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Kinetic, equilibrium and thermodynamic studies for the sorption of metribuzin from aqueous solution using banana peels, an agro-based biomass a

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Atta ul Haq , Jasmin Shah , Muhammad Rasul Jan & Saif ud Din

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Department of Chemistry, Government College University, Faisalabad, Pakistan

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Institute of Chemical Sciences, University of Peshawar, Pakistan Accepted author version posted online: 16 Apr 2015.Published online: 15 May 2015.

To cite this article: Atta ul Haq, Jasmin Shah, Muhammad Rasul Jan & Saif ud Din (2015) Kinetic, equilibrium and thermodynamic studies for the sorption of metribuzin from aqueous solution using banana peels, an agro-based biomass, Toxicological & Environmental Chemistry, 97:2, 124-134, DOI: 10.1080/02772248.2015.1041528 To link to this article: http://dx.doi.org/10.1080/02772248.2015.1041528

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Toxicological & Environmental Chemistry, 2015 Vol. 97, No. 2, 124 134, http://dx.doi.org/10.1080/02772248.2015.1041528

Kinetic, equilibrium and thermodynamic studies for the sorption of metribuzin from aqueous solution using banana peels, an agro-based biomass Atta ul Haqa*, Jasmin Shahb, Muhammad Rasul Janb and Saif ud Dinb Department of Chemistry, Government College University, Faisalabad, Pakistan; bInstitute of Chemical Sciences, University of Peshawar, Pakistan


a

(Received 29 August 2014; accepted 12 April 2015) Banana peels were employed for the removal of metribuzin from aqueous solution. Sorption in the batch mode was optimized regarding pH, contact time, sorbent dose, initial pesticide concentrations, and temperature. The sorption data were fitted to pseudo-first-order, pseudo-second-order, intraparticle diffusion, Elovich, and liquid film diffusion model, the pseudo-second-order exhibiting best fit (R2 D 0.9803). Of the four most common sorption isotherm models (Langmuir, Freundlich, Tempkin, and Dubinin Radushkevich), the data followed the Langmuir isotherm with highest correlation. The maximum adsorption capacity was found to be 167 mg g¡1. Gibbs free energy, enthalpy, and entropy showed that the sorption was exothermic and spontaneous. Keywords: metribuzin; banana peels; isotherms; kinetics; thermodynamics

1. Introduction The groundwater contaminated with pesticides not only affect the human health when it is directly used for drinking purpose but the food chain is also affected by these contaminated groundwater when used for irrigation purposes (Majumdar and Singh 2007). Metribuzin is a selective triazine herbicide which inhibits the photosynthesis in susceptible plant species (Fountoulakis et al. 2010). It is used for the pre- and post-emergence control of annual grasses and broadleaf weeds in sugarcane, soybean, wheat, etc. (Peter and Weber 1985; Harper 1988; Kim and Feagley 1988; Bedmar et al. 2004). Metribuzin is adsorbed weakly in the soils and is highly soluble (1050 mg L¡1) in water, as a result it moves downward in the soil and consequently gets incorporated into water bodies (Sensemann et al. 1997). Several results showed the presence of the metribuzin in the ground and surface water (Potter et al. 2007). According to the United States Environmental Protection Agency (US EPA), the maximum advisory concentration for metribuzin in drinking water is 0.175 mg L¡1 (Goodrich, Benjamin, and Robert 1991). Various methods have been employed for the cleanup of water containing pesticides such as ion exchange, reverse osmosis, photo-catalytic degradation, electrochemical oxidation, oxidation with ozone, and adsorption (Singh 2009). Among these methods, still the adsorption is considered as the best method due to its non-specificity and can be used for varieties of contaminants (Adams and Watson 1996). Therefore, the exploitation of newer, low cost, and indigenous waste materials as biosorbents for the removal of pesticides has been the focus of intense research nowadays (Singh 2009). In the past few years, *Corresponding author. Email: [email protected] Ó 2015 Taylor & Francis


Toxicological & Environmental Chemistry 125 a large number of such type of materials have been investigated for the removal of metribuzin pesticide and other organic pollutants like Corn Cob (Ara et al. 2013), activated granular carbon (Kitous et al. 2009), electro-activated granular carbon (Kitous et al. 2012), electrochemical reactor combined with ultraviolet oxidation (Yahiaoui et al. 2011), higharea carbon cloth (Ayranci and Hoda 2004), lignin (Ludvik and Zuman 2000), co-composting of green waste and sewage sludge (Fountoulakis et al. 2010), coal fly ash (Singh 2009), bottom fly (Khan, Singh, and Ali 2009), chestnut peel (Khan, Momina, and Khan 2013), walnut shells (Shah et al. 2013), apricot stone activated carbon (Demirbas, Kobya, and Sulak 2008), rice husk-based porous carbon (Guo et al. 2005), de-oiled soya (Mittal Krishnan, and Gupta 2005), and low-cost adsorbents (Ali, Asim, and Khan 2012). Banana belongs to Musaceae family which is one of the most consumed fruits in the world and cultivated in tropical and sub-tropical region (Juliana et al. 2011). It has been reported that several tons of the banana peels are produced in market places and household garbage daily, creating an environmental nuisance and disposal problems (Xiao et al. 2010). The banana peels are the main residue of the fruit which accounts 30% 40% of the total fruit weight (Oberoi et al. 2011). The banana peel surface consists of various functional groups like hydroxyl, carboxyl, and amide. The main objective of the present work was to investigate the adsorption efficiency of banana peels for the removal of metribuzin pesticide from aqueous solution. Banana peel is an agricultural waste of low cost and available in large quantities. The sorption data were analyzed using various adsorption isotherms (Freundlich, Langmuir, Tempkin, and DR isotherms) and kinetic models (pseudo-first-order, pseudo-second-order, intraparticle diffusion, Elovich, and liquid film diffusion) to find out the most suitable models explaining our experimental data.

2. Materials and methods 2.1. Instruments Spectrophotometer SP-300 (Optima, Tokyo, Japan), orbital shaker (Model OS-340C, Digisystem Laboratory Instruments Inc., New Taipei City, Taiwan), analog pH meter (Model-7020, Electronic Instruments, Richmond, Surrey, UK), and thermostatic water bath (Guangdong Yujia, China) were used during this work.

2.2. Chemicals and reagents All chemicals and reagents used were of analytical grade purity. Acetic acid, sulfuric acid, phosphoric acid, boric acid, sodium hydroxide, iodine, potassium iodide, potassium iodate, sodium thiosulfate pentahydrate, and formaldehyde were purchased from Merck, (Darmstadt, Germany) and were used without further purification.

2.3. Collection and preparation of banana peels Banana peels were collected from juice shops and washed with distilled water to remove any dirt particles. Then, the peels were cut into small pieces with knife and kept in sunlight for several days until completely dry. After that these peels were ground in a domestic grinder. The bigger particles were separated and crushed with pestle and mortar, and sieved through US Standard Sieve Series, Sieve No.40. For decolorization, 20 g of uniform-sized banana peels powder was transferred into a 250 mL beaker and distilled

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water was added upto a volume of 200 mL for complete soaking of banana peels powder in water. The materials were kept overnight and after completely settling down, the water was decanted several times after each addition of water. This process was repeated until water become clear and colorless. The materials were filtered through ordinary filter paper and washed further with distilled water. Cleaned and decolorized powder of banana peels was dried at 120 C in an oven till constant weight and stored in an air tight bottle for further use.

The sorption of metribuzin onto banana peels were carried out in batch systems by taking known weights (0.1 g) of banana peels in a flask and added 10 mL of metribuzin solution in the concentration range of 40 240 mg mL¡1. Distilled water was added to each flask to soak the biosorbent completely but the volume of the solution did not exceed to 25 mL in each flask. The pH of the solution was adjusted with Britton Robinson buffer of pH 3.0. The mixture was shaken on an orbital shaker for 60 min at 100 rpm for complete equilibration of metribuzin. After equilibration time, the solution was filtered and diluted upto the mark in 100 mL volumetric flasks. The residual concentration of metribuzin in filtrates was determined with the help of spectrophotometer (SP-300) at 300 nm wavelength.

3. Results and discussion 3.1. Optimization One of the most important parameter which affects the sorption process is the pH of sorption medium (Goyal, Jain, and Banerjee 2003). It significantly affects the physicochemical interactions of the species in the solution and the adsorptive sites of adsorbents and the adsorption mechanism on the surface of adsorbent (Aksu, Gonen, and Demircan 2002). Therefore, the effect of solution pH on sorption of metribuzin was studied by varying the pH from 2 to 6 and it can be seen from Figure 1 that sorption percentage increases from pH 2 to 3 and then a slight decrease in sorption of metribuzin was observed. This can be explained by assuming that at lower pH, the amino group of the metribuzin accepts 50

% sorption of metribuzin


2.4. Sorption study

40 30 20 10 0 1

2

3

4 pH

5

6

7

Figure 1. Effect of pH on sorption of metribuzin onto banana peels (initial concentration of metribuzin 40 mg mL¡1, pH 2.0 6.0, sorbent dose 0.1 g and contact time 30 min at room temperature).

Toxicological & Environmental Chemistry 127


38 37 36 35 34


33 0.00

0.04

0.08 Sorbent dose (g)

0.12

0.16

Figure 2. Effect of sorbent dose on sorption of metribuzin onto banana peels (initial concentration of metribuzin 40 mg mL¡1, pH 3.0, sorbent dose 0.02 0.14 g and contact time 30 min at room temperature).

proton and the metribuzin become cationic species. As a result, an electrostatic interaction is developed between positively charged metribuzin and negatively charged caboxylate group of banana peels but beyond pH 3, deprotonation of the metribuzin takes place due to an increase in pH. Therefore, a decrease in the adsorption of metribuzin onto banana peels was observed above pH 3, the optimum pH for adsorption. The effect of sorbent dose on adsorption of metribuzin using banana peels was studied by varying the concentration of sorbent from 0.02 to 0.14 g in 25 mL. It can be seen from Figure 2 that the adsorption percentage of metribuzin increases with an increase in the sorbent dose. The adsorption percentage of metribuzin onto banana peels is increasing from 34% to 37% as the sorbent dose increases. The adsorption process significantly depends upon the contact time. Therefore, its effect was studied in the range of 30 70 min with and without shaking the reaction contents while keeping constant the other parameters. It can be seen from Figure 3 that the adsorption percentage of metribuzin increases very slowly with the increase in contact time in both cases. This result suggests that as the contact time increases, there are more chances of interaction of metribuzin molecules with the active sites on the surface of the banana peels. As a result, more adsorption taken place as the contact time increases. The adsorption of metribuzin onto banana peels as a function of initial pesticide concentration was investigated by varying the initial pesticide concentration in the range of 40 240 mg mL¡1 while keeping constant the other parameters. As shown in Figure 4, the amount of metribuzin adsorbed per unit mass of adsorbent increases with increasing the initial pesticide concentration. This phenomenon may be due the increasing of driving force of the concentration gradient with increase in the initial pesticide concentration. The effect of temperature on percentage adsorption of metribuzin onto banana peels was studied by varying the temperature of the reaction mixture from 50 to 90 C and keeping the other parameters constant. It can be seen from the Figure 5 that the percentage adsorption of metribuzin decreases gradually when the temperature increases from 50 to 90 C. This indicates that the adsorption of metribuzin onto banana peels is an exothermic

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50 40 30 20 10 0 30

40

50 60 Contact time (min)

Without shaking

70

80

With shaking

Figure 3. Effect of contact time on adsorption of metribuzin onto banana peels (initial concentration of metribuzin 40 mg mL¡1, pH 3.0, sorbent dose 0.1 g and contact time 30 70 min at room temperature).

process and the mechanism is significantly chemical adsorption which is also confirmed from the value of mean free energy of adsorption (E) (Otero et al. 2003). The thickness of the boundary layer decreases at high temperatures due to the increased tendency of the pesticide to escape from the biomass surface to the solution phase and therefore, the decreasing in adsorption occur with increase in temperature (Polipalli and Pulipati 2013).

1.20E+06 1.00E+06 qe (mg g -1 )


20

8.00E+05 6.00E+05 4.00E+05 2.00E+05 0.00E+00 0

50

100

150

200

250

300

Initial metribuzin concentration (µg mL -1 ) Figure 4. Effect of initial metribuzin concentration on adsorption capacity of banana peels (initial concentration of metribuzin 40 240 mg mL¡1, pH 3.0, sorbent dose 0.1 g and volume of metribuzin solution 25 mL, contact time 60 min at room temperature).

Toxicological & Environmental Chemistry 129


50 40 30 20 10


0 40

50

60

70

80

90

100

Temperature (ºº C) Figure 5. Effect of temperature on adsorption of metribuzin using banana peels (initial concentration of metribuzin 40 mg mL¡1, pH 3.0, sorbent dose 0.1 g and volume of metribuzin solution 25 mL, contact time 60 min, temperature 50 90 C).

3.2. Kinetic studies The mechanism and dynamics of the adsorption process can be evaluated using kinetic data (Ma et al. 2012; Silva et al. 2011). Several steps are involved during adsorption process such as migration of pesticide from the bulk solution to the external surface of adsorbent, migration of pesticide molecules to the active sites on adsorbent, and internal diffusion of pesticide within the particle (Berrios, Martin, and Martin 2012; Yao, Lai, and Shi 2012). Depending upon various parameters, single step or the combinations of these steps are involved during the adsorption of pesticide (Ma et al. 2012). The most commonly used four kinetic models; pseudo-first, pseudo-second, intraparticle diffusion, and Elovich and liquid film diffusion models, were tested to fit the sorption data obtained from batch metribuzin adsorption experiments. The details of these models are given in our previously published papers (Shah et al. 2011; Shah, Jan, Haq, and Sadia 2012, Shah, Jan, Haq, and Zeeshan 2012; Shah et al. 2013; Shah, Jan, Jamil, and Haq 2014; Shah, Jan, and Haq 2014). The values of the constant parameters of these models were calculated from the linear forms of their respective models and are given in Table 1. The table revealed that the value of correlation coefficient (R2) for the pseudo-second-order kinetic model is greater than that of the pseudo-first-order indicating the applicability of the pseudo-second-order kinetic model to describe the adsorption process. However, the value of experimental sorption capacity is much closer to the value of calculated sorption capacity for pseudofirst-order kinetic model than pseudo-second-order kinetic model which is showing that kinetic data follows pseudo-first-order kinetic model but due to small value of the correlation coefficient of pseudo-first-order, the kinetic data do not follow the pseudo-first-order kinetic model. It can be seen from the literature that if the kinetic data follows pseudosecond- order, the sorption process will be chemisorption. In our study, the data follow pseudo-second-order which is also confirmed by the fitness of equilibrium data into Langmuir isotherm; explains the chemisorption nature of the sorption process.

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A. ul Haq et al. Table 1. Comparison of various kinetic parameters for the adsorption of metribuzin on banana peels. Model

¡1

Value

First-order kinetic

qe (mg g ) (exp) qe (mg g¡1) (cal) k1 (min¡1) R2

72.334 72.260 0.0308 0.8123

Second-order kinetic

qe (mg g¡1) k2 (g mg¡1 min¡1) R2

97.080 4.801 £ 10¡4 0.9803

Intraparticle diffusion model


Parameter

Elovich equation

Liquid film diffusion model

Kint (mg g¡1 min1/2) C R2

3.896 41.427 0.8112

a (mg g¡1 min¡1) b (g mg¡1) R2

20.440 0.059 0.8075

Kfd (min¡1) Intercept R2

0.0949 ¡1.718 0.9116

It can also be seen from the table that the data do not follow intraparticle diffusion model because the line does not pass through the origin indicating that some other mechanisms play an important role (Crini et al. 2007). Similarly, the correlation coefficient value for Elovich equation is not so high as compared to the other equations. Therefore, it may be concluded from the kinetic studies that the experimental data fitted well to the pseudo-second-order kinetic model with a high R2 value (R2 D 0.9803). The boundary plays an important role in adsorption process when solute molecules transport from the liquid phase up to the solid phase. In order to check that the adsorption process is controlled by film diffusion; the liquid film diffusion is applied to metribuzin biosorption on banana peel as given in the literature (Nagy et al. 2013; Oladoja, Aboluwoye, and Oladimeji 2008). In case of liquid film diffusion, if the plot of ¡ln (1¡F) versus t passing from the origin, i.e. the intercept, is zero, then it will suggest that the kinetics of adsorption process is controlled by film diffusion model. However, it can be seen from our study that the value of intercept is not zero (¡1.718), suggesting that the sorption of metribuzin onto banana peel is not controlled by liquid film diffusion model and some other mechanisms are involved. 3.3. Equilibrium studies The relationship between the adsorbate in the liquid phase and the adsorbate adsorbed on the surface of the adsorbent at constant temperature is known as adsorption isotherm. The adsorption isotherm is used for the description of adsorption systems and several isotherms are available for solid liquid systems (Ho, Malarvizhi, and Sulochana 2009). The experimental data were fitted into four most commonly used isotherms; Freundlich,

Toxicological & Environmental Chemistry 131 Table 2. Comparison of various isotherm constants for the adsorption of metribuzin onto banana peels.


Isotherm

Parameter ¡1

Value

Freundlich

KF (mg g ) 1/n N R2

0.248 2.136 0.467 0.9312

Langmuir

aL (L mg¡1) KL (L g¡1) Qo(mg g¡1) R2

0.030 5000.000 166.666 0.9371

Tempkin

AT BT bT R2

0.0762 388497 6.377£10¡3 0.7709

Qm(mg g¡1) K E (kJmol¡1) R2

1052.838 0.0007 26.737 0.8302

Dubinin Radushkevich (D-R)

Langmuir, Tempkin, and Dubinin Radushkevich (D-R). A complete descriptions of these isotherms are given in our previously published data (Shah et al. 2011; Shah, Jan, Haq, and Sadia 2012; Shah, Jan, Haq, and Zeeshan 2012; Shah et al. 2013; Shah, Jan, Jamil, and Haq 2014; Shah, Jan, and Haq 2014). The constant parameters of these isotherms were calculated from slope and intercept of the linear form of their respective equations and are given in Table 2. The n value of the Freundlich isotherm shows that metribuzin is not adsorbed favorably on banana peels because it is less than unity. The table showed that the value of correlation coefficient of the Langmuir isotherm is higher as compared to other isotherms indicating the fitness of equilibrium data in to Langmuir isotherm. Maximum adsorption capacity was calculated from the linear form of Langmuir isotherm and was found to be 166.666 mg g¡1. It can be concluded from the comparison of various isotherms constant parameters that our data follows the Langmuir isotherm due to its higher correlation coefficient value. The value of E is also greater than 25 kJmol¡1, which further confirms that the data follow Langmuir isotherm. Table 3 shows a comparison of the sorption capacities of various biosorbents used for the removal of metribuzin. It can be seen from the table that the sorption capacity of the banana peel is greater than the rest of biosorbents suggesting that banana peel is an effective and a promising biosorbent as compared to the other available biosorbents. 3.4. Thermodynamic study The spontaneity of the adsorption process can be explained with the help of thermodynamic studies. Thermodynamic parameters like change in free energy (DG ), enthalpy (DH ), and entropy (DS ) for the adsorption of metribuzin onto banana peels at various temperatures were calculated from the van’t Hoff equation ((¡22.77, ¡22.87, ¡23.37,

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Table 3. Comparison of the sorption capacities of various biosorbents used for the removal of metribuzin. Biosorbent


Corn cob Activated granular carbon (GAC) Fly ash Banana peel

Sorption capacity (mg g¡1)

Reference

1.23 22 0.56 166.66

Ara et al. (2013) Kitous et al. (2009) Singh (2009) Present study

¡23.46, ¡23.81), (¡14.08), (0.026)), respectively. It can be seen that the value of enthalpy change (DH ) is negative indicating that the adsorption of metribuzin on banana peels is an exothermic process. The positive value of entropy (DS ) showed the affinity of banana peels for metribuzin whereas the negative value of DG showed that the adsorption process is spontaneous at the studied temperature range.

4. Conclusions It may be concluded from the present study that an agricultural waste, banana peels, acts as an efficient biosorbent for the removal of metribuzin herbicide. The pH study showed that maximum sorption of metribuzin was achieved at pH 3.0. The kinetic revealed that pseudo-second-order is the best choice to explain the data, due to the high value of correlation coefficient of the pseudo-second-order suggesting the process of chemical adsorption. The equilibrium data were fitted well into Langmuir isotherm as depicted by the high value of correlation coefficient. The values of thermodynamic parameters like Gibb free energy, enthalpy and entropy showed that the sorption of metribuzin onto banana peels is an exothermic and spontaneous process. Banana peels are easily and abundantly available in different parts of the world which make them a suitable, cost effective, and efficient biosorbent for the removal of other pollutants like heavy metal ions, pesticides, and dyes.

Acknowledgement The authors highly acknowledge the support of University of Peshawar, Higher Education Commission, Pakistan and Government College University Faisalabad, Pakistan.

Disclosure statement No potential conflict of interest was reported by the authors.

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