Journal of Analytical Chemistry, Vol. 58, No. 3, 2003, pp. 240245. Translated from Zhurnal Analiticheskoi Khimii, Vol.

58, No. 3, 2003, pp. 273279.

Original Russian Text Copyright 2003 by Saprykin, Shelpakova, Chanysheva, Zaksas.

ARTICLES

Some Aspects of Sample Preparation for Determining Trace

Elements by Atomic Emission and Mass Spectrometry
A. I. Saprykin, I. R. Shelpakova, T. A. Chanysheva, and N. P. Zaksas
Institute of Inorganic Chemistry, Siberian Division, Russian Academy of Sciences,
pr. Akad. Lavrenteva 3, Novosibirsk, 630090 Russia
Received January 23, 2002; in final form, June 3, 2002

AbstractMethods of sample preparation for chemical analysis by atomic emission and mass spectrometry
are described. Depending on the analytical problem to be solved, the proposed methods provide the unification
of procedures for the quantitative analysis of samples differing in nature and chemical composition and/or the
attainment of low detection limits for impurity elements.

The solution of a wide range of problems (from the
investigation of geological and environmental samples
to the analytical provision of technologies for func-
tional materials and high-purity substances) requires
concerted efforts aimed at the development of such
steps of quantitative chemical analysis as sample prep-
aration and instrumental elemental analysis. Atomic
emission and mass spectrometry are the most informa-
tive instrumental methods for determining trace ele-
ments. The experience of chemical analysis testifies
that, with the use of preliminary sample preparation, by
which we mean the operations the sample is passed
through at the laboratory, the detection limits for trace
elements can be significantly lowered and samples dif-
fering in chemical composition can be analyzed using
the same set of reference samples. To optimize the
chemical sample preparation procedure for a particular
instrumental method of analysis, one should study both
the behavior of analytes in the course of sample prepa-
ration and the analytical capabilities of the instruments
in use.
It is known that, in many cases, sample preparation
governs the quality and information content of the
results of quantitative chemical analysis. The problems
of sample preparation and, in particular, of trace ele-
ment preconcentration, have received much attention in
the works of Yu.A. Zolotov [1, 2]. In this paper, we have
considered methods of sample preparation that were
developed recently in the analytical laboratory of the
Institute of Inorganic Chemistry of the Siberian Divi-
sion of the Russian Academy of Sciences for determin-
ing low concentrations of impurity elements by atomic
emission (AES) and mass spectrometry (MS) using dif-
ferent excitation sources and atomization techniques.
Sample preparation for AES analysis using a uni-
fied method of element excitation in a direct-current
arc. We have proposed a method for the simultaneous
quantitative determination of several dozens of impu-
rity elements present in concentrations n(105101) wt %
in different samples, irrespective of the sample nature.
The method implies the use of a unique set of reference
materials (RMs) based on graphite powder and the
same conditions of spectrochemical analysis (direct-
current arc, I = 12 A; graphite electrodes; an RSC spec-
trograph; and electronic [3] or photographic spectrum
registration in the region 210330 nm) for all of the
samples. The procedures differ only in the method of
sample preparation for each particular sample. The
methods of sample preparation were developed for use
with the procedure of the multielement spectrochemi-
cal analysis using graphite powders. This procedure
involves the addition of 4% NaCl (an enhancing modifier)
to the reference and test samples and provides the deter-
mination of more than 50 elements in a graphite powder
with limits of detection at a level of n(106103) wt % (a
relative standard deviation of 1020%). In determining
impurities in other samples at a level of n(105101) wt %,
the samples should be diluted with a buffer (a graphite
powder containing NaCl) to suppress the matrix effect.
Powdered samples (oxides, fluorocarbon materials,
sludge, and so on) should be mixed with the buffer in
the ratio from 1 : 10 to 1 : 1000. Metals should be dis-
solved, and an aliquot portion of the metal solution
should be evaporated on a graphite powder. To select
the optimal sample-to-buffer ratio, the effect of sample
matrix on the analytical signal should be studied. At the
step of sample preparation, it is desirable to prevent the
formation of nitrates in the dry residue formed after the
evaporation of the solution, because the majority of
nitrates undergo explosive decomposition in the elec-
trode crater, giving rise to systematic errors in the
results of analysis. It is also important that the form of
sodium compounds in the enhancing modifier remained
unchanged. This is attained by adding an aqueous solu-
tion of NaCl to the dry residue obtained after the evapo-
ration of the test solution. With such sample preparation,
a unified set of reference materials based on graphite
powder can be used in the analysis of different samples.

1061-9348/03/5803-0240$25.00 2003 AIK Nauka /Interperiodica

 SOME ASPECTS OF SAMPLE PREPARATION FOR DETERMINING TRACE ELEMENTS
Note that, according to the adopted standards (branch
and state standards, technical specifications), it was rec-
ommended that the majority of test samples use refer-
ence materials that simulate the composition of the
sample matrix. These reference materials are expen-
sive, often unavailable, and difficult to synthesize. At
the same time, reference materials based on high-purity
graphite powder are relatively easy to prepare. In addi-
tion, GSO 4519-89 and 4523-89 standard samples
based on graphite powder are available. These samples
are manufactured by the Ural State Technical Univer-
sity. Test samples for which the proposed method was
proved to be efficient are listed in Table 1. The proposed
procedures are highly competitive with the certified
procedures in performance characteristics. Some of
them extend the range of determinable impurities and
lower their detection limits. In addition to the analysis
of test samples listed in Table 1, these procedures can
be used for the analysis of ores, ore concentrates, and
environmental samples.
Sample preparation for AES analysis with exci-
tation in a two-jet arc plasmatron. The two-jet arc
plasmatron (TJAP) designed by Engelsht, Urmanbetov,
and Zheenbaev [4] is a promising excitation source for
AES analysis. This high-power instrument (~10 kW)
provides an efficient atomization and excitation of pow-
dered samples. Simple sample preparation without the
use of dissolution is one of the main advantages of the
two-jet arc plasmatron over ICP AES. The zone before
the confluence of the plasmatron jets was used as the
analytical zone. A sample portion of 20 mg was mixed
with the buffer. The spectrum was recorded on an EGS
spectrograph in the region 200380 nm. It was found
that, for the majority of impurity elements, the maxi-
mum ratio between the intensities of the analytical lines
and the background was attained when a graphite pow-
der buffer contained 15% NaCl. Another important
result of the addition of 15% NaCl to the graphite pow-
der was the suppression of the matrix effects [5]. For
example, it was found that, under the optimal analysis
conditions, gallium affects the intensities of analytical
lines measured in a direct-current arc when present in
the graphite powder in concentrations higher than
0.5%. In the two-jet arc plasmatron, the effect of gal-
lium was not detected up to a concentration 30%.
Because of weak matrix effects in the analysis using a
two-jet plasmatron and a unified set of reference mate-
rials based on graphite powder, we could use lower
dilution ratio than in the analysis using a direct-current
arc. Therefore, the detection limits for impurities could
be lowered with the use of a two-jet plasmatron. Thus,
in the analysis of gallium metal, sample preparation
consists in mixing a sample heated to the melting point
(~30) with the buffer in the ratio 1 : 3 [6]; in the anal-
ysis of quartz, in the ratio 1 : 4; and in the analysis of
dried fragments of plants, soils, and bottom sediments,
in the ratio 1 : 10 [7, 8]. To provide the necessary degree
of dispersion of plant fragments bearing poorly soluble
JOURNAL OF ANALYTICAL CHEMISTRY Vol. 58 No. 3
241
fibers, these fragments should be charred in a quartz
furnace for 15 min at 200250.
The detection limits for impurities (Cmin, P = 0.95)
in graphite powders are listed in Table 2. For the other
samples, the detection limits were proportional to the
ration of sample dilution with the buffer. The correct-
ness of the results of analyses was confirmed by the
absence of a significant systematic error in the analysis
of GSO 2498-83, GSO 2502-83, OSO-10-86-98, OSO-
87-98, and other certified reference materials of soils
and samples. The use of a two-jet arc plasmatron in the
analysis of plants soils, bottom sediments, and other
powdered samples by AES, on the one hand, simplified
and shortened the analysis procedure and, on the other
hand, prevented the loss of impurities and sample con-
tamination in the course of sample preparation for the
analysis.
TJAP AES was used to develop a hybrid procedure
for the analysis of high-purity gallium with an impurity
preconcentration. In this procedure, the matrix was par-
tially distilled as volatile gallium ammine trichloride
(GaCl3 NH3); the sample mass was ~1 g [6]. Gallium
ammine trichloride formed (and was removed by distil-
lation) in the reaction of gallium with ammonium chlo-
ride in a quartz furnace at 230. Because of partial
matrix distillation (to a drop <1 mm in diameter), such
impurities as Ge, Au, and Sn, which are lost as volatile
chlorides upon the complete matrix distillation, were
retained in the residue (concentrate). The detection lim-
its attained for impurities in gallium using the direct
method and the method with sample preconcentration
are listed in Table 3.
Sample preparation for the determination of
trace impurities in high-purity acids, silicon, and
germanium by ICP MS. The instrumental analysis
was performed using an ELEMENT high-resolution
ICP ionization mass spectrometer (Finnigan, Ger-
many). It assured the simultaneous determination of up
to 70 impurity elements, except for gas-forming ele-
ments and halogens. Sample preparation for the ICP
MS analysis involved transferring test samples to a 1 M
(5%) nitric acid solution containing no more than 0.1
0.5% of matrix elements. In this case, the optimal con-
ditions of sample ionization were attained, so that the
possibilities of the method can be most fully realized.
The use of hydrofluoric and hydrochloric acid solutions
for sample dissolution was undesirable, because these
acids facilitate the wear of the sample injection (injec-
tor, burner) and beam formation (sampler, skimmer)
systems. Standard samples of solutions like the ICP
Multi Element Standard (Merck) were used to deter-
mine trace elements.
Inorganic acids (HNO3, HCl, HF, H2SO4) are often
used to decompose various solid samples. Therefore,
the determination of trace impurities in these acids, in
addition to the estimation of their purity, is of signifi-
cant importance for the determination of the level of
contamination introduced at the step of sample decom-
2003
 242
Table 1. Possibilities of a unified AES procedure using direct-current arc excitation

Test sample Analytical task Method of sample preparation *

K min Analytical possibilities

Bismuth oxide, tung- Correspondence to the adopted TU Mixing of sample portion (0.55.0 mg) with a graphite pow- 1050 Determination of 20 to 30
sten oxide, and tung- (Technical specifications) or GOST der containing 4% NaCl in a fluoroplastic cup (weighing impurities at a level
stic acid (State Standards) for a finished prod- on an analytical balance like Sartorius with an accuracy of n (105 to 102 wt %)
uct of about 0.01 mg)

Fluorocarbon Control of production technology; the Similar to that described above 50 Determination of 17 impuri-
materials development of technical specifica- ties at a level of n (104 to
tions for the finished product 102 wt %)

Scandium oxide, fluo- Optimization of the production tech- Similar to that described above 100 Determination of 30 impuri-
ride, hydride, and chlo- nology for scandium metal ties, rare-earth elements
ride among them, at a level
of n (104 to 102 wt %)

Nickel, copper, gold, Correspondence to the adopted TU Sample dissolution in HCl, HNO3, or their mixture. Evapo- 50200 Determination of 30 impuri-
ties at a level of n (104 to
JOURNAL OF ANALYTICAL CHEMISTRY

silver, platinum, and (Technical specifications) or GOST ration of an aliquot portion of the solution obtained on

SAPRYKIN et al.
palladium (State Standards) for a finished prod- a graphite powder followed by the treatment of the dry resi- 102 wt %)
uct due with HCl. The addition of a solution of NaCl

Iron, gallium, cadmi- The development of purification tech- Similar to that described above 50200 Determination of 40 impuri-
um, arsenic, tin, anti- nology ties at a level of n 103 wt %
mony, and tellurium

Zirconium, niobium, Correspondence to the adopted TU Sample dissolution in a mixture of HF with HNO3 . Treating 200 Determination of 30 impuri-
tantalum, and tungsten (Technical specifications) or GOST dry residue with water, storage at 100120C for 20 min. ties at a level of n (104 to
(State Standards) for a finished prod- The addition of a solution of NaCl. Drying 102 wt %)
uct

Tungsten sludge and The development of the technology Successive dilution of a sample portion with a graphite pow- 1000 Determination of rare-earth
products of their of the comprehensive processing for der containing 4% NaCl using trituration in a mortar. Sam- elements, Sc, and Sn at a
processing the extraction of rare-earth elements, ple mass of 100 mg, maximum dilution in the ratio 1 : 10 level of n (101 to 100 wt %)
scandium, and tin
Vol. 58

Silicon, silicon diox- Determination of impurity composi- Dissolution of a 50-mg sample in a mixture of HF with 1 Determination of up to
ide, and mercury tion HNO3 or HNO3 . Evaporation of an aliquot portion of the so- 35 impurities at a level of
lution followed by acid treatment to the complete removal of n (106 to 101 wt %)
the matrix. Dissolution of the dry residue, the addition
No. 3

of 50 mg of a graphite powder, drying, treatment with HCl.

The addition of a NaCl solution. Drying
2003

* The minimum factor of sample dilution with the buffers; graphite power of high-purity grade.
 SOME ASPECTS OF SAMPLE PREPARATION FOR DETERMINING TRACE ELEMENTS 243

Table 2. Limits of the detection (LD) of impurities in TJAP AES using graphite powder (20 mg)
Element LD, wt % Element LD, wt % Element LD, wt %
Ag 1 106 Ga 2 106 Pt 1 105
Al 1 105 Ge 2 105 Sb 4 105
As 3 104 Hf 1 104 Sc 1 105
Au 3 105 Hg 1 104 Si 3 105
B 1 106 In 5 106 Sn 1 105
Ba 1 105 Ir 4 104 Ta 1 104
Be 2 106 La 1 105 Te 1 104
Bi 6 106 Mg 4 106 Ti 1 105
Ca 3 105 Mn 1 106 Tl 1 105
Cd 3 106 Mo 2 106 V 1 106
Co 1 105 Nd 4 105 W 2 105
Cr 2 105 Ni 4 106 Y 1 106
Cu 1 106 Pb 2 105 Zn 1 105
Fe 3 105 Pd 1 105

Table 3. Limits of the detection (LD) of impurities in the (1) direct analysis of gallium and (2) analysis with impurity pre-
concentration, K = 40
LD, wt % LD, wt % LD, wt %
Element Element Element
1 2 1 2 1 2
Ag 8 106 2 107 Ge 3 104 8 106 Pt 7 105
Al 1 104 3 106 Hf 4 104 1 105 Sb 4 104
As 2 103 Hg 4 104 Sc 3 105 8 107
Au 1 104 3 106 In 2 105 5 107 Si 5 104
Be 8 106 2 107 La 4 105 1 106 Sn 5 105 1 106
Bi 7 105 2 106 Mg 6 106 2 107 Ti 3 105 8 107
Ca* 4 104 3 105 Mn 1 105 3 107 Tl 1 105 5 107
Cd 5 105 1 106 Mo 8 106 2 107 V 5 106 1 107
Co 7 105 2 106 Nb 2 104 6 106 Y 4 106 1 107
Cr 1 104 3 106 Ni 3 105 8 107 Zn 1 104 5 106
Cu 5 106 1 107 Pb 2 104 5 106
Fe 2 104 5 106 Pd 3 105 8 107
* LD for calcium is determined by its concentration in the distilled NH4Cl used to prepare gallium ammine trichloride.

position. The known procedures for the AES and MS
analysis of high-purity water and acids provide the
determination of from 30 to 50 impurity elements at a
level of 109 to 106 wt % [9, 10]. In the direct analysis
of inorganic acids by ICP MS, samples should be
diluted with deionized water in a ratio of at least 1 : 20.
To lower the limits of detection, we evaporated the sam-
ple at ~80 at a rate of no higher than 0.2 mL h1 cm2
and then diluted the concentrate with deionized water
containing nitric acid. These operations were per-
formed as follows.
A sample of ~10 mL was placed in a fluoroplastic
cup with a conical bottom, and ~0.5 mL of twice-dis-
tilled HNO3 was added to prevent the losses of fluoride-
and chloride-forming impurities due to their adsorption
on the cup walls (for H2O). Evaporation was performed
in an acrylic plastic box equipped with Petryanov filters
to purify the entering air. The time of evaporation was
from three to four hours. The acid samples to be ana-
lyzed were evaporated in a beaker to ~0.1 mL, and
deionized water was added to a volume of 510 mL.
Five to ten milliliters of a sample is sufficient to
record a mass spectrum in the whole mass range from 7
to 240 amu. More than 500 scans can be made if the
solution is fed with a peristaltic pump at a flow rate of
~150 l/min. Under these conditions, about 50 impu-
rity elements can be determined with detection limits of
from 107 to 1012 wt % (Table 4). In instrumental ICP

JOURNAL OF ANALYTICAL CHEMISTRY Vol. 58 No. 3 2003

244 SAPRYKIN et al.

Table 4. Limits of detection (LD) of impurities in water and mineral acids (HNO3 , HF, HCl, H2SO4) by ICP MS* (from
a 10-mL sample)
LD, wt % Impurity elements
n 1012and lower V, Co, Rh, Sb, Cs, Hf, Ta, Ir, Pt, Au, Tl, Pb, Bi, Th, U, rare-earth elements
n 10 11 Sc, Ga, Se, Rb, Sr, Y, Ru, Ag, Pd, Cd, In, Sn, Te, W, Re
n 1010 Be, Ge, Zr, Nb, Mo
n 109 Li, P, Cr, Mn, Ni, Cu, As, Ba
n 108 Mg, Al, Ti, Fe, Zn
n 107 Na, Si, K, Ca
* Impurities for which LD is restricted by the blank experiment are italicized.

Table 5. Concentrations of impurities in deionized water and twice-distilled nitric acid

LD, wt % Impurity elements
n 1011
and lower Se, Rb, Sr, Y, Nb, Mo, Ru, Rh, Ag, Pd, Cd, In, Sn, Sb, Te, Cs, Hf, Ta, W, Re, Ir, Pt, Au, Tl, Pb, Bi,
Th, U, rare-earth elements
n 1010 Be, Sc, V, Co, Ga, Ge
n 109 Li, Cr, Mn, As, Zr
n 108 P, Ti, Fe, Ni, Cu, Zn, Ba
n 107 Na, Mg, Al, Si, K, Ca

Table 6. Concentrations of impurities in twice-distilled hydrofluoric and hydrochloric acids

LD, wt % Impurity elements
n 1011 Ge, Rb, Y, Ru, Rh, Ag, Pd, Cd, In, Sn, Sb, Te, Cs, Hf, Ta, W, Re, Ir, Pt, Au, Tl, Pb, Bi, Th, U, rare-earth
and lower elements
n 1010 Be, Sc, Nb, Mo
n 109 V, Co, Zn, Ga, As, Se, Sr, Zr
n 108 Li, P, Ti, Cr, Mn, Ni, Cu, Ba
n 107 Na, Mg, Al, Si, K, Ca, Fe

MS, the detection limits for elements not present in the
blank experiment may be several orders of magnitude
lower (to 1014 wt %), whereas the determination of the
most wide-spread elements like Na, K, Ca, Si, Fe, and
others is limited by their concentrations found in the
blank experiment. Therefore, there is usually little
sense in increasing sample volume and the time of
scanning the overall mass region. From the data pre-
sented in Tables 5 and 6, one can estimate the purity of
chemical reagents synthesized and used in analytical
laboratories that are not equipped with a special clean
room for working with high-purity substances. A blank
sample of 1 M nitric acid triply distilled in a quartz appa-
ratus and dissolved in deionized water with a residual
resistance of ~18 M contains up to 20 impurity ele-
ments (these elements are italicized in Tables 4 and 7).
These elements are most widespread impurities of
alkali, alkaline-earth, and transition metals. Their
detection limits cannot be lowered with the use of cur-
rently available analytical instruments, because the
blank value is determined mainly by the purity of water,
the glassware, the room class, and, to a significant
extent, by the qualification of the staff of the analytical
laboratory.
The requirements currently imposed on high-purity
substances, in particular, semiconductors like silicon
and germanium, are much more stringent than the lim-
its of impurity detection in direct AES and MS [11]. To
estimate the impurity content of these materials, it is
necessary to develop hybrid methods of analysis
involving impurity preconcentration. For silicon and
germanium, an appropriate method is matrix distilla-
tion as volatile compounds (silicon fluoride and germa-
nium chloride). In this method, silicon and germanium
are separated almost completely, whereas trace impuri-
ties are retained in solutions of corresponding acids.
These solutions are then analyzed using the above-
described procedure.
Our experience shows that sample mass of 1 g is
most suitable for the survey (multielement) analysis of

JOURNAL OF ANALYTICAL CHEMISTRY Vol. 58 No. 3 2003

 SOME ASPECTS OF SAMPLE PREPARATION FOR DETERMINING TRACE ELEMENTS 245

Table 7. Limits of detection (LD) of impurities in silicon and germanium in ICP MS* (from a 1-g sample)
LD, wt % Impurity elements
n 1011 and lower Rh, In, Cs, Hf, Ta, Ir, Pt, Au, Tl, Pb, Bi, Th, U
n 1010 Sc, Ga, Rb, Y, Ru, Ag, Pd, Cd, Sn, Te, W, Re, rare-earth elements
n 109 Be, Zr, Nb, Mo
n 108 V, Co, Sb
n 107 Li, P, Cr, Mn, Ni, Zn, As, Se, Sr, Ba
n 106 Na, Mg, Al, K, Ca, Ti, Fe, Cu
* Impurities for which LD is restricted by the blank experiment are italicized.

silicon and germanium. To dissolve 1 g of silicon, one ACKNOWLEDGMENTS

should add 10 mL of conc. hydrofluoric acid, 5 mL of
conc. nitric acid, and 7 mL of deionized water. To dis-
solve 1 g of comminuted germanium, one should add
15 mL of conc. hydrochloric acid and 7 mL of 14.5 M
nitric acid. The samples were dissolved in a closed flu-
oroplastic beaker thermostatted at 7075 for 33.5 h.
The resulting solution was evaporated under an IR lamp
to a volume of ~50 l; volatile silicon fluorides and ger-
manium chlorides were removed on evaporation. The
residue was then dissolved in 5 mL of 1 M nitric acid,
which is the best solution for use in ICP MS.
Knowing the concentrations of impurities in water
and acids (Tables 5 and 6) and the volumes of acids
consumed for sample preparation, one can estimate ele-
ment concentrations in the blank experiment and the
limits of detection of trace impurities in silicon and ger-
manium using the proposed method (Table 7). In this
method, the value of the detection limit was taken equal
to a twofold concentration of the impurity found in the
blank experiment. In the case when the impurity was
not detected in the blank experiment, its detection limit
was calculated using the 3sbackground-test, taking into
account the experimental dependence of the analytical
signal on the atomic mass of the element. As can be
seed in Table 7, the determination of about twenty of
the most widespread impurity elements is restricted by
their concentrations in the blank samples of hydrofluo-
ric, hydrochloric, and nitric acids and water. It is known
that, in real samples of silicon semiconductors, these
elements occur in lower concentrations; therefore, to
obtain the data on the actual concentrations of impurity
elements in silicon and germanium, one should sophis-
ticate the methods for purifying chemical reagents and
cleaning glassware used at the step of sample prepara-
tion and perform analyses is special clean rooms. Nev-
ertheless, with the use of the proposed procedure, we
could significantly (by two or three orders of magni-
tude) lower the detection limits compared to those
attained in the known AES and MS procedures for ana-
lyzing the above materials [12]. The proposed proce-
dure is simple and can be recommended for use as a
basic analytical procedure for the development of new
technologies for the production of silicon and germa-
nium semiconductors.
We are grateful to Yurii Aleksandrovich Zolotov for
his interest in the experiments conducted at the labora-
tory of analytical chemistry of the Institute of Inorganic
Chemistry of the Siberian Division of the Russian
Academy of Sciences and the support of these experi-
ments. The cornerstone of our success is in his scien-
tific and teaching activity and his attentive and benevo-
lent interest in our research.
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