Advertisement

SN Applied Sciences

, 1:106 | Cite as

Removal of paraquat herbicide from water by textile coated with anionic cyclodextrin polymer

  • Jatupol Junthip
  • Numhom Jumrernsuk
  • Prapin Klongklaw
  • Warangkana Promma
  • Somchai Sonsupap
Research Article
  • 75 Downloads
Part of the following topical collections:
  1. 1. Chemistry (general)

Abstract

The coating of anionic cyclodextrin polymer on polyethylene terephthalate (PET) textile was achieved by crosslinking between β-cyclodextrin (β-CD) and citric acid (CTR) to adsorb paraquat herbicide from aqueous solution. This coating performance (30 min, 170 °C) was 22.18% of weight gain which was corresponded to 0.51 mmol/g of ion exchange capacity (IEC). Then, the samples were characterized by scanning electron microscopy (SEM), attenuated total reflection–Fourier transform infrared spectroscopy (ATR–FTIR) and thermogravimetric analysis (TGA). The appropriated pH was 6.5 and the equilibrium time was 420 min. At 30 °C, the adsorption capacity towards paraquat (PQ) was enhanced (4.5, 18.9 and 23.7 mg/g) when the initial concentration of paraquat was increased (10, 50 and 250 mg/L). The adsorption kinetics was fitted to the pseudo-second-order model and the adsorption isotherm was suitable to Langmuir model. For the thermodynamic studies, the negative ∆G° revealed a spontaneous process, the negative ∆H° showed an exothermic process and the positive ∆S° displayed an enhanced disorder. Finally, the reusability of functionalized textile in methanol was reached 78.6% after six regeneration cycles and the stability of sample in various solvents was also studied.

Graphical abstract

Anionic cyclodextrin polymer coated on PET textile issued from the crosslinking between β-cyclodextrin and citric acid was used as an efficient adsorbent for paraquat removal from aqueous solution.

Keywords

Paraquat Adsorption Cyclodextrin polymer Functional textile Water pollution 

1 Introduction

The use of pesticides in agriculture become more important because it is a rapid, efficient and easy way to reduce production costs and increase agricultural productivity. Moreover, the disadvantage of pesticides have resulted in contamination of ecosystem, accumulation of pesticides is harmful to biotic and abiotic components. Most of these chemical substances are toxic which are difficult to eliminate from the environment, especially contamination of water is a ubiquitous problem which requiring water treatment. Paraquat (PQ) is a non-selective herbicide classified in bipyridinium groups. PQ is a famously used pesticide in the world [1, 2] according to a low price, a high efficiency at low concentration and a minor accumulative effect on soil. Paraquat is employed in plantations (rice, sugar cane, coffee, beans and other crops) [3] as well as in defoliation (grass and weed) [4]. This agrochemical is very hydrosoluble (620 g/L of solubility in water at 25 °C) because of the presence of cationic charge on the molecule, which eradicates plants by interrupting photosynthesis [1]. Nevertheless, paraquat is very dangerous for health such as dermal exposure [5], respiratory failure [6], pulmonary fibrosis [7, 8], neurotoxicity [9], damage of digestive apparatus [1] and Parkinson’s disease [10, 11]. The paraquat amount of 35 mg/kg displays lethal dose for human being owing to European standards [12]. The paraquat concentration of 0.1 and 1–3 μg/L exhibits respectively the maximum permissible concentration for drinking water and for surface waters [13].

Recently, various wastewater treatment processes have been reported in the literature so as to eliminate paraquat contaminated in water such as physical methods (adsorption [14], filtration [15, 16] and ion-exchange [17, 18]), chemical methods (extraction [19], photocatalytic degradation [20, 21], oxidation [22, 23] and electrochemical process [24]) and biological method (fungi decomposition [25]). Among the methods mentioned above, the adsorption process demonstrates a simplicity of operation, a low-cost process and a high efficiency. Up to now, several adsorbents have been prepared to remove paraquat from aqueous solution: activated carbon [12] [26], biochar [27], membrane based on chitosan and alginate [16], activated bleaching earth [28], goethite [29, 30], clays [31], rice husk [32], phillipsite–faujasite tuff [33], bentonite [34], graphene oxide nanocomposite [35], multi-walled carbon nanotubes [36], silica [37, 38], faujasite zeolite [39], iron oxide coated quartz particles [40], pillararene based porous polymer [41] and magnetic hybrid nanosorbent [42].

Cyclodextrins (CD) are cyclic oligosaccharides produced from starch by enzyme cyclodextrin glucanotransferase (CGTase), which are composed of 6, 7 and 8 units of d-glucose linked by α-(1,4) glycosidic bonds (named α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin successively). The specific and well-defined structure like bowl-shaped displays a hydrophobic cavity and a hydrophilic exterior. This hydrophobic cavity provides encapsulation with suitable size and polarity of organic substances by the formation of inclusion complexes according to reversible host–guest interaction, especially inclusion with aromatic compounds. Cyclodextrin polymers are obtained from polymerization of native cyclodextrin to gain different structures which could give better encapsulation properties than pristine cyclodextrin. Moreover, the addition of charge on cyclodextrin or cyclodextrin polymers allows a good ionic interaction with the opposite charge of the guest molecule [43, 44]. Cyclodextrin and their derivatives have fascinated important attention as selective and greater efficiency for environmental applications [45, 46] so as to eliminate organic substances or heavy metal [47] such as organic substances [48, 49], volatile organic compounds [50, 51], dyes [52, 53] and pesticides [54, 55]). Anionic cyclodextrin polymer issued from crosslinking between β-cyclodextrin as a monomer and citric acid as a crosslinker was coated on the textile surface in order to remove organic substances [56] and heavy metals [57, 58] which were contaminated in water. Nowadays, this cation-exchange textile has never reported and used for PQ removal from aqueous solution.

In relevance of this work, we aimed to carry out adsorption efficiency of paraquat from water by textile coated with anionic cyclodextrin polymer using citric acid as a bridging agent with an environment-friendly process (Fig. 1). The effect of the initial concentration of paraquat, pH of the solution and adsorption temperature on the removal of paraquat were investigated. The appropriated models were chosen for adsorption kinetics and adsorption isotherm. Thermochemical studies were also operated at different temperatures. This adsorption technique could be an alternative way for wastewater treatment.
Fig. 1

Functionalization of textile with anionic cyclodextrin polymer for paraquat adsorption

2 Materials and methods

2.1 Materials

PET textile was kindly given by Luckytex (Thailand) Public Company Limited. β-CD (Acros organics), CTR monohydrate (RCI labscan), sodium bicarbonate (RCI labscan) sodium hypophosphite (CARLO ERBA Reagents) and paraquat dichloride hydrate (Sigma Aldrich) were gained from commercial sources. Other chemicals used in this work were analytical grade. Milli-Q ultrapure water was used for all experiments.

2.2 Functionalization and characterization of PET textile

PET textile was cut off (10 × 10 cm2), it was firstly washed with soxhlet apparatus (250 mL) using ethanol (1 h) and ultrapure water (2 h) before drying at 100 °C in hot air oven (UF10, Memmert). Cleaned textile was dipped into 100 mL of solution containing 10%w/v of β-CD, 10%w/v of CTR and 3%w/v sodium hypophosphite, then it was rolled on aluminum foil by homemade roller for both sides several times before curing at 170 °C during 30 min in hot air oven (UF10, Memmert). Finally, treated sample was washed again with soxhlet apparatus (250 mL) using ultrapure water (2 h) so as to eliminate unreacted products before drying at 100 °C in hot air oven (UF10, Memmert). Weight gain referring to coating yield was calculated according to this equation:
$$\% \;{\text{Weight}}\;{\text{gain}} = \frac{{{\text{m}}_{\text{f }} - {\text{m}}_{\text{i}} }}{{{\text{m}}_{\text{i}} }} \times 100$$
(1)
where mi and mf relate respectively to textile weight before and after curing. Experiments were carried out in triplicate.
Functionalized textile was quantified ion exchange capacity (IEC) by pH-metric titration using calcium acetate method [59]. Textile (0.5 g) cut in small pieces was dipped into 50 mL of calcium acetate solution (2% w/v) for 4 h under agitation at 150 rpm. Textile was removed and clear solution (production of acetic acid) was titrated by NaOH solution (0.05 M) employing phenolphthalein as an indicator. IEC value was expressed in mmol of COOH groups per gram of textile and it was obtained from the following equation:
$${\text{IEC}}\;({\text{mmol/g}}) = \frac{{{\text{C}}_{\text{NaOH}} \times {\text{V}}_{\text{NaOH}} }}{\text{m}} \times 100$$
(2)
where CNaOH and VNaOH correspond respectively to the concentration and equivalent volume of NaOH. The symbol m stands for sample weight. Experiments were performed in triplicate.

After that, functionalized textile was activated by soaking in 0.15 M of NaHCO3 for 30 min, washed with water until obtaining a neutral pH of the rinsed solution and dried at 100 °C. This activation step was realized so as to convert carboxylic groups into carboxylate form without polymer hydrolysis before using this activated textile in all adsorption experiments. Experiments were performed in triplicate.

TGA (Thermogravimetric analysis) experiments were performed in an alumina pan with Thermal Analyzer—STA 449 F3 (NETZSCH) from ambient to 500 °C with a heating rate of 10 °C/min under nitrogen gas.

ATR–FTIR (Attenuated total reflection–Fourier transform infrared spectroscopy) experiments were performed with Nicolet Nexus iS5 spectrometer (Thermo Scientific) which collected from 16 scans in 650–4000 cm−1 range with a resolution of 32 cm−1.

Samples were preliminarily coated with gold before SEM (Scanning Electron Microscopy) investigation on a JEOL 6010 electron microscope, operating with an acceleration voltage of 15 kV.

2.3 Adsorption experiment

Functionalized textile (0.1 g) was added into 50 mL of PQ solution (50 mg/L of initial concentration) with different pH from 2 to 10 under stirring at 150 rpm during 420 min at 30 °C. Solution pH was adjusted with 1 M NaOH and 1 M HCl. The measurement of PQ was investigated by GENESYS 10S UV–Vis spectrophotometer (Thermo Scientific) at 257 nm using the extinction coefficient (ε) of PQ in water which was 0.066 L mg−1 (with R2 = 0.9994). The adsorption capacity at time t (mg/g) was computed by the following equation:
$${\text{Q}}_{\text{t}} =\frac{{({\text{C}}_{0} - {\text{C}}_{\text{t}} ){\text{V}}}}{\text{m}}$$
(3)
where C0 and Ct relate successively to the initial and real-time concentration of PQ, V is solution volume and m is the weight of functionalized textile. Experiments were carried out in triplicate.

2.4 Adsorption kinetics

Functionalized textile (0.1 g) was put into 50 mL of PQ solution with 10 50 and 250 mg/L of initial concentration with optimal pH at different times (15, 30, 60, 180, 300, 420, 1440 min) under agitation (150 rpm and 30 °C). The quantification of PQ was previously mentioned in Sect. 2.3. Raw data was then fitted with two kinetics models:
$${\text{Pseudo-first-order model}}\quad \quad { \ln }\left( {{\text{Q}}_{{\rm e}} - {\text{Q}}_{{\rm t}} } \right) = { \ln }\;{\text{Q}}_{{\rm e}} {-}{\text{ k}}_{ 1} {\text{t}}$$
(4)
$${\text{Pseudo-second-order model}}\quad \quad \frac{\text{t}}{{{\text{Q}}_{{\rm t}} }} = \frac{ 1}{{{{\rm k}}_{ 2} {\text{Q}}_{{\rm e}}^{ 2} }} + \frac{ 1}{{{\text{Q}}_{{\rm e}} }}{\text{t}}$$
(5)
where Qe and Qt are the amounts of PQ adsorbed (in mg/g) at equilibrium and at time t respectively, k1 (1/min) and k2 (g/(mg min)) are adsorption rate constant and t is contact time (min).

2.5 Adsorption isotherm

Functionalized textile (0.1 g) was put into 50 mL of PQ solution with 10, 50 and 250 mg/L of initial concentration with optimal pH at equilibrium time under agitation (150 rpm and 30 °C). The quantification of PQ was previously mentioned in Sect. 2.3. Raw data was then fitted with two isotherm models:
$${\text{Langmuir isotherm}}\quad \quad \frac{{{{\text{C}}_{{\rm e}}} }}{{{\text{Q}}_{{\rm e}} }} = \frac{ 1}{{{\text{K}}_{{\rm L}} {\text{Q}}_{{\rm m}} }} + \frac{{{\text{C}}_{{\rm e}} }}{{{\text{Q}}_{{\rm e}} }}$$
(6)
$${\text{Freundlich}}\;{\text{isotherm}}\quad \quad {\text{ln Q}}_{{\rm e}} {\text{ = ln K}}_{{\rm F}} + \frac{1}{\text{n}}\ln {\text{C}}_{{\rm e}}$$
(7)
where Ce is the equilibrium concentration of PQ, Qe is the amount of PQ adsorbed (in mg/g) at equilibrium, Qm is the theoretical maximum adsorption capacity, KL is Langmuir isotherm constant, KF is Freundlich constant and 1/n is heterogeneity factor.
The same experiments as mentioned above were also performed at 40 °C and 50 °C in order to estimate thermodynamic parameters which indicated energy change in adsorption process according to the following equations:
$$\ln \frac{{{\text{Q}}_{\text{e}} }}{{{\text{C}}_{\text{e}} }} = \frac{{\Delta {\text{S}}^{ 0} }}{\text{R}} - \frac{{\Delta {\text{H}}^{ 0} }}{\text{RT}}\quad {\text{for}}\;{\text{determination}}\;{\text{of}}\; \, \Delta {\text{H}}^\circ \;{\text{ and}}\; \, \Delta {\text{S}}^\circ$$
(8)
$$\Delta {\text{G}}^\circ = \Delta {\text{H}}^\circ - {\text{T}}\Delta {\text{S}}^\circ \; {\text{for}}\;{\text{determination}}\;{\text{of}}\;\Delta {\text{G}}^\circ$$
(9)
where Ce is equilibrium concentration of PQ, Qe is amount of PQ adsorbed (in mg/g) at equilibrium, ΔH° is the standard enthalpy change in kJ/mol, ∆S° is the standard entropy change in J/K mol, ∆G° is the standard free energy change in kJ/mol, T is temperature in Kelvin and R is gas constant (8.3124 J/K mol).

2.6 Regeneration experiments

Functionalized textile (0.1 g) was placed into 50 mL of PQ solution (50 mg/L of initial concentration with optimal pH) at equilibrium time under agitation (150 rpm and 30 °C). The quantification of PQ was previously mentioned in Sect. 2.3. Then, the adsorbent was separated and regenerated by washing in different solvents such as methanol, water and 50%v/v of acetic acid for PQ desorption. After 420 min of soaking, the adsorbent was cleaned with ultrapure water and reconditioned for sorption in posterior cycles.

2.7 Adsorbent stability

The stability of functionalized textile was performed in different solvents used in the regeneration process such as methanol, water and 50%v/v of acetic acid. Modified textile (0.1 g) was placed into 50 mL of each solvent under agitation (150 rpm and 30 °C). At the desired time, this textile was removed, dried at 110 °C for 30 min and finally weighed. The percentage of weight loss was calculated using the following equation:
$$\% \;{\text{Weight}}\;{\text{loss}} = \frac{{{\text{m}}_{\text{f }} - {\text{m}}_{\text{d}} }}{{{\text{m}}_{\text{f}} }} \times 100$$
(10)
where mf and md relate respectively to functionalized textile weight and degraded textile weight. Experiments were carried out in triplicate. Then, this textile was put back in the fresh solvent with the previous process before recalculating the weight loss.

3 Results and discussion

3.1 Functionalization and characterization of adsorbent

The coating of anionic cyclodextrin polymer on PET textile surface was achieved by crosslinking between β-CD and CTR through esterification reaction in order to promote negative character on PET textile surface thanks to the presence of non-crosslinked carboxylic groups from CTR, which this thermofixation process was previously reported [58, 59]. Coating performance was measured by weight gain of polymer (22.18 wt%, S.D. = 0.89) and ionic exchange capacity (0.51 mmol/g, S.D. = 0.03). So, the loading amount of cyclodextrin polymer on the textile surface could be quantified by coating performance because the unreacted crosslinked polymer was previously removed after washing with soxhlet apparatus in order to ensure the presence of polymer on the textile surface.

As observed in Fig. 2a, the coating of anionic cyclodextrin polymer was assessed by FTIR spectroscopy with ATR mode which displayed functionalized textile comparing with untreated textile, pristine β-CD and CTR. PET textile spectra revealed the specific bands at 1709 cm−1 corresponding to C=O stretching of ester, at 2965 cm−1 assigning to C–H stretching of CH2, at 1623, 1573, 1503 and 1468 cm−1 attributing to stretching of benzene skeleton, at 1410 cm−1 ascribing to C–C stretching of phenyl ring, at 1336 cm−1 allocating to wagging vibration of CH2 and at 1236 and 1089 cm−1 mentioning to C-O asymmetric and symmetric of ester respectively. β-CD spectra showed the characteristic peaks at 3265 cm−1 corresponding to OH stretching, at 2910 cm−1 assigning to CH2 stretching, at 1151 cm−1 mentioning to C–C stretching and at 1021 cm−1 notifying to C–O–C stretching of the glycosidic bond. CTR spectra exhibited the peak of carboxylic groups at 1683–1732 cm−1 corresponding to C=O stretching and at 1012 cm−1 ascribing to C–O stretching. After surface modification, some absorption bands altered in the spectra of treated textile by polymer coating because of the presence of particular peaks of each component such as at 3500–3200 cm−1 ascribing to O–H stretching of residual hydroxyls of β-CD and at 1710 cm−1 corresponding to C=O stretching of textile, CTR or anionic polymer.
Fig. 2

ATR-FTIR spectra (a) and TGA thermograms (b) of virgin textile, β-CD, CTR and modified textile

Thermal stability and degradation profile of raw materials and modified textile were evaluated by TGA as illustrated in Fig. 2b. The first stage below 100 °C, the loss of mass was 13% and 3% for β-CD and modified textile respectively which indicated dehydration of materials. The second stage, thermal degradation began at 135, 260, 300 and 303 °C for CTR, modified textile, β-CD and untreated textile successively. Apparently, modified textile had two degradation steps as a virgin textile. Functionalized textile displayed a lower thermal stability at the temperature below 360 °C but a higher thermal stability at the temperature upper than 360 °C, compared with untreated textile. The final stage of degradation of each component was constantly seen due to a tardy decomposition of a residue which was thermally stable.

The yellow color of functionalized textile was remarked because of crosslinking with citric acid at high temperature which was different from PET virgin textile as seen in Fig. 3. The morphology of fibrous structure was observed with two magnifications. No difference could be distinguished for untreated textile (Fig. 3a) and functionalized (Fig. 3b) at 100 × magnification. However, the coating of polymer on the textile surface was clearly seen at 2000 × magnification as rough surface thanks to deposition of anionic polymer, comparing with virgin textile which exhibited smooth surface.
Fig. 3

Pictures and SEM images of virgin textile (a) and functionalized textile (b) with two magnifications (× 100 resolution with 100 μm of full scale and × 2000 resolution with 10 μm of full scale)

3.2 pH optimization of paraquat adsorption onto the modified textile

Preliminary studies also displayed that the adsorption of PQ on non-modified textile was negligible in all experimental conditions because the maximum adsorption capacity of virgin textile reached only 0.04 (S.D. = 0.02), 0.23 (S.D. = 0.05) and 0.56 (S.D. = 0.09) respectively for these initial concentrations of PQ (10, 50 and 250 mg/L). pH of the solution is an important factor for adsorption performance depending on the characteristics of both adsorbate (PQ) and adsorbent (modified textile). In this study, the PQ molecule which is a quaternary compound and pH-independent. So, the essential factor is focused on the adsorbent. The initial pH of the PQ solution was evaluated in the pH range of 2–10 (Fig. 4b). Adsorption capacity was very poor at pH of 2, adsorption process could only occur by network capture (imprisonment of PQ molecules in three-dimensional crosslinked polymer network) and inclusion complex (entrapment of PQ molecules in the β-CD cavity by host–guest interaction), as seen in Fig. 4a. Indeed, modified textile showed mediocre acidity in aqueous solution at very low pH due to the crosslinking agent which was citric acid. Although, activated textile had already been in carboxylate form after alkaline treatment but actual functional groups could become carboxylic form at very low pH. At this state, carboxylic groups of citric acid on the textile surface were not fully dissociated to carboxylate groups because pH solution was lower than the pKa of this triprotic acid (3.13, 4.76 and 6.40). Adsorption ability was very bad at low pH which was previously reported for a citric-crosslinked CD with sawdust [60]. So, adsorption of PQ was inferior.
Fig. 4

a Proposed adsorption mechanism of PQ adsorption on textile coated with anionic β-CD polymer by inclusion complex, network capture and ionic interaction b effect of pH on adsorption capacity of PQ (2 g/L of adsorbent dosage, 50 mg/L of PQ initial concentration, 420 min of contact time and temperature at 303 K)

Then, adsorption capacity increased up to 13.9 mg/g at pH of 3 and enhanced slightly with pH raise while the maximum adsorption capacity reached (18.9 mg/g) at pH of 6.5. In this case, adsorption procedure could happen by network capture, inclusion complex and electrostatic interaction between the cationic character of PQ and anionic character of citric acid crosslinked on finished textile (Fig. 4a). Effectively, carboxylic functions were partially or totally ionized to carboxylate functions while pH of the solution was higher than pKa of citric acid which improved adsorption capacity between 16.5 and 18.9 mg/g. Thus, adsorption capacity at this condition was enhanced thanks to electrostatic interaction which gave a supplementary force and could play an important role in the adsorption process. Thus, optimal pH was equal to 6.5 for following adsorption experiments as a mild condition.

3.3 Adsorption kinetics

The adsorption capacity of modified textile against contact time were carried out at various initial concentrations of PQ (10, 50 and 250 mg/L) at 30 °C (Fig. 5a). It was found that adsorption of PQ enhanced rapidly for the first 60 min, followed by a slow adsorption rate for the next 360 min until achieving a saturation of adsorption thanks to the replete occupation of available sites. At equilibrium time, adsorption capacity increased with the higher initial concentration of PQ and contact time of 420 min was selected for adsorption isotherm studies to endorse attainment of saturation state in different initial concentrations of PQ.
Fig. 5

a Effect of contact time on adsorption capacity of PQ b pseudo-second-order kinetics of PQ adsorption c equilibrium isotherm d Langmuir isotherm e Freundlich isotherm of PQ adsorption for 10–250 mg/L of initial concentration of PQ (2 g/L of adsorbent dosage, temperature at 303 K and pH at 6.5)

The pseudo-first-order model and pseudo-second-order model were employed to further study adsorption process relating to chemical reaction, mass transfer and the adsorption order. According to fitting curves with two models (Table 1), it noted that all values of correlation coefficient (R2) were much higher for pseudo-second-order model (R2 = 0.9994, 0.9995 and 0.9980) than pseudo-first-order model (R2 = 0.7588, 0.6455 and 0.8322) for these initial concentrations of PQ (10, 50 and 250 mg/L respectively). These R2 values of pseudo-second-order model were approximately closed to 1 so as to obtain a straight line (Fig. 5b), which adsorption kinetics was described by pseudo-second-order model. Moreover, adsorption capacity at equilibrium calculated by pseudo-second-order model (Qe,cal = 4.6 19.3 and 24.1 mg/g) was nearly to experimental values (Qe,exp = 4.5, 18.9 and 23.7 mg/g) for these initial concentrations of PQ (10, 50 and 250 mg/L respectively).
Table 1

Kinetics parameters of adsorption of PQ on modified textile for 10, 50 and 250 mg/L of initial concentration (2 g/L of adsorbent dosage, temperature at 303 K, and pH at 6.5)

C0 (mg/L)

Qe,exp

Pseudo-first-order model

Pseudo-second-order model

R2

Qe,cal

k1

R2

Qe,cal

k2

10

4.5

0.7588

1.2

0.0035

0.9994

4.6

0.0095

50

18.9

0.6455

8.2

0.0030

0.9995

19.3

0.0015

250

23.7

0.8322

11.7

0.0023

0.9980

24.1

0.0008

3.4 Adsorption isotherm

Adsorption isotherm displays how pesticide interacts with modified textile at equilibrium state. The adsorption capacity of modified textile against concentration at equilibrium was performed at various initial concentrations of PQ (from 10 to 250 mg/L) at 30 °C (Fig. 5c). Adsorption capacity at equilibrium was very fast at a low initial concentration of PQ, but it became stable because of the unavailability of active sites on the adsorbent.

Langmuir and Freundlich isotherm models were applied to fit raw data (Fig. 5d, e respectively). Isotherm parameters were calculated and listed in Table 2. Due to fitting curves with two models, correlation coefficient (R2) value was much higher for Langmuir isotherm model (R2 = 0.9990) than Freundlich isotherm model (R2 = 0.8539). This R2 value from Langmuir isotherm model was imminent to 1 in order to obtain a linear relationship. So, Langmuir isotherm appeared a good demonstration of adsorption behavior which indicated that monolayer adsorption for PQ dominated on the homogenous surface of the functionalized textile. Additional information from Langmuir isotherm model, the separation factor (RL) revealed the tendency of the adsorption process. The RL values were 0.349, 0.097 and 0.021 for various initial concentrations of PQ (10, 50 and 250 mg/L successively), which displayed a great affinity between PQ molecule and treated textile because this tendency is advantageous if 0 < RL < 1. The functionalized textile could be used as an adsorbent for paraquat removal from aqueous solution and the maximum adsorption capacity of modified textile was 24.2 mg/g. However, it showed the mediocre adsorption efficiency comparing with other adsorbents listed in Table 3.
Table 2

Isotherm parameters of adsorption of PQ on modified textile for 10, 50 and 250 mg/L of initial concentration (2 g/L of adsorbent dosage, temperature at 303 K, 420 min of contact time and pH at 6.5)

Langmuir isotherm

Freundlich isotherm

Qe,exp

R2

Qm

KL

RL when

R2

Kf

1/n

C0 = 10 mg/L

C0 = 50 mg/L

C0 = 250 mg/L

23.7

0.9990

24.2

0.186

0.349

0.097

0.021

0.8539

6.5

0.29

Table 3

Comparison with other adsorbents described by the Langmuir isotherm for paraquat removal

Adsorbent

Adsorption dosage

Paraquat concentration

Adsorption kinetics

Maximum adsorption capacity

Polyester textile coated with cyclodextrin polymer (this work)

0.1 g in 0.05 L

10–250 mg/L

Pseudo-second-order

24.2 mg/g

Activated carbon derived from used tires [12]

1 g in 0.2 L

100–1000 mg/L

Pseudo-second-order

61.0 mg/g

Swine-manure-derived biochar [27]

0.3 g in 1 L

0.5–6 mg/L

Pseudo-second-order

14.8 mg/g

Clays and organoclays [31]

0.1 g in 0.02 L

 0.1–1 mmol/L

0.19 mmol/g

Rice husk silica [32]

0.05 g in 0.02 L

80–1000 mg/L

185.2 mg/g

Multi-walled carbon nanotubes [36]

0.16 g in 0.1 L

20–200 mg/L

Pseudo-second-order

79.4 mg/g

Pillararene porous polymers [41]

5 mg in 5 mL

0.6–2 mmol/L

Pseudo-second-order

209 mg/g

Magnetic hybrid nanosorbents [42]

2.5 mg in 5 mL

30–900 μg/mL

242.2 mg/g

3.5 Thermodynamic parameters

The influence of temperature on adsorption circumstance at different temperatures (30, 40 and 50 °C) was studied as shown in Fig. 6. The fitted curve of Qe/Ce against 1/T was executed to determine different thermodynamic parameters by Vant’ Hoff equation which exhibited a straight line with a good correlation coefficient (R2 = 0.9953). The standard enthalpy change (∆H°) was − 1.0 kJ/mol, this negative sign indicated exothermic process and the reduction of adsorption capacity with temperature raised were earlier reported for paraquat adsorption [38, 61]. Furthermore, the weak ∆H° (∆H° < 40 kJ/mol) was also described physisorption mechanism as the host–guest interaction between β-CD and PQ. Herein, it was probably that inclusion complex mechanism was dominant than two others proposed mechanism because the size of PQ (13.4 Å × 3.6 Å [62]) was suitable for CD cavity (7.8 Å of the internal cavity). By the way, the adsorption of the cationic organic compound on crosslink CD polymer was also informed about the important role of the CD cavity for methylene blue entrapment [47]. The standard entropy change (∆S°) was 0.438 J/mol·K, this positive number exhibited an increase of randomness at the solid–liquid interface for PQ adsorption process. The standard Gibbs free energy change (∆G°) was − 1.106, − 1.111 and − 1.115 kJ/mol for the temperature at 30, 40 and 50 °C respectively. All negative values expressed a spontaneous behavior of PQ adsorption. Moreover, the ∆G° value decreased with temperature enhanced which PQ adsorption was suitable at a lower temperature.
Fig. 6

Thermodynamic parameters of PQ adsorption at 303, 313 and 323 K (2 g/L of Adsorbent dosage, 50 mg/L of initial concentration, 420 min of contact time and pH at 6.5)

3.6 Regeneration

For economic reasons, reusability and stability of adsorbent are important criteria for the adsorption process. The appropriated solvent could play a significant role in the desorption process which is composed of the regeneration cycle. Water, 50%v/v of acetic acid solution and methanol were selected for PQ desorption from functionalized textile. As demonstrated in Fig. 7, PQ could be easily recycled in methanol and the regeneration efficiency reached 78.6–81.7% which revealed a good stability for desorption performance. Regeneration with methanol was formerly notified a good PQ removal efficiency by pillararene based porous polymers [41]. Nevertheless, the reusability efficiency of 50%v/v of acetic acid solution was only 39.9% after six cycles and this efficiency of water was very poor after only one cycle.
Fig. 7

Regeneration of modified textile for PQ removal by using water, 50%v/v of acetic acid and methanol respectively. (2 g/L of Adsorbent dosage, 50 mg/L of initial concentration, temperature at 303 K, 420 min of contact time and pH at 6.5)

3.7 Adsorbent stability

The adsorbent stability was carried out in various solvents (water, 50%v/v of acetic acid solution and methanol) so as to ensure its physical endurance after solvent contact in adsorption and desorption process. After 7 h of contact time indicated equilibrium time for adsorption and desorption process, the weight loss of functionalized textile was 9.3%, 8.1% and 5.1% respectively for water, 50%v/v of acetic acid solution and methanol (as observed in Fig. 8). However, no degradation change was observed for virgin textile. As expected, the anionic cyclodextrin polymer coated on the textile surface was hydrosoluble which degraded easily in water because the presence of ester bonds from polymer could be hydrolyzed rapidly and the hydroxyl groups from cyclodextrin molecule could create certainly hydrogen bonds with water molecules. This result could explain the reduction of regeneration efficiency in water for the second cycle due to the extreme loss of polymer coating on the textile surface. This kind of polymer was employed to build the multilayer assembly which showed the fast degradation rate for the multilayer assembly without thermal crosslinking [44]. Other organic solvents displayed less impact than water. By the way, no weight loss was rarely observed after the first contact with the solvent.
Fig. 8

Adsorbent stability in various solvents (water, 50%v/v of acetic acid solution and methanol)

4 Conclusion

The surface modification of PET textile was firstly accomplished by crosslinking between β-CD and CTR through the environmentally friendly process so as to promote anionic charge on the textile surface, resulting modified textile was also characterized and employed as an adsorbent for PQ removal from aqueous solution. The adsorption of PQ on functionalized textile was better at neutral pH and lower temperature. Adsorption kinetics was achieved at 420 min which was suitable for pseudo-second-order-model and adsorption isotherm was appropriated to Langmuir model. Thermodynamic study displayed a spontaneous process, an exothermic procedure and an increased disorder. Ultimately, recyclability of functionalized textile was accomplished in methanol for 78.6% of regeneration efficiency. This kind of textile could be a promising material for cationic pesticide contaminated in water.

Notes

Acknowledgements

The authors would like to thank all of the technicians for providing the facilities to accomplish experiments.

Funding

This study was partially funded by Faculty of Science and Technology, Nakhon Ratchasima Rajabhat University for the first author.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

References

  1. 1.
    Nanseu-Njiki CP, Dedzo GK, Ngameni E (2010) Study of the removal of paraquat from aqueous solution by biosorption onto Ayous (Triplochiton scleroxylon) sawdust. J Hazard Mater 179:63–71CrossRefGoogle Scholar
  2. 2.
    Mhammedi MAE, Bakasse M, Chtaini A (2007) Electrochemical studies and square wave voltammetry of paraquat at natural phosphate modified carbon paste electrode. J Hazard Mater 145:1–7CrossRefGoogle Scholar
  3. 3.
    Recena MCP, Caldas ED, Pires DX, Pontes ERJC (2006) Pesticides exposure in Culturama, Brazil-knowledge, attitudes, and practices. Environ Res 102:230–236CrossRefGoogle Scholar
  4. 4.
    Núñez O, Kim JB, Moyano E, Galceran MT, Terabe S (2002) Analysis of the herbicides paraquat, diquat and difenzoquat in drinking water by micellar electrokinetic chromatography using sweeping and cation selective exhaustive injection. J Chromatogr A 961:65–75CrossRefGoogle Scholar
  5. 5.
    Brown R, Clapp M, Dyson J, Scott D, Wheals I, Wilks M (2004) Paraquat in perspective. Outlooks Pest Manag 15:259–267CrossRefGoogle Scholar
  6. 6.
    Dinis-Oliveira RJ, Duarte JA, Sánchez-Navarro A, Remião F, Bastos ML, Carvalho F (2008) Paraquat poisonings: mechanisms of lung toxicity, clinical features, and treatment. Crit Rev Toxicol 38:13–71CrossRefGoogle Scholar
  7. 7.
    Lacerda ACR, Rodrigues-Machado MDG, Mendes PL, Novaes RD, Carvalho GMC, Zin WA, Gripp F, Coimbra CC (2009) Paraquat (PQ)-induced pulmonary fibrosis increases exercise metabolic cost, reducing aerobic performance in rats. J Toxicol Sci 34:671–679CrossRefGoogle Scholar
  8. 8.
    Cho Il Kyu, Mihye Jeong KHP, You Are-Sun, Li QX (2015) Pulmonary proteome and protein networks in response to the herbicide paraquat in rats. J Proteomics Bioinform 8:67–79Google Scholar
  9. 9.
    Smeyne RJ, Breckenridge CB, Beck M et al (2016) Assessment of the effects of MPTP and paraquat on dopaminergic neurons and microglia in the substantia nigra pars compacta of C57BL/6 mice. PLoS ONE 11:e0164094CrossRefGoogle Scholar
  10. 10.
    Zhang X, Thompson M, Xu Y (2016) Multifactorial theory applied to the neurotoxicity of paraquat and paraquat-induced mechanisms of developing Parkinson’s disease. Lab Invest 96:496–507CrossRefGoogle Scholar
  11. 11.
    Dinis-Oliveira RJ, Remião F, Carmo H, Duarte JA, Navarro AS, Bastos ML, Carvalho F (2006) Paraquat exposure as an etiological factor of Parkinson’s disease. NeuroToxicol 27:1110–1122CrossRefGoogle Scholar
  12. 12.
    Hamadi NK, Swaminathan Sri, Chen XD (2004) Adsorption of Paraquat dichloride from aqueous solution by activated carbon derived from used tires. J Hazard Mater 112:133–141CrossRefGoogle Scholar
  13. 13.
    Akhtar M, Hasany SM, Bhanger MI, Iqbal S (2007) Low cost sorbents for the removal of methyl parathion pesticide from aqueous solutions. Chemosphere 66:1829–1838CrossRefGoogle Scholar
  14. 14.
    Santos MSF, Schaule G, Alves A, Madeira LM (2013) Adsorption of paraquat herbicide on deposits from drinking water networks. Chem Eng J 229:324–333CrossRefGoogle Scholar
  15. 15.
    Burns IG, Hayes MHB, Stacey M (1973) Studies of the adsorption of paraquat on soluble humic fractions by gel filtration and ultrafiltration techniques. Pestic Sci 4:629–641CrossRefGoogle Scholar
  16. 16.
    Cocenza DS, de Moraes MA, Beppu MM, Fraceto LF (2012) Use of biopolymeric membranes for adsorption of paraquat herbicide from water. Water Air Soil Pollut 223:3093–3104CrossRefGoogle Scholar
  17. 17.
    Leite MP, dos Reis LGT, Robaina NF, Pacheco WF, Cassella RJ (2013) Adsorption of paraquat from aqueous medium by Amberlite XAD-2 and XAD-4 resins using dodecylsulfate as counter ion. Chem Eng J 215–216:691–698CrossRefGoogle Scholar
  18. 18.
    Humbert H, Gallard H, Suty H, Croué J-P (2008) Natural organic matter (NOM) and pesticides removal using a combination of ion exchange resin and powdered activated carbon (PAC). Water Res 42:1635–1643CrossRefGoogle Scholar
  19. 19.
    Zayats MF, Leschev SM, Petrashkevich NV, Zayats MA, Kadenczki L, Szitás R, Dobrik HS, Keresztény N (2013) Distribution of pesticides in n-hexane/water and n-hexane/acetonitrile systems and estimation of possibilities of their extraction isolation and preconcentration from various matrices. Anal Chim Acta 774:33–43CrossRefGoogle Scholar
  20. 20.
    Cantavenera MJ, Catanzaro I, Loddo V, Palmisano L, Sciandrello G (2007) Photocatalytic degradation of paraquat and genotoxicity of its intermediate products. J Photochem Photobiol Chem 185:277–282CrossRefGoogle Scholar
  21. 21.
    Sorolla MG, Dalida ML, Khemthong P, Grisdanurak N (2012) Photocatalytic degradation of paraquat using nano-sized Cu-TiO2/SBA-15 under UV and visible light. J Environ Sci 24:1125–1132CrossRefGoogle Scholar
  22. 22.
    Santos MSF, Alves A, Madeira LM (2011) Paraquat removal from water by oxidation with Fenton’s reagent. Chem Eng J 175:279–290CrossRefGoogle Scholar
  23. 23.
    Dhaouadi A, Adhoum N (2010) Heterogeneous catalytic wet peroxide oxidation of paraquat in the presence of modified activated carbon. Appl Catal B Environ 97:227–235CrossRefGoogle Scholar
  24. 24.
    Dhaouadi A, Adhoum N (2009) Degradation of paraquat herbicide by electrochemical advanced oxidation methods. J Electroanal Chem 637:33–42CrossRefGoogle Scholar
  25. 25.
    Carr RJ, Bilton RF, Atkinson T (1985) Mechanism of biodegradation of paraquat by Lipomyces starkeyi. Appl Environ Microbiol 49:1290–1294Google Scholar
  26. 26.
    Nakamura T, Kawasaki N, Ogawa H, Tanada S, Kogirima M, Imaki M (1999) Adsorption removal of paraquat and diquat onto activated carbon at different adsorption temperature. Toxicol Environ Chem 70:275–280CrossRefGoogle Scholar
  27. 27.
    Tsai W-T, Chen H-R (2013) Adsorption kinetics of herbicide paraquat in aqueous solution onto a low-cost adsorbent, swine-manure-derived biochar. Int J Environ Sci Technol 10:1349–1356CrossRefGoogle Scholar
  28. 28.
    Tsai WT, Lai CW, Hsien KJ (2004) Adsorption kinetics of herbicide paraquat from aqueous solution onto activated bleaching earth. Chemosphere 55:829–837CrossRefGoogle Scholar
  29. 29.
    Iglesias A, López R, Gondar D, Antelo J, Fiol S, Arce F (2010) Adsorption of paraquat on goethite and humic acid-coated goethite. J Hazard Mater 183:664–668CrossRefGoogle Scholar
  30. 30.
    Brigante M, Zanini G, Avena M (2010) Effect of humic acids on the adsorption of paraquat by goethite. J Hazard Mater 184:241–247CrossRefGoogle Scholar
  31. 31.
    Seki Y, Yurdakoç K (2005) Paraquat adsorption onto clays and organoclays from aqueous solution. J Colloid Interface Sci 287:1–5CrossRefGoogle Scholar
  32. 32.
    Rongchapo W, Sophiphun O, Rintramee K, Prayoonpokarach S, Wittayakun J (2013) Paraquat adsorption on porous materials synthesized from rice husk silica. Water Sci Technol 68:863–869CrossRefGoogle Scholar
  33. 33.
    Ibrahim KM, Jbara HA (2009) Removal of paraquat from synthetic wastewater using phillipsite–faujasite tuff from Jordan. J Hazard Mater 163:82–86CrossRefGoogle Scholar
  34. 34.
    Ait Sidhoum D, Socías-Viciana MM, Ureña-Amate MD, Derdour A, González-Pradas E, Debbagh-Boutarbouch N (2013) Removal of paraquat from water by an Algerian bentonite. Appl Clay Sci 83–84:441–448CrossRefGoogle Scholar
  35. 35.
    Hao Y, Wang Z, Gou J, Wang Z (2015) Kinetics and thermodynamics of diquat removal from water using magnetic graphene oxide nanocomposite. Can J Chem Eng 93:1713–1720CrossRefGoogle Scholar
  36. 36.
    Hao H, Feng JG, Liu WJ, Wu XM (2015) Removal of paraquat from aqueous solutions using multi-walled carbon nanotubes: kinetic, isotherm and thermodynamic studies. Adv Mater Res 1088:13–17CrossRefGoogle Scholar
  37. 37.
    Barna SF, Ott EA, Nguyen TH, Shannon MA, Scheeline A (2013) Silica adsorbents and peroxide functionality for removing paraquat from wastewater. J Environ Eng 139:975–985CrossRefGoogle Scholar
  38. 38.
    Brigante M, Schulz PC (2011) Adsorption of paraquat on mesoporous silica modified with titania: effects of pH, ionic strength and temperature. J Colloid Interface Sci 363:355–361CrossRefGoogle Scholar
  39. 39.
    Rongchapo W, Keawkumay C, Osakoo N, Deekamwong K, Chanlek N, Prayoonpokarach S, Wittayakun J (2017) Comprehension of paraquat adsorption on faujasite zeolite X and Y in sodium form. Adsorpt Sci Technol 36:684–693CrossRefGoogle Scholar
  40. 40.
    Pateiro-Moure M, Bermúdez-Couso A, Fernández-Calviño D, Arias-Estévez M, Rial-Otero R, Simal-Gándara J (2010) Paraquat and diquat sorption on iron oxide coated quartz particles and the effect of phosphates. J Chem Eng Data 55:2668–2672CrossRefGoogle Scholar
  41. 41.
    Lan S, Zhan S, Ding J, Ma J, Ma D (2017) Pillar[n]arene-based porous polymers for rapid pollutant removal from water. J Mater Chem A 5:2514–2518CrossRefGoogle Scholar
  42. 42.
    Fernandes T, Soares SF, Trindade T, Daniel-da-Silva AL (2017) Magnetic hybrid nanosorbents for the uptake of paraquat from water. Nanomaterials 7:68CrossRefGoogle Scholar
  43. 43.
    Brusseau ML, Wang X, Wang W-Z (1997) Simultaneous elution of heavy metals and organic compounds from soil by cyclodextrin. Environ Sci Technol 31:1087–1092CrossRefGoogle Scholar
  44. 44.
    Junthip J, Tabary N, Chai F et al (2016) Layer-by-layer coating of textile with two oppositely charged cyclodextrin polyelectrolytes for extended drug delivery. J Biomed Mater Res A 104:1408–1424CrossRefGoogle Scholar
  45. 45.
    Morin-Crini N, Crini G (2013) Environmental applications of water-insoluble β-cyclodextrin–epichlorohydrin polymers. Prog Polym Sci 38:344–368CrossRefGoogle Scholar
  46. 46.
    Leudjo Taka A, Pillay K, Mbianda XY (2017) Nanosponge cyclodextrin polyurethanes and their modification with nanomaterials for the removal of pollutants from waste water: a review. Carbohydr Polym 159:94–107CrossRefGoogle Scholar
  47. 47.
    Zhao F, Repo E, Yin D, Meng Y, Jafari S, Sillanpää M (2015) EDTA-Cross-Linked β-cyclodextrin: an environmentally friendly bifunctional adsorbent for simultaneous adsorption of metals and cationic dyes. Environ Sci Technol 49:10570–10580CrossRefGoogle Scholar
  48. 48.
    Gong T, Zhou Y, Sun L, Liang W, Yang J, Shuang S, Dong C (2016) Effective adsorption of phenolic pollutants from water using β-cyclodextrin polymer functionalized Fe3O4 magnetic nanoparticles. RSC Adv 6:80955–80963CrossRefGoogle Scholar
  49. 49.
    Li X, Zhou M, Jia J, Jia Q (2018) A water-insoluble viologen-based β-cyclodextrin polymer for selective adsorption toward anionic dyes. React Funct Polym 126:20–26CrossRefGoogle Scholar
  50. 50.
    Alzate-Sánchez DM, Smith BJ, Alsbaiee A, Hinestroza JP, Dichtel WR (2016) Cotton fabric functionalized with a β-cyclodextrin polymer captures organic pollutants from contaminated air and water. Chem Mater 28:8340–8346CrossRefGoogle Scholar
  51. 51.
    Celebioglu A, Sen HS, Durgun E, Uyar T (2016) Molecular entrapment of volatile organic compounds (VOCs) by electrospun cyclodextrin nanofibers. Chemosphere 144:736–744CrossRefGoogle Scholar
  52. 52.
    Ghemati D, Aliouche D (2014) Dye adsorption behavior of polyvinyl alcohol/glutaraldehyde/β-cyclodextrin polymer membranes. J Appl Spectrosc 81:257–263CrossRefGoogle Scholar
  53. 53.
    Massaro M, Colletti CG, Lazzara G, Guernelli S, Noto R, Riela S (2017) Synthesis and characterization of halloysite-cyclodextrin nanosponges for enhanced dyes adsorption. ACS Sustain Chem Eng 5:3346–3352CrossRefGoogle Scholar
  54. 54.
    Flaherty RJ, Nshime B, DeLaMarre M, DeJong S, Scott P, Lantz AW (2013) Cyclodextrins as complexation and extraction agents for pesticides from contaminated soil. Chemosphere 91:912–920CrossRefGoogle Scholar
  55. 55.
    Lannoy A, Bleta R, Machut-Binkowski C, Addad A, Monflier E, Ponchel A (2017) Cyclodextrin-directed synthesis of gold-modified TiO2 materials and evaluation of their photocatalytic activity in the removal of a pesticide from water: effect of porosity and particle size. ACS Sustain Chem Eng 5:3623–3630CrossRefGoogle Scholar
  56. 56.
    Euvrard É, Morin-Crini N, Druart C, Bugnet J, Martel B, Cosentino C, Moutarlier V, Crini G (2016) Cross-linked cyclodextrin-based material for treatment of metals and organic substances present in industrial discharge waters. Beilstein J Org Chem 12:1826–1838CrossRefGoogle Scholar
  57. 57.
    Degoutin S, Saffre C, Ruffin D, Bacquet M, Martel B (2015) Metallic pollutant removal in leachates extracted from sediment by geotextiles based on crosslinked bio-sourced polymers. Rev Sci Eau 28:43Google Scholar
  58. 58.
    Ducoroy L, Bacquet M, Martel B, Morcellet M (2008) Removal of heavy metals from aqueous media by cation exchange nonwoven PET coated with β-cyclodextrin-polycarboxylic moieties. React Funct Polym 68:594–600CrossRefGoogle Scholar
  59. 59.
    Ducoroy L, Martel B, Bacquet M, Morcellet M (2007) Ion exchange textiles from the finishing of PET fabrics with cyclodextrins and citric acid for the sorption of metallic cations in water. J Incl Phenom Macrocycl Chem 57:271–277CrossRefGoogle Scholar
  60. 60.
    Hu Q, Gao D-W, Pan H, Hao L, Wang P (2014) Equilibrium and kinetics of aniline adsorption onto crosslinked sawdust-cyclodextrin polymers. RSC Adv 4:40071–40077CrossRefGoogle Scholar
  61. 61.
    Tsai WT, Hsien KJ, Chang YM, Lo CC (2005) Removal of herbicide paraquat from an aqueous solution by adsorption onto spent and treated diatomaceous earth. Bioresour Technol 96:657–663CrossRefGoogle Scholar
  62. 62.
    Draoui K, Denoyel R, Chgoura M, Rouquerol J (1999) Adsorption of Paraquat on minerals: a thermodynamic study. J Therm Anal Calorim 58:597–606CrossRefGoogle Scholar

Copyright information

© Springer Nature Switzerland AG 2018

Authors and Affiliations

  1. 1.Faculty of Science and TechnologyNakhon Ratchasima Rajabhat UniversityNakhon RatchasimaThailand
  2. 2.The Petroleum and Petrochemical CollegeChulalongkorn UniversityBangkokThailand
  3. 3.School of PhysicsSuranaree University of TechnologyNakhon RatchasimaThailand

Personalised recommendations