Journal of Analytical Chemistry, Vol. 58, No. 9, 2003, pp. 856–861. Translated from Zhurnal Analiticheskoi Khimii, Vol.

58, No. 9, 2003, pp. 960–966.

Original Russian Text Copyright © 2003 by Chuparina, Gunicheva.

ARTICLES

Nondestructive X-ray Fluorescence Determination

of Some Elements in Plant Materials
E. V. Chuparina and T. N. Gunicheva
Vinogradov Institute of Geochemistry, Siberian Division,
Russian Academy of Sciences, ul. Favorskogo 1a, Irkutsk, 664033 Russia
e-mail: lchup@igc.irk.ru
Received May 8, 2002; in final form, September 9, 2002

Abstract—Possible matrix effects in the direct x-ray fluorescence determination of Na, Mg, Al, Si, P, K, Ca,
Mn, Fe, S, Sr, and Cl in powdered plant materials were considered; their contributions were evaluated, and dom-
inant effects were estimated that should be taken into account to ensure the required accuracy of the analytical
results. It was shown that the main matrix effects are the absorption and scattering of the incident and fluores-
cence x-rays by the sample as well as the additional excitation of the analyte fluorescence by the fluorescence
of heavier elements. The efficiency of α correction with theoretical coefficients for their account was shown.

1 The assertion that solving an analytical problem
should begin with an exhaustive study of the matrix
effects is an axiom of analytical chemistry. Compre-
hensive information about the matrix effects in pow-
dered plant materials in direct x-ray fluorescence anal-
ysis has not been found in the available literature [1–
21]. This problem is frequently not even touched upon
[1–6]. Without any quantitative proof, some authors
note that matrix effects in the x-ray fluorescence analy-
sis of plants are mainly due to the absorption of the
exciting and fluorescence beams by the sample [7–13].
The available data on the fluorescence enhancement
and scattering are sporadic and have not been corre-
lated to the composition of plant materials [14–19].
Kumar et al. affirm that only the absorption of exciting
and fluorescence radiations should be taken into
account for samples composed mainly of light elements
(Z < 8), whereas the enhancement effects could be dis-
regarded [13]. The contributions of the scattering of pri-
mary and secondary beams to the intensity of Ag and
Cu Kα lines were evaluated for binary mixtures of silver
and copper with light elements (the problem of the
determination of heavy elements in light matrices) [19].
The corresponding values were 28 and 6.7% for oxy-
gen-containing mixtures and 55.6 and 20% for beryl-
lium-containing mixtures, respectively. However, these
estimates can only be considered as evidence of a close
correlation between the matrix effects and the compo-
sition of the studied material. It should be noted that
contradictory opinions exist regarding the variation of
matrix effects in ashed and unashed plant samples [20,
21]. Revenko states that more significant effects of
1 The abstract of this paper was published in the Proceedings of the
Conference “Actual Problems of Analytical Chemistry,” 2002,
vol. 1 under the title “Nondestructive X-ray Fluorescence Deter-
mination of Na, Mg, Al, Si, P, K, Ca, Mn, Fe, S, Sr, and Cl in
Plant Materials.”
chemical composition on the intensity of short-wave-
length analytical lines are observed for unashed plant
materials [20]. Ondar argues that the difference in the
interelement effects in the x-ray fluorescence analysis
of plant ashes increases compared to that observed for
unashed materials because of the wider variation in the
ash composition [21].
Publications dealing with x-ray fluorescence analy-
sis give more information about matrix effects that arise
in the excitation of x-ray fluorescence in natural mate-
rials, such as rocks, soils, and bottom sediments [22–
28]. It was shown that, in order to ensure the required
accuracy of the analysis of these natural materials, one
should take into account the dominating effect of the
adsorption of the exciting and fluorescence radiation by
the sample and make an approximate adjustment to the
enhancement of the analytical lines of analytes due to
fluorescence from heavier elements [22]. This concept
is efficiently implemented in the method of α correc-
tion with theoretical (computed) coefficients, which are
not related to the compositions of test samples, are ori-
ented to the maximum possible change in the concen-
tration of interfering element j, and are universal for the
specific conditions of the excitation and recording of x-
ray fluorescence [29].
Plant materials differ from the materials mentioned
above in composition and in analyte concentrations.
Three light elements (carbon, oxygen, and hydrogen)
make up 98% of the plant weight. The total of the other
elements is about 2–12%. This inevitably affects the
components of x-ray fluorescence and the contributions
of matrix effects related primarily to scattering. The lat-
ter were insignificant for materials with high concentra-
tions of the mineral phase and should not be taken into
account.

1061-9348/03/5809-0856$25.00 © 2003 åAIK “Nauka /Interperiodica”

 NONDESTRUCTIVE X-RAY FLUORESCENCE DETERMINATION OF SOME ELEMENTS 857

Table 1. Ranges of analyte concentrations in plant materials, %

GSOs + GSV
Analyte NBS samples BAFPs Birch leaves Grasses Mushrooms Pine needles
samples
Na 0.0044–1.5300 0.0036–1.3900 0.0600–1.3000 0.0150–0.1760 0.0320–0.2250 0.0270–0.1690 0.0027–0.0476
Mg 0.095–0.384 0.118–0.850 0.340–0.550 0.342–0.797 0.147–0.965 0.088–0.143 0.117–0.200
Al 0.0020–0.3000 0.0087–0.1130 0.0240–0.1200 0.0106–0.1050 0.0070–0.6266 0.0010–0.0322 0.0180–0.2330
Si 0.009–0.590 0.129–1.050 0.315–1.145 0.027–0.406 0.047–6.739 0.010–0.110 0.033–0.630
P 0.092–0.360 0.121–0.520 0.228–0.626 0.186–0.534 0.105–0.929 0.486–0.745 0.128–0.179
K 0.885–2.390 0.369–4.440 1.700–3.600 0.770–1.430 0.440–3.880 2.600–4.630 0.380–0.550
Ca 0.054–1.950 0.420–3.140 0.985–2.060 0.695–1.870 0.560–4.280 <0.005 0.379–0.551
Mn 0.0007–0.1240 0.0022–0.0660 0.0120–0.1725 0.0124–2.8368 0.0092–0.1862 0.0012–0.0052 0.0040–0.0151
Fe 0.0056–0.1045 0.0092–0.0600 0.0500–0.4380 0.0066–0.0629 0.0063–0.3375 0.0040–0.0222 0.0042–0.0459
S 0.130–0.525 0.125–0.610 0.158–0.406 0.131–0.256 0.151–0.804 0.142–0.984 0.079–0.165
Sr 0.0002–0.0296 0.0004–0.0099 0.0093–0.0210 0.0020–0.0086 0.0019–0.0246 0.0010–0.0024 0.0010–0.0021
Cl 0.023–1.540 0.049–1.050 0.191–1.800 0.010–0.089 0.010–0.586 0.027–0.431 0.010–0.033

The aims of this work were to evaluate the contribu-
tions of matrix effects possible in the excitation of x-ray
fluorescence in powdered plant materials, to reveal the
dominating effects that should be taken into account to
ensure the accuracy necessary in a wide range of
geochemical problems, and to substantiate the suitabil-
ity of α correction with theoretical αij coefficients [29]
for taking into account the effects revealed.
THEORETICAL
Along with the published analytical data for certi-
fied reference plant materials, we used our archive data
on the concentrations of Na, Mg, Al, Si, P, K, Ca, Mn,
Fe, S, Sr, and Cl in various plant species. A total of
50 plant compositions were considered, including
12 certified reference samples: three domestic state ref-
erence samples (GSOs) of biological materials (mixed
grasses SBMT-02, wheat grain SBMP-02, and potato
tubers SBMK-02 [30]), three China GSV reference
samples (poplar twigs and leaves, and tea) [31], and six
US NBS reference samples (spinach, tomato, lemon,
orchid, pine needles, and wheat flour) [32]. Samples of
birch leaves from the background and technogenic
regions of Irkutsk oblast, mushrooms, herbaceous
plants, Baikal aquatic flowering plants (BAFPs), and
pine needles were also analyzed in our laboratory. The
analyte concentrations in the reference samples as well
as for each plant species are given in Table 1. It can be
seen that the analyte concentrations varied significantly
between plant species and within each plant species.
Element concentrations varied by a factor of 10 for Mg,
P, K, and S; by a factor of 100 to 180 for Fe, Sr, and Cl;
and by factors of 400, 600, and 3000 for Na, Al and Si,
and Mn, respectively.
The theoretical intensities of the Kα lines of analytes
were calculated for a thick homogeneous emitter using
a program simulating the intensity of x-ray fluores-
cence (Ii ) as the sum of the first- and second-order
effects [33]:
( I i ) = ( I f ) + ( I ff ) + ( I fs ), (1)
where If is the x-ray fluorescence excited by the direct
beam from the x-ray tube (first-order effect); Iff is the x-
ray fluorescence excited by the fluorescence from
heavier elements, and If s is the total x-ray fluorescence
resulting from the coherent and incoherent scattering of
the exciting and fluorescence x-rays in the sample (sec-
ond-order effects).
A calculation was made for the excitation and
recording of x-ray fluorescence using a CPM-25 multi-
channel x-ray spectrometer with a Rh-anode x-ray tube
operated at 30 kV, a Be window 0.025 cm thick, the
incidence angle of primary radiation of 90°, and the
take-off angle of the fluorescence radiation equal to 44°
for Na, Mg, Al, Si, K, Ca, Fe, and Sr and 35° for P, Mn,
S, and Cl. The ratios between O, C, and H in the plant
materials were assumed to be equal to those in cellu-
lose, and their total concentration was determined as 1
– ∑ c i , where ∑ c i is the sum of analyte concentra-
tions. The intensities were calculated with respect to the
emitter composition used as the reference sample in
routine analyses.
RESULTS AND DISCUSSION
Comparative characterization of the matrix
effects. The contributions of matrix effects to the
results of the direct x-ray fluorescence analysis of
plants are given in Tables 2–4. It is evident that the flu-
orescence excited by the x-ray tube radiation is the
major component of the x-ray fluorescence, as it was
for rocks. Its contribution runs as high as 84.6–99.6%.
The enhancement and scattering effects differ from
those observed for materials with high concentrations

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858 CHUPARINA, GUNICHEVA

Table 2. Contribution of the tube-excited x-ray fluorescence for different plant materials, %
GSOs + GSV
Analyte line NBS samples BAFPs Birch leaves Grasses Mushrooms Pine needles
samples
NaKα 99.5 99.5 99.2 99.4 99.5 99.2 99.6
MgKα 99.5 99.5 99.1 99.4 99.5 99.2 99.5
AlKα 99.4 99.5 99.0 99.3 99.4 99.1 99.5
SiKα 99.4 99.4 99.0 99.2 99.4 99.0 99.5
PKα 99.4 99.4 99.0 99.2 99.4 99.1 99.4
KKα 98.6 98.0 97.6 97.8 98.3 98.9 98.2
CaKα 98.6 99.1 98.8 98.7 99.0 98.9 98.4
MnKα 97.7 98.2 98.0 97.7 98.2 97.7 96.7
FeKα 97.2 97.9 97.7 97.3 97.8 97.3 96.1
SKα 99.4 99.3 98.9 99.2 99.3 99.0 99.4
SrKα 89.0 91.5 90.8 91.0 91.2 88.9 84.6
ClKα 99.2 99.1 98.4 98.8 99.0 98.5 99.1

Table 3. Contribution of the enhancement effect for different plant materials, %

GSOs + GSV
Analyte line NBS samples BAFPs Birch leaves Grasses Mushrooms Pine needles
samples
NaKα 1.0 1.4 1.2 0.7 1.6 0.9 0.4
MgKα 1.0 1.5 1.2 0.7 1.7 0.9 0.4
AlKα 1.0 1.5 1.3 0.7 1.7 1.0 0.4
SiKα 1.0 1.5 1.2 0.8 1.2 1.1 0.3
PKα 1.1 1.5 1.2 0.8 1.2 1.0 0.3
KKα 2.1 3.5 2.2 4.4 4.1 0.1 0.8
CaKα 0.2 0.2 0.7 3.7 0.5 0.1
SKα 1.0 1.5 1.2 0.9 1.1 1.0 0.3
ClKα 1.1 2.0 1.6 0.6 1.7 1.5 0.4

of the mineral phase. For rocks, the contribution of the
enhancement effect was 13–16% for the line of K in the
extreme case (in carbonates) [34], whereas the scatter-
ing effect was negligibly small. For plant materials, the
role of the scattering processes for both primary and
fluorescence radiations increases abruptly. Among the
secondary effects, scattering makes the largest contri-
bution, which increases to 16.7% when the x-ray fluo-
rescence wavelength decreases from Ca to KKα, Fe,
and Sr. As for the enhancement effect (see Table 3), its
contribution exceeds 1% for the majority of elements
and attains a maximum for the KKα line of K (2–4%)
because of the significant Ca concentration in plant
materials. The results presented in Tables 2–4 indicate
that, along with changes in primary x-ray fluorescence
and enhancement effects, variations in scattering
effects should also be taken into account in the proce-
dure for the direct x-ray fluorescence analysis of plant
materials.

Table 4. Contribution of scattering to the intensity of short-wavelength analytical lines for different plant materials, %
GSOs + GSV
Analyte line NBS samples BAFPs Birch leaves Grasses Mushrooms Pine needles
samples
CaKα 1.6 1.5 1.2 1.4 1.5 1.2 1.6
MnKα 3.6 3.4 2.6 3.0 3.3 2.8 3.5
FeKα 4.3 4.1 3.1 3.6 4.0 3.3 4.2
SrKα 16.7 15.9 12.3 14.4 15.7 13.3 16.2

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 NONDESTRUCTIVE X-RAY FLUORESCENCE DETERMINATION OF SOME ELEMENTS 859

The effectiveness of a correction for matrix Table 5. Parameters of discrepancies between the intensi-
effects. When the number of certified reference sam- ties theoretically calculated [33] and derived from Eq. (2)
ples of plant materials is far from sufficient for calibra-
Analyte t-test RSD, % RSD1 , % [35]
tion, theoretical methods, including α correction with
theoretical αij coefficients, are a priori acceptable for Na 0.0006 +0.1 0.15
the correction of matrix effects [29]. The concentra- Mg Ⰶ0.0001 +0.1 –7.5
tions of analytes are calculated using the equation
Al 0.025 0.1 9.5
r 1+ ∑
( α ij ) ( c j )
( c i ) = ( R i ) ( c ) -------------------------------------
-, (2)
Si 0.01 1 11

∑
( α ij ) ( c j )
1+
where
( R i ) = a i0 + ∑a
r r
ij I j /I j + I i /I i
∑ ∑ q jj ( I j /I j )/ ( I sc /I sc ) ,
r r
+ I sc /I sc d ij I j /I j +
r r
Ii , I i , Ij , and I j denote the pulse sets corrected for the
apparatus effects in the spectrometer channels for the
test (i) and reference (r) samples, and Isc is the intensity
of the scattered radiation at the characteristic line of the
x-ray tube anode. The parameters ai 0, aij , bij , dij , and qij
are evaluated by the least-squares method from the
intensities measured for reference samples identical in
composition to the test materials.
To assess the suitability of the α correction method
for the direct x-ray fluorescence analysis of plants, the
discrepancies between the two arrays of relative inten-
sities were estimated for each analyte. One of the arrays
consisted of the intensities found using a known pro-
gram [33], which were considered as true intensities.
They were used for calculating the αij coefficients. The
other array consisted of intensities calculated using
Eq. (2). Probability values calculated by the Student
t-test, which are indicative of the presence or absence of
a bias between the arrays compared, are given in Table 5
along with the relative standard deviations (RSDs)
quantitatively characterizing the discrepancies. It can
be seen that for Al, Si, Ca, Mn, Fe, and Sr, both data
arrays belong to the same general population, and the
discrepancies between them are of random nature. Sys-
tematic discrepancies of both signs were observed for
the other elements. The highest RSD values were found
for Si (0.01) and Sr (0.022); for the other elements, they
were significantly lower. In most cases, the RSD values
were lower than the RSD1 component characterizing
the differences between data of the x-ray fluorescence
analysis obtained using different reference standard
sample sets for calibration [35]. Therefore, it can be
concluded that the studied procedure of α correction for
matrix effects cannot compete with other techniques
until the RSD1 values (dependent on the quality and
quantity of reference samples used for calibration) are
decreased by at least an order of magnitude.
Practical application of the method. The results of
the direct x-ray fluorescence analysis of various species
of terrestrial herbaceous plants and aquatic flowering
plants from the Baikal region are given in Table 6. To
P Ⰶ0.0001 –0.1 –9
r
K 0.0015 +0.4 –2
Ca 0.07 0.4 –4
∑b
r Mn 0.4 0.6 9
ij I j /I j
(3) Fe 0.52 0.6 7
r r
S Ⰶ0.0001 –0.3 1.3
Sr 0.127 2.2
Cl 0.003 –0.7
prepare an emitter, 7.2 g of an air-dry powered plant
material to which ethanol and 0.8 g of high-purity boric
acid (used as a binding agent) were added was mixed in
an agate mortar for 10 min and pelletized. The pellets
were kept in a desiccator and brought out only for mea-
surements. The intensities of the Kα lines were mea-
sured with a CPM-25 multichannel x-ray spectrometer
(Rh tube, V = 30 kV, I = 40 mA, counting time 60 s).
In Table 6, the highest and lowest analyte concentra-
tions for each group of plants are given in bold. The last
column contains the ratios of the highest and lowest
analyte concentrations for the set of analytical results
considered, demonstrating variations in the composi-
tion of real plants. Terrestrial plants included meadow
(chamomile (Anthemis nobilis L.) and yarrow (Achillea
millefolium L.)) and steppe (thyme (Thymus vulgaris
L.) and northern wormwood (Artemisia campestris L.))
species. Amphibious bistort (Persicaria amphibia (L.)
S.F. Gray), perfoliate pondweed (Potamogeton perfo-
liatus L.), common water milfoil (Myriophyllum sibiri-
cum Kom.), common hornwort (Ceratophyllum demer-
sum L.), and Canadian waterweed (Elodea canadensis
Michaux.) are aquatic plants. These groups differ in
habitat, and in their ways of finding nutrients in partic-
ular. The habitat of the aquatic plants intensifies the
extraction of elements as it is favorable for their conver-
sion to a form usable by the plant. In addition, most of
the aquatic plants are completely immersed in water
and absorb elements by their whole surface, as distinct
from the terrestrial plants, which extract elements from
soil solutions by means of their root system. These fac-
tors should affect the composition of plants. It is seen in
Table 6 that significant differences in composition are
observed not only between the terrestrial and aquatic
plants, but also within each biogeocenosis species. For
the majority of analytes, their lowest concentrations in
aquatic plants are higher than those in terrestrial plants.

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860 CHUPARINA, GUNICHEVA

Table 6. Direct x-ray fluorescence analysis of different plants species, % of air-dry weight
Aquatic plants Terrestrial plants
BAFPs meadow steppe
Analyte Cmax /Cmin
chamo- worm-
bistort pondweed hornwort milfoil waterweed yarrow thyme
mile wood
Na 0.062 0.210 0.502 1.130 1.300 0.242 0.115 0.052 0.080 21.0
Mg 0.342 0.549 0.451 0.366 0.367 0.682 0.586 0.244 0.246 2.8
Al 0.0296 0.0240 0.1200 0.0706 0.0660 0.0190 0.0819 0.0600 0.1365 7.2
Si 0.315 0.838 1.150 0.947 0.780 0.093 1.091 0.412 0.426 12.4
P 0.235 0.228 0.417 0.248 0.448 0.555 0.463 0.229 0.304 2.4
K 1.71 1.91 2.64 1.90 3.61 3.19 2.56 4.24 1.52 2.4
Ca 1.35 2.06 0.99 1.88 1.94 1.17 1.63 1.10 0.84 2.5
Mn 0.0122 0.0155 0.1725 0.0982 0.0670 0.0276 0.0097 0.0444 0.0092 18.8
Fe 0.0754 0.0504 0.4380 0.4162 0.3181 0.0185 0.0358 0.0619 0.1237 23.7
S 0.158 0.307 0.248 0.406 0.355 0.401 0.213 0.120 0.160 3.4
Sr 0.0093 0.0139 0.0118 0.0190 0.0216 0.0061 0.0155 0.0084 0.0043 5.0
Cl 0.191 0.912 1.010 1.800 0.893 1.254 0.503 0.118 0.136 15.3

Table 7. Specific intensities of the analytical lines of analytes in unashed plant materials
Analyte 1 2 3 4 5 6 7 8 K1 K2 [20]
Na 0.990 0.992 0.990 0.999 0.984 0.989 0.997 0.992 1.0
Mg 1.031 1.033 1.025 1.001 1.015 1.030 1.032 1.018 1.0 1.5
Al 1.049 1.050 1.033 0.998 1.008 1.048 1.039 1.003 1.1 1.5
Si 1.068 1.069 1.045 0.993 1.009 1.065 1.023 0.999 1.1 1.5
P 1.102 1.102 1.068 1.005 0.990 1.093 0.956 0.923 1.4 2.1
K 1.262 1.281 1.101 1.010 0.942 1.295 1.094 0.930 1.5
Ca 1.223 1.367 0.993 0.853 0.754 1.378 1.146 0.824 1.8 2.2
Mn 1.475 1.695 1.108 0.893 0.713 1.620 1.262 0.740 2.4
Fe 1.489 1.718 1.083 0.892 0.709 1.638 1.263 0.737 2.4 2.6
S 1.109 1.100 1.061 0.988 0.977 1.104 0.957 0.903 1.4
Sr 1.589 1.870 1.108 0.893 0.695 1.732 1.229 0.725 2.7
Cl 1.154 1.143 1.082 1.001 0.975 1.152 0.989 0.900 1.4 1.5

For the highest concentrations, this is true only for Na,
Mn, Fe, Sr, and Cl. For the other analytes, most of
which are biophilic elements, the highest concentra-
tions are comparable in the plant groups considered.
The results obtained agreed with the idea that the rate
and degree of element extraction affect their concentra-
tion in a plant organism [36]; therefore, they were used
subsequently for solving specific biogeochemical prob-
lems [37, 38]. Thus, direct x-ray fluorescence analysis
based on corrections for matrix effects using theoretical
αij coefficients is suitable for the analysis of various
plant species with variations in chemical composition.
Comparison of interelement effects in plants and
ashes. To substantiate our opinion on the comparability
of interelement effects in plants and their ashes, we
present the specific intensities of the analytical lines of
analytes in Table 7. The specific intensities were calcu-
lated for individual plant species: (1) potato tubers
(SBMK-02), (2) wheat grain (SBMP-02), (3) mixed
grasses (CBMT-02), (4) spinach leaves (NBS-1570),
(5) tomato leaves (NBS-1573), (6) pine needles (NBS-
1575), (7) sphagnum, and (8) nettle. For each element,
we estimated the relative standard deviations (K1) char-
acterizing the variability of the specific intensities
determined. It was seen that the widest variations in the
specific intensity (by two times and more) were
observed for the short-wavelength analytical lines of
Ca, Mn, Fe, and Sr, which agreed with the conclusions
drawn above. The values characterizing the variability

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 NONDESTRUCTIVE X-RAY FLUORESCENCE DETERMINATION OF SOME ELEMENTS
of specific intensities for plant ashes (K2) were calcu-
lated from the reported data [20]. The values of K1 and
K2 are similar, which suggests that the pretreatment of
a plant material by dry ashing should not reduce the
interelement effects. When ashing is conducted under
conditions excluding the loss of analytes, the ratios
between the element concentrations in ashes and
unashed plants have to remain constant; therefore, the
ratios between the contributions of the effects consid-
ered should not change.
The study performed allows us to conclude that sig-
nificant matrix effects are observed in the direct x-ray
fluorescence analysis of plant materials. The absorption
of the exciting and fluorescence x-rays, the enhance-
ment of the analyte fluorescence by the radiation from
heavier elements, and scattering are the predominant
effects. Adequate accuracy of the analytical results can
be achieved only by taking into account the effects con-
sidered. The α correction of the measured analytical
signal using theoretical αij coefficients is an efficient
method for solving this problem.
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