Waste Management 21 (2001) 671676

www.elsevier.nl/locate/wasman

Technical note

Kinetics and thermodynamics of copper ions removal from

wastewater by use of zeolite
M.I. Panayotova *
University of Mining and Geology, Department of Chemistry, 1100 Soa, Bulgaria

Received 18 November 1999; accepted 16 October 2000

Abstract
Natural Bulgarian zeolite was tested for its ability to remove Cu2+ from model wastewater. Inuence of process variables was
investigated. It was found that the optimum wastewater to zeolite ratio is 100:1 and the optimum pH value of water to be treated is
5.5 to 7.5. Zeolite with ner particles shows a higher uptake capacity. The simultaneous presence of Ca2+ and Mg2+ in con-
centrations similar to their concentrations in Bulgarian natural water does not signicantly inuence the uptake of Cu2+. Zeolite
modication by treating it with NaCl, CH3COONa and NaOH increases its uptake ability. Copper ions are strongly immobilized
by modied zeolite and secondary pollution of water caused by its contact with preloaded zeolite is very low (1.52.5% of Cu2+
preliminary immobilized have been released back into acidied water). Contacting with 2 mol dm 3 NaCl can easily regenerate
loaded zeolite; best results were obtained for zeolite modied with NaCl. Requirements of Bulgarian standards for industrial was-
tewater can be met by a one-stage process for an initial Cu2+ concentration of 10 mg dm 3, and by a two stage process for an initial
Cu2+ concentration of 50 mg dm 3. Uptake of Cu2+ by zeolite from neutral wastewater has proved to be as eective as Cu2+
removal by precipitation of copper hydroxide. The process of Cu2+ uptake by natural zeolite is best described by the kinetic
equation for adsorption. This fact, together with the correlation found between the Cu2+ uptake and the amount of Na+, Ca2+
and K+ released into solution by zeolite shows that the ion exchange sorption plays the basic role in Cu2+ uptake by natural
zeolite. The value obtained for the apparent activation energy (26.112 kJ mol 1) implies that the process can be easily carried out
with a satisfactory rate. The uptake equilibrium is best described by the Langmuir adsorption isotherm, with Langmuir constants
KL=6.410 2 dm3 mg 1 and M= 6.74 mg g 1. The apparent equilibrium constant found shows moderate anity of zeolite for
Cu2+. Values of
G and
H found show the spontaneous and endothermic nature of the process of Cu2+ uptake by natural
zeolite. # 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Natural and modied zeolite; Wastewater treatment; Copper ions removal

1. Introduction concentrations higher than 50100 mg dm 3 can be

Utilization of natural zeolite in pollution control,
including euents polluted with heavy metal ions has
increased recently [13]. Zeolites represent an appro-
priate material for removing heavy metal ions from
wastewater because of their relatively low price coupled
with the fact that their exchangeable ions (Na+, Ca2+
and K+) are relatively harmless. In addition, zeolite
loaded with heavy metal ions can be easily regenerated.
Copper ions (Cu2+) represent a hazardous pollutant
in wastewater and are released by metallurgical, plating,
printing circuits and mining activities. Copper
* Fax: +359-2-9624940.
E-mail address: marichim@sta.mgu.bg
0956-053X/01/$ - see front matter # 2001 Elsevier Science Ltd. All rights reserved.
PII: S0956-053X(00)00115-X
easily decreased by means of an electrochemical treat-
ment [4], reverse osmosis [5] or chemical treatment [6] of
the wastewater. Application of methods mentioned
above becomes costly at lower concentrations of Cu2+.
Use of natural zeolites represents an attractive means
for Cu2+ removal from wastewater both in terms of
removal ability and cost eectiveness. Removal of cop-
per ions from wastewater by use of natural zeolites has
been reported [13,7,8].
The goals of the present work were to: (a) investigate
the ability of Bulgarian natural zeolite to remove Cu2+
from wastewater; (b) study the inuence of specic pro-
cess parameters and of zeolite modication on the
uptake eectiveness; (c) determine the kinetic equation
best describing data obtained and to nd the activation
672 M.I. Panayotova / Waste Management 21 (2001) 671676

energy, important for the practical application of zeo-
lites in wastewater treatment; and (d) determine the
adsorption equation which best describes the equili-
brium uptake and to calculate thermodynamic para-
meters (
G ,
H , and
S ) for the practical
implementation of zeolites technology.
2. Methods and materials
Bulgarian natural zeolite was used. It had the following
chemical compositions, in mass %: SiO2 68:70,
Fe2 O3 2:28, TiO 0:15, Al2 O3 11:83, CaO 2:66,
MgO 0:76, MnO 0:04, Na2 O 1:60, K2 O 4:01,
P2 O3 0:14, SO3 0:225, ignition loss=7.62, totalling
100.02. Clinoptilolite was found to be the predominate
material. Its cation exchange capacity determined as
described in Kallo and Sherry [1] was 134.3 meq/100 g.
Zeolite was modied by heating and by placing it in con-
tact (at solution to mass of zeolite ratio equal to 1 dm3:100
g) with chemicals as shown in Table 1. Solutions contain-
ing Cu2+ in concentrations of 50 and 10 mg dm 3 were
prepared by dissolving corresponding quantities of
Cu(NO3)2 in distilled water. Solutions of Ca(NO3)2 and
Mg(NO3)2, prepared with distilled water, were added to
Cu(NO3)2 solutions in the amounts necessary to obtain
the corresponding ratios of concentrations of Ca2+ and
Mg2+ to concentrations of Cu2+. A Merck SQ 118 spec-
trophotometer and Merck reagents were used to deter-
mine the Cu2+ concentration in each solution.
Determination of Na+, K+, Ca2+ and Mg2+ concentra-
tions in treated solution were made with an inductively
coupled plasmaatomic emission spectroscopy (ICP
AES) analysis. The composition of zeolite was determined
by means of classical silicate analysis. pH values were
measured with a Metrohm E 588 pH-mV-meter. Experi-
ments were conducted batchwise; 1 g zeolite was stirred
with a LR 40 Medingen/Dresden paddle stirrer (at 400
rpm) in each solution. Temperature was kept constant
with a universal UTU-2/77 ultra-thermostat (Poland).
The inuence of a specic process parameter was
determined by calculating Cu2+ uptake by zeolite and
changing that parameter and keeping other parameters
constant. Uptake eciency was calculated using the
equation:
Uptake; % Co Ceq =Co  100 1
where Co and Ceq are the initial and the equilibrium
concentration of pollutant, mg dm 3.
Desorption experiments were made in order to check
how strongly Cu2+ ions were immobilised by zeolite.
One gram of preloaded natural and modied (by con-
tacting with NaCl, CH3COONa and with NaOH) zeolite
which showed the highest uptake was placed in contact
with (a) distilled water acidied to pH=2.5 by HNO3
addition, and (b) 2 mol dm 3 NaCl solution for 6 h.
Each experimental result was obtained by averaging
the data from two parallel experiments. Kinetic equa-
tions for the rst order reversible [9] and rst and sec-
ond order irreversible reactions [10] are the equations
most often used to describe the removal of heavy metal
ions from polluted water by use of natural material. It
has been stated [3] that the uptake of heavy metal ions
by zeolite is controlled by ion exchange adsorption.
That is why the kinetic equation describing adsorption
[11] was also considered. Data tting to the equations
mentioned above were tested in the usual way [12]. The
data were processed in a suitable manner and checked
whether they t to one of the following straight lines
found after mathematical transformations of the corre-
sponding kinetic equations.
For the rst order reversible reactions:
ln 1 Co Ct =Co Ceq k0 t 2
where Ct is the concentration of Cu2+ at any time t, k0
is the overall rate constant, Co and Ceq are as described
above.
For the rst order irreversible reactions:
ln Co =C k   3
For the second order irreversible reactions:

Table 1
Conditions for zeolite modication Co C =Co C k   4

Type of Temperature Modifying solution Contact time

modication (K) (h) where k denotes the reaction rate constant in (3) and (4)
and Co, Ct and t are as described above.
A 378 2 For the adsorption:
B 503 24
3
C 373 2 mol dm NaOH 24
D 295 2 mol dm 3
NaOH 168 ln dw=d ln a w 5
3
E 295 2 mol dm CH3COOH 168
F 373 2 mol dm 3
NaCl 24 where w is the amount of substance adsorbed for time t,
3
G 295 2 mol dm NaCl 168 a and a are constants which depend on the adsorbent/
3
H 373 2 mol dm HCl 24
I 295 2 mol dm 3
HCl 168
adsorbate system and on the temperature. The kinetic
equation found describes the uptake process at room
 M.I. Panayotova / Waste Management 21 (2001) 671676
temperature. The apparent activation energy of the
process was determined in the usual way, using Arrhe-
nius equation and the fact that the concentration of
reagents does not depend on the temperature, [12].
Activation energy was found from the plot of ln v vs. 1/
T, where
v Co C=
 6
was the average rate of Cu2+ uptake by zeolite, at tem-
perature T,
 is the time of the contact between zeolite
and Cu2+ containing solution, Co and Ct as described
above.
Equilibrium uptake data found at room temperature
were processed for tting to the Freundlich, linear tra-
ditional Langmuir and double reciprocal Langmuir iso-
therm [13]. The following expressions of a straight line
were used, found by means of mathematical transfor-
mation of isotherms:
For the Freundlich isotherm:
log x=m logKf n  log C 7 50 mg dm 3 Cu2+; a pH of 5; a contact time of 5 h; zeo-
where x is the concentration of the solute adsorbed, m is
the mass of the adsorbent, Kf and n are Freundlich
constants, C is the equilibrium concentration of the
solute.
For the linear traditional Langmuir isotherm:
C=x=m 1=KL  M C=M 8 value is below the maximum permissible concentration
For the double reciprocal Langmuir isotherm:
1=x=m 1=KL  M  C 1=M 9 initial Cu2+ concentration of 50 mg dm 3.
where KL and M are Langmuir constants, x, m and C
are as mentioned above. To calculate values of the
thermodynamic parameters describing the Cu2+ uptake
by zeolite the following equations were used:

G R:T: ln K 10

H R  T1  T2 =T2 T1  ln K2 =K1 11

S
H
G =T 12
where R is the gas constant, K, K1 and K2 are the
equilibrium constants at the temperature T, T1 and T2,
respectively. The equilibrium constant was calculated
from:
K Ceq;s =Ceq;l 13
673
where Ceq,s and Ceq,l were the equilibrium concentra-
tions of Cu2+ in solution and on the sorbent corre-
spondingly.
3. Results and discussion
3.1. Inuence of process variables and modication
It has been found that modication by treating with
NaOH causes desilication of zeolite and a decrease of
Si/Al ratio, as well as an increase in the relative quantity
of Na+, Mg2+ and Ca2+ in zeolite. Treatment with
NaCl and CH3COONa causes an increase in Na+ and a
decrease in Ca2+ concentrations in zeolite, leading to an
increase of the ratios Na+/K+ and Mg2+/Ca2+. Treat-
ment with HCl increases to some extent Si/Al ratio and
also increases the relative amount of K+ in zeolite,
subsequently decreasing Na+/K+ ratio.
Solution to zeolite mass ratio of 100:1 was found to be
the optimum by means of experiments made under the
following conditions: solution concentrations of 10 and
lite particle sizes between 0.09 and 0.325 mm; and solu-
tion to zeolite ratios (v:m) of 20:1, 50:1, 100:1, 200:1.
The kinetics of Cu2+ uptake by natural zeolite (at
v:m=100:1, pH = 5, and particles size of 0.090.325
mm) are presented in Fig. 1. Concentration of Cu2+
found at the end of the treatment was 0.5 mg dm 3 for
an initial Cu2+ concentration of 10 mg dm 3. This
for the third category of surface water, i.e. industrial
water that can be emptied in rivers according to the
Bulgarian State Standard [14]. A concentration of 12
mg dm 3 was found at the end of the treatment for an
Over 85 and over 60% of the initial Cu2+ amount (for
solutions containing 10 and 50 mg dm 3, respectively)
Fig. 1. Kinetics of Cu2+ uptake by natural zeolite: (a) 10 mg dm 3
Cu2+, (b) 50 mg dm 3 Cu2+.
674 M.I. Panayotova / Waste Management 21 (2001) 671676
were removed in the rst 20 min, as can be seen in Fig. 1.
Then up to the third hour the uptake increased only
about 10%. That is why, a contact time of 10 min was
chosen in experiments aimed at revealing possible dif-
ferences in Cu2+ removal, due to the inuence of parti-
cle sizes, pH value of solution and modication of
zeolite.
To investigate the inuence of zeolite particle size on
Cu2+ removal, tests were made under the following
conditions: solution concentrations of 10 and 50 mg
dm 3 Cu2+; a pH of 5; a contact time of 10 min; and
v:m ratio of 100:1. Results obtained are presented in
Table 2.
Use of zeolite with ner particles leads to an increase
in Cu2+ uptake both for higher and lower copper con-
centrations. Application of zeolite with more coarse
particles considerably decreases Cu2+ removal for solu-
tions with higher Cu2+ concentration. This probably is
due to the smaller number of sites available for ion
exchange and adsorption.
The inuence of solution pH value on Cu2+ uptake
was investigated under the following conditions: solu-
tion concentrations of 10 and 50 mg dm 3 Cu2+; a
contact time of 10 min; v:m ratio of 100:1; zeolite par-
ticle sizes between 0.09 and 0.325 mm; and pH values
(referred to as pHini.) of 3.0, 5.0, 7.0, 9.3, and 10.8.
Results obtained are presented in Fig. 2.
Table 2
Inuence of zeolite particle size on Cu2+ removal
Zeolite particles Removal at an initial Removal at an initial
size (mm) concentration of concentration of
10 mg dm 3 Cu2+ (%) 50 mg dm 3 Cu2+ (%)
<0.09 89.34 73.89
0.090.325 82.64 56.90
0.3250.400 78.33 41.04
2+
Fig. 2. Inuence of solution pH value on Cu uptake: (a) 10 mg
dm 3 Cu2+, (b) 50 mg dm 3 Cu2+.
Having in mind results shown in Fig. 2, it can be sta-
ted that higher Cu2+ removal due to uptake by zeolite
(most probably by ions exchange adsorption) is
observed in neutral water. An increase in Cu2+ removal
was observed at pHini. of 10.8. It could be assigned to
precipitation of Cu(OH)2. Taking into consideration a
solutions pH value, concentration of Cu2+ and the
solubility product of copper hydroxide [16], that is
5.610 20, it was estimated that Cu(OH)2 could be
precipitated. Removal eciency due to precipitation
was 88.4 and 93.7% for initial Cu2+ concentrations of
10 and 50 mg dm 3 correspondingly. These values are in
the range of values for Cu2+ uptake by natural zeolite
from neutral solution.
Natural water, consequently the main part of indus-
trial wastewater, contains Ca2+ and Mg2+. The average
concentrations of Mg2+ and Ca2+ in Bulgarian water
are 26 and 70 mg dm 3, respectively, and generally the
ratio CCa2+/CMg2+ is about 2 to 2.8 [15]. That is why,
the inuence of Ca2+ and Mg2+ presence on the uptake
of Cu2+ was investigated during the simultaneous
addition of Ca2+ and Mg2+ (to Cu2+ solution) in con-
centrations giving ratios of CCa2+/CCu2+=2 and
CMg2+/CCu2+=1. All other parameters were kept con-
stant. Signicant changes in Cu2+ uptake by natural
zeolite were not observed.
The inuence of zeolite modication on Cu2+ uptake
was investigated under the following experimental con-
ditions: solutions containing 50 mg dm 3 Cu2+; v:m
ratio of 100:1; pHini.of 5.0; contact time of 10 min; and
zeolite particle sizes between 0.09 and 0.325 mm.
Results obtained are presented in Table 3.
Treatment of zeolite with HCl decreases the eciency
of Cu2+ uptake, as can be seen from Table 3. As shown
previously [1], the cation exchange capacity of zeolites is
reduced by the presence of K+, and the smaller the Si/
Al ratio the greater is the ion exchange capacity. Con-
sequently, the lower uptake ability of treated zeolite is
expected, bearing in mind changes in zeolite composi-
tion caused by zeolite treatment with HCl. Increased
Cu2+ uptake by zeolite modied with NaCl and
CH3COONa is probably due to the raised relative con-
centration of more easily exchangeable Na+, as a result
of the modication. This statement is supported by
results from the ICP analysis showing that Na+ were
predominately exchanged in that case. Increased Cu2+
Table 3
Inuence of zeolite modication on Cu2+ removal
Type of None A B C D E F G H I
modicationa
Cu2+uptake 56.9 54.2 51.8 94.5 92.9 91.2 94.6 91.8 29.0 30.6
(%)
a
As described in Table 1.
 M.I. Panayotova / Waste Management 21 (2001) 671676 675

uptake by zeolite modied with NaOH could be con-

nected with the inuence of the decreased Si/Al ratio.
Desorption experiments showed that Cu2+ were
strongly immobilized by zeolite modied with NaCl,
CH3COONa and NaOH. Immobilization by natural
zeolite was weaker. Quantity of Cu2+ released into
acidied water after a contact of 6 h represented about
1.52.5% (for modied zeolite) and about 15% (for
natural zeolite) from the initially immobilized amount.
Loaded natural and modied with NaCl zeolite was
easily regenerated by contacting it with a solution con-
taining 2 mol dm 3 of NaCl.

3.2. Kinetics and thermodynamics of the uptake process

It has been found that the Cu2+ uptake process obeys Fig. 3. Adsorption isotherm of Cu2+.
the kinetic equation describing adsorption with correla-
tion coecients of r=0.994 and r=0.939 correspond-
ingly for solutions containing initially 50 and 10 mg Ka=0.4308. Figures obtained for KL, M and Ka are in
dm 3 of Cu2+. Hence, it could be stated that ion the range of values found for adsorption of heavy metals
exchange adsorption plays the main role in Cu2+ on natural materials, such as soil [13] and natural and
immobilization by natural zeolite, on the basis of: (a) activated bentonite [17] and show a medium anity of
kinetic equations describing the process, (b) a correlation zeolite for Cu2+. By placing the values found for M and
observed between Cu2+ uptake and the amount of metal KL in the Langmuir equation, a predictive expression
ions (mainly Na+, Ca2+ and K+) released into the describing Cu2+ sorption by zeolite could be obtained:
solution by zeolite, and (c) ndings on the inuence of
the solutions pH value. Probably, more easily accessible
zeolite cations are being exchanged in the rst hour. It is x=m6:39510 26:737C=16:39510 2C 14
likely that exchange ions situated deeper in zeolite chan-
nels are being exchanged in the next few hours. Thermodynamic parameters for the process of Cu2+
It was found that Cu2+ uptake increased with tem- uptake by natural zeolite are presented in Table 4.
perature for natural unmodied zeolite. An apparent Values found for Go, Ho and So are indicative of the
activation energy of 26.112 kJ mol 1 was found for spontaneous nature of the uptake process. The increase
Cu2+ uptake from solutions containing initially 50 mg of the equilibrium constant with increasing temperature
dm 3 of Cu2+. The value obtained shows that the pro- and positive values obtained for Ho show the endother-
cess can be easily carried out with a satisfactory rate. A mic nature of Cu2+ uptake. Results obtained in our
small decrease in the uptake rate with increasing tem- experiments generally agree with the results previously
perature was observed for zeolite modied with NaCl, found for the uptake of heavy metal ions by natural
perhaps due to the increased desorption of Cu2+ with materials [9,18].
increasing temperature.
The isotherm for Cu2+ uptake by zeolite (at pHini.=
5, contact time of 240 min, v:m=100:1 and particles size 4. Conclusions
0.090.325 mm) is presented in Fig. 3. Processing the
data obtained at room temperature and tting them to Natural Bulgarian zeolite can be used to remove
adsorption isotherms has shown that the equilibrium is Cu2+ from nearly neutral wastewater at a water to
best described by the traditional linear Langmuir iso-
therm, with a correlation coecient of r=0.998. Values
Table 4
obtained for Langmuir constants are correspondingly: Thermodynamic parameters for the Cu2+ adsorption on natural zeo-
KL=6.39510 2 dm3 mg 1and M=6.737 mg g 1. The lite
constant M is generally accepted as the adsorption
Temperature Uptake K
G ,
H ,
S , J mol 1
maximum of the adsorbent with respect to the specic 1 1
(K) (%) J mol J mol K 1
solute, and KL is related to the energy of adsorption [13]
The apparent equilibrium constant Ka can be assumed 295 67.54 2.385 2131.6 +23988.7 +88.5
as a relative indicator for zeolite anity for Cu2+ [17]. 305 76.05 3.285 3017.7 +27355.4 +99.6
315 78.47 4.625 4006.7 +18745.6 +72.2
It may be calculated as the product of the Langmuir 323 83.11 5.521 4590.8
equation parameters KL and M, [17], in our case
676 M.I. Panayotova / Waste Management 21 (2001) 671676
zeolite ratio of 100:1. Concentrations meeting the
requirements of Bulgarian standards for releasing
industrial wastewater into rivers can be reached by a
one-stage treatment for an initial Cu2+ concentration of
10 mg dm 3 and by a two to three stage treatment for
an initial Cu2+concentration of 50 mg dm 3. Use of
zeolite with ner particles increases its uptake ability.
The optimum pH value of water to be treated is between
5.5 and 7.5. Simultaneous presence of Ca2+ and Mg2+
in concentrations similar to their concentrations in Bul-
garian natural water does not signicantly inuence the
uptake of Cu2+. It was found that treatment of neutral
wastewater with natural zeolite is as eective as the
water alkalization leading to Cu2+ removal by pre-
cipitation of Cu(OH)2. Modication of zeolite with
NaCl, CH3COONa and NaOH increases its uptake
ability. Copper ions are strongly immobilized by mod-
ied zeolite. Consequently, contact of preloaded zeolite
with acidic water does not cause pollution of the water.
Loaded natural and modied with NaCl zeolite can be
easily regenerated by contacting it with 2 mol dm 3 of
NaCl solution.
The Cu2+ uptake process by natural zeolite obeys the
kinetic equation describing adsorption. This fact, together
with the correlation found between the uptake of Cu2+
and amounts of exchangeable ions of zeolite released into
solution, shows that the ion exchange adsorption is the
basic mechanism of Cu2+ uptake by zeolite.
The uptake equilibrium is best described by the
Langmuir adsorption isotherm. Values of
G and
H
found show the spontaneous and endothermic nature of
the process of Cu2+ uptake by natural zeolite.
References
[1] Kallo D, Sherry H. Occurrence, properties and utilisation of
natural zeolites. Budapest: Akademiai Kiado, 1988.
[2] Ouki S, Christopher R, Roger R. Natural zeolite utilisations in
pollution control: a review of applications to metals euents. J
Chem Tech Biotechnol 1994;59:121.
[3] Ouki S, Kavannagh M. Performance of natural zeolites for the
treatment of mixed metal-contaminated euents. Waste Manage
Res 1997;15:383.
[4] Dohse D, Dold A, Czeska B. Electrochemical wastewater treat-
ment. Metalloberaeche 1995;49:365.
[5] Bingau, P., Lonsdale, H., Pinho M., Eds. Synthetic membranes:
Science, Engineering and Application, NATO ASI Series, Series
C: Mathematical and Physical Sciences, Vol. 181. D. Ridel Pub-
lishing Company, Dordrecht 1986.
[6] Hartiger L. Handbuch der Abwasser-und Recyclingtechnik.
Munchen, Wien: Carl Hanser Verlag, 1991.
[7] Curkovich L, Cerjan-Stefanovic S, Filipan T. Metal ion exchange
by natural and modied zeolites. Water Res 1997;31:1379.
[8] Carland R, Aplan F. Use of natural sedimentary zeolites for
metal ion recovery from hydrometallurgical solutions and for
environmental remediation. Proc Int Miner Processing Congr 19-
th 1995;4:95.
[9] Bereket G, Aroguz A, Ozel M. Removal of Pb (II), Cd (II), Cu
(II) and Zn (II) from aqueous solutions by adsorption on bento-
nite. J Colloid Appl Sci 1997;187:338.
[10] Walter J, Weber J, McGinley M, Linn E. Sorption phenomena in
subsurface systems: concepts, models and eects on contaminants
fate and transport. Water Res 1991;25:449.
[11] Karetnikov G, Kozireva N, Kudrjashov I. Manual on Physical
Chemistry. Moscow: Visshaja Shkola, 1986.
[12] Emanuel N, Knorre D. Course on Chemical Kinetics. Moscow:
Visshaja Shkola, 1984.
[13] Roy W, Krapac I, Chou S, Grin R. Batch Type Procedures for
Estimating Soil Adsorption of Chemicals. Technical Resource
Document. EPA/530-SW-87-006-F, Ohio 1991.
[14] Bulgarian State Standard No. 7. State Newspaper No. 96/1986.
[15] Velikov B. Hydrochemistry. Soa: Ministry of Education, 1986.
[16] Lidin P, Andreeva L, Molochko V. Guide on inorganic chem-
istry. Constants of inorganic substances. Moscow: Chemistry,
1987.
[17] Pradas E, Sanchez M, Cruz F, Viciana M, Perez M, Adsorption
of Cd Zn from aqueous solution on natural, activated bentonite
J. Chem. Tech Biotechnol 1994;59:289.
[18] Pode R, Burtica G, Iovi A, Pode V, Mihalache T. Ion exchange
of Zn2+ and Cu2+ on clinoptilolite type zeolite. Rev Chim
(Bucharest) 1995;46:530.