessler, Bull. Chem. Soc. Ethiop., 2000, 14,
99.
4 P. Schramel and J. Ovcar-Pavlu, Fresenius J. Anal. Chem., 1979,
298, 28.
5 G. Knapp, B. Maichin and U. Baumgartner, At. Spectrosc., 1998,
19(6), 220.
6 L. Jian, W. Goessler and K. J. Irgolic, Fresenius J. Anal. Chem.,
2000, 366, 48.
7 P. Schramel and S. Hasse, Fresenius J. Anal. Chem., 1993, 346, 794.
8 P. Schramel, GSF, Munich, Germany, personal communication.
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