Preconcentration of environmental waters by agar for XRF analysis

Kazuhiko Nakanoa兲
Department of Applied Chemistry, Graduate School of Engineering, Osaka City University, 3-3-138
Sugimoto, Sumiyoshi-ku, Osaka 558-8585, Japan
JST-Innovation Plaza Osaka, 3-1-10 Technostage, Izumi-city, Osaka 594-1144, Japan
Kenta Okubo
Department of Applied Chemistry, Graduate School of Engineering, Osaka City University, 3-3-138
Sugimoto, Sumiyoshi-ku, Osaka 558-8585, Japan
Kouichi Tsujib兲
Department of Applied Chemistry, Graduate School of Engineering, Osaka City University, 3-3-138
Sugimoto, Sumiyoshi-ku, Osaka 558-8585, Japan
共Received 30 September 2008; accepted 20 January 2009兲
We have developed a convenient and effective XRF analysis procedure for trace amount of K, Ca,
V, Mn, Fe, Ni, Cu, Zn, Cd, and Pb in environmental waters by using a preconcentration using
the natural polymer 共agar兲. The thin agar film was prepared by drying a homogeneous agar gel after
mixing the aqueous sample solution with the agar powder. XRF analysis of the preconcentrated thin
agar films containing trace metals showed a good repeatability because agar films were
homogeneous enough. SB 共signal to noise兲 ratios of the XRF intensity of the analytes were
improved drastically. The linear calibration curves of K, Ca, V, Mn, Fe, Ni, Cu, Zn, Cd, and Pb
showed a good linearity within the calibration ranges. The lower limits of detection 共LLD兲 were
1.4 ␮g / mL for K, 0.26 ␮g / mL for Ca, 0.088 ␮g / mL for V, 0.029 ␮g / mL for Mn, 0.11 ␮g / mL
for Fe, 0.016 ␮g / mL for Ni, 0.030 ␮g / mL for Cu, 0.017 ␮g / mL for Zn, 0.20 ␮g / mL for Cd,
and 0.066 ␮g / mL for Pb, respectively. The proposed preconcentration method was applied
to several environmental water samples. © 2009 International Centre for Diffraction
Data. 关DOI: 10.1154/1.3132596兴

Key words: XRF analysis, preconcentration, environmental water, agar

I. INTRODUCTION study is development of a simple and effective preconcentra-

tion for XRF analysis. For sensitive XRF analysis, it is nec-
The analysis of the trace amount of the elements in the essary to increase the amount of the analyte in the X-ray
environmental water is generally performed by spectroscopic irradiation area. Another approach is a reduction of the back-
methods, such as ICP-AES, ICP-MS, and atomic absorption ground and matrix effect, that is, the thin layer sample is
spectrometry 共AAS兲. XRF spectrometry is widely used on more desirable for the sensitive XRF analysis.
environmental samples for routine analysis such as rock, We have proposed a convenient and effective XRF
sediment, airdust, and plastic. However, in the case of envi- analysis procedure for trace amount of elements in environ-
ronmental water, the XRF method is not widely used, be- mental waters with a preconcentration using the natural poly-
cause the sensitivity of the usual XRF spectrometer except
for the SR-XRF or TXRF is lower than ICP-AES and AAS
due to the influence of the matrix effect.
Therefore, XRF method for the analysis of the environ-
mental water generally requires the preconcentration of the
analytes through the sample pretreatments, such as dried spot
method 共Meltzer and King, 1991; Nakamura et al., 1988兲 ion
exchange 共Campbell et al., 1966兲, and precipitation by the
chelating agent 共Akagi et al., 1985; Abe et al., 2006兲. The
dried spotted method is a rapid and simple method for cor-
recting the trace metals in aqueous solutions on flat substrate
or filter paper. However, the dried spot method has the dis-
advantage that the sample volume on the substrate is limited
to the small volume less than 100 ␮L. A preconcentration
procedure with the chelating disk or ion-exchange resin can
correct the large amount of the metal ions with the large
volume sample solution. However, these methods require the
tedious and time-consuming pretreatment. The aim of our

a兲
Electronic mail: nakano@a-chem.eng.osaka-cu.ac.jp Figure 1. XRF spectra of the agar gel 共a兲, and the agar film after dying 共b兲
b兲
Electronic mail: tsuji@a-chem.eng.osaka-cu.ac.jp corrected in 1 ppm of Mn, Fe, Ni, Cu, and Zn aqueous standard solutions.

135 Powder Diffraction 24 共2兲, June 2009 0885-7156/2009/24共2兲/135/5/$25.00 © 2009 JCPDS-ICDD 135
TABLE I. Instrumental conditions for XRF spectrometer.

X-ray tube 3 kW Rh-W dual target

Tube voltage—current 50 kV to 50 mA
Atmosphere Air
Diameter 30 mm
K Ca V Mn Fe Ni Cu Zn Cd Pb
Target Rh Rh Rh Rh Rh Rh Rh Rh Rh Rh
Filter - - - - - - - - Zr -
Crystal Ge Ge LiF LiF LiF LiF LiF LiF LiF LiF
Detector PC PC SC SC SC SC SC SC SC SC
Analytical lime K␣ K␣ K␣ K␣ K␣ K␣ K␣ K␣ K␣ L␣
Counting time/s 80 80 80 80 80 80 80 80 80 80
• Ge: Ge共111兲, LiF: LiF共200兲
• PC: Proportional counter
• SC: Scintillation counter

mer 共agar兲. The pretreatment of the water using natural poly-
mer 共gelatin or agar兲 has been investigated in previous
papers 共Rothe and Köster-Pflugmacher, 1964; Pavel and
Frey, 1983; Eksperiandova et al., 2002; Eksperiandova et al.,
1999兲. Also, we have an experience of using gelatin includ-
ing certain amount of metals for standard samples for XRF
analysis 共Tsuji et al., 2006兲. In this study, we attempted to
preconcentrate with the thin agar film, after correcting the
analyte in the agar gel, and drying.
II. EXPERIMENTAL
A. Apparatus
A Rigaku Rix2100 wavelength-dispersive XRF spec-
trometer equipped with an 3kW Rh-W dual target was used
for this measurement. The X-ray tube was operated at 50 kV
and 50 mA, and measurement diameter was 30 mm. A LiF
analyzing crystal was used for Cd, Cr, Fe, Mn, Pb and Zn,
and Ge analyzing crystal was used for K and Ca. X-ray de-
tectors used for this study were a scintillation counter and a
gas flow proportional counter in which PR gas 共Ar90%
+ CH410%兲 flowed at 50 cm3 min−1. From the XRF intensity
of the analytical line, the average on both sides of the back-
ground was subtracted. The instrumental conditions are listed
in Table I.
The micro-XRF analysis was applied to check the micro-
region homogeneities of the sample. The micro-XRF system
was constructed by our laboratory 共Nakano and Tsuji, 2006;
Tsuji and Nakanao, 2007; Matsuda et al., 2008兲. A sealed-
type 30 W Mo X-ray tube 共MCBM 50 to 0.6B, Rtw, Ger-
many兲 共spot size: 50⫻ 50 ␮m兲 was operated at a tube volt-
age of 50 kV and 0.5 mA. The X-ray microbeam was
obtained by using a polycapillary X-ray lens made by XOS
共X-Ray Optical System Inc.,兲. The micro-X-ray beam size
was about 80 ␮m at Ni K␣. A silicon drift detector 共SDD;
X-Flash Detector Type 1201 Bruker, Germany兲 共sensitive
area: 10 mm2 energy resolution ⬍150 eV at 5.9 keV兲 was
used for the detection of X-ray fluorescence. The sample
stage was placed on the X-Y-Z stage 关YA05A-R1 共X-Y
stage兲 and ZA07AR3S 共Z stage兲; Kohzu Precision, Japan兴;
motor drivers and a motor controller 共NT2400, Laboratory
Equipment Co., Japan兲 were used to control the sample
stage. The mapping conditions were 1600 points in an area
12⫻ 12 mm of the scanning area and a counting time of 200
s per pixel.

TABLE II. Repeatability results of the proposal preconcentration for XRF

measurement.

RSD
Element 共%兲

K 3.6
Ca 0.6
V 6.6
Mn 3.6
Fe 1.1
Ni 5.7
Cu 3.0
Zn 5.8
Cd 2.6
Pb 4.4
RSD: relative standard delivery 共n = 6兲. The samples were prepared by the
Figure 2. Comparison with the signal to background ratio 共SB ratio兲 be- preconcentration from the aqueous standard solution containing 5 ppm of
tween agar film and agar gel samples after preconcentration with the 1 ppm K, Ca, V, Mn, Fe, Ni, Cu, Zn, Cd, and Pb.
of Mn, Fe, Ni, Cu, and Zn standard solutions.

136 Powder Diffr., Vol. 24, No. 2, June 2009 Nakano, Okubo, and Tsuji 136
TABLE III. Analytical results for K, Ca, V, Mn, Fe, Ni, Cu, Zn, Cd, and Pb in the five water samples.

Concentration/mg kg1

K Ca V Mn Fe Ni Cu Zn Pb Cd

City water 2.3 11 n.d n.d n.d n.d n.d 0.046 n.d n.d
Rain water n.d n.d n.d n.d n.d n.d n.d n.d n.d n.d
Mineral water n.d 3.7 0.09 n.d n.d n.d n.d n.d n.d n.d
Green tea 110 n.d n.d 2.3 n.d 0.024 n.d 0.10 n.d n.d
Oolong tea 56 n.d n.d 1.7 n.d 0.018 n.d 0.027 0.12 n.d
n.d: not detected

B. Chemicals III. RESULT AND DISCUSSIONS

An agar powder 共JIS guaranteed grade, Wako, Japan兲
was previously dried in a thermostated dryer at 110 ° C for
24 h to constant weight. To prepare calibration solutions,
1000 mg/kg standard solution 共Wako兲 of K, Ca, V, Mn, Fe,
Ni, Cu, Zn, Cd, and Pb were used.
C. Analytical procedure of the preconcentration with
agar
70 mg of the dried agar powder and 10 mL volume of
the aqueous sample were mixed in a glass beaker at a room
temperature. A 100 ␮L volume of buffer solution added in
the mixture for the pH adjusting. The mixed solution was
heated for 10 min on hot plate with stirring, and poured into
a hollow Teflon cup 共inner diameter: 36 mm␸兲 where the
polyimide film 共7.5 ␮m thick, Niraco Co. Ltd.兲 had been
stretched on the bottom. The thick solidifying agar gel was
obtained after cooling for 20 min at the room temperature.
The solidifying agar-gel was dried at 100 ° C for 3 h, and
that in form of thin film 共50 ␮m thick兲 was obtained.
Figure 1 shows XRF spectra of the agar gel 共a兲, and the
agar film after drying 共b兲 preconcentrated aqueous standard
solutions 共1 ppm of Mn, Fe, Ni, Cu, and Zn兲. As shown in
Figure 1, the background spectrum of the agar film is re-
duced drastically. Moreover, XRF intensities of all elements
were enhanced because of inhibiting of the matrix effect.
Figure 2 shows the comparison with the signal to back-
ground ratio 共SB ratio兲 between agar film and agar gel
samples after preconcentration with the 1ppm of Mn, Fe, Ni,
Cu and Zn standard solutions to confirm the effect of the
preconcentration with agar. The SB ratios of the analytes
were improved by approximately 6 to 16 times by preparing
it on the thin film. In particular, the proposed preconcentra-
tion procedure is more effective for the high-Z elemental
analysis, such as Cu, Zn, and Pb, because the XRF analysis
for high-Z elements was strongly influenced by scattering
X-rays due to the sample matrix.

Figure 3. 共Color online兲 Elemental mapping images and histograms of XRF intensities of Ni, Fe, Zn, and Pb in an agar film after preconcentration of the
aqueous standard solution 共10 ppm of Ni, Fe, and Zn, and 20 ppm of Pb兲 measured by micro-XRF analysis.

137 Powder Diffr., Vol. 24, No. 2, June 2009 Preconcentration of environmental waters by agar for XRF analysis 137
 Figure 4. Calibration curves of K, Ca, V, Mn, Fe, Ni, Cu, Zn, Cd, and Pb in the agar film.
A. Repeatability and homogeneity test
The repeatability of the sample preparation was investi-
gated by XRF measurement in order to confirm the devia-
tions of XRF intensities of the analytes. Six agar films were
prepared and then measured by WDXRF analysis. The tested
agar films were prepared by the preconcentration from the
aqueous standard solution containing 5 ppm of K, Ca, V, Mn,
Fe, Ni, Cu, Zn, Cd, and Pb. Deviations of the XRF intensities
varied slightly, and the relative standard deviations 共RSDs兲
共%兲 for all analytes were approximately less than 6% 共Table
II兲.
Next, the microhomogeneity of the samples was investi-
gated by micro-XRF analysis to confirm the elemental dis-
tribution in the microregion of an agar film. Figure 3 shows
the elemental mapping images and histograms of the XRF
intensities of four elements preconcentrated with the agar
film. The prepared agar film had a homogeneous elemental
distribution, and all histograms showed the Gaussian distri-
bution. The RSDs 共%兲 of the XRF intensities were: Ni, 3.7%;
Fe, 5.9%; Zn, 5.4%; and Pb, 7.9% 共n = 1600兲, respectively.
B. Calibration curves
Figure 4 shows the calibration curves of K, Ca, V, Mn,
Fe, Ni, Cu, Zn, Cd, and Pb preconcentrated with the agar
film. The calibration curves of 10 elements showed a good
linearity within the calibration ranges. The lower limits of
detection 共LLD兲 corresponding to 3␴n−1 of blank values
were 1.4 ␮g / mL for K, 0.26 ␮g / mL for Ca, 0.088 ␮g / mL
for V, 0.029 ␮g / mL for Mn, 0.11 ␮g / mL for Fe,
138 Powder Diffr., Vol. 24, No. 2, June 2009
0.016 ␮g / mL for Ni, 0.030 ␮g / mL for Cu, 0.017 ␮g / mL
for Zn, 0.20 ␮g / mL for Cd, and 0.066 ␮g / mL for Pb, re-
spectively.
C. Application
The proposed preconcentration method was applied to
several environmental water samples 共city water, rain water,
mineral water, green tea, and oolong tea兲 for the determina-
tion. Table III shows the analytical results for K, Ca, V, Mn,
Fe, Ni, Cu, Zn, Cd, and Pb in five water samples obtained
under the proposed procedure. The detected elements in wa-
ter samples were K, Ca, V, Mn, Ni, Zn, and Pb. The proposed
preconcentration by using the agar was successfully prepared
for the environmental water samples with a typically repeat-
ability and homogeneity. However, in the case of the acid
water samples, such as acid rain or acidic hot spring water,
the buffer solution must be added in the sample solution for
pH adjusting, because the agar solution cannot be solidified
under the acid condition less than pH 3.
IV. CONCLUSIONS
We have developed a convenient and effective precon-
centration of environmental water for XRF analysis by using
the natural polymer 共agar兲. The preconcentrated thin agar
films containing trace metals have been successfully made
with a typically repeatability and homogeneity. The advan-
Nakano, Okubo, and Tsuji 138
tage of the proposed method enables simple and quick pre-
concentration of the environmental water at the ppb level for
XRF analysis.
ACKNOWLEDGMENTS
This work was financially supported Practical Applica-
tion Research by the Innovation Plaza Osaka, JST, Japan
Society for Promotion of Science 共JSPS兲 Grant-in-Aid for
Young Scientists 共Grant No. B-1875136兲, and Grand-in-Aid
for Scientific Research 共B兲 共Grant No. 19350042兲.
Abe, W., Isaka, S., Koike, Y., Nakano, K., Fujita, K., and Nakamura, T.
共2006兲. “X-ray fluorescence analysis of trace metals in environmental
water using preconcentration with an iminodiacetate extraction disk,”
XRay Spectrom. 35, 184–189.
Akagi, T., Fuwa, K., and Haraguchi, H. 共1985兲. “Simultaneous multi-
element determination of trace metals in sea water by inductively-
coupled plasma atomic emission spectrometry after coprecipitation with
gallium,” Anal. Chim. Acta 177, 139–151.
Campbell, W. J., Spano, E. F., and Green, T. E. 共1966兲. “Micro and trace
analysis by a combination of ion exchange resin-loaded papers and
X-ray spectrography,” Anal. Chem. 38, 987–996.
Eksperiandova, L. P., Blank, A. B., and Makarovskya, Y. N. 共1999兲. “Pecu-
liarities of making gel-like specimens for X-ray fluorescence analysis,”
139 Powder Diffr., Vol. 24, No. 2, June 2009 Preconcentration of environmental waters by agar for XRF analysis
XRay Spectrom. 28, 24–26.
Eksperiandova, L. P., Blank, A. B., and Makarovskya, Y. N. 共2002兲. “Analy-
sis of waste water by X-ray fluorescence spectrometry,” XRay Spec-
trom. 31, 259–263.
Matsuda, A., Nodera, Y., Nakano, K., and Tsuji, K. 共2008兲. “X-ray energy
dependence of the properties of the focused beams produced by poly-
capillary X-ray lens,” Anal. Sci. 24, 843–846.
Meltzer, C. and King, B.-S. 共1991兲. “Trace element analysis of solutions at
the PPB level,” Adv. X-Ray Anal. 34, 41–55.
Nakamura, T., Hayakawa, T., Masaki, K., and Sato, J. 共1988兲. “Determina-
tion of Na, Mg, Al, S, Cl, K, Ca, Mn, and Fe in hot-spring water by
X-ray fluorescence analysis,” Onsen Kogakkaishi 22, 1–7.
Nakano, K. and Tsuji, K. 共2006兲. “Development of confocal 3D micro XRF
spectrometer and its application to rice grain,” Bunseki Kagaku 55,
427–432.
Pavels, J. and Frey, U. 共1983兲. “Gelatinefolien als eichstandards fuer roent-
genspektrometrische element-bestimmungen in proben duenner schicht-
dicket,” Int. J. Environ. Anal. Chem. 13, 89–113.
Rothe, G. and Köster-Pflugmacher, A. 共1964兲. “Die Gelatine-Methode,” Fre-
senius’ J. Anal. Chem. 201, 241–245.
Tsuji, K., Matsuda, A., Nakano, K., and Okhrimovskyy, A. 共2006兲. “X-ray
fluorescence analysis of soft materials using needle-type collimators en-
abling greater tolerance in analysis depth,” Spectrochim. Acta, B At.
Spectrosc. 61, 460–464.
Tsuji, K. and Nakanao, K. 共2007兲. “Development of confocal 3D micro-
XRF spectrometer with dual Cr–Mo excitation,” XRay Spectrom. 36,
145–149.
139