Talanta 70 (2006) 933–939

Rapid determination of aluminum by UV–vis diffuse reflectance

spectroscopy with application of suitable adsorbents
M.A. Zanjanchi ∗ , H. Noei, M. Moghimi
Department of Chemistry, Faculty of Science, University of Guilan, P.O. Box 1914, Rasht, Iran
Received 15 September 2005; received in revised form 25 February 2006; accepted 18 May 2006
Available online 23 June 2006

Abstract
Diffuse reflectance spectroscopy (DRS) can be used as a rapid and sensitive method for the quantitative determination of low amounts of
aluminum. In this analytical technique, the analyte in samples are extracted onto a solid sorbent matrix loaded with a colorimetric reagent and
then quantified directly on the adsorbent surface. Alternatively, colored aluminum complexes formed in solution can also be immobilized onto
adsorbent surface and be measured by DRS technique. Octadecyl silica disk, methyltrioctylammonium chloride–naphthalene and MCM-41 were
examined as adsorbents. Eriochrome cyanine R and quinalizarin were used as coloring reagents. Optimal sorption conditions were found for each
system of analyte–reagent–adsorbent. The concentration of analyte is determined using the appropriate form of the Kubelka–Munk function. We
obtained for each of the aluminium–reagent–adsorbent system a calibration curve by plotting the absorbance versus the log 102 [Al3+ ] ␮g ml−1 .
The linear dynamic range extends over two orders of magnitude within 0.01–15 ␮g ml−1 with little differences in the range and in the correlation
coefficients among the adsorbents. We consider that for a rapid determination of aluminum a spot-test-DRS combination with a detection limit of
1.0 × 10−2 ␮g ml−1 is the more facile and preferred technique.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Aluminum; Diffuse reflectance spectroscopy; Spot-test; MCM-41; Octadecyl silica; Eriochrome cyanine R

1. Introduction technique capable of highly selective for removal of metal ions

Instrumental techniques such as atomic absorption spectrom-
etry, inductively coupled plasma atomic emission spectrometry,
neutron activation analysis and ICP-mass spectrometry are pow-
erful tools for the trace determination of metal ions. However,
these methods have the disadvantages of high cost of instru-
ments and matrix interference. Separation of analyte from other
elements present and use of a pre-concentration step prior to the
determination is a useful alternative approach. Solvent extrac-
tion of different metal ions has been widely employed in chem-
istry for many years. However, the use of classical extraction
methods are usually time-consuming labor-intensive and require
relatively large volume of high purity solvents. Additional con-
cern is the disposal of the solvent used, which can create a
severe environmental problem. Replacing the conventional sol-
vent extraction methods with solid-phase extraction provides a
∗ Corresponding author. Tel.: +98 131 3226643; fax: +98 131 3220066.
E-mail address: zanjanchi@guilan.ac.ir (M.A. Zanjanchi).
from solution containing matrices, which normally make sepa-
ration difficult. In this technique usage of organic compounds
is reduced considerably. However, final part of the procedure
usually contains stripping the membrane disk or columns from
the extracted metal ions using water or other solvent prior to
the determination. One other way to perform a determination
of this type involves the use of diffuse reflectance spectroscopy
(DRS) in the final part of the procedure. By employing this
technique the elusion step can be eliminated from the process.
In this technique, direct measurement of the adsorbed species
on the solid supports offers the advantage of avoiding the loss
usually encountered during elution of the analyte from the adsor-
bent. Also, this technique simplifies and speeds up the analytical
procedure. This technique would also be in the program of the
analytical methodologies designed to achieve the green chem-
istry ambitions [1]. There is an evident demand to the develop-
ment of greener, yet reliable, analytical procedures to minimize
or eliminate the use of toxic reagents.
The development of reflectance spectroscopy was initially
considered for several applications such as dye-stuffs, printing

0039-9140/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.talanta.2006.05.056
934 M.A. Zanjanchi et al. / Talanta 70 (2006) 933–939
inks, paints and pigments, textiles, paper, ceramics, building
materials, metallurgy and optical materials. But extensive pro-
gresses have been recently achieved in diffuse reflectance spec-
troscopy for studying inorganic materials [2–4]. Although, the
reflectance spectroscopy is not widely recognized in analytical
chemistry as is the use of transmittance spectroscopy, but with
the development of optical devices such as integrating sphere
assemblies, the situation has changed and satisfactory results
were obtained [4–6].
Application of diffuse reflectance spectroscopy has been
reported for many cations [7–19] and some anions [20–22]
after adsorption onto a proper solid support. There are different
ways for formation and collection of colorimetrically measur-
able analyte. These are include complexation in solution and
extraction of the soluble complex [7,8], reagent immobilization
with the subsequent extraction and complexation of the analyte
[9–14,21,22], analyte extraction fallowed by exposure to com-
plex reagent solutions [16–19] and also formation of an insoluble
complex and collecting it on an extraction membrane [15].
In this paper, three sensitive and efficient spot-test and pre-
concentration techniques in combination with diffuse reflectance
spectroscopy were developed for measurement of aluminum.
The determination of trace amount of aluminum has become
increasingly very important because exposure of the metal to
human threaten his health due to the diseases such as Alzheimer
disease and Parkinson disease [23–25]. In our primer technique
either of the reagent eriochrome cyanine R (ECR) or quinalizarin
was loaded on octadecyl-bonded silica (ODS) membrane disks
and then aluminum solution was passed through the modified
disks. We also employed adsorbent columns containing either
MCM-41 (a mesoporous material) or methyltrioctylammonium
chloride–naphthalene for extraction of Al–ECR complexes prior
to DRS measurements. Finally we examined the efficiency of a
spot-test method by adsorbing ECR on a home made MCM-41
disk followed by spotting the disk by drops of aluminum solu-
tion. To the best of our knowledge, these modifications have not
been employed previously for aluminum measurements.
2. Experimental
2.1. Reagents and adsorbents
All the reagents used were of chemical purity or analytical
purity grade. All solutions were prepared with deionised water.
The stock aluminum solution (1000 ␮g/ml) was prepared by
dissolving the exact amount of high purity aluminum powder
(Aldrich no. 20258, 99.99%) in concentrated HCl and diluting
to 500 ml. More diluted solutions were prepared daily from the
stock solution. A 0.01 M solution of ECR (Merck no. 103164)
was prepared and used throughout. Buffer solution of pH 6.1
was prepared by addition of drops of 1 M hydrochloric acid to
50% (w/v) sodium acetate solution using the pH meter to adjust
the desired pH.
The MCM-41 mesoporous adsorbent was synthesized by
a room temperature method with some modification in the
described procedure in the literature [26]. We used tetraethy-
lorthosilicate (TEOS, Merck, 800658) as a source of silicon
and hexadecyltrimethylammonium bromide (HDTMABr, BDH,
103912) as a surfactant template for preparation of MCM-41.
The details of the procedure have been described elsewhere
[27]. The molar composition of the reacting mixture was as
follows: SiO2 :1.6 EA:0.215 HDTMBr:325 H2 O. EA stands for
ethylamine. The as-synthesized MCM-41 sample is calcined at
550 ◦ C for 5 h to decompose the surfactant and generating the
adsorption property of the material. This powder sample is white
and used for loading the colored species (ECR or Al–ECR).
The naphthalene adsorbent was prepared by addition of
0.6309 g of methytrioctylammonium chloride (Merck, 818079)
to 12.5 g naphthalene in 23 ml acetone on a hot-plate stirrer. The
mixture was stirred at 40 ◦ C until a clear solution was obtained.
The solution was transferred into 750 ml of deionised water
while stirring it at room temperature. It was then stirred for 1 h.
After being allowed to stand for 30 min, the supernant solution of
naphthalene coprecipitated with methyltrioctylammonium chlo-
ride was drained off by decantation and washed with deionised
water for several times. This adsorbent was kept in a caped bottle
for further use.
Quinalizarin (Fluka, 22570) solution was prepared by dis-
solving 10.0 mg of reagent in 25 ml acetone. Octadecyl-
bounded silica membrane disks were of the type Empore
(47 mm × 0.5 mm, 3 M Co).
2.2. Apparatus
A Shimadzu UV-2100 spectrophotometer equipped with an
integrating sphere assembly was used to collect all the spectral
data from the 12 mm disks or pressed materials. The spectrum
is recorded at room temperature against barium sulfate and plot-
ted in terms of absorbance. The crystalline structure of our-made
MCM-41 was checked by a Philips PW1840 diffractometer with
Cu K␣ radiation at room temperature. XRD pattern was recorded
using an automatic divergent slit system within 2θ = 2–10◦ .
Chemical analysis of the MCM-41 was done by energy disper-
sive X-ray analysis (EDX) joined to a Philips XL-30 scanning
electron microscope.
The 12 mm disk (∼230 mg MCM-41 is lightly pressed to
obtain a disk with 12 mm diameter) elaborated in our laboratory
is used as adsorbent support for spot-test performance.
2.3. Extraction procedure
2.3.1. ODS disk
Extraction was performed with 47 mm × 0.5 mm (diame-
ter × thickness) Empore membrane disks containing octadecyl-
bonded silica used as a matrix for collection of the colored
complex. The disk was used in conjunction with a standard
47 mm filtration apparatus. After placing the membrane in the
filtration apparatus, it was washed with 10 ml methanol and
10 ml acetonitrile to remove all contaminants arising from the
manufacturing process and environment. After drying the disk
by passing air through it for several minutes, a solution of
5.364 mg ECR dissolved in 10 ml water or 10 mg quinalizarin
dissolved in 4 ml acetone was introduced to the reservoir of the
apparatus and was drawn slowly through the disk by applying
 M.A. Zanjanchi et al. / Talanta 70 (2006) 933–939
a slight vacuum until the reagent penetrated the membrane
completely.
The disk modified by ECR or quinalizarin was then washed
with 10 ml water followed by passing 2 ml of buffer solution (pH
6.1) through it. Finally the disk was dried at room temperature.
The procedure for extraction of Al3+ ions on the modified disk
was as follows: the modified disk was first wetted with 1 ml water
prior to extraction. Then, aluminum solution with known con-
centration was passed through the disk (flow rate ≈ 7 ml min−1 ).
After the extraction, the disk was dried at room temperature and
then part of it was cut for diffuse reflectance measurement.
2.3.2. Methyltrioctylammonium chloride–naphthalene
column
A funnel tipped glass tube (50 mm × 5 mm i.d.) with a very
fine bore was used as a preconcentration column. It was filled
with the adsorbent slurry to a height of 2 cm after slightly press-
ing the adsorbent into the column with a flat glass rod. The
column was then conditioned to pH 6.1 with 2–3 ml of buffer.
After 2 min, solution of Al–ECR was passed through the col-
umn at a flow rate of ∼1 ml min−1 . Finally the column packing is
removed out and part of it was pushed down into a sample holder
designed for the solid materials ready for diffuse reflectance
measurement.
2.3.3. MCM-41 column
A glass tube (50 mm × 5 mm i.d.) was packed with the cal-
cined MCM-41 powder employing a vacuum pump to obtain
a homogenous packing. The column was first eluted with 5 ml
of deionized water. Then 3.5 ml of buffer pH 6.1 was passed
through the column. Now, the adsorbent column is ready for
elution of Al–ECR solution. Procedure for elution is the same
as that described for naphthalene-modified column. At the end
of elution the packing is removed out and part of it was used to
fill the specific sample holder.
2.4. Spot-test
The calcined MCM-41 was used for preparation of the sup-
port disks for spot-test reaction. About 0.5 g of the calcined
MCM-41 was added to 25 ml of ECR solution (5 × 10−4 M) and
was stirred for 24 h. After 24 h the color of the matrix is stabilized
implying that the dye molecules are adsorbed on MCM-41. The
mixture is then centrifuged and solid was washed with deionized
water and dried at 40 ◦ C. The fine powder of the solid is then
pressed with our elaborated disk-preparing system to provide
disks with a diameter of 20 mm and a thickness of ≈0.4 mm.
When drops of aluminum solution come into contact with the
surface of the disk a colored product is formed on the surface.
The aluminum solution is buffer to pH 6.1 prior to spotting.
2.5. Diffuse reflectance measurements
The Kubelka–Munk equation provides an adequate approach
for quantitatively relating the observed signal to the sample
concentration in diffuse reflectance measurements [28]. The
935
Kubelka–Munk function, F(R), is defined as
(1 − R)2
F (R) =
2R
where R is the percent reflection measured with respect to a
standard white. F(R) is related to analyte concentration by
εC
F (R) =
s
where ε is the molar absorbtivity, C the concentration of the com-
plexed analyte, and s is the scattering coefficient of the sample
surface. By assuming the absorbtivity and scattering coefficient
of our surface are constant at a given wavelength, F(R) can
therefore be related directly to analyte concentration. For quanti-
tative measurements, the literature proposed many types of plots
relating the signal and concentration [9]. In this work, we have
obtained quantitative data by plotting: Abs = −log IR /ÍR versus
log C. IR is the intensity of radiant energy reflected by the sam-
ple and ÍR is the intensity reflected by the white blank. Abs is
analogous to absorbance with the only difference being that Abs
represents the optical density for reflectance measurement and
not for absorbance.
3. Result and discussion
3.1. Al–ECR complex formation as a function of pH
It was found that the formation of aluminum–eriochrome
cyanine R complex (Al–ECR) was more complete in the pH
range 5.8–6.2 (Fig. 1). Effect of pH on absorbance for Al–ECR
adsorbed on MCM-41 and MTOAC–naphthalene are shown in
Fig. 2a and b. According to those, pH 6.1 was chosen as opti-
mum pH. Adjustment of the pH of the adsorbents was done
either by eluting the adsorbent columns (MTOAC–naphthalene
or MCM-41) with buffer solutions, passing the buffer through
Fig. 1. Absorption spectra of Al–ECR at the indicated pH (a = 2, b = 4, c = 5,
d = 6, e = 7 and f = 10).
936 M.A. Zanjanchi et al. / Talanta 70 (2006) 933–939

Fig. 2. Effect of pH on the absorbance of Al–ECR adsorbed on (a)

MCM-41, λmax = 530 nm and (b) MTOAC–Naph, λmax = 570 nm; conditions:
[Al3+ ] = 0.1 ␮g ml−1 , CECR = 1 × 10−5 M.

the adsorbent disk (ODS) or addition of buffer to aluminum

solution (spot-test).

3.2. Optical characteristics of aluminum complexes on the

surface of adsorbents

The diffuse reflectance spectra of Al/ECR–ODS, Al/Q–ODS,

Al–ECR/MTOAC–Naph, Al–ECR/MCM-41 are shown in
Fig. 3. The DR spectra of ECR–MCM-41 and Al/ECR–MCM-
41 obtained for spot-test are shown in Fig. 4. Table 1 describes
that how these designations have been chosen to represent the
method used for determination of aluminum.
Diffuse reflectance spectrum of ECR–MCM-41 (Fig. 4a)
shows a band at about 420 nm which corresponds to the ECR.
This indicates that ECR is adsorbed by MCM-41. The maxi-
mum of the DR spectrum obtained for the aluminum spotted
on MCM-41 (Al/ECR–MCM-41) is observed at about 530 nm
(Fig. 4b). The comparison of the DR spectra of reagent and
Fig. 3. Diffuse reflectance spectra of (a) Al/ECR–ODS, (b) Al/Q–ODS, (c)
Al–ECR/MTOAC–Naph and (d) Al–ECR/MCM-41.
complex clearly shows the progress of reaction occurred on
the surface of adsorbent. The reflectance spectra for Al–ECR
complexes formed on other solid phases (Fig. 3) shows this
characteristics band within 530–570 nm which can be used for
calibration and quantitative measurements. The shift in maxima
is related to the gust-host effects usually observed in spectra of
adsorbed species on the solid supports.

Table 1
Method used prior to a diffuse reflectance spectrophotometric determination of aluminum
Solid adsorbent Techniquesa Reagent Designation of the reflecting sample

Octadecyl silica disk SPE Eriochrome cyanine R Al/ECR–ODS

Octadecyl silica disk SPE Quinalizarin Al/Q–ODS
Methyltrioctylammonium chloride–naphthalene SPE Eriochrome cyanine R Al–ECR/MTOAC–Naph
MCM-41 SPE Eriochrome cyanine R Al–ECR/MCM-41
MCM-41 ST Eriochrome cyanine R Al/ECR–MCM-41
a SPE stands for solid phase extraction and ST stands for spot-test.
 M.A. Zanjanchi et al. / Talanta 70 (2006) 933–939
Fig. 4. Diffuse reflectance spectra of (a) ECR–MCM-41 and (b) Al/ECR–MCM-
41; condition: pH 6.1, CECR , 5 × 10−4 M.
3.3. Calibration curves
The calibration curves for Al/Q–ODS and Al/ECR–ODS
are shown in Fig. 5. The details of experimental conditions
such as pH, λmax , flow rate of sample through the disks are
described in caption to the Fig. 5. The calibration graph was lin-
ear (r2 = 0.997) in the range 0.08–1.6 ␮g ml−1 of aluminum for
Al/Q–ODS and the correlation coefficient was r2 = 0.988 in the
Fig. 5. Calibration curve for aluminum (a) Al/ECR–ODS adsorbent system,
pH 6.1, CECR = 1 × 10−3 M, λmax = 540 nm, flow rate = 6 ml min−1 and (b)
Al/Q–ODS adsorbent system, pH 6.8, CQ = 1 × 10−3 M, λmax = 519 nm, flow
rate = 7 ml min−1 .
937
Fig. 6. Calibration curve for aluminum for Al–ECR/MTOAC–Naph adsorbent
system, pH 6.1, CECR = 1 × 10−3 M, λmax = 570 nm, flow rate = 2.5 ml min−1 .
range 0.03–0.25 ␮g ml−1 of aluminum for Al/ECR–ODS. The
relative standard deviations (R.D.S.) of six replicate determina-
tion of 1 ␮g ml−1 of aluminum were 9.6 × 10−5 and 1.9 × 10−5
for Al/Q–ODS and Al/ECR–ODS, respectively. The detec-
tion limit was found from the calibration curve by plotting
the intersection of the curve with the abscissa. The LOD
was 0.004 ␮g ml−1 for Al/ECR–ODS and 0.02 ␮g ml−1 for
Al/Q–ODS.
The calibration curve for Al–ECR/MTOAC–Naph is shown
in Fig. 6. The calibration curve was performed from 0.1 up to
3 ␮g ml−1 . The correlation coefficient r2 shows a good linearity
between Abs and log C. The same procedure was carried out in
order to find out the detection limit. The LOD was 0.001 ␮g ml−1
for this system.
The calibration curves for Al–ECR/MCM-41 (column pre-
concentration method) and for Al/ECR–MCM-41 (spot-test) are
shown in Fig. 7a and b, respectively. In order to improve the per-
formance of aluminum determination by spot-test on MCM-41,
factors such as concentration of reagent, thickness of adsorbent
and time of measurement following the color appearance on the
adsorbent disk was modified. Fig. 8 shows how these parameters
have been obtained. The pH used was previously chosen as 6.1.
The calibration curves for Al–ECR/MCM-41 and
Al/ECR–MCM-41 shows good linearity for both (r2 = 0.996 for
Al–ECR/MCM-41 and r2 = 0.973 for Al/ECR–MCM-41). How-
ever the linear dynamic range is higher for Al–ECR/MCM-41.
The detection limits are rather similar and is about 0.01 ␮g ml−1
for both of Al–ECR/MCM-41 and Al/ECR–MCM-41 systems.
3.4. Interference problem
There are three main species: beryllium, vanadium and zir-
conium where interfere in the determination of aluminum with
ECR under chosen condition (pH 6.1) [29]. In the present study
our material was free from these ions. Our complementary inves-
tigation will be focused on studying the problem of interference
by mixing these species separately with our pure aluminum sam-
ple and carrying out the DR studies. The type and property of the
938 M.A. Zanjanchi et al. / Talanta 70 (2006) 933–939

Fig. 7. Calibration curve for aluminum for (a) Al–ECR/MCM-41 adsorbent

system, pH 6.1, CECR = 1 × 10−3 M, λmax = 530 nm, flow rate = 2.5 ml min−1
and (b) Al/ECR–MCM-41 spot-test system, pH 6.8, CECR = 5 × 10−4 M,
λmax = 530 nm.

adsorbent in better adsorbing desirable species and not adsorb-

ing the interference ions will be our target.
The results of some common interfere ions for our spot-test
measurement of aluminum is summarized in Table 2. Synthetic
solution containing 0.2 ␮g ml−1 of aluminum and various con-
centration of ions were prepared and the procedure was followed
(at λmax = 530 nm). A relative error of ±3% in the Abs reading
was considerated tolerable.
Fig. 8. Effect of some experimental parameters on the efficiency of spot-test for
3.5. Analytical application determination of aluminum spotted on MCM-41 adsorbent, (a) ECR concentra-
tion, (b) thickness of adsorbent and (c) time of measurement after spotting.
The proposed methods were applied to aluminum determi-
nation in tap water in Rasht. The results obtained are shown in Table 3. The results obtained by DRS methods are higher in
comparison with that given by Rasht Water Authority Labora-
Table 2 tory (0.12 ␮g ml−1 ). This is most probably due to interference
Effect of interfere ions from Mg2+ and Ca2+ cations present in high amounts in the city
Ion added Tolerance limit (␮g ml−1 ) water. In this condition, preseparation of these cations should be
recommended.
Ca2+ 200
In order to evaluate the accuracy and applicability of the rapid
Mg2+ 165
Mn2+ 130 Al/ECR–MCM-41 technique for the analysis of real samples,
Ba2+ 150 it was also applied to the determination of aluminum in two
Cu2+ 220 commercial bottled mineral waters (distributed in Iran) and in
Cl− 125 “soft-water” used in a textile factory in Rasht (water passed
Co2+ 25
through zeolite and green sands). The results are compared with
Ni2+ 40
atomic absorption data (Table 4).
 M.A. Zanjanchi et al. / Talanta 70 (2006) 933–939 939

Table 3
Determination of aluminum in tap water by DRS techniques
Reflecting sample Sample no. Standard aluminum added (␮g ml−1 ) Found (␮g ml−1 )a

Al/ECR–MCM-41 (spot-test) 1 – 0.16 (±0.01)

2 0.5 0.71 (±0.01)
3 1.0 1.21 (±0.04)
Al–ECR/MCM-41 1 – 0.17 (±0.01)
2 0.5 0.71 (±0.02)
3 1.0 1.23 (±0.01)
Al–ECR/MTOAC–Naph 1 – 0.18 (±0.01)
2 0.5 0.73 (±0.02)
3 1.0 1.26 (±0.01)
a Mean of three determinations.

Table 4
Analysis of aluminum by Al/ECR–MCM-41 reflecting system and atomic
absorption (concentrations in ␮g ml−1 )
Sample Proposed techniquea Atomic absorption
Damash mineral water 0.039 (±0.004) 0.042
Damavand mineral water 0.029 (±0.004) 0.033
Soft water 0.018 (±0.005) 0.013
a [5] M. Tubino, A.R. Vitorino, M.E.A. De Magalhaes, Anal. Lett. 30 (1997)
Mean of three determinations.
4. Conclusion
The results show that the appropriate use of the dif-
fuse reflectance spectroscopy allows determining low con-
centration of aluminum preadsorbed on a suitable adsorbent
disk by pre-concentration or spot-test techniques. Commercial
octadecyl silica disk or home-made methyltrioctylammonium
chloride–naphthalene and MCM-41 disks provide proper media
for adsorbing the colored species. Eriochrome cyanine R or
quinalizarin were employed as coloring reagents. To ensure sat-
isfactory results, some conditions such as pH of the adsorbing
media, concentration of the reagent, thickness of the home-made
disks and time of the reflectance reading were optimized. The
adaptation of spot-test method in conjunction with the DRS,
provide a very simple and relatively rapid determination of
aluminum. The linear range is relatively wide for all of the com-
bination of the employed reagents and the adsorbents within
general range of 0.01–15 ␮g ml−1 .
In this method, no solvent elution is required because the
amount of the colored analyte complex is directly measured on
the disk by reflectance spectroscopy. Also, a better environmen-
tal impact is achieved due to lower production of toxic wastes.
Possibility of construction of a portable reflectometer can be
envisaged for the spot-test technique improving the performance
and speed of the measurement of aluminum.
Acknowledgement
The authors wish to acknowledge the financial support of the
Graduate Office of the University of Guilan.
References
[1] P.T. Anastas, M.M. Kirchhoff, Acc. Chem. Res. 35 (2002) 686.
[2] B.M. Weckhuysen, R.A. Schoonheydt, Catal. Today 49 (1999) 44.
[3] G. Schulz-Ekloff, D. Wöhrle, B. van Duffel, R.A. Schoonheydt, Microp-
orous Mesoporous Mater. 51 (2002) 91.
[4] Y. Moliner-Martinez, R. Herráez-Hernández, P. Campins-Falco, Anal.
Chim. Acta 534 (2005) 327.
271.
[6] A. Ghauch, J. Rima, C. Amine, M. Martin-Bouyer, Chemosphere 39 (1999)
1309.
[7] R.F. Gur’eva, S.B. Savvin, J. Anal. Chem. 55 (2000) 280.
[8] R.F. Gur’eva, S.B. Savvin, J. Anal. Chem. 56 (2001) 1032.
[9] A. Ghauch, C. Turnar, C. Fachinger, J. Rima, A. Charef, J. Suptil, M.
Martin-Bouyer, Chemosphere 40 (2000) 1327.
[10] N.I. Ershova, V.M. Ivanov, Anal. Chim. Acta 408 (2000) 145.
[11] N.I. Ershova, V.M. Ivanov, Fresenius J. Anal. Chem. 371 (2001) 556.
[12] M. Ahmad, R. Narayanaswamy, Sci. Total Environ. 163 (1995) 221.
[13] A. Ghauch, J. Rima, A. Charef, J. Suptil, C. Fachinger, M. Martin-Bouyer,
Talanta 48 (1999) 385.
[14] O.A. Zaporozhets, L.Y. Tsyukalo, Talanta 58 (2002) 861.
[15] D.B. Gazda, J.S. Fritz, M.D. Porter, Anal. Chim. Acta 508 (2004) 53.
[16] O.P. Shvoeva, V.P. Dedkova, S.B. Savvin, J. Anal. Chem. 53 (1998)
1184.
[17] O.P. Shvoeva, V.P. Dedkova, S.B. Savvin, J. Anal. Chem. 55 (2000) 607.
[18] O.P. Shvoeva, V.P. Dedkova, S.B. Savvin, J. Anal. Chem. 56 (2001)
1080.
[19] O.P. Shvoeva, V.P. Dedkova, S.B. Savvin, J. Anal. Chem. 56 (2001) 758.
[20] M.N. Abbas, Anal. Sci. 19 (2003) 1303.
[21] M.P. Arena, M.D. Porter, J.S. Fritz, Anal. Chem. 74 (2002) 185.
[22] S.G. Dmitrienko, O.A. Sviridova, L.N. Pyatkova, V.A. Zhukova, Yu.A.
Zolotov, Anal. Chim. Acta 405 (2000) 231.
[23] L.L. Sombra, R.G. Wuilloud, R.A. Olsina, L.P. Fernandez, L.D. Martinez,
J. Trance Microprobe Tech. 18 (2000) 431.
[24] A. Martinesteban, P. Fernandez, C. Perezconde, A. Gutierrez, C. Camara,
Anal. Chim. Acta 304 (1995) 121.
[25] U. Tamer, N.O. Pekmez, A. Yildiz, Fresenius Environ. Bull. 11 (2002)
1087.
[26] A.C. Voegtlin, A. Matijasic, J. Patarin, C. Saucrland, Y. Grillet, L. Hure,
Microporous Mater. 10 (1997) 137.
[27] M.A. Zanjanchi, S. Asgari, Solid State Ionics 171 (2004) 277.
[28] J.P. Blitz, Modern Techniques in Applied Molecular Spectroscopy, Wiley,
New York, 1998, p. 185.
[29] G. Charlot, Chimie Analytique Quantitative, vol. II, Masson et Cie , Paris,
1974, p. 330.