Physico-Chemical Studies On The Adsorption of Atrazin On Locally Mined Montmorillonites

International Journal of Advanced Research in Engineering and Technology (IJARET), ISSN 0976IN INTERNATIONAL JOURNAL OF ADVANCED RESEARCH 6480(Print),
, ISSN 0976 6499(Online) Volume 4, Issue 1, January - February (2013), IAEME
ENGINEERING AND TECHNOLOGY (IJARET)
ISSN 0976 - 6480 (Print) ISSN 0976 - 6499 (Online) Volume 4, Issue 1, January- February (2013), pp. 79-95 IAEME: www.iaeme.com/ijaret.asp
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PHYSICO-CHEMICAL STUDIES ON THE ADSORPTION OF ATRAZIN ON LOCALLY MINED MONTMORILLONITES

P.S. Thu1, J. M. Silichi 2*, P.P. Ndibewu3, R. Kamga1 1 ENSAI, University of Ngaoundere, P.O. Box. 455 Ngaoundr, Cameroon pascalsilasthue@yahoo.fr, ; rickamga@yahoo.fr, 2 IUT, University of Ngaoundr, P.O. Box. 455 Ngaoundr, Cameroon jsieliechi@yahoo.fr, 3 Tshwane University of Technology, Private Bag X680, Pretoria 0001, South Africa ndibewup@tut.ac.za,
ABSTRACT Atrazin is an herbicide used intensively on large plantations for crop protection. Unfortunately, this toxic usuallyin water intended for human consumption due to the well known phenomena of leaching and infiltration. In the present work, the efficiency of local montmorillonite for atrazin removal from aqueous solution is described. The adsorption kinetics study showes that atrazin is quickly adsorbed on the surface of montmorillonite and the adsorption equilibrium is attaind after 30 to 40 min. The adsorbed amount increases with atrazin initial concentration and with the increased of the ionic strength. On the contrary, there was a reduction of the amount adsorbed when the pH varied from 2 to 12 and when the clay mass increased from 100 to 400 mg. The kinetics studies indicated that the adsorption process was best described by the pseudo-first-order and intra-particle kinetics. The Freundlich isotherm with a correlation coefficient of R2 = 0.99 and n = 1.76 was found to be the model that best explain the adsorption of atrazin on the montmorillonite. It was also shown that the affinity between the adsorbent and the adsorbate was strong for this type of material. The application of the Temkin isotherm to the experimental data allowed to infer that the adsorbate-adsorbent interaction energy was low (0.347 J.mol-1). This lead to the conclusion that the mechanism of atrazin adsorption onto montmorillonite is probably a physisorption process. Keywords: Atrazin, adsorption, montmorillonite, kinetic, modelling
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International Journal of Advanced Research in Engineering and Technology (IJARET), ISSN 0976 6480(Print), ISSN 0976 6499(Online) Volume 4, Issue 1, January - February (2013), IAEME
1.
INTRODUCTION
The intensification of agriculture in response to the increase of the world population in recent years has resulted in an equal increase in the use of fertilizers and pesticides to improve crop yields. Despite their strength in the protection of crops and increase in agricultural yields, these chemicals have caused tremendous damage to the environment and human, especially when it is not appropriately used. Pollution of surface and underground water by infiltration or leaching of pesticides was reported [1] ely into surface and ground waters are examples that need not be demonstrated. The principal active components of these chemical compounds are highly biologically active, toxic and represent a potential risk to human health, flora and fauna [1]. Atrazin (ATR) (6-chloro-N-ethyl-N'-(propan-2-yl)-1,3,5triazine-2,4-diamine) is one of the most widely used herbicides because of its ability to kill many type of weeds on various crop fields. High concentration of atrazin has been detected in surface and underground waters in Europe and North America [3,4] . Despite the fact that it has been baned since November 2010 in the list of obsolete herbicides [5], atrazin is still being used in many parts of Africa country including Cameroon. In areas where the use is very intense, atrazin and its metabolites may contaminate surface and ground waters [6,7]. Atrazin is a compound classified as potentially carcinogenic to humans [8]. The U.S. Environmental Protection Agency (USEPA) has also shown that atrazin and its metabolites (Figure 1(a)) act as endocrine disruptors. The maximum admissible amount fof atrazin in drinking waters in the United State is 3ppb (3g/L) [8].
Cl CH3 H3C NH N N N NH CH3
ATR
Cl N H2N N N NH CH3 CH3 N H2N Cl N H2N N N NH2 N Cl N NH CH3 H2N N N OH N NH CH3 CH3
DEA
HYA
DIA
DDA
Figure 1(a)
Chemical structures of atrazin (ATR) and its major degradation products, desethylatrazin (DEA), deisopropylatrazin (DIA), didealkylatrazin (DDA), and hydroxyatrazin (HYA) [9]
Once in the environment, ATR can remain chemically intact, or it can degrade. The physicalchemical properties of ATR greatly enhance its mobility in both aqueous solution and it can bind easily to soils. Hence, this compound travels long range, seap or leaches through the soil and enters groundwater, especially in areas where table or groundwater is close to the surface. This is true for areas where soils are loamy and well-drained (very permeable) [10].
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Once applied to the field, ATR can be carried with runoffs or storm water to surface water and percolate to groundwater, or be retained in the soil column [9]. Degradation products are subject to these same processes. [11] found that desethylatrazin (DEA) and hydroxyatrazin (HYA) are the most prevalent degradation products in bulk soil, depending on the depth of the soil and the incubation period [12]. HYA is the least mobile degradation product [13]; DEA and deisopropylatrazin (DIA) are expected to be more mobile than the other compounds [14]. Considering the negative effects of atrazin and its metabolites on the environment, many studies have been carried out aimed at their elimination from water intended for human consumption. Conventional [6,7] water treatment process are ineffective for the removal of atrazin from drinking water [16,17]. Ozonation [18,19] and membrane filtration [20, 21, 22] has been successful for atrazin removal from water,however thes technique are too expensive. Adsorption of atrazin on activated carbons also successful [23,24], but production and regeneration of activated carbon is costly. Other studies have focused on the elimination of pesticides by clay. For example, investigation by two co-workers [25] on the adsorption of atrazin and its metabolites (degradation products) by vermiculite and montmorillonite modified by intercalation with iron (III) appeared to improve the adsorption rate but with too long an adsorption reaction time of more than 24h. Also, from research conducted by [26] on the removal of atrazin, lindane and diazinon from water using organo-zeolites, it appeared that the adsorption capacity of atrazin was the lowest (2.0 mmoL.g-1). [27] using modified clays for adsorbing atrazin in water showed that the adsorption coefficient was, hitherto, low. Furthermore, work carried out by [28,29] on the adsorption of atrazin on montmorillonite showed that with a mass of 20 gL-1 of montmorillonite solution in distilled water doped with atrazin , 38% removal was obtained. However, these studies do not provide clear understanding of the mechanistic processes involved in the montmorillonite-atrazin interaction.. Montmorillonite, are microscopic crystals of the 2:1 clay type, classified as phyllosilicate group of minerals. They are known as a member of the smectite family [30]. Chemically, montmorillonite is hydrated sodium, calcium, aluminum and magnesium silicate hydroxide (Figure (b)).
Figure 1(b)
Structure of montmorillonite (Na,Ca)0.3(Al,Mg)2Si4O10(OH)2.nH2O)
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Many studies has been carried out on atrazin adsorption from water on clay. Kaolinite type have low adsorption capacity, natural montmorillonite have medium capacity and pillared montmorillonite have very high efficiency. This study reported on the influence of pH, ionic strength, the clay mass and concentration of atrazin on the retention of atrazin in water by montmorillonite. Modelling of the kinetic and isotherms data are also reported. 2. EXPERIMENTAL STUDY
2.1. Study materials 2.1.1. Montmorillonite sampling, fractionation and characterization Soil aggregates were collected from Koussrie, a locality in the Far North region of Cameroon (Africa). Aggregates were collected by digging with a shovel to a depth of 50cm on average. These aggregates were placed in nylon bags and transported to the laboratory. The aggregates were dried in the laboratory by spreading them on the surface of a clean and dry bench top. They were then disaggregated by pounding in a wooden mortar and then homogenized for at least ten minutes using a roller mixer (Heindolph, Type Reax 2 from Germany). 1500 g of this sample were soaked in 3L of distilled water for 24 hours. The <2m fraction was obtained by gravity separation after 8 hours of decantation. The water was then removed by drying at 105C in an oven (Type P180 Jumo No. 84001 from USA). The dried fraction was pulverized in an agate mortar and the powder obtained was stored in a tightly closed glass jar for adsorption studies. The particle size distribution of the clay fraction was performed using a Mastersizer 2000 particle size analyzer (Malvern Instrument Ltd, UK). For the <2m fraction, it was found that more than 50% of the particles had a size of about 1.952 microns. Earlier investigation by [31] on this clay fraction had confirmed that it is actually a type 2:1 clay. 2.1.2. Atrazin Pure atrazin molecule (99%) was obtained from Riedel de Haen (Germany). 2.1.3 Physicochemical and associated chemical properties of atrazin and its metabolites (degradation products) Evaluation of the physicochemical and their associated chemical properties of atrazin and its metabolites was performed using ACD/Structure Design Suite Version 12 [32]. 2.2. Adsorption Studies 2.2.1. Preparation of synthetic solution The initial atrazin solution was prepared at 9.37 x 10-3M in methanol with 99.5% (obtained from Aldrich, Germany) for spectroscopic analysis, by dissolving 0.02 g of atrazin in 10mL of methanol. This solution was stored at 6C in the refrigerator in a brown glass bottle. The synthetic water solution was thus prepared by dissolving a given amount of this initial solution of atrazin in a 1L of distilled water as per the desired concentration. The preparation of the clay slurry was carried out in a batch of 1L beakers containing a known mass of the prepared clay fraction and 1L of water containing atrazin as previously described.
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2.2.3. Adsorption Kinetics The study of the adsorption of atrazin on montmorillonite was carried out in a stirred reactor using a Jar test device (Fisher Bioblock, France). The adsorption kinetics was determined at 25 1 C in a dispersed medium by putting into contact the atrazin in aqueous solution with the clay suspension of known quantity. The mixture was subjected to fast stirring (200 rpm) for 2 min followed by slow stirring at 60rpm. The adsorption kinetics was carried out by varying the pH of the suspension, the concentration of atrazin, the mass of montmorillonite and ionic strength. The atrazin concentration in solution was determined at regular time intervals of 10 min. for 2 h. For this purpose, 3mL of the mixture were taken using a pipette bulb, centrifuged at 3700rpm (DL 6000 B, USA) for 20 min. The supernatant was collected and analyzed using a UV-Visible spectrophotometer (Metertech Spectrophotometer UV / Vis. SP8001, Taiwan) at 230 nm using a quartz cuvette. The absorption spectrum was obtained in the range of 200 to 500 nm. This spectrum has an absorption band at wavelengths between 215 and 230 nm with a maximum absorption peak at 230 nm. The reference solution was the supernatant from centrifugation of the clay suspension prepared under the same conditions as the sample but without any atrazin. The values of residual atrazin concentrations were established on the basis of triplicate adsorption tests. 2.2.4 Modelling of adsorption kinetics The adsorption kinetics was modelled using the pseudo-first-order model and intra-particle diffusion model. The intra-particle diffusion kinetic equation is given by:
qt = k int t 1 / 2 + C
Where qt is the relative amount of atrazin adsorbed at time t, kint is the intra-particle diffusion constant and C is a constant. The kinetic equation for the pseudo-first order model is given by the relation:
Ln(qe q adsorbed k1t Where qt is the amountt ) = Lnqe after a stirring time t, qe the amount adsorbed at equilibrium,
and k1 is the rate constant. Representing the function Ln(qe-qt) = f(t), we obtain a line with slopek1 and the intercept ln(qe). 2.2.4. Adsorption isotherms The adsorption of atrazin on montmorillonite was carried out in a stirred reactor in a 1L beakers prepared in batches. In these beakers were introduced a mass (m) of clay, of 200mg to which was added various concentrations of atrazin. These beakers were stirred in the Jar test (Fisher Bioblock, France) at 60rpm for a contact time of 40 min. Then, 3mL of suspension was removed from each beaker using a pipette followed by centrifugation at 3700rpm (DL 6000 B, USA). The adsorption was carried out at a temperature of 25C, pH of 6.5 and an ionic strength of 5.10-3 M. The adsorbed amount of atrazin (q) was determined by the difference between the initial concentration of atrazin introduced into the solution and the residual concentration after adsorption. The absorbed quantity expressed as per unit mass of clay is given by the relation:
q=
C C0 V m
Where Co is the initial concentration of atrazin introduced in g.L-1; C: Concentration of atrazin in solution at time t; m: mass of adsorbent used in g, V: The volume of the solution in L.
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3. 3.1
RESULTS AND DISCUSSION
Physicochemical and associated chemical properties of atrazin and its metabolites ACD/Structure Design Suite (SDS) is a valuable computational tool that uses proven predictive algorithms and models to help optimize lead compounds towards producing analogues with improved physicochemical characteristics in pharmacokinetic studies [33, 34] . This tool was used in this study to provide advanced knowledge for the understanding of structure-property relationships and improved physicochemical properties of atrazin and its degradation products. Table 1a compares the physicochemical and associated chemical properties of atrazin (ATR) and two most prevalent metabolites, hydroxyatrazin (HYA) and desethylatrazin (DEA) in soil. This is, probably, due the similarities in parameters such as molar refractivity, molar volume, parachor, index of refraction, surface tension and density between them. Although these physicochemical parameters are distinctively different in deisopropylatrazin (DIA) when compared with DEA, these two degradation compounds of atrazin are the most mobile [10]. The difference between ATR and DDA (didealkylatrazin) (the most infrequent metabolite of atrazin) is illustrated in Table 1b. The surface tension of this molecule is very high and this may explain its almost complete immobility, hence, not often detected in both soil and ground water.
Comparison of the physicochemical and associated chemical properties of atrazin (ATR) and two most prevalent metabolites (DEA & HYA). ATR DEA HYA C6H11N5O Molecular formula C8H14ClN5 C6H10ClN5 169.18444 215.68326 187.6301 HYA*** Formula weight Atrazin* DEA** 3 3 45.47 0.3 cm3 58.49 0.3 cm 48.49 0.3 cm 122.6 3.0 cm3 Composition 169.8 3.0 cm3 136.1 3.0 cm3 366.4 4.0 cm3 Molar refractivity 460.1 4.0 cm3 387.2 4.0 cm3 1.663 0.02 1.604 0.02 1.630 0.02 Molar volume 53.8 3.0 dyne/cm 65.3 0.05 dyne/cm 79.6 3.0 dyne/cm 3 Parachor 1.269 0.06 g/cm3 1.377 0.06 g/cm3 1.379 0.06 g/cm -24 3 Index of refraction 23.19 0.5 10-24cm3 19.22 0.5 10-24cm3 18.02 0.5 10 cm 169.09636 Da 215.093773 Da 187.062473 Da 169.1844 Da Surface tension 215.6833 Da 187.6301 Da Density Polarizability Monoisotopic
Table 1a
mass
Average mass ATR*:C(44.55%)H(6.54%)Cl(16.44%)N(32.47%) ; DEA**: C(38.41%) Cl(18.90%) N(37.33%); HYA***: C(42.60%) H(6.55%) N(41.39%) O(9.46%)
H(5.37%)
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Table 1b Comparison of the physicochemical and associated chemical properties of atrazin (ATR) with the most mobile (DIA) and the most infrequent (DDA) metabolites. ATR Molecular Formula formula weight C8H14ClN5 215.68326 Atrazin* 58.49 0.3 cm3 169.8 3.0 cm3 460.1 4.0 cm3 1.604 0.02 53.8 3.0 dyne/cm 1.269 0.06 g/cm3 23.19 0.5 10-24cm3 215.093773 Da 215.6833 Da DIA C11H19ClN10O 342.78796 DIA**** NA NA NA NA NA NA NA 342.143183 Da 342.788 Da DDA C3H4ClN5 145.55036 DDA***** 33.89 0.3 cm3 85.6 3.0 cm3 277.2 4.0 cm3 1.722 0.02 109.9 3.0 dyne/cm 1.700 0.06 g/cm3 13.43 0.5 10-24cm3 145.015523 Da 145.5504 Da
Composition Molar refractivity Molar volume Parachor Index of refraction Surface Density Polarizability Monoisotopic tension
mass
Average mass ATR*:C(44.55%)H(6.54%)Cl(16.44%)N(32.47%); DIA****: C(38.54%) H(5.59%) Cl(10.34%) N(40.86%) O(4.67%); DDE*****:(24.76%) H(2.77%) Cl(24.36%) N(48.12%); NA: Not available 3.2 Atrazin adsorption on montmorillonite
3.2.1 Adsorption kinetics of atrazin Figure 2 (a and b) show changes in the quantity of atrazin adsorbed as a function of contact time for atrazin concentrations ranging from 100 to 400 g.L-1 and pH of 3 and 10. The adsorption kinetics has two phases: a rapid growth phase which indicates that atrazin is rapidly adsorbed whatever the pH or the concentration of atrazin in solution and the second phase, which is in the form of a plateau wherein the adsorption of the solute is at the maximum.
1,6 1,4
2,0
Atrazin adsorbed (mg.g )
-1
1,5
100 g.L 200 g.L 300 g.L 400 g.L
-1 -1 -1 -1
-1
1,2 1,0 0,8 0,6 0,4 0,2 0,0 0 20 40 60 80 100 120 100 g.L 200 g.L -1 -1 300 g.L -1 400 g.L
-1
1,0
0,5
(a)
(b)
Contact time (min)
0,0 0 20 40 60 80 100 120
Contact time (min)
Figure 2
Kinetics of adsorption of atrazin at pH = 3 (a) and pH = 10 (b) FI = 2M,100mg
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The first phase corresponds to the adsorption of the pesticide on the most accessible sites located on the outer surface of the particles as well as on the interlayer spaces of the clay. At the end of this phase the retained amount of atrazin stops evolving and the presence of a plateau on the kinetic curves in the second step indicate that the adsorption equilibrium has been attained. The equilibrium time is almost identical and varied between 30 and 40 min. 3.3 Influence of parameters on the adsorption kinetics of atrazin
3.3.1 Influence of the concentration of atrazin Figure 3 shows the changes in the amounts of atrazin adsorbed on montmorillonite as a function of the contact time for different initial concentrations of 100g.L-1, 200 g.L-1; 300 g.L-1 and 400 g.L-1 at pH = 6.5, temperature of 25 C and 200 mg of clay. It can be seen from figure 3 that the maximum amount of atrazin has been adsorbed after 20 min.
Quantity adsorbed (mg.g-1)
1,2
1,0
0,8
0,6
100 g.L-1 200 g.L-1 300 g.L-1 400 g.L-1
0,4
0,2
0,0
20
40
60
80
100
120
Contact time (min)
Figure 3
Influence of the concentration of atrazin adsorption kinetics: 200 mg, pH = 6.5 and FI = 5.10-3 M
The concentration adsorbed after 20 min. ranges from 0,2 to 1.0 mg.g-1for initial load concentrations from 100 to 400 g.L-1. The adsorption efficiency increases with an increase in the initial adsorbent. Table 2 shows the influence of the concentration of atrazin on the parameters of the pseudo-first-order model and intra-particulate diffusion model. From this data (Table 2), it appears that the pseudo-first order model and intra-particle diffusion model best describes the phenomenon studied in view of the correlation coefficient. The speed constant of the pseudo-first order model increases with increasing atrazin concentration. Similarly, the speed constants of the intra-particle diffusion model increases with increasing atrazin concentration. It can thus be deduced that an increase in the concentration of atrazin have a positive influence on its retention rate. 86
Table 2
Influence of atrazin concentration on the kinetic parameters of the pseudofirst-order and intra-particulate diffusion models. Pseudo-first order model R2 Intra-particle diffusion model R12 R22
C (g/ L-1)
K1 (min-1) 100 200 300 400 0,0868 0,147 0,185 0,244
qe cal
0,347 0,516 0,706 0,934
1 0,991 0,990 0,997
Kint1 (g/mg. min) 0,077 0,183 0,289 0,325
C1
- 0,047 - 0,077 - 0,052 - 0,124
0,995 0,995 0,976 0,992
Kint2 (g/mg. min) 0,017 0,019 0,022 0,064
C2
0,215 0,495 0,738 0,678
0,985 0,814 0,848 0,901
This could be explained by the fact that at low concentrations of atrazin, the diffusion of the molecule to the adsorption sites on the surface of the clay is much lower than at high concentrations. [35] observed similar results in the adsorption of endrin on montmorillonite. 3.3.2 Influence of the clay mass introduced Figure 4 shows changes in the quantity of atrazin adsorbed on montmorillonite as a function of the contact time for various masses of clay introduced which ranged from 100, 200, 300, 400 mg, at pH of 6.5, temperature of 25 C and 250 g.L-1.
1,2
Atrazin adsorbed (mg.g-1)
1,0
0,8
0,6 m=100 mg m=200 mg m=300 mg m=400 mg
0,4
0,2
0,0 0 20 40 60 80 100 120
Contact time (min)
Figure 4
Influence of the clay mass introduced on the adsorption kinetics
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The shapes of the kinetic curves are the same as previously described whatever the mass of clay introduced. We however noticed that the amount of atrazin adsorbed decreases as the clay mass introduced into the medium increases. This amount reduces by almost four-folds with masses of clay introduced from 400 to 100 mg. Table 3 shows the influence of the mass of clay on the model parameters of pseudo-first-order and intra-particle diffusion models.
Table 3
C (g/ L-1) M100 M200 M300 M400
Influence of the mass of clay on the kinetic parameters of the model pseudo-first-order and intra-particle diffusion. Pseudo-first order model Intra-particle diffusion model K1 qe cal R2 Kint1 C1 R12 Kint2 C2 R22 -1 (g/mg. (min ) min) 0,235 0,909 0,997 0,354 - 0,119 0,992 0,063 0,693 0,951 0,2851 0,808 0,998 0,263 - 0,062 0,982 0,027 0,617 0,977 0,197 0,406 0,999 0,115 - 0,060 0,998 0,027 0,249 0,948 0,141 0,326 0,997 0,094 - 0,037 0,993 0,011 0,24 0,911
From Table 3, it was found that the pseudo-first order model and intra-particle diffusion best describe the phenomenon studied with correlation coefficient greater than 0.9. The rate constant of the pseudofirst order model decreases with an increase in the mass of clay. Similarly, the rate constants of intraparticle diffusion model decreases with increasing mass of clay. This confirms that the increase in mass of clay has a negative influence on the retention rate of atrazin. This result could be explained by the fact that the increase in mass would reduce the mobility of atrazin in solution. Indeed, atrazin is a weak base which is strongly hindered by the presence of a triazine cycle, two amino groups and two alkyl groups in position 4 and 6. This molecular structure does not only give atrazin an electronegative character, that is to say the same charge as that on the surface of the clay in solution, but also reduces the possibility of attaching another molecule to neighbouring adsorption sites.
3.3.3
Influence of the pH of the mixture
Figure 5 shows the change in amounts of atrazin adsorbed on montmorillonite as a function of the contact time at different pH values (from 2 12), 250g.L-1, 200mg and at 25C.
1 ,0
-1
0 ,8
0 ,6
0 ,4
pH =2 pH =6 pH =7 pH =8 pH =9 p H = 12
0 ,2
0 ,0 0 20 40 60 80 100 120 140
C o n t a c t t im e ( m in )
Figure 5
Effect of pH on the adsorption kinetics of atrazin

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It can be noted from figure 5 that the amount of atrazin adsorbed increases significantly when the pH of the mixture decreases and tends towards to be more acidic. Table 4 shows the influence of pH on the kinetic parameters of the pseudo-first-order and intra-particle diffusion models. Apparently, the pseudo-first order model and intra-particle diffusion model best describe the phenomenon studied with a correlation coefficient greater than 0.9 (Table 4). The velocity constant of the pseudo-first order model decreases with increasing pH. Similarly, the velocity constants of the intra-particle diffusion model decreases with increasing pH. This confirms that pH increase has a negative influence on the retention of atrazin. Table 4 C (g.L-1) Effect of pH on the kinetic parameters of the model pseudo-first-order and intra-particle diffusion. pseudo-first order model Intra-particle diffusion model K1 (min-1) pH=2 pH=6 pH=7 pH=8 pH=9 pH=12 0,252 0,218 0,201 0,217 0,197 0,117 qe cal R2 Kint1 (g/mg. min) 0,269 0,22 0,21 0,190 0,116 0,066 C1 R12 Kint2 (g/mg.m in) 0,056 0,055 0,036 0,030 0,020 0,0126 C2 R22
0,784 0,626 0,609 0,504 0,451 0,208
0,999 0,999 0,999 0,997 1,000 0,999
- 0,107 - 0,086 - 0,064 - 0,064 - 0,062 - 0,023
0,995 0,995 0,989 0,991 0,995 0,992
0,526 0,392 0,438 0,403 0,318 0,139
0,926 0,962 0,947 0,924 0,930 0,909
This could be explained by the fact that a decrease in the pH of the solution leads to an increase in the cationic fraction of atrazin, which would therefore favour its retention by the negatively charged clay at this pH. Indeed, at low pH, atrazin through its amine function fixes the proton H+ (protonation) and forms cations that are easily removed (Figure 6).
Cl CH3 H3C NH N N N CH3 N N Cl N NH CH3
+
NH CH3
H3C
NH
Figure 6
Reaction of protonation of atrazin in aqueous medium
Similarly, at low pH, the adsorbent capacity of clay is increased due to the replacement of exchangeable cations (Ca2+, Na+, Mg2+ and K+) by H+ ions. This greatly increases their negative charge. This result was also observed by [29] who showed that the adsorption of atrazin on modified montmorillonite was best in acidic than alkaline conditions. A negative adsorption correlation with pH was also reported in the case of the adsorption of basic pesticides such as prochloraz [39], atrazin, terbuthylazine or the fluoroxypyr (family of triazines) [37].
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3.3.4 Influence of ionic strength Figure 7 shows the variation of the amount of atrazin adsorbed on montmorillonite as a function of the contact time at different values of ionic strength at 250g.L-1, with pH = 6.5, temperature of 25 C and 200 mg clay.
0,7
-1
0,6
0,5
0,4
0,3
0,2
0,1
FI=10-3M FI=10-2M FI=10-1M
0,0 0 20 40 60 80 100 120
Contact time (min)
Figure 7
Effect of ionic strength on the adsorption kinetics of atrazin
It is clear from figure 7 that increasing the ionic strength of the mixture results in a net increase in the amount of atrazin adsorbed. Table 5 shows the influence of ionic strength on the kinetic parameters of the pseudo-first-order and intra-particle diffusion models. Table 5 Effect of ionic strength on the kinetic parameters of the model pseudo-first-order and intra-particle diffusion. C Pseudo-first order model Intra-particle diffusion model -1 (g.L ) K1 qe cal R2 Kint1 C1 R12 Kint2 C2 R22 -1 (min ) (g/mg. (g/mg. min) min) -1 FI=10 0,256 0,611 0,998 0,200 - 0,061 0,988 0,027 0,442 0,899 FI=10-2 0,247 0,522 0,991 0,149 - 0,048 0,990 0,019 0,351 0,832 FI=10-3 0,122 0,253 0,999 0,065 - 0,035 0,995 0,021 0,130 0,963 From Table 5, it is found that the pseudo-first order model and intra-particle diffusion better describe the phenomenon studied with correlation coefficient greater than 0.8. The velocity constant of the pseudo-first order model decreases with increasing ionic strength. Similarly, the velocity constants of intra-particle diffusion model decreases with increasing ionic strength. This confirms that a decrease in ionic strength has a negative influence on the
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retention of atrazin. This result could be explained by the fact that the ionic solution has an influence on the diffused double layer of the clay [37]. Indeed, the addition of salt in the medium would result in compression of the diffused double layer and promote interaction between atrazin and the surface of montmorillonite. [35] also observed similar results. 3.3.5. Adsorption isotherm of atrazin The adsorption isotherm of atrazin was obtained for concentrations ranging from 10, 100, 200, 300, and 400g.L-1. The contact time between the clay and atrazin was the equilibrium time which was determined in the adsorption kinetics study (40 min.). This is shown in Figure 8.
1,2
Qe (mg.g-1)
1,0 0,8 0,6 0,4 0,2 0,0 0 50 100 150 200 250
Ce ( g.L-1)
Figure 8
Adsorption isotherm of atrazin at pH = 6.5, m = 200 mg; FI = 5.10-3M, T = 25C)
The analysis of the isotherm shows a resemblance with the type L isotherm. Such type of isotherm, indeed, indicates that the available adsorption sites decreases gradually as the concentration of solute in solution increases. This implies that the solid has a greater affinity for the solute in solution. We note, however, that the isotherm does not present a plateau, indicating that the adsorption sites are not saturated in the concentration range used (10-400 g.L-1). A significant difference in the amounts of atrazin adsorbed was nevertheless observed. For the same mass introduced, significant amounts of atrazin was adsorbed on the clay at pH = 6.5 (0.045 mg.g-1 1 mg.g qe-1). This was not is thought not only to be facilitated by the influence of the concentration of atrazin introduced but also by the pH. These results are in agreement with the observations made during the study of the influence of atrazin concentration and pH on the adsorption kinetics of atrazin [36]. 3.4 Modelling the adsorption isotherm of atrazin
The Langmuir, Freundlich and Temkin models which are widely used for modelling adsorption isotherms were used in this work to describe those of atrazin. The Langmuir model parameters (qmax and KL), Freundlich (Kf and n) and Temkin (A and B) were obtained by linearization of the model equations and are presented in Table 6. A comparison of the regression coefficients (R2) shows that the adsorption isotherm of atrazin can be described by the three models. However, the Freundlich model was found to be
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the one that best describes the adsorption relative to the Langmuir and Temkin models (R2Freundlich> R2Langmuir> R2Temkin). Table 6 Parameters of Langmuir, Freundlich and Temkin obtained by linearization of the adsorption isotherm of atrazin. Freundlich Kf (L.mg-1) 0,051 Temkin A B 0,089 0,347
Langmuir KL (L.mg-1) 0,011
qm(mg.g ) 1,375
-1
R 0,989
n 1,760
R 0,994
R2 0,978
Indeed, the Freundlich model assumes that the adsorption of molecules at the solid-solution interface occurs on heterogeneous surfaces having different types of adsorption sites, while the Langmuir model describes adsorption taking place on homogeneous sites. The Temkin model assumes that the adsorption energy of any molecule decreases linearly with the covering of the surface of the adsorbent by the adsorbed species. It is clear from this table that the maximum adsorption capacity, qm , predicted by the Langmuir model is greater than the amount adsorbed which correspond to a concentration of atrazin of 400 g.L-1 given by the plot of the isotherm. Thus, the determined value of qm suggest that this model may well be used to describe the adsorption of atrazin in solution. In addition, the value of the constant, n, of the Freundlich model which is greater than 1 indicates a good affinity between atrazin and clay. This confirms the idea that it is an isotherm of type L. However, the correlation coefficient given by the Freundlich model (R2 = 0.994) allows us to deduce that there do not only exist sites of same adsorption energy on the surface of the clay, but there also exists sites of variable energy in smaller proportion. The B constant of the Temkin model, which translate the interaction energy between the atrazin molecule and clay, is very low (B = 0.347 J.mol-1), thus we can deduce that the adsorption is physical. The main bonds implicated are therefore weak links of low adsorption energies such as hydrogen bonds and Van der Waals bonds. 4. CONCLUSION
It is clear from this work that the kinetic data for the adsorption of atrazin on montmorillonite is described by the maximum growth exponential model which consists of two steps: the first which is the growth phase, corresponding to adsorption of molecule on the most accessible sites located on the external surface of the clay and the second, constant phase, corresponding to the equilibrium adsorption. The equilibrium time obtained varies between 30 and 40 min. From the study of the influence of parameters on the adsorption kinetics, it was found that the adsorbed amounts were better when working at pH of 3 or 38 mg of clay or at high ionic strength, or at high atrazin concentrations (491g.L-1). The pseudo-first-order and intraparticle diffusion kinetic models can be used to describe the adsorption kinetics of atrazin in solution. The experimental results on the adsorption of atrazin were compared with theoretical models of Langmuir, Freundlich and Temkin. Although the three models showed correlation factors R2>0.95, the best correlation was obtained with the Freundlich model. This strong correlation indicates the heterogeneity of the surface of the clay (montmorillonite) used. Moreover, the
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coefficient n>1, indicates that there is a great affinity between atrazin and clay. Maybe, the most important interpretation of montmorillonite excellent sorptive ability as proven by the physical and chemical parameters measured in this work would be their relationship with its colloidal size and crystalline structure in layers, resulting in a high specific surface area and optimum rheological characteristics. ACKNOWLEDGEMENT This work was supported in part by the Tshwane University of Technology (TUT), Arcadia campus, Pretoria South Africa. Their assistance in data analysis and presentation is much appreciated. The authors acknowledge the Department of Chemistry & Environmental Engineering (ENSAI-IUT) of the University of Ngaoundr, Cameroon, for their help in sample collection and experimental work. Finally, the Advanced Chemistry Development, Inc. (ACD/Labs), 8 King St. E., Ste. 107, Toronto, Ontario M5C 1B5, Canada, is acknowledged as physical chemical data of atrazin and its metabolites were generated using their ACD/Structure Design Suite (SDS) and advanced in-silico chemistry tools. REFERENCES 1. Kordel. W., et. al. (1997), The importance of natural organic material for environmental processes in water and soils, Pure Appl. Chem., Vol.69, pp.1571-1600. 2. Kiely. T., et. al. (2004), Pesticide Industry Sales and Usage: 2000 and 2001 Market Estimates. U.S. Environmental Protection Agency, Washington, DC. 3. Graziano. N., et. al. (2006), 2004 National Atrazine Occurrence Monitoring Program using the Abraxis ELISA method, Environ. Sci.Technol., Vol. 40, pp.11631171. 4. U.S. Geological Survey. (2003), Pesticides in Streams and Ground Water, http://ca.water.usgs.gov/pnsp/pestsw/Pest-SW_2001_Text.html [Accessed, 1/12/2012]. 5. MINAGRI (2003), Liste des produits homologues pour dix ans,Yaounde, Cameroon. 6. Jiang. H., et. al. (2005), Determination of chloro-s-triazines including didealkylatrazine using solid phase extraction coupled with gas chromatography/mass spectrometry, J. Chromatogr. A, Vol.1064, No.2, pp. 219226. 7. Jiang. H., et. Al.(2006), Occurrence and removal of chloro-s-triazines in water treatment plants, Environ. Sci. Technol., Vol.40, No.11, pp. 3609-3616. 8. USEPA (2000), Ofce of Pesticide Programs, Health Effects Division, Washington DC http://www.epa.gov/pesticides/cumulative/triazines/newdocket.htm [Accessed, 18/01/2013]. 9. Panshin. S.Y., et. al. (2000), Analysis of atrazine and four degradation products in the pore water of the Vadose Zone, Central Indiana, Environ. Sci. Technol., Vol.34, pp. 2131-2137. 10. Kruger. E.L., et. al. (1996), Relative mobilities of atrazine, five atrazine degradates, metolachlor, and simazine in soils of Iowa, Environ. Toxicol. Chem., Vol.15, pp. 691695. 11. Koskinen. W. C.,et. al. (1996), In Herbicide Metabolites in Surface Water and Groundwater; Meyer, M. T., Thurman, E. M., Eds.; ACS Symposium Series 630; American Chemical Society: Washington, DC, U.S.A.125-139. 12. Kruger. E.L., et. al. (1997), Comparative fates of atrazine and deethylatrazine in sterile and nonsterile soils, J. Environ. Qual., Vol.26, pp.95-101.
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31. Nguetnkam. J.P., et. al. (2005), Assessment of the surface areas of silica and clay in acid-leached clay materials using concepts of adsorption on heterogeneous surfaces, Journal of Colloid and Interface Science, Vol. 289, pp.104115. 32. Advanced Chemistry Development, Inc. (ACD/Labs), 8 King St. E., Ste. 107, Toronto, Ontario M5C 1B5, Canada, http://www.acdlabs.com/products/percepta/sd_more.php[Accessed 10/01/2013] 33. Ndibewu. P. and Ngobeni. P (2012), Use of Analytical Methods and In-silico Techniques, In: Current Topics in Public Health. Book edited by Alfonso J. RodriguezMorales. ISBN 980-953-307-868-2. Intech, Croatia. 34. Bhal. S.K (2007), Lipophilicity Descriptors: Understanding When to Use LogP & LogD.ACD/LogD Suite, www.acdlabs.com/logdsuite/ Advanced Chemistry Development, Inc., Toronto, ON, Canada. 24 April[Accessed 15/01/2013]. 35. Peng. X., et. al. (2009), Sorption of endrin to montmorillonite and kaolinite clays, Journal of Hazardous Materials, Vol.168, pp. 210214. 36. De Jonge. H. and De Jonge. L.W (1999), Influence of pH and solution composition on the sorption of glyphosate and prochloraz to a sandy loam soil, Chemosphere, Vol. 39, pp.753-763. 37. Gao. J. and Pedersen. J.A (2005), Adsorption of sulfonamide antimicrobial agents to clay minerals, Environ. Sci. Technol., Vol.39, pp. 95099516. 38. P.Muthamilselvi ,E.Poonguzhali and Dr.R.Karthikeyan, Removal Of Phenol From Aqueous Solutions By Adsorption International journal of Advanced Research in Engineering & Technology (IJARET), Volume 3, Issue 2, 2012, pp. 280 - 288, Published by IAEME.
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Physico-Chemical Studies On The Adsorption of Atrazin On Locally Mined Montmorillonites

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International Journal of Advanced Research in Engineering and Technology (IJARET), ISSN 0976IN INTERNATIONAL JOURNAL OF ADVANCED RESEARCH 6480(Print),

, ISSN 0976 6499(Online) Volume 4, Issue 1, January - February (2013), IAEME

ENGINEERING AND TECHNOLOGY (IJARET)

PHYSICO-CHEMICAL STUDIES ON THE ADSORPTION OF ATRAZIN ON LOCALLY MINED MONTMORILLONITES

Structure of montmorillonite (Na,Ca)0.3(Al,Mg)2Si4O10(OH)2.nH2O)

RESULTS AND DISCUSSION

Atrazin adsorbed (mg.g )

100 g.L 200 g.L 300 g.L 400 g.L

Atrazin adsorbed (mg.g )

0,0 0 20 40 60 80 100 120

Contact time (min)

Kinetics of adsorption of atrazin at pH = 3 (a) and pH = 10 (b) FI = 2M,100mg

100 g.L-1 200 g.L-1 300 g.L-1 400 g.L-1

Contact time (min)

K1 (min-1) 100 200 300 400 0,0868 0,147 0,185 0,244

0,347 0,516 0,706 0,934

1 0,991 0,990 0,997

Kint1 (g/mg. min) 0,077 0,183 0,289 0,325

- 0,047 - 0,077 - 0,052 - 0,124

0,995 0,995 0,976 0,992

Kint2 (g/mg. min) 0,017 0,019 0,022 0,064

0,215 0,495 0,738 0,678

0,985 0,814 0,848 0,901

Atrazin adsorbed (mg.g-1)

0,6 m=100 mg m=200 mg m=300 mg m=400 mg

0,0 0 20 40 60 80 100 120

Contact time (min)

Influence of the clay mass introduced on the adsorption kinetics

C (g/ L-1) M100 M200 M300 M400

Influence of the pH of the mixture

Atrazin adsorbed (mg.g )

0 ,0 0 20 40 60 80 100 120 140

Effect of pH on the adsorption kinetics of atrazin

0,784 0,626 0,609 0,504 0,451 0,208

0,999 0,999 0,999 0,997 1,000 0,999

- 0,107 - 0,086 - 0,064 - 0,064 - 0,062 - 0,023

0,995 0,995 0,989 0,991 0,995 0,992

0,526 0,392 0,438 0,403 0,318 0,139

0,926 0,962 0,947 0,924 0,930 0,909

Reaction of protonation of atrazin in aqueous medium

Atrazin adsorbed (mg.g )

FI=10-3M FI=10-2M FI=10-1M

0,0 0 20 40 60 80 100 120

Contact time (min)

Effect of ionic strength on the adsorption kinetics of atrazin

Adsorption isotherm of atrazin at pH = 6.5, m = 200 mg; FI = 5.10-3M, T = 25C)

Langmuir KL (L.mg-1) 0,011

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