Application of natural zeolites for preconcentration
of arsenic species in water samples†
Received 14th August 2000, Accepted 11th December 2000
First published on 4th January 2001
Abstract
Zeolites of the clinoptilolite type produced in Mexico and Hungary
were investigated with respect to their sorption efficiency for various redox
species of arsenic. Long-term experiments showed that arsenate remains
stable for a long period in spiked deionised water and drinking water, as
well as in the surface water of the Biela valley in Saxony, Germany. Both
clinoptilolites are able to decrease the initial arsenic concentration of
200 µg l−1 by more than 75% in
deionised, drinking, ground and surface waters. In the case of the Mexican
zeolite, both the arsenite and the arsenate concentrations (200 µg l−1)
can be lowered from 200 µg l−1 to 10 µg l−1,
which is the World Health Organisation's (WHO's) recommended
maximum level. It was found that the presence of cations and anions in the
natural waters of Biela, Germany, and Zimapán, Mexico, did not reduce
the efficiency of the selected zeolites. The Hungarian zeolite removed 75%
of the arsenate in the Zimapán water and only 50% when the sample
was first acidified. This zeolite totally desorbed the fixed arsenic into
a water volume that was half the volume in the adsorption experiment.
Introduction
Several drinking water sources around the world1–5
are contaminated by toxic arsenic originating from the oxidation of arsenic-containing
minerals or mining activities. Using untreated water contaminated by arsenic
causes numerous diseases of the skin and internal organs.6,7
Therefore, one of the World Health Organisation's (WHO's)8 most pressing aims in solving the world's drinking
water problems9 is to develop and introduce
low-cost pretreatment procedures to effectively remove various arsenic
species from natural water. The use of the cation exchange properties of zeolite
has received much attention over the past decade in water and industrial waste
treatment.10,11 The crystalline structure
of zeolites is responsible for a number of properties which are specific and
favourable for catalytic reactions. The adsorption processes observed are
the result of the specific interactions with the cations in the window rings
or presumably with the oxygen atoms in the framework.Recently, we reported12 the sorption and
desorption of arsenite and arsenate from deionised water model solutions by
natural zeolites. The kinetics and the influence of pH on the sorption process
were also studied. Moreover, we devoted a complete study to the oxidation
of arsenite by a synthetic zeolite.13 As part
of our research on arsenic, the present paper deals with the applicability
of natural zeolites for arsenic removal from natural water sources, as well
as from water solutions spiked with arsenic. One report concerning the concentration
of arsenate from a spiked potable water solution on iron-modified clinoptilolite
and chabazite can be found in the literature.14
However, Bonnín14 did not perform speciation
and the final filtrates were analysed after 24 h.
Because the dominant forms of arsenic in the typical pH range of natural
waters are H2AsO4−, HAsO42−,
H3AsO3 and, to a lesser extent, H2AsO3−,
we decided to conduct a long-term monitoring study of the stability of
arsenite and arsenate in different aqueous media in the absence of and in
contact with zeolite in identical static experiments. The identification and
quantification of the species were conducted over 4 weeks by ion chromatography
separation coupled with inductively coupled plasma mass spectrometric detection (IC-ICP-MS).
The zeolites ZME and ZH were selected from a variety of natural zeolites because
their interaction with arsenite and arsenate, as well as with some organoarsenic
compounds, had been previously studied.12,13
ZME exhibited saturation capacities of am = 3 µg g−1
and 25 µg g−1 for arsenite and arsenate,
respectively, while for ZH these values were am = 2 µg g−1
and 6 µg g−1.15
Experimental
Chemicals
Stock solutions of arsenite and arsenate with concentrations of 1 mg l−1
were prepared from arsenic trioxide (Fluka) and arsenate solution (Titrisol,
Merck), respectively, using deionised water. The concentration of the
arsenic species is always given as the concentration of elemental arsenic.
Effluent water from the Biela valley in Germany and groundwater from Pozo
5 in Zimapán, Mexico, were filtered, analysed and placed in contact
with the zeolites without any further pretreatment. Biela water was used unspiked
and spiked with 200 µg l−1 arsenite.
Both matrices were used at their original pH value and also acidified with
0.01 M HCl. Deionised water (Milli-Q, Millipore) and
drinking water from Leipzig, Germany, were also spiked with both arsenate
and arsenite for this study. Reference solutions (Merck) were used
for the spectrometric and chromatographic quantification of cations and anions
in the natural waters.Analytical procedures
The IC-ICP-MS system for the determination of the arsenic species
consisted of an LC 250 binary pump (Perkin-Elmer) coupled with
an Elan 5000 ICP-MS (Perkin-Elmer)
via a cross-flow
nebuliser. A volume of 200 µl was always injected. The guard
and separation columns used were IonPac AG7 and IonPac AS7 (Dionex),
respectively. The mobile phase was a nitric acid solution with a flow rate
of 1 ml min−1. Elution was performed using
the following gradient elution:16 100%
E1 for 1 min, linear gradient 0–100% E2 in 1 min,
100% E2 for 6 min, linear gradient 100–50% E2 in
2 min, 50% E2 for 5 min, linear gradient 50–0%
E2 in 1 min, 100% E1 for 5 min, where eluent E1 was 0.4 mM
HNO3 and eluent E2 50 mM HNO3. The cation concentration
of the natural waters and the total amount of arsenic released after desorption
were determined by atomic emission spectrometry (ICP-AES) using
a Spectroflame P/M (Spectro A.I.) with pneumatic nebulisation (cross-flow
nebuliser). The cations analysed were: K+, Mg2+,
Ca2+, Al3+, Mn2+, Fe3+,
Ni2+, Cu2+, Zn2+, Cd2+
and Pb2+. The anion concentration was determined by ion chromatography
using a DX 500 Dionex chromatograph with conductivity detection, an IonPac
AS11 analytical column and an AG11 guard column. Elution was performed at
a flow rate of 2 ml min−1 by means of the Elugen
EGC-KOH cartridge for the hydroxide gradient: 0.5 mM KOH for 2.5 min,
0.5–5.0 mM KOH in 3.5 min, 5.0–38.3 mM KOH
in 12 min, 0.5 mM NaOH for 7 min. The anions analysed
were: F−, Cl−, Br−, NO2−,
NO3− and SO42−.Zeolites
The zeolites used in this work were natural Mexican and Hungarian clinoptilolites
with a mesh size of 60 and are described in Table 1.
They were characterised by X-ray diffraction, fluorescence spectroscopy
and IR spectroscopy. Their activation was described in a recent paper.12 Synthetic mordenite was used as a powder, while
the natural zeolites ZME and ZH were studied as grain and as powdered samples.
Table 1 Studied zeolite types and their composition
Zeolite | Type | Si/Al | Fe2O3
(%) | Origin |
---|
naa | ab | na | a |
---|
na, Raw zeolitic material. a, Activated zeolite. |
---|
ZH | Clinoptilolite | 6.25 | 6.34 | 1.07 | 0.60 | Hungary, natural |
ZME | Clinoptilolite | 5.18 | 5.54 | 1.76 | 1.56 | Mexico, natural |
ZS | Mordenite | 6.97 | 7.38 | 0.18 | 0.20 | Synthetic |
Procedures
A given volume of arsenic solution was equilibrated with a weighed amount
of zeolite for a definite time. It was initially shaken for 3 min in
an ultrasonic bath and then for 60 min in a horizontal shaker. Our
initial experiments on the application of zeolites for arsenic removal12 demonstrated that, during shaking, the temperature
of the solution rose by 3
°C. This heating had no effect on the
equilibrium state of the arsenic redox pair when the arsenic species were
determined in the equilibrium solution immediately after immersing the zeolite
into the solution. Due to the acid properties of the zeolites, static experiments
prepared at acidic pH values maintain a very stable acidity. In the initial
trials, the solid to solution ratio was varied and then maintained at 1 ∶ 5.
The experiments were carried out at 23
°C using glass containers
as batch reactors. Every week, 2 ml of the supernatant was removed
for analysis. For the post-concentration trials by means of desorption,
the zeolites in the batch solutions were filtered after adsorption. They were
dried on filter paper and then at 100
°C for 3 h. A weighed
amount (15 g) of the zeolite containing arsenic was put in
contact with HCl 1 M, 2 M and 3 M, HNO3 1 M
and H3PO4 1 M. For the adsorption experiments,
75 ml of the arsenic solution was used, with 35 ml for desorption.
This enabled the arsenic to be recovered into a smaller solution volume. After
7 days the supernatant solution was analysed by ICP-AES.Calculations
The IC-ICP-MS chromatograms on mass 75As were quantitatively
evaluated by integrating the peaks corresponding to As(III)
and As(V), applying the Peak Fitting Module of the software
Microcal Origin 5.0. The relative species content was calculated as 100(Ca/C0),
where Ca is the adsorption equilibrium concentration of
the solution in contact with the zeolite and C0 is the
initial concentration of the species in the solution in the absence of zeolite.
The desorption ratio d was evaluated by means of the relation d = 100[Cd/(C0 − Ca)],
where Cd is the concentration of the resulting solution
in contact with zeolite after desorption.Results and discussion
Stability of arsenite and arsenate solutions
The complete water–zeolite systems studied are listed in Table 2. A detailed analysis of the natural
Biela and Zimapán waters is presented in Table 3.
Note the relatively high arsenate concentration and the absence of heavy metals,
at least in concentrations above the ICP-AES detection limits in water
samples, which are quoted in parentheses: Cu2+
(60 µg l−1),
Zn2+
(60 µg l−1),
Cd2+
(100 µg l−1)
and Pb2+
(270 µg l−1).
The most abundant anion in the Biela water was sulfate and in the Zimapán
water chloride, since municipal water supplies are chlorinated by adding chlorine
gas to water. Chlorine's powerful oxidising action acts as a germicide
to safeguard public health. Both natural waters contained a high concentration
of calcium compared to the levels of potassium, magnesium, aluminium, manganese,
iron and nickel. Examination of Fig. 1
reveals that the species arsenite is stable for a long period in spiked (200 µg As l−1)
deionised water (Fig. 1a)
as well as in the Biela water (Fig. 1c).
By contrast, arsenite from a 1 mg l−1 stock
solution in deionised water is immediately transformed into arsenate (Fig. 1b) when it is diluted in drinking
water to give a 200 µg l−1 arsenate solution.
Arsenate is stable in both spiked (200 µg As l−1)
deionised (Fig. 1d) and drinking (Fig. 1e) water. The stability of different
arsenic solutions was first monitored without zeolites. Hence any future observation
in the systems containing zeolites was related to the action of the zeolite.
Each point in the figures of this study was calculated from a duplicate analysis
by IC-ICP-MS. Comparable chromatograms presenting species separation
can be consulted in other studies.12,15,16 |
| Fig. 1 Monitoring curves of
the arsenic concentration variation in different acidified solutions: (a)
deionised water spiked with As(III); (b) drinking
water spiked with As(III); (c) Biela water
spiked with As(III); (d) deionised water spiked
with As(V); (e) drinking water spiked with
As(V). Spiking levels, 200 µg l−1.
Arsenite, filled symbols; arsenate, open symbols. | |
Table 2 Monitored aqueous systems in contact with
zeolites
Sample | Zeolitea | As removed after 30 days (%) |
---|
By ZME | By ZH |
---|
For zeolite names, abbreviations
and description, see Table 1. |
---|
Deionised water spiked with 600 µg l−1
As(III) and acidified | ZH | | |
ZME | | |
ZS | | |
Deionised water spiked with 200 µg l−1
As(III) and acidified | ZH | 95 | 74 |
Drinking water spiked with 200 µg l−1
As(III) and acidified | ZME | 97 | 97 |
Deionised water spiked with 200 µg l−1
As(V) and acidified | | 98 | 95 |
Drinking water spiked with 200 µg l−1
As(V) and acidified | | 97 | 95 |
Biela water spiked with 200 µg l−1
As(III) and acidified | | 98 | 75 |
Biela water | | 98 | |
Zimapán water acidified | | 95 | 51 |
Zimapán water | | 95 | 76 |
Table 3 Origin and composition of the studied natural
water samples
Sample | Origin | Anions/mg l−1 | Cations/mg l−1 | Arsenite/µg l−1 | Arsenate/µg l−1 |
---|
F− | Cl− | Br− | NO3− | SO42− | Mg2+ | K+ | Ca2+ |
---|
Biela | Saxony, Germany | 9.8 | 13.7 | 0.1 | 2.1 | 64.5 | 5.3 | 9.1 | 29.6 | 0 | 177 |
Zimapán | Hidalgo, Mexico | 1.0 | 331 | 0.4 | 0.6 | 64.8 | 13.4 | | 50.9 | 0 | 445 |
Zeolite–arsenic solution systems
Different procedures for the activation of zeolites can have a significant
impact on their behaviour. We performed acid washing, which removes the non-zeolitic
minerals from the active crystalline zeolite. We studied the effect of activation
on the behaviour of the synthetic ZS and the natural ZME zeolite (see Table 1) in contact with arsenic solutions.
As shown in Fig. 2, the powdered and
unactivated synthetic mordenite (ZS-pna) induced the oxidation
of arsenite into arsenate. Hence we found 45% arsenate and 35%
arsenite in the solution after contact with this zeolite. The difference (20%)
can be considered as the sorbed amount of arsenite. By contrast, only arsenite
was found in the solution after contact with the activated12
synthetic mordenite (ZS-pa). The cause of arsenate formation
has been ascertained previously.13 Arsenate
sorption (13%) by ZME was the same when the zeolite samples
were taken before activation in powder (ZME-pna) or grain (ZME-gna)
form. However, after the activation of ZME, the removal of arsenate from the
solution increased drastically. The reason for the different arsenic sorption
capacities of zeolites is probably the different chemical compositions of
these materials. Speciation in this case was useful since it revealed the
transformation of arsenite into arsenate, an effect that could be used to
lower the toxicity of waters polluted with arsenite. This result could not
be detected by spectroscopic methods, which quantify the total arsenic content.14 Although activation of the synthetic mordenite
did not improve the efficiency of arsenite removal, oxidation into arsenate
was inhibited. The natural clinoptilolite ZME showed an increase in efficiency
after activation from 15 to 90%
(see Fig. 2),
with no influence of the solid material particle size being observed. In the
following studies, granular natural zeolites were used.![Effect of zeolite activation
on the removed and formed species in deionised water solutions (200 µg l−1
arsenite) and non-acidified Biela water (177 µg l−1
arsenate) after 7 days contact with powdered zeolite ZS [unactivated (ZS-pna)
and activated (ZS-pa)], unactivated zeolite ZME [as
powder (ZME-pna) and as grain (ZME-gna)]
and activated ZME as grain (ZME-ga).](/image/article/2001/EM/b006636m/b006636m-f2.gif) |
| Fig. 2 Effect of zeolite activation
on the removed and formed species in deionised water solutions (200 µg l−1
arsenite) and non-acidified Biela water (177 µg l−1
arsenate) after 7 days contact with powdered zeolite ZS [unactivated (ZS-pna)
and activated (ZS-pa)], unactivated zeolite ZME [as
powder (ZME-pna) and as grain (ZME-gna)]
and activated ZME as grain (ZME-ga). | |
The first step in setting up the batch experiments was to select the ratio
between the zeolite mass and the solution volume. For this purpose, two zeolites
of the clinoptilolite type (see Table 1)
and synthetic mordenite were selected. Arsenite and arsenate species were
studied individually in deionised water containing 600 µg l−1
arsenic, a value exceeding the concentration in the real water samples from
Biela and Zimapán. From our experience with a larger set of natural
zeolites,12 the mass to volume ratio (m/V)
interval analysed was 1 ∶ 100 to 1 ∶ 4,
which corresponds with the fractions 0.01 and 0.25 on the x-axis
of the respective plot (Fig. 3).
The lowest removal efficiency for arsenite was achieved after 7 days contact
with the mordenite ZS, as can be seen in Fig. 3A,
while the highest removal of both arsenite (Fig. 3A)
and arsenate (Fig. 3B) was
accomplished by the zeolite ZME. Our previous kinetic studies12
demonstrated that arsenate removal strongly depends on the contact time. For
two different contact periods, Fig. 3B
shows the dependence of arsenate removal on the mass to volume ratio after
contact for 1 day and 7 days in the case of ZME. Both curves exhibit a decay
profile, with the rate of change being appreciably smoothed out by 0.18. Therefore,
the value m/V = 0.2 was chosen for
subsequent experiments.
 |
| Fig. 3 Variation of the arsenite (A)
and arsenate (B) concentrations as a function of the relation of
zeolite mass to solution volume for the zeolites ZME, ZH and ZS after 7 days
contact (A) and for zeolite ZME (B) after 1 day and 7
days contact. Solution initial concentration, 600 µg l−1. | |
Zeolite–natural water systems
Based on this result, 15 g of the clinoptilolites ZME and ZH were
immersed in 75 ml of the aqueous media systems specified in Table 2. The main idea was to apply zeolites
by simply adding them to polluted natural water sources under static treatment,
instead of filling cartridges with these materials, a procedure which would
lead to a separate dynamic filtration system with defined energetic and maintenance
requirements. For arsenite, the results presented in Fig. 4B
indicate that, in the worst case, 75% is removed from a 200 µg l−1
aqueous solution, as well as from the Biela water spiked with 200 µg l−1
arsenite, after 25 days contact with the zeolite ZH. The resulting residual
arsenite concentration would comply with the Mexican limit of 50 µg l−1
total arsenic. In the case of the zeolite ZME (Fig. 4A
and 4C), utilised for both arsenite and arsenate removal in
all the aqueous media studied, the data are more satisfactory since 95%
removal would signify a residual amount of 10 µg l−1,
which meets the German and American limits of 10 and 25 µg l−1
arsenic, respectively. The amount of arsenite and arsenate remaining in the
solution (10 µg As l−1)
was within the detection limit of the IC-ICP-MS method employed in
this work for these species and the reported contents correspond to the mean
value ± 5%. Long-term monitoring of the investigated
solutions, together with speciation analysis, confirmed the removal of a given
arsenic species from solution by zeolites ZME and ZH. After 5 days contact
with ZME and ZH, 75% arsenate removal can be achieved in all systems (Fig. 4C) except in Zimapán water (Fig. 4D). After a longer contact period (20
days), 95% arsenate removal was reached. It was found that the
presence of alkali cations and anions (see Table 3)
in the natural matrices of the Biela and Zimapán waters did not affect
the efficiency of the selected zeolites. The concentrations of iron, nickel,
copper, zinc, cadmium and lead, if present, were below the ICP-AES analysis
detection limit. An explanation for the generally better performance of ZME
in removing arsenite and arsenate in comparison to ZH may be due to the almost
twofold higher content of iron (see Table 1)
in the zeolite ZME, which can form insoluble compounds containing arsenic,
such as FeAsO4.12 |
| Fig. 4 Effect of contact time
on the arsenite (A, B) and arsenate (C, D) concentration
diminution of different acid solutions in contact with zeolites ZME (A,
C) and ZH (B, D). (a) Deionised water spiked with
As(III); (b) Biela water spiked with As(III); (c)
Zimapán water; (d) deionised water spiked with As(V); (e)
drinking water spiked with As(V); (f) drinking
water spiked with As(III). | |
Monitoring solutions in contact with clinoptilolites indicates that zeolite
performance is acceptable for the removal of arsenite and arsenate in both
deionised and natural water. To elucidate whether or not the addition of HCl
to the Biela and Zimapán water affects the removal of arsenate, long-term
analysis of these systems was performed and compared with the acidified systems (see Fig. 5). The acidified medium has practically
no effect on the activity of the zeolite ZME (Fig. 5A)
in contact with both water matrices (95% arsenic removal),
whereas the zeolite ZH (Fig. 5B)
removed 75% of arsenate when the Zimapán water was not previously
acidified and only 50% when the sample was acidified. Slight differences
in the results obtained for the two natural water matrices could be attributed
to their ionic composition. The removal results are summarised in Table 2.
 |
| Fig. 5 Effect of the acidification
of the batch solution on the removal of arsenate in Biela water and Zimapán
water in contact with zeolites ZME (A) and ZH (B). Full
lines, without HCl addition; broken lines, with HCl addition. (a)
Biela water without zeolite; (b) Biela water; (c) Zimapán
water. | |
Zeolite regeneration by desorption
Natural zeolites transformed into contaminated waste can be stored or regenerated.
Their storage after arsenic preconcentration requires the strong fixation
of arsenic to the solid to avoid pollutant transfer from water to soil. When
fixation is weak, desorption can be induced in order to regenerate the zeolites
and to produce the recovery of arsenic. In order to manage adequate solution
volumes during desorption, smaller solution volumes after desorption can be
produced in comparison with those taken during adsorption. A diminution in
the solution volume handled is then described by quotient values Vd/Va < 1
in Table 4, where Vd
and Va are the volumes in the desorption and adsorption
steps, respectively. In order to achieve arsenic desorption from the zeolites,
the zeolites enriched with arsenic were treated with different acids. Table 4 shows the desorption ratio [d
(%)]
in the different trials and demonstrates the viability of the procedure when
1 M HCl was used. In general, almost the total amount of sorbed arsenic
at the zeolite ZH can be released (92 < d < 100%)
with the ratio Vd/Va = 0.5.
In the natural Zimapán water, the increase in hydrochloric acid concentration
from 1 to 3 M had a small effect on desorption, whereas nitric and
phosphoric acid did not bring about the recovery of the adsorbed arsenic in
the Biela water. Another factor influencing the desorption ratio d
is the mass to desorption volume relation m/Vd,
as was demonstrated by us above for adsorption. The variation of m/Vd
from 0.4 to 0.2 led to an increase in the desorbed ratio from 48 to 79%
for the Biela water in contact with zeolite ZME.
Table 4 Desorption of arsenic by leaching the zeolites
for 7 days in different mediaa
Sample | Zeolite | dtotal As (%) | Leaching solution | m/Vd | Vd/Va |
---|
Acid | Molarity |
---|
d, Desorption
ratio; m, zeolite mass (in g); Vd,
volume in the desorption step (in ml); Va, volume
in the adsorption step (in ml). |
---|
Deionised water spiked with 200 µg l−1
As(III) and acidified | ZME | 95 | HCl | 1 M | 0.4 | 0.5 |
ZH | 100 | | | | |
Drinking water spiked with 200 µg l−1
As(III) and acidified | ZME | 57 | | | | |
ZH | 100 | | | | |
Deionised water spiked with 200 µg l−1
As(V) and acidified | ZME | 71 | | | | |
ZH | 100 | | | | |
Drinking water spiked with 200 µg l−1
As(V) and acidified | ZME | 66 | | | | |
ZH | 100 | | | | |
Biela water spiked with 200 µg l−1
As(III) and acidified | ZME | 48 | | | | |
ZH | 92 | | | | |
Zimapán water | ZH | 92 | HCl | 1 M | | |
100 | 2 M | | |
100 | 3 M | | |
Biela water | ZME | 48 | HCl | 1 M | | |
0 | HNO3, H3PO4 | | | |
79 | HCl | | 0.2 | 0.3 |
Conclusions
These results demonstrate that natural zeolites remove arsenic from contaminated
natural waters. Additionally, the materials studied can be regenerated by
thorough leaching in acid solutions to induce desorption of the previously
fixed arsenic species.Acknowledgements
MPEG is grateful to the Alexander von Humboldt Foundation,
Germany, for providing a Georg Forster fellowship to carry out this research
work. We are thankful to F. Pérez-Moreno for kindly providing the
Zimapán water samples.References
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Footnote |
† Presented at the Whistler 2000 Speciation Symposium, Whistler
Resort, BC, Canada, June 25–July 1, 2000. |
|
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