Sorption of chlorpyrifos onto zinc oxide nanoparticles impregnated Pea peels (Pisum sativum L): Equilibrium, kinetic and thermodynamic studies

Journal Pre-proof Sorption of chlorpyrifos onto Zinc Oxide nanoparticles impregnated Pea peels (Pisum sativum L): Equilibrium, kinetic and thermodynamic studies Atta ul Haq, Muhammad Saeed, Muhammad Usman, Syed Ali Raza Naqvi, Tanveer Hussain Bokhari, Tahir Maqbool, Haroon Ghaus, Tayyab Tahir, Huma Khalid

PII: DOI: Reference:

S2352-1864(19)30349-9 https://doi.org/10.1016/j.eti.2019.100516 ETI 100516

To appear in:

Environmental Technology & Innovation

Received date : 16 July 2019 Revised date : 11 September 2019 Accepted date : 21 October 2019 Please cite this article as: A.u. Haq, M. Saeed, M. Usman et al., Sorption of chlorpyrifos onto Zinc Oxide nanoparticles impregnated Pea peels (Pisum sativum L): Equilibrium, kinetic and thermodynamic studies. Environmental Technology & Innovation (2019), doi: https://doi.org/10.1016/j.eti.2019.100516. This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of record. This version will undergo additional copyediting, typesetting and review before it is published in its final form, but we are providing this version to give early visibility of the article. Please note that, during the production process, errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

© 2019 Published by Elsevier B.V.

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Sorption of Chlorpyrifos onto Zinc Oxide Nanoparticles Impregnated Pea Peels (Pisum Sativum L): Equilibrium, Kinetic and Thermodynamic studies Atta ul Haq1*, Muhammad Saeed1, Muhammad Usman1, Syed Ali Raza Naqvi1, Tanveer

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Hussain Bokhari1, Tahir Maqbool1, Haroon Ghaus1, Tayyab Tahir1, Huma Khalid1

Department of Chemistry, Government College University Faisalabad, Pakistan

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Abstract

This study was focused on the sorption of chlorpyrifos from aqueous media utilizing synthesized zinc oxide nanoparticles impregnated Pea peels (ZnONPs-IPPs) in batch mode under the impact of pH of solution, dosage of sorbent, time of contact, temperature and initial pesticide concentration. The prepared composite was characterized by SEM, EDX, Surface area pore size

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analyzer and FTIR before and after sorption of chlorpyrifos. It was observed that the sorption of chlorpyrifos depends upon pH and maximal sorption (56%) was occurred at pH 2. The data of sorption process were fitted into Freundlich, Langmuir, Temkin and Dubinin–Radushkevich (DR) isotherm models and the results indicate that Temkin isotherm is a suitable choice to describe the data owing to higher R2 value (0.99). Monolayer sorption capacity of ZnONPs-IPPs for chlorpyrifos of the Langmuir isotherm was found to be 47.846 mg g-1. Kinetics of sorption were described by fitting data into pseudo-1st-order, pseudo-2nd-order, Elovich, intraparticle and liquid

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film diffusion models and the results showed that pseudo-2nd order interprets the data well owing to the higher R2 (0.99) well as the close agreement between the calculated and experimental

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sorption capacity. Thermodynamic parameters (ΔG° is negative and ΔH° is positive) imply that sorption process of chlorpyrifos utilizing ZnONPs-IPPs is spontaneous and endothermic in nature.

The prepared composite is an economical and eco-friendly biomass and may be efficiently used for the removal of other pollutants.

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Keywords: Chlorpyrifos; pea peels; zinc oxide; kinetics; equilibrium; thermodynamics

  * Corresponding Author: [email protected], [email protected]

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1. Introduction Agriculture takes place a vital role in worldwide economy; as a result the use of pesticides in agriculture to control the pest is common for maximum production (Gupta and Saleh 2013; Saravanan et al., 2015a; Saravanan et al., 2015b;

Saravanan et al., 2015c). However, the

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incorporation of these chemicals into the water bodies by point source contamination or diffusion results in negative effect on ecosystems (Alharbi et al., 2018; Ali et al., 2017; Ali et al., 2013; Basheer, 2018a; Basheer and Ali, 2018; Basheer, 2018b; Ali, 2012). These chemicals cause

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adverse effects such as totipotency in human beings, blocks the absorption of those nutrients which are necessary for normal growth and strong disrupting carcinogens for endocrine system (Abou-Donia, 2003; Mikes el al., 2009; Ali et al., 2019a; Ali et al., 2019b; Gupta and Ali, 2002). Chlorpyrifos belong to organophosphate insecticides whose chemical formula is O,O-diethyl-O3,5,6-trichloro-2-pyridyl phosphorothionate and extensively utilized throughout the world for the

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control of domestic and urban pest such as turf (Reddy et al., 2015). Its residues may present in different environmental matrices include soil, air, crops and its product and water due to its use in crops and non-crops. It is not soluble in aqueous media owing to persistent recalcitrant. However, it causes secondary pollution problems which are soluble in water (Baskaran et al., 2003; Sinclair et al., 2006). It also inhibits the function of acetyl cholinesterase, a significant enzyme for activities of neuromuscular system of insects and humans (Reddy et al., 2015). There

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is no regularity standard for Chlorpyrifos in water for drinking purpose as indicates by the roles of Environmental Protection Agency of US. However, a drinking water recommendation of 2 μg L-1 has been established while World Health Organization has established a maximal residue

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limit of 0.05 μg L-1 (Pareshkumar et al., 2017). Its persistency in the environment makes Chlorpyrifos very harmful for both human and other living organisms (Gupta et al., 2002). Its constant use causes various diseases such as cancer, disorder of neurobehavioral, disorder sensation reaction mainly of the skin and infertility (Andersen et al., 2006; Murray et al., 2005). In the last few decades, several scientists applied various methods to remove pesticides like

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ozonation (Maldonado et al., 2006), advanced oxidation processes (Zhou et al., 2011), Photocatalytic degradation (Ugurlu and Karaoglu, 2011; Gong et al., 2011), aerobic degradation (Murthy and Manonmani, 2007), ultrasound combined with photo-Fenton treatment (Katsumata et al., 2011), electrodialysis membranes (Banasiak et al., 2011) and biosorption (Al-Muhtaseb et al., 2011; Gupta et al., 2016). However, among these methods biosorption received more

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attention due to economical, effectiveness and eco-friendliness (Ahmad et al., 2009; Burakova et al., 2018; Ali et al., 2014; Ali and Jain, 2004; Ali et al., 2015; Ali et al., 2012; Ali et al., 2016a; Ali et al., 2017; Ali et al., 2002; Ali et al., 2016b; Ali et al., 2016c; Ali et al., 2018a;). Biosorption based on the uses of biological materials to remove contaminants from water

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samples (Nodeh et al., 2016; Ali, 2018; Ali el al., 2018b; Ali el al., 2018c; Ali el al., 2018d; Ali el al., 2019; ALOthman et al., 2019; Ali el al., 2016d). In the past, several sorbents have been tested for the removal of pesticides like bark (Boudesocque et al., 2008), bagasse fly ash (Traub-

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Eberhard et al., 1995), charcoal from agro waste (Sudhakar and Dikshit, 1999), straw (Akhtar et al., 2007), coal fly ash (Singh, 2009), lignocellulosic substrate from agro industry (Bakouri et al., 2009) and activated carbon (Ohno et al., 2008; Castro et al., 2009).

Naturally occurring biosorbents are highly soft due to which they are easily agglomerate in aqueous solution. As a result, the availability of their active sites for binding of contaminants is

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decreased. Moreover, the physical support is also necessary for biosorbents to enhance the accessibility of sorption sites for contaminants (Boddu et al., 2003; Gupta et al. 2015; Saleh and Gupta, 2014). Therefore, it has been recognized to improve the sorption ability by further modification of biosorbents. Several attempts have been carried out for the aforesaid reason for enhancement of the sorption ability of biosorbents (Asfaram et al., 2015; Gupta el al. 2013; Khan el al., 2017; Gupta el al. 2014a; Guibal et al., 1999; Kawamura et al., 1993; Rorrer et al., 1993;

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Hsein and Rorrer, 1995; Yang and Yuan, 2001; Tan et al., 1999; De-Dantas et al., 2001; Tianwei et al., 2001). However, the impregnation of biosorbents with metal oxides is one of the most effective one due the unique features of metal oxides like small size and large surface area

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(Saravanan et al., 2014a; Saravanan et al., 2013a; Saravanan et al., 2013b;). Moreover, the metal oxides improve the performance of polymeric materials such as increase the hardiness and stiffness and hence increase the service life of polymeric materials (Rahmanifar and Dehaghi, 2014; Saravanan et al., 2013c; Cestari et al., 2008). Therefore, an effort was made to prepare pea peels impregnated with zinc oxide nanoparticles for

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the removal of chlorpyrifos pesticide from watery media (Saravanan et al., 2014b; Saravanan et al., 2016; Saravanan et al., 2013d; Saravanan et al., 2013e; Saravanan et al., 2013f; Saravanan et al., 2013g; Saravanan et al., 2013h). The removal study was performed under the influence of solution pH, dosage of sorbent, temperature, time of contact and initial pesticide concentration to achieve optimum conditions for the removal of chlorpyrifos.

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2. Materials and Methods 2.1. Preparation of standard solutions of chlorpyrifos Standard solutions of chlorpyrifos were prepared by dissolving appropriate amount (0.25 mL) of chlorpyrifos (40%) in isopropanol: water (30:70) mixture. Dilute solutions were then prepared

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from the stock solution in 100 mL volumetric flasks with the same solvent mixture by dilution formula. 2.2. Collection of pea peels

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A huge amount of pea peels was collected from hotels nearer to the University in Jinnah colony, Faisalabad city. First, the peels were washed completely with tap water to get rid from dirty materials and finally washed with distilled water. After complete washing of the peels these were kept in sun light for several days for drying. The dried materials were then ground in an electric 2.3. Preparation of ZnONPs-IPPs

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grinder to convert the pea peels into powder and sieved to separate large particle. A specific amount of zinc oxide (usually 0.75 g) was dissolved in 1% CH3COOH (100 mL) and 65% of HNO3 (10 mL) in a beaker. A particular amount of pea peels powder (1.0 g) was then transferred into the beaker and contents of the beaker was sonicated for 30 min. After sonication, sodium hydroxide solution of I.0 M was added drop wise till the pH reached up to 10 and kept for three hours in water bath at 60 ⁰C. The suspension was filtered and washed numerous times

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using distilled water. These materials were then died for one hour at 50 ⁰C in an oven. After drying the materials were ground and stored for further study (Dehaghi et al., 2014). 2.4. Sorption study

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Sorption studies of chlorpyrifos from aqueous media onto ZnONPs-IPPs were performed in batch system. The sorption experiments were conducted by taking 20 mL chlorpyrifos of certain concentration (10-60 mg L-1), fixed dosage of sorbent (0.01-0.06 g) and initial solution pH (2.08.0) in an Erlenmeyer flask and agitated in an orbital shaker (150 rpm) for desirable time of contact (10-80 min) at a temperature range of 298-323 K. After completion of agitation duration,

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the filtered residual amount of chlorpyrifos was determined at 290 nm using UV/Visible spectrophotometer.

The following formulae were used to calculate the amount of chlorpyrifos sorbed onto per gram of ZnONPs-IPPs and the percent sorption of the chlorpyrifos. 𝑞

𝑉

(1)

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𝑆𝑜𝑟𝑝𝑡𝑖𝑜𝑛 %

100

(2)

In the above formulae Co and Ce represent initial and equilibrium concentration (μg mL-1), qe is the sorbed amount of pesticide (mg g-1) while solution volume (mL) and mass of sorbent are

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represented by “V” and “m” respectively. 2.5. Desorption study Desorption of the sorbate is necessary for the reuse of the sorbent for further study. Therefore,

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desorption of the loaded chlorpyrifos onto ZnONPs-IPPs was performed using NaOH of various concentrations (0.01 M, 0.1 M and 1.0 M) because at high pH the removal chlorpyrifos was minimum. In the desorption procedure, a particular amount of ZnONPs-IPPs loaded chlorpyrifos was taken in a beaker along with 50 mL of NaOH (0.01 M, 0.1M and 1.0 M) and stirred for 30 min. After completion of stirring the beaker content was filtered and the residual amount of

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chlorpyrifos was determined at 290 nm using UV/Visible spectrophotometer. 2.6. Characterizations of ZnONPs-IPPs

The prepared ZnONPs-IPPs composite was characterized before and after removal of chlorpyrifos using various techniques. The morphology of ZnONPs-IPPs was studied by the help scanning electron microscope (SEM-Model-JSM-5910, Japan JEOL) and Elemental analysis was performed using Energy Dispersive X-ray (EDX-INCA 200 Oxford Instruments UK). Surface analysis of ZnONPs-IPPs was carried out using Surface Area Pore Size Analyzer (Model

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NOVA2200e, Quantachrome, USA) and Fourier Transform Infrared spectrometer (Bruker ALPHA) was used for identification of functional groups of ZnONPs-IPPs. 3.1. Effect of pH

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3. Results and discussion

It has been reported in the literature that pH of solution affects the sorptive site, sorption mechanism and physiochemical interaction between sorbate and sorbent (Goyal et al., 2003; Aksu, 2002; Saleh and Gupta, 2011). Hence, the impact of pH on chlorpyrifos sorption was

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scrutinized from 2.0 to 8.0 with an initial concentration of 30 μg mL-1 of chlorpyrifos. Fig. 1 illustrates that the sorption is higher at low pH and then continuously declined with progress in pH. This outcome designates that sorption of chlorpyrifos was enhanced in the acidic medium and reduced in the basic medium. At low pH, protonation of the chlorpyrifos occurs owing to the presence of nitrogen atom in the molecule (Sheng et al., 2005; Saleh and Gupta 2012a). As a

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result, an electrostatic interaction was happened during sorption at low pH between protonated amino group of chlorpyrifos and negatively charges such as COO- and SO3- on surface of ZnONPs-IPPs (Dod et al., 2012; Al-Qodah et al., 2007). Hence, in acidic medium maximal sorption of chlorpyrifos was observed owing to the rest of the studies was performed in acidic

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medium. Fig. 1 3.2. Effect of dosage of ZnONPs-IPPs

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Most of the sorption studies revealed that dosage of sorbent affects sorption capacity of sorbent for a particular initial sorbate concentration (Gupta et al., 2012). For this reason, the sorption of chlorpyrifos was investigated regarding the influence of dosage of ZnONPs-IPPs by changing dose of ZnONPs-IPPs from 0.01 to 0.06 g while rest of the parameters were kept fixed. It may be depicted from Fig. 2 that the percent sorption of chlorpyrifos increased from 41% to 64% as the

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amount of ZnONPs-IPPs dose was increased. The figure also revealed that the sorption of chlorpyrifos was increased up to 0.03 g and then no appreciable change was observed. Such result indicates that availability of sorptive sites was increasing with increase in sorbent dose. Consequently, an increase in percent sorption of chlorpyrifos was observed in the initial stage (Pourata et al., 2009). At high sorbent dose, no appreciable change in sorption was noted due to increase in sorbent-sorbent interaction. However, the sorption capacity was decreased with

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addition of sorbent dose as demonstrated by the figure. This may be due the unsaturation of the sorbent sites for a particular amount of the chlorpyrifos and aggregation of the sorbent particles takes place at higher dose which results in net decline in the total surface area (Wagner et al.,

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2012). In view of the fact that maximum sorption of chlorpyrifos was observed at 0.03 g of ZnONPs-IPPs and further study was performed at this dosage of sorbent. Fig. 2

3.3. Effect of contact time

Sorption phenomenon significantly depends upon the contact time. Therefore, to scrutinize the

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dependency of sorption of chlorpyrifos on time, the contact time was changed from 10 to 80 min with an initial concentration of chlorpyrifos of 30 ppm and stirring speed of 150 rpm at room temperature. The result is depicted in Fig. 3 which demonstrates that the sorption of chlorpyrifos onto ZnONPs-IPPs was increased with stirring time up to 30 min. Nevertheless, after 30 min, no appreciable increase in sorption was observed means that the sorption sites were occupied and no

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further sorption was observed. Such finding reflects that initially more sites are available for the interaction of sorbate molecules to the sorptive sites but after saturation of these sites no prominent change in sorption was observed (Abdelhady, 2012). Fig. 3

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3.4. Effect of initial concentration of chlorpyrifos The influence of initial chlorpyrifos concentration on the sorption of chlorpyrifos onto ZnONPsIPPs was explored by changing the initial concentration from 10 to 60 μg mL-1 while rest of the

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factors was kept constant. Fig. 4 represents the sorption percentage and sorption capacity of chlorpyrifos versus initial concentrations of chlorpyrifos which depicts that percent sorption of chlorpyrifos was decreased with progress in initial concentration of the chlorpyrifos. Such findings indicate that at low initial concentration of chlorpyrifos, ratio of chlorpyrifos to the sites onto ZnONPs-IPPs was high and a large amount of the chlorpyrifos molecules undergo a better

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interaction with sorptive sites of ZnONPs-IPPs which results in higher sorption of pesticide. However, the sorption process was declined with the progress in initial concentration of pesticide. Perhaps such result can be owing to saturation of sorptive sites on ZnONPs-IPPs as concentration of chlorpyrifos was increased (Rangabhashiyam et al., 2018). Conversely, as the initial chlorpyrifos concentration was increased the sorption capacity was also enhanced as depicted in figure. Such results indicate that initially, the number of pesticide molecules as

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compare to sorption sites on sorbent was low which leads to small sorption capacity. However, with each increment in initial concentration the number of pesticide molecules as compare to al., 2018).

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sorptive sites was increased due to which an increase in sorption capacity was observed (Jin et Fig. 4

3.5. Effect of Temperature

Sorption of chlorpyrifos onto ZnONPs-IPPs was studied under the influence of temperature by changing temperature from 303 to 323 K while kept all other parameters constant. The result of

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this parameter is depicted in Fig. 5 which shows that the sorption of chlorpyrifos onto ZnONPsIPPs was decreased with progress in temperature. Such tendency may be owing to modification of sorption sites responsible for the sorption onto ZnONPs-IPPs due to which an obvious decrease in sorption took place with increasing the temperature ( Golie and Upadhyayula, 2017). Thickness of the boundary layer was reduced with increase temperature owing to which the

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escaping tendency of chlorpyrifos from the surface of ZnONPs-IPPs occurred (Polipalli and Pulipati, 2013). As a result the sorption of chlorpyrifos onto ZnONPs-IPPs was decreased with increasing the temperature. Fig. 5

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3.6. Sorption isotherm studies To explore the interaction between the sorbate and sorbent, sorption isotherms are used which provide a relationship between amount of sorbate in liquid phase under equilibrium and sorption

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capacity at constant temperature. The applicability of the sorption process can be evaluated from the fundamental physiochemical data obtained by applying sorption isotherm models (Mohammadi et al. 2011). Significant information about the surface properties of sorbent, affinities of sorbent toward sorbate, nature of sorption and the sorption capacity of sorbent may be obtained from the values of constant parameters which are the characteristics of each isotherm

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(Rangabhashiyam et al., 2014). In the present study various isotherms like Dubinin– Radushkevich (DR), Freundlich, Langmuir and Temkin and were applied to understand the nature of sorptive process of chlorpyrifos onto ZnONPs-IPPs. 3.6.1. Freundlich isotherm

This isotherm represents sorption on heterogeneous surfaces and suggests multilayer sorption process (Mittal et al., 2010). This isotherm may be expressed as: 𝑙𝑜𝑔𝐾

𝑙𝑜𝑔𝐶

(3)

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𝑙𝑜𝑔𝑞

Where qe (mg g-1) stand for sorption capacity, KF (mg g-1) indicates relative sorption capacity while n represents affinity between sorbate molecules and sorbent. Usually, the magnitude of n

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for physical sorption is greater than one while for chemical sorption its magnitude is less than one (Donmez and Aksu, 2002).

These parameters were calculated from above equation and summarized in Table 1. It is obvious from this table that n is greater than one which suggests that sorption of chlorpyrifos onto

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ZnONPs-IPPs is favorable and physical in nature. 3.6.2. Langmuir isotherm According to this isotherm a monolayer sorption takes place on a homogeneous surface and there is no interaction among the sorbate molecules (Haddad et al., 2014; Gupta et al., 2011). This isotherm is given as: 𝐶

(4)

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Where Q0 and KL are the constant parameters indicate the sorption capacity (mg g-1) and sorption rate (L mg-1) respectively. Langmuir isotherm may be demonstrated in one of the most important factor known as dimensionless constant also called separation factor (RL) which can be represented in the

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following equation: 𝑅

(5)

In the above equation KL (L mg-1) represents Langmuir constant while C0 (μg mL-1) stand for

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initial chlorpyrifos concentration. The magnitude of RL between 0 and 1 indicates favorable sorption, while greater than one represents unfavorable sorption. Likewise, the linear sorption is reflected if the magnitude of RL is equal to one and irreversible sorption process is indicated by RL value equal to zero (Rangabhashiyam et al., 2018). The values of separation factor lie chlorpyrifos onto ZnONPs-IPPs.

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between 0 and 1 as shown in Fig. 6 suggesting the favorability of the sorption process of Fig. 6

3.6.3. Dubinin–Radushkevich (D-R) isotherm

This isotherm demonstrates mechanism of sorption that either this process occurs physically or chemically (Tural et al., 2017). This model is expressed in the following equation: 𝑙𝑛𝑞

𝑙𝑛𝑄

𝐾𝜀

(6)

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In the above equation Qm represents maximum sorption capacity (mg g-1), K denotes DR constant which is associated with mean sorption free energy (mol2 J-2) and ε represents Polanyi

𝜀

𝑅𝑇𝑙𝑛 1

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potential. The magnitude of ε was evaluated employing the following equation: (7)

The energy needed to transport one mole of sorbate molecule from the bulk solution to sorbent surface is known as mean sorption free energy (E). The relationship between mean sorption free

𝐸

√

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energy and the DR constant (K) can be represented as: (8)

The magnitude of E is one of the most informative parameter regarding the nature and mechanism of sorption process. If the sorption occurs physically then E is less than 8 kJ mol-1 and E is greater 16 kJ mol-1 then sorption occurs chemically (Suganya et al., 2016). 3.6.4. Temkin isotherm

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This model explains sorbent-sorbate interaction and assumes a linear reduction of sorption heat with respect to temperature not logarithmically. This isotherm also considers that sorption free energy is a function of coverage of the surface (Srivastava et al., 2015; Gupta and Bhattacharyya, 2006). This isotherm can be represented in the following equation: 𝑅𝑇𝑙𝑛𝐾

𝑙𝑛𝐶

(9)

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𝑞

In the above equation R represents universal gas constant, T denotes temperature, bT (Jmol-1) is associated with heat of sorption and KT (Lg-1) represents Temkin constant (Salem and Awwad,

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2014).

The constant factors of each isotherm were evaluated from the slope and intercept of their respective linear plots and listed in Table 1. It is obvious from this table that R2 value of Temkin isotherm is higher (R2 > 0.99) from other isotherms, suggesting that sorption data of chlorpyrifos

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onto ZnONPs-IPPs well fitted into Temkin isotherm. Monolayer sorption capacity of ZnONPsIPPs for chlorpyrifos of the Langmuir isotherm was found to be 47.846 mg g-1. The sorption capacity of ZnONPs-IPPs was compared to other sorbents used for removal of pesticides as shown in Table 2. This table illustrates that sorption capacity of ZnONPs-IPPs is comparable with other sorbents which indicates the significance of ZnONPs-IPPs as a sorbent. The value of E was obtained from the DR isotherm (0.353 kJmol-1) which indicates that sorption of chlorpyrifos onto ZnONPs-IPPs is physical in nature.

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Isotherm

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Table 1 Comparison of isotherm constant parameters for sorption of chlorpyrifos onto ZnONPsIPPs

Freundlich

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Langmuir

Temkin

Parameter

Values

KF, mg g-1

2.504

n

1.400

R2

0.9808

K1, L mg-1

0.040

Qo, mg g-1

47.846

R2

0.9869

KT, L g-1

0.972

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261.93

R2

0.9923

Qm, mg g-1

20.926

K

4 x 10-6

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Dubinin-Radushkevich

bT, Jmol-1

E, kJ mol-1

0.353

R2

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0.8939

Table 2 Comparison of the sorption capacities of various sorbents with ZnONPs-IPPs Sorbent

Pesticide

Sorption

capacity Reference

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(mg g-1) Nanocellulose

Chlorpyrifos 12.325

Pareshkumar et al., 2017

Pumpkin seeds shell

Atrazine

74.62

Haq et al., 2019

Banana peels

Metribuzin

167

Haq et al., 2015

Pistia strationtes biomass

Carbaryl

3.1

Chattoraj et al., 2014

Cantaloupe seed shell

Butachlor

142.857

Haq et al., 2018

powder

Zinc oxide nanoparticles

Chlorpyrifos 47.846

In the present study

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impregnated Pea peels

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powder

3.7. Sorption kinetic studies

Sorption kinetics gives information that whether it occurs through diffusion, mass transfer or chemical reaction. These studies explain the uptake of sorbate onto sorbent, which successively controls time takes by sorbate at the interface between sorbent and bulk solution

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(Rangabhashiyam et al., 2018; Ncibi, 2008). To obtain all such information the sorption chlorpyrifos onto ZnONPs-IPPs data were analyzed by Elovich, intraparticle diffusion, liquid film diffusion, and pseudo-1st and pseudo-2nd kinetic models. 3.7.1. Pseudo-first order

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This model describes a relationship between sorption rate and equilibrium time (Taşar et al., 2014; Gupta et al. 2014b). This model may be exhibited in the following equation: 𝑙𝑜𝑔 𝑞 𝑞

𝑙𝑜𝑔𝑞

.

𝑡

(10)

In the above equation K1 (min-1) is the rate constant, qt and qe denote the sorption capacities (mg

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g-1) at particular and equilibrium time respectively. 3.7.2. Pseudo-second order

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According to this model, sorption behavior is controlled by chemisorption process occur either electronic sharing or electronic exchange (Liu et al., 2018; Ghaedi et al., 2015). This model is represented by the following equation:

(11)

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In the above equation K2 (g mg-1 min-1) is the rate constant for pseudo-2nd order model, qt and qe denote the sorption capacities (mg g-1) at certain and equilibrium time respectively. 3.7.3. Intraparticle diffusion model

The sorption process occurs through various steps; first, sorbate molecules transfer from bulk solution to outer surface of sorbent, second, sorbate molecules transfer from the outer surface into the inner sites of sorbent and finally, sorption of sorbate molecules occurs on the inner surface (Fatih and Saadet, 2010). According to the Morris and Weber, a plot of sorption capacity

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versus t0.5 should produce a straight line having zero intercept if rate determining is intraparticle diffusion (Ofomaja, 2010). This model may be exhibited in the following equation: 𝐾 𝑡

.

𝐶

(12)

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𝑞

Where C (mg g-1) is the boundary layer thickness and Kid (mgg-1min1/2) denotes the rate constant for intraparticle diffusion model. It is obvious from Table 3 that intercept of this model is not one which implying that sorption of chlorpyrifos using ZnONPs-IPPs was not totally controlled by

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the intraparticle diffusion but some other mechanisms are involved in the process. 3.7.4. Elovich model

This model describes the kinetics of chemisorption onto a surface having heterogeneous sites (Deniz and Karabulut, 2017). This model can be demonstrated as: 𝑞

𝑙𝑛 𝛼𝛽

𝑙𝑛 𝑡

(13)

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In the above equation α (mg g-1 min-1) denotes initial sorption rate while β (g mg-1) represents Elovich constant and associated to degree surface coverage. 3.7.5. Liquid film diffusion During sorption process different steps are involved but this model is applicable to the step al., 2006). This model is represented in following equation: 𝑙𝑛 1

𝐹

𝐾

𝑡

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occurring through transportation of sorbate from liquid phase to solid phase boundary (Gupta et (14)

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Where Kfd denotes the rate constant and F is known as fractional attainment of equilibrium. The value of F is numerically equal to qt/qe.

Sorption kinetics of chlorpyrifos would be controlled by diffusion of sorbate molecules across the liquid film formed around the ZnONPs-IPPs if the plot of –ln(1-F) against time is linear

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having zero intercept (Khan et al., 2015). However, in our study the intercept is not zero which suggest that this model is not merely controlled the kinetics of the sorption of chlorpyrifos onto ZnONPs-IPPs but there are the possibilities of the involvement of some other mechanisms. The slope and intercept of each kinetic model was utilized to calculate the values of constant parameters and listed in Table 3. This table depicts that R2 (R2 = 0.99) value of pseudo-2nd- order model is higher than the rest of other models suggesting that sorption of chlorpyrifos onto ZnONPs-IPPs may be interpreted well by pseudo-2nd-order kinetic model. Furthermore, there is a

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close agreement between experimental and calculated qe values which indicates a confirmation of the appropriateness of kinetic data in to pseudo-2nd-order kinetic model.

Model

Parameter

Values

Pseudo-1st-order

qe, mg g-1, (exp)

25.521

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IPPs

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Table 3 Comparison of the kinetic parameters for the sorption of Chlorpyrifos onto ZnONPs-

qe, mg g-1, (cal)

7.308

K1, min-1

0.025

R2

0.9871

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Intraparticle diffusion

K2, g mg-1min-1

0.014

qe, mg g-1

26.385

R2

0.9999

Kid, mg g-1 sec1/2

0.781

C

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R2

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Pseudo-2nd- order

Liquid film diffusion

0.7896

α, mg g-1 min-1

1916.009

β, g mg-1

0.425

R2

0.8961

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Elovich

19.253

Kfd, min-1

0.003

Intercept

0.181

R2

0.6806

3.8. Sorption thermodynamic studies

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Thermodynamics of the sorption of chlorpyrifos onto ZnONPs-IPPs were investigated by evaluating enthalpy (ΔH⁰), entropy (ΔS⁰) and Gibbs free energy (ΔG⁰). The following equations 𝐾 𝑅𝑇𝑙𝑛𝐾

𝑙𝑛𝐾

∆ °

∆ °

(15) (16) (17)

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∆𝐺°

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were used to calculate these parameters:

In the above equations KD represents equilibrium constant, Ce denotes equilibrium concentration of chlorpyrifos (mg L-1), qe expresses the sorption capacity at equilibrium (mg g-1), T (K) is the temperature and R is the universal gas constant. Magnitudes of enthalpy and entropy were calculated from slope and intercept of the plot lnKD versus 1/T and listed in Table 4. This table

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showed that ΔH⁰ is positive which suggests that the sorption of chlorpyrifos onto ZnONPs-IPPs is endothermic process (Ahmaruzzaman and Gupta, 2011; Martín-Lara et al., 2017). The randomness and disorder at solid solution interface of chlorpyrifos with ZnONPs-IPPs was increased as suggested by the positive ΔS⁰ that result in various structural variations in

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chlorpyrifos and ZnONPs-IPPs. The favorability and spontaneity of the sorption process of chlorpyrifos onto ZnONPs-IPPs was confirmed from the negative values of Gibb’s free energy.

-ΔG⁰ (kJmol-1)

303

0.198

308

0.612

313

0.682

ΔH⁰ (kJmol-1)

ΔS⁰ (kJmol-1 K-1)

12.047

0.053

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Temperature (K)

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Table 4 Thermodynamic parameters for the sorption of Chlorpyrifos onto ZnONPs-IPPs

318

0.630

323

0.527

3.9. Desorption study Desorption data of chlorpyrifos onto ZnONPs-IPPs were listed in Table 5 which demonstrates

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that chlorpyrifos is not completely desorbed in the first cycle and only 23% of the retained chlorpyrifos was recovered with 0.01 M NaOH solution. It also be demonstrated from the table that desorption of chlorpyrifos was enhanced with increasing the concentration of NaOH and

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maximum desorption (45%) was achieved with 1.0 M of NaOH solution.

Table 5 Desorption of chlorpyrifos after adsorption onto ZnONPs-IPPs

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Concentration of NaOH (M)

Desorption (%)

0.01

23.25

0.1

34.65

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1.0

45.75

3.10. Characterizations of ZnONPs-IPPs The composite material prepared in the study was characterized using the following well known

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techniques to strengthen the results. 3.10.1. SEM analysis

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To identify and locate the presence of sorbate molecules on sorbent surface, the SEM technique was applied before and after sorption studies (Xu et al., 2018; Saleh and Gupta, 2012b). The SEM of the raw material (pea peels powders) before impregnation of ZnO is somewhat smooth and regular as illustrated in Fig. 7a. However, the texture of the material become very rough and contains several pores that indicated adequate surface area as depicted in Fig. 7b. These features

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could help for the penetration of chlorpyrifos molecules into ZnONPs-IPPs and consequently could enhance the sorption process. As illustrated in the Fig. 7c, the pores and roughness of the surface of ZnONPs-IPPs after sorption of chlorpyrifos become filled and somewhat smooth indicating the sorption of chlorpyrifos onto ZnONPs-IPPs. 3.10.2. EDX analysis

EDX was utilized for the analysis of any variation in element levels of the sorbent before and after sorption of chlorpyrifos. It can be seen from the Fig. 7d that Zn absent but the Zn was

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present after impregnation of the pea peels as illustrated in Fig. 7e. As depicted in Fig. 7f, the EDX spectrum consists of phosphorus (P) after sorption of chlorpyrifos which indicates the phosphorus.

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sorption of chlorpyrifos onto ZnONPs-IPPs because the chlorpyrifos molecule contains Fig. 7

3.10.3. Surface area analysis

It has been proved that surface area of sorbent greatly affects the removal ability of sorbent.

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Therefore, the surface analysis of the ZnONPs-IPPs before and after removal of chlorpyrifos was carried out using nitrogen adsorption isotherm. These results are listed in Table 6 which shows that surface area of ZnONPs-IPPs was found to be decreased indicating the removal of chlorpyrifos from aqueous solution (Lizano-Fallas et al. 2017). Table 6 Surface analysis data of ZnONPs-IPPs

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Before removal of

After removal of

Chlorpyrifos

Chlorpyrifos

Surface area (m2 g-1)

305.50

285.65

Pore radius (Å)

30.23

Pore volume (mL g-1)

0.215

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Parameter

31.35

p ro

0.201

3.10.4. FTIR analysis

The sorbent derived from plants usually consists of various functional groups which play a vital

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role in the sorption process. Therefore, the FTIR analysis of the raw material and composite was performed before and after sorption of Chlorpyrifos onto ZnONPs-IPPs. The spectra consist of various peaks which were assigned to particular groups according to their wavenumbers as mentioned in literature. Fig. 8 (A) composed of broad band at 3270 cm-1 which may be assigned to O‐H group and usually present in polymeric compounds. The absorption band appeared at 2918 cm-1 was assigned to C‐H symmetric or asymmetric stretching aliphatic acids. Another peak at 1626 cm-1 indicated the presence of C=O group in the raw material. This peak shifted to

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lower frequency i.e. 1589 with significant decrease in intensity indicating a strong interaction of raw material with ZnO nanoparticles. While peak at 1243 cm-1 may be assigned to stretching

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vibration of C-OH alcoholic and carboxylic groups (Iqbal et al., 2009; Devaraj et al., 2016). As illustrated in Fig. 8 (B) the broad and sharp peaks on the raw material showed a significant change in wavenumbers and most of these peaks shifted to lower wavenumbers on the ZnONPsIPPs composite which indicates the attachment of ZnO to the pea peels (Dehaghi et al., 2014; Xu et al., 2018). Similarly, after sorption of chlorpyrifos onto ZnONPs-IPPs somewhat changes

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in the intensities of various peaks were observed as depicted in Fig. 8 (C) which confirms sorption of Chlorpyrifos onto ZnONPs-IPPs (Dirbaz and Roosta, 2018). Fig. 8

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4. Conclusions The present study demonstrated synthesized zinc oxide nanoparticles impregnated Pea peels (ZnONPs-IPPs) have the ability to remove the chlorpyrifos from aqueous solution successfully. Characterizations of the prepared composite by SEM, EDX, Surface area pore size analyzer and

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FTIR revealed the occurrence of the sorption of chlorpyrifos. The pH study revealed that sorption of chlorpyrifos significantly based on solution pH and maximal sorption was acquired at pH 2. The isotherms study exhibited that Temkin model is an appropriate option to describe the

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data owing to higher R2 (0.99). Monolayer sorption capacity of ZnONPs-IPPs for chlorpyrifos of the Langmuir model was found to be 47.846 mg g-1. Similarly, kinetic study affirmed that the data well interpreted by pseudo-2nd order kinetic model due to higher R2 (0.99) value and also the nearness of calculated and experimental sorption capacity values. Thermodynamic study demonstrated that sorption of Chlorpyrifos onto ZnONPs-IPPs from aqueous solution is Acknowledgement

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spontaneous and endothermic process.

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The authors highly acknowledge the support of Higher Education Commission Pakistan.

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Figure Captions Fig. 1 The effect of pH on % sorption of chlorpyrifos onto ZnONPs-IPPs, initial conc. of chlorpyrifos is 30 ppm; contact time 60 min; volume of solution 25 mL; sorbent dose 0.03 g; pH range 2-8.

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Fig. 2 The effect of sorbent dose on % sorption of Chlorpyrifos onto ZnONPs-IPPs, initial conc. of chlorpyrifos is 30 ppm; contact time 60 min; volume of solution 25 mL; pH 2; sorbent dose range 0.01-0.6 g

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Fig. 3 The effect of contact time on % sorption of chlorpyrifos onto ZnONPs-IPPs, initial conc. of chlorpyrifos 30 μg mL-1; volume of solution 25 mL; pH 2; sorbent dose 0.03g; contact time range 10-80 min

Fig. 4 The effect of initial concentration of chlorpyrifos on % sorption of chlorpyrifos onto

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ZnONPs-IPPs, contact time 60 min; volume of solution 25 mL; pH 2; sorbent dose 0.03g; initial concentration range of chlorpyrifos 10-60 μg mL-1

Fig. 5 The effect of temperature on % sorption of Chlorpyrifos onto ZnONPs-IPPs, contact time 60 min; initial conc. of Chlorpyrifos 30 μg mL-1; volume of solution 25 mL; pH 2; sorbent dose 0.03g; temperature range 303-323 K

Fig. 6 The effect of initial chlorpyrifos concentration on dimensionless separation factor using ZnONPs-IPPs, contact time 60 min; volume of solution 25 mL; pH 2; sorbent dose 0.03g; initial

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concentration range of chlorpyrifos 10-60 μg mL-1 Fig. 7 (a) SEM micrograph of pea peels raw material, (b) SEM micrograph of ZnONPs-IPPs, (c) SEM micrograph of ZnONPs-IPPs after sorption of chlorpyrifos, (d) EDX of pea peels raw

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material, (e) EDX of ZnONPs-IPPs before sorption of chlorpyrifos, (f) EDX ZnONPs-IPPs after sorption of chlorpyrifos

Fig. 8 (A) FTIR spectrum of the pea peels (B) FTIR spectrum of the ZnONPs-IPPs before

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sorption of chlorpyrifos (C) FTIR spectrum of the ZnONPs-IPPs after sorption of chlorpyrifos

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Highlights

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ZnONPs-IPPs is a promising and efficient sorbent for the removal of chlorpyrifos from aqueous media

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Zinc Oxide Nanoparticles Impregnated Pea Peels (ZnONPs-IPPs) composite was prepared and used for the sorption of chlorpyrifos in batch system. The sorption data well fitted in to Temkin isotherm among various adsorption isotherm models. Pseudo-second- order kinetic model is the most suitable model to explain the kinetics of the sorption of chlorpyrifos Sorption of chlorpyrifos is spontaneous and endothermic process in nature.

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Conflict of Interests

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All the authors are agreed and there is no conflict of interest among the authors.