1Received 21 September 2017

2Received in revised form 10 November 2017

3Accepted 17 January 2018
4

5 Artificial intelligence, regression model, and cost estimation for removal of

6 chlorothalonil pesticide by activated carbon prepared from casuarina charcoal

8 Mohamed Gar Alalm a, *, Mahmoud Nasr b

10
a
11 Department of Public Works Engineering, Mansoura University, Mansoura 35516, Egypt

12

b
13 Sanitary Engineering Department, Alexandria University, Alexandria 21544, Egypt

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15

16

17

18

19

20* Corresponding author

21Email: m_gar_alalm@mans.edu.eg
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23 ABSTRACT

24 Chlorothalonil is a pesticide that can contaminate water bodies, detriment aquatic organisms,

25and cause cancers of the forestomach and kidney. In this study, a powdered activated carbon

26prepared from casuarina wood was used for the adsorption of chlorothalonil from aqueous

27solutions. Based on Scanning Electron microscopy and Fourier Transform Infrared Spectroscopy

28analyses, the adsorbent material comprised pores and multiple functional groups that favored the

29entrapment of chlorothalonil onto its surface. At initial chlorothalonil concentration of 480 mg L -

301, the equilibrium uptake capacity was 187 mg g -1 at pH: 7, adsorbent dosage: 0.5 g L -1, contact

31time: 40 min, and room temperature (25 ± 4 °C). The kinetic and isotherm studies indicated that

32the rate constant of pseudo-second-order model (k2) was 0.003 g mg-1 min-1, and the monolayer

33adsorption capacity was 192 mg g-1. Results from a quadratic model demonstrated that the plot of

34adsorption capacity versus pH, chlorothalonil concentration, adsorbent dosage, and contact time

35caused quadratic-concave, linear-up, flat, and quadratic-linear concave up curves, respectively.

36An artificial neural network with a structure of 4–5–1 was able to predict the adsorption capacity

37(R2: 0.982), and the sensitivity analysis using connection weights showed that pH was the most

38influential factor. An economic estimation using amortization and operating costs revealed that

39an adsorption unit subjected to 100 m3 d-1 containing chlorothalonil concentration of 250 ± 50

40mg L-1 could cost 1.18 $ m-3.

41

42Keywords: activated carbon; artificial neural network; chlorothalonil pesticide; cost estimation;

43kinetics and isotherms

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451. Introduction

46 Chlorothalonil is the anion of 4-hydroxy-2,5,6-tetrachloroisophthalonitrile, which belongs to

47class U (i.e., unlikely to present acute hazard in normal use) of the World Health Organization

48classification of pesticides [1]. This non-systemic foliar fungicide has been widely used to limit

49several fungal diseases in turf and ornamental plants and to treat various crops such as celery,

50potatoes, peanuts, onions, and tomatoes [2]. However, chlorothalonil can contaminate water

51bodies adjacent to agricultural areas by means of spray drift, runoff, or sediment transport [3]. It

52is highly toxic to fish, causing gill damage at a concentration of 0.002 mg L -1 [4]. It is also

53harmful to several organisms (e.g., earthworms, frogs, and shrimps) and can be converted into

54hazard compounds such as 4-hydroxy chlorothalonil. In addition, chlorothalonil can cause mild

55anemia, embryo loss during pregnancy, liver and oxidative DNA damages, eye and skin

56irritations, and cancers of the forestomach and kidney [5]. Hence, the treatment of chlorothalonil-

57contaminated water is a crucial challenge for environmental safety and public health.

58 Recently, several methods such as photocatalytic oxidation, membrane separation, Fenton

59oxidation, and adsorption have been investigated for the treatment of wastewater containing

60hazardous substances [6]. Amongst them, adsorption is considered one of the most efficient and

61useful methods that can eliminate pesticides and other toxic elements from aqueous solutions [7].

62During adsorption, the solute ions (adsorbate) propagate from the bulk solution phase to the

63external surface of a rigid material, namely adsorbent [8]. This mechanism is known as “film

64diffusion”, which is followed by particle diffusion from the surface into the interior pores of the

65adsorbent [9]. Adsorption undertakes a short treatment time, consumes a small amount of energy,

66and does not require sludge-handling processes [10]. Additionally, it comprises low capital cost

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67and space requirement and can be employed as a single stage for the treatment of low-level

68polluted water [11].

69 Mathematical modeling of the uptake capacities of sorbent materials is a major step for an

70appropriate design of adsorption treatment units. In addition, the adsorption mechanism is

71affected by various environmental conditions such as the solution pH, concentration of

72adsorbate, adsorbent dosage, and reaction time [12]. Regression analysis can be employed to

73investigate the effects of these experimental factors on the adsorption performance via a

74collection of statistical and mathematical procedures. Moreover, it can improve and optimize the

75complex adsorption process using a minimum number of experiments [13]. Artificial neural

76network (ANN) is another modeling methodology that can describe the relationship between

77adsorption rate and one or more independent factors. ANN is a type of artificial intelligence that

78has been employed for predicting and optimizing complex systems [14], as well as, solving

79nonlinear and linear multivariate regression problems [15]. ANN is a simple model of the human

80brain consisting of successive layers, in which each layer is composed of a large number of

81highly interconnected processing elements, called neurons [16]. Recently, ANN has been applied

82for the prediction of adsorption efficiencies and capacities for the removal of various toxic

83elements from wastewater [17].

84 Adsorbents can be originated from agricultural residues, domestic and municipal wastes, or

85industrial by-products [18]. Activated carbon is a carbonaceous material that has a highly porous

86surface structure (active heterogeneous surface) [19] and a large surface area with different

87functional groups [20]. However, the high cost of activated carbon limits its broad application

88under some adsorption conditions. Thus, the preparation of activated carbon from waste

89materials, viz., bamboo dust, cheap wood, rice husk, and palm kernel, can be an attractive trend

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 90according to environmental and economic points of view [21]. Casuarina tree is ubiquitous in

91Egypt and considered a low-cost source of wood and charcoal for several applications.

92Additionally, Casuarina wood is rich in carbonaceous components, and thus it is feasible to be

93employed for the preparation of an adsorbent material.

94 To the best of our knowledge, there is a lack of research on the application of low-cost

95adsorbents for the removal of toxic chlorothalonil from wastewater. Thus, this study investigated

96the application of powdered activated carbon derived from casuarina wood (CAC) for the

97removal of chlorothalonil pesticide. The prepared CAC was characterized using Scanning

98Electron Microscopy (SEM) and Fourier Transform Infrared Spectroscopy (FTIR). Adsorption

99kinetics was studied by pseudo-first-order and pseudo-second-order models. In addition, the

100equilibrium data were analyzed by Langmuir and Freundlich isotherms. A quadratic model and

101an ANN were employed to determine the relationship between experimental conditions and the

102uptake capacity of CAC. The amortization and operating costs of an adsorption unit for the

103removal of chlorothalonil from a real-case wastewater were also presented.

1042. Materials and methods

1052.1. Materials

106 Chlorothalonil having a molecular formula of C8Cl4N2 (Fig. S1 of Supplemental Materials)

107was used as a single adsorbate substance in this study. Chlorothalonil and acetonitrile chemicals

108were purchased from Sigma-Aldrich. All chemicals were of analytical grade and used without

109further purification. Charcoal was obtained from a charcoal company in Damietta, Egypt

110utilizing Casuarina tree for material preparation.

1112.2. Preparation of CAC adsorbent

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112 The raw charcoal was delivered as pieces having a cylindrical-like shape with diameter: 3–5

113cm and height: 10–15 cm. The charcoal pieces were scraped by a rasp to obtain finely powdered

114charcoal. The powdered charcoal was placed in covered silica crucibles and heated inside a

115muffle furnace at 950 °C for 180 min. Afterward, the crucibles were removed from the muffle

116and allowed for cooling to room temperature (25 ± 4 °C). The powder was treated with 1 M HCl

117solution to eliminate the ash content and then washed with distilled deionized water. Further, the

118treated powder was dried at 105 °C for 24 h. The final product was stored in closed glass

119containers.

1202.3. Adsorption experiments

121 A series of batch experiments were performed in 250 mL flasks filled with 200 mL of a

122solution containing chlorothalonil. The flasks were positioned on a magnetic stirrer that provided

123a vigorous stirring with a speed of 150 rpm. In the first experiment, the medium pH was adjusted

124to different values between 2.5 and 10.5 using 0.1 M HCl or 0.1 M NaOH solutions. The initial

125chlorothalonil concentrations were 60, 240, and 480 mg L -1, while maintaining the adsorbent

126dosage at 0.5 g L-1 and the contact time at 10 min. The second experiment was conducted at

127different initial chlorothalonil concentrations from 60 to 480 mg L-1. The adsorption

128performances were measured at a time interval of 5–60 min, while the solution pH was selected

129from experiment-1 and the adsorbent dosage was 0.5 g L-1. In the third experiment, the studied

130CAC dosages were 0.50, 0.75, and 1.00 g L -1 and the samples were analyzed at various periods

131from 5 to 60 min. The solution pH and initial chlorothalonil concentration obtained from

132previous investigations were used in the third experiment.

133 The adsorption capacity of CAC was calculated by Eq. (1) [22].

11 6
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 qt 
 C o  Ct   V
134 (1)
m

135

136where, qt is the mass of adsorbed matter per CAC mass at time t (mg g -1), Co and Ct are the

137concentration of the adsorbate at time = 0 (initial) and at time = t, respectively (mg L -1), V is the

138volume of solution (L), and m is the mass of dry adsorbent (g).

1392.4. Analytical method

140 The chlorothalonil concentrations were quantified by an Agilent 1200 series HPLC system,

141including a quaternary pump (G1311A; flow range: 0.2–10.0 mL min -1), an autosampler

142(G1329A: 100 µL metering head), and a photodiode array detector. For this purpose, the sample

143was filtered through Whatman filter paper (0.45 μm) and an aliquot of 25 μL was injected into

144the HPLC-Column Apollo C18: Diameter (4.6 mm) × Length (150 mm) at a flow rate of 1.5 mL

145min-1 and column temperature: 40°C. Two mobile phases, i.e., mobile phase A: 30% distilled

146water and mobile phase B: 70% acetonitrile, were used during the analysis. The peak of

147chlorothalonil was detected at a wavelength of 230 nm.

148 The surface morphology of the CAC was performed by a SEM (JEOL JSM-6460, Japan).

149The samples were sputter-coated with gold before scanning. The CAC adsorbent was

150characterized by FTIR (VERTEX 70 spectrometer; Bruker) with a wavenumber range from 4000

151to 400 cm-1. The solid material was analyzed in a pressed potassium bromide (KBr) based pellets.

1522.5. Quadratic model

153 As seen in Eq. (2), a pure-quadratic model composed of constant, linear, and squared terms

154was used to fit the adsorption data. The quality of the regression model was determined by the

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155coefficient of determination (R2) and adjusted-R2. The statistically significant effect of each

156factor on the response was evaluated by the p-value (probability) with 95% confidence level. The

157parameters of the model were estimated using a least square method in MATLAB R2015a.

k k
158 Y   0    i X i    ii X i2 (2)
i 1 i 1

159

160where, Y is the model response (adsorption capacity), Xi are the experimental factors (X1: pH,

161X2: chlorothalonil concentration, X3: CAC dosage, and X4: contact time), β are the regression

162model coefficients (β0, βi, and βii are intercept, linear effect, and quadratic effect, respectively),

163and k is the number of factors.

1642.6. Artificial neural network (ANN)

165 The developed ANN model consisted of three layers, i.e., the input layer that received

166adsorption data from four experimental factors, the hidden layer of five neurons, and the last

167layer of one output neuron. Thus, the structure of the network was expressed as 4–5–1 (Fig. 1a).

168The tan-sigmoid transfer function, as seen from Eq. (3), was used in the hidden layer to introduce

169nonlinearity into the network, whereas the linear activation function, as seen in Eq. (4), was

170considered in the output layer. The number of neurons and hidden layers and the activation

171functions were selected by the trial-and-error approach.

1  1  f  x   1 (3)
f  x 
1 ex
f  x  x    f  x    (4)

172

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173 ANN is initiated with certain connection weights and biases, which are then adjusted through

174a training procedure to generate outputs approximately equal to the targets [23]. In this study, the

175back-propagation method with a Levenberg-Marquardt (trainlm) algorithm was used for the

176network training. The training process undergoes two phases: i.e., in the forward phase, the

177external signals are propagated from the input layer to the output layer, whereas in the backward

178phase, the error between the predicted and observed values at the output layer is propagated

179backward to modify the weights and biases [16]. These trials are repeated several times

180(consecutive numbers of iterations) until the least mean squared error (MSE) between the desired

181and computed values is achieved.

182 The adsorption data were randomly divided into three subsets: i.e., 60% for training to

183determine the optimum weights and biases, 15% for validation to define the number of epochs

184that prevents data overfitting, and 15% for the testing phase to examine the stability level of the

185trained network.

1863. Results and discussion

1873.1. Characterization of adsorbent

188 The SEM image in Fig. 2a shows that the CAC material contained cross-interconnected holes

189with diameters up to 2 nm, indicating a microporous feature and high surface area. The particles

190had irregular sizes and shapes, and the surface was rough with heterogeneous pores. In a similar

191study, Ioannidou et al. [24] reported that woody materials are mainly composed of lignin; and

192hence, the activated carbons synthesized from agricultural woody residues could simulate the

193structure and morphology of lignin. These characteristics could favor the entrapment of

194chlorothalonil onto the CAC surface [25].

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195 The functional groups of the prepared CAC were determined by the FTIR analysis (Fig. 2b).

196The observed bands can be illustrated as follows: The peak at 3441 cm -1 (3500–3200 cm-1) could

197be assigned to the O–H stretching vibration band or N–H functional group [26]. This band was

198followed by hydrogen bonding (e.g., saturated C–H) at the peaks of 2960, 2923, and 2853 cm -1

199(3000–2800 cm-1) [21]. The peak at 1642 cm-1 (1700–1600 cm-1) was originating from stretching

200of conjugated C=C [18]. The peak at 1542 cm-1 could represent C–N stretching with N–H

201bending of Amide II. The peak at 1403 cm -1 (1500–1400 cm-1) could be due to the presence of

202C–C stretching [27]. The peaks at 1116 and 1063 cm -1 (1260–1050 cm-1) indicated the existence

203of C–O single bonds in carboxyl acids, alcohols, phenols, and esters. The small peaks appeared

204from 800 to 700 cm-1 could be assigned to C–OH (out of plane bending) in phenol [20]. The

205presence of multiple functional groups, viz., ketones, esters, alkenes, aromatic, alcohol,

206hydroxyl, and carboxyl, demonstrated high chemical heterogeneity of the prepared activated

207carbon.

2083.2. Effect of pH

209 Fig. 3a shows the effect of initial pH on the uptake capacity of CAC at different

210chlorothalonil concentrations (Co) of 60, 240, and 480 mg L-1. At Co of 480 mg L-1, an increase in

211pH from 2.5 to 7.0 caused insignificant change in the uptake capacity at approximately 186–188

212mg g-1 (r: -0.5958, p: 0.2891). Further, an increase in initial pH from 7.0 to 10.5 depicted a

213significant drop in the uptake capacity from 186 to 67 mg g -1, respectively (r: -0.9793, p:

2140.0207). Similar trends were observed for Co of 60 and 240 mg L-1.

215 In the acidic condition, the activated carbon became protonated (i.e., availability of H + ions),

216and thus the overall surface charge was positive [19]. This trend favored the electrostatic

217attraction between the CAC surface and the chlorothalonil ions. On the contrary, with an increase

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218in the solution pH, the functional groups on CAC surface became partially or fully deprotonated

219(i.e., releasing H+ ion) [28]. Hence, the alkaline condition resulted in liberating the positive

220charges and/or increasing the amount of negatively charged sites, which caused a net negative

221charge on the activated carbon surface. This trend ensured the electrostatic repulsion between the

222chlorothalonil ions and the negatively charged CAC surface; i.e., consequently, the adsorption

223performance decreased.

224 At the neutral condition, the uptake capacity was insignificantly lower than that at acidic pH

225medium. This result could be linked to the hydrophobic nature of the synthesized carbon, which

226could agglomerate H+ ions onto the surface when submerged in water and make attraction force

227with the adsorbate [9]. Moreover, adding chemical reagents to adjust the solution pH at the large-

228scale application is costly and may endure several problems to the mechanical parts and tank

229walls. Accordingly, the neutral condition was maintained in the current study.

2303.3. Effect of chlorothalonil concentrations

231 Fig. 3b shows the effect of initial chlorothalonil concentration (Co: 60–480 mg L-1) on the

232uptake capacity of CAC at various time intervals between 5 and 60 min. The solution pH was

233maintained at 7, whereas the adsorbent dosage was 0.5 g L-1.

234 At Co: 60 mg L-1, the equilibrium condition (qe = 24 mg g-1) was achieved after only 10 min

235of contact time. The high adsorption mechanism at the initial phase could be attributed to [29]:

236(a) the availability of vacant/active sites on the surface compared to the density of chlorothalonil

237ions, and (b) the increased concentration gradient between the adsorbate in solution and that on

238the CAC surface. However, a further increase in adsorption time over 10 min provided a

239comparable uptake capacity of 24 mg g-1. After reaching the equilibrium condition, an

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240electrostatic hindrance or repulsion occurs between the negatively charged ions adsorbed onto

241the surface and those available in the solution [24]. In addition, the mass transfer of the ions from

242the bulk solution to the external surface of CAC became limited, followed by a subsequent

243decrease in the internal mass transfer within the sorbent particles [30]. These trends could

244decrease the pore diffusion of the solute ions into the adsorbent at equilibrium, causing no

245enhancement in the adsorption capacity.

246 An increase in Co over 60 mg L-1 required a longer reaction time (i.e., over 10 min) to attain

247the equilibrium state. For example, at Co: 240 mg L-1, an increase in contact time from 5 to 20

248min delivered a significant enhancement in the adsorption capacity from 53 to 94 mg g-1,

249respectively (r: 0.9424, p: 0.0476). However, a further increase in contact time from 20 to 60

250min observed non-significant (p > 0.05) enhancement in the uptake performance. Similarly, the

251equilibrium time for Co: 360 mg L-1 was 20 min, which increased to 40 min at C o of 480 mg L-1.

252Hence, the higher the Co, the longer the equilibrium time. This result could be due to at high C o,

253large repulsive forces occur between the solute ions on the solid phase and those in the bulk

254solution [27].

255 Moreover, an increase in Co from 60 to 480 mg L-1 caused a significant increase in the

256equilibrium uptake capacity from 24 to 187 mg g -1, respectively (r: 0.9999, p < 0.05). This result

257could be attributed to: (a) the high Co permits more driving force to overcome the mass transfer

258boundaries of chlorothalonil between the solid and liquid phases [10], (b) the active sites can

259undergo high opportunity to adsorb a large amount of pesticide with an increase in C o, and (c)

260An increase in Co also encourages the interaction between molecules and the surface active sites

261[20].

2623.4. Effect of adsorbent dosage

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263 Fig. 3c displays the effect of CAC dosage (0.5–1.0 g L -1) on the adsorption capacity at

264solution pH: 7 and Co: 480 mg L-1.

265 At a CAC dosage of 0.5 g L -1, an increase in contact time from 5 to 40 min resulted in a

266significant enhancement in the uptake capacity from 85 to 186 mg g -1, respectively (r: 0.9196, p:

2670.0034). However, a further increase in contact time over 40 min exhibited no considerable

268improvement in the adsorption performance. This result could be due to, at equilibrium, the

269active sites were filled and covered, and thus no more species could be adsorbed.

270 Results also showed that the equilibrium time was 40 min at CAC dosage of 0.5 g L -1, which

271declined to 20 and 15 min at the dosages of 0.75 and 1.00 g L -1, respectively (r: -0.9449, p:

2720.2123). At low adsorbent dosage, the bare surface rapidly diminishes (i.e., became saturated)

273and a large amount of ions remains in the solution. Hence, the sorbate ions have to compete for

274the readily adsorption sites. Kumar et al. [10] suggested that at a later process time, the occupied

275pores could oppose the adsorbate species into the bulk phase, and thus the driving forces

276undertaken by the adsorbate molecules to enter the available sites become incompetent. This

277trend results in decreasing the rate of adsorption and prolonging the equilibrium time. On the

278contrary, the reduction in equilibrium time at high adsorbent dosage could be attributed to the

279increase of surface area and the availability of vacant active/adsorption sites that fasten the

280adsorption process [27].

281 In addition, results indicated that the equilibrium capacity was 186 mg g -1 at CAC dosage of

2820.50 g L-1, which decreased to 124 and 94 mg g-1 with an increase in the adsorbent dosage to 0.75

283and 1.00 g L-1, respectively. Hameed et al. [21] reported that high adsorbent dosage could result

284in particles aggregation and overlapping of binding sites, which in turn increase diffusional path

285length, and/or shield the binding sites from sorbate ions.

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2863.5. Adsorption kinetics

287 The kinetic process is used to describe the uptake rate of ions (adsorbate) onto an adsorbent

288surface at the solid-solution interface [27].

2893.5.1. Pseudo-first-order

290 The linear form of pseudo-first-order reaction can be described by Eq. (5). A plot of ln(q e –

291qt) versus time results in a straight line with a slope of (–k1) and an intercept of ln(qe).

292 ln  qe  qt   ln qe   k1  t (5)

293

294where, k1 is the rate constant of first-order sorption (min-1), qe and qt are the amounts of solute

295sorbed onto the solid surface at equilibrium and time t, respectively (mg g-1).

296 Fig. 4a shows a plot of the linearized form of the pseudo-first-order equation for the sorption

297mechanism. The pseudo-first-order equation fitted well during the initial stage (where rapid

298adsorption occurred) but failed to describe the entire adsorption process. In addition, the

299experimental uptake capacity (qe,exp. = 187 mg g-1) differed greatly from the corresponding

300calculated value (qe,calc. = 218 mg g-1). These observations suggested the unsuitability of the

301pseudo-first-order kinetic model in describing the chlorothalonil adsorption onto CAC material.

3023.5.2. Pseudo-second-order

303 The non-linear form of pseudo-second-order model can be expressed by Eq. (6).

k 2 qe2 t
304 qt  (6)
1  k 2 qe t

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305

306where, k2 is the rate constant of pseudo-second-order model (g mg-1 min-1).

307 The curve of pseudo-second-order kinetic was obtained from the plot of q t against time, and

308fitted to the experimental data (Fig. 4b). The experimental q e,exp. = 187 mg g-1 was in agreement

309with qe,calc. = 192 mg g-1 of the pseudo-second-order equation and the R2 value was 0.853. This

310trend indicated that the pseudo-second-order model provided a reliable description for the

311adsorption kinetics of chlorothalonil onto CAC. This result suggested that the rate-limiting step

312could be chemical sorption, also known as chemisorption, involving valence forces via exchange

313or sharing of electrons between CAC (adsorbent) and chlorothalonil (adsorbate) [9].

3143.6. Adsorption isotherm studies

315 Adsorption isotherm models are used to describe the correlation between the number of

316species/ions adsorbed onto the solid phase and that in the solution at equilibrium and constant

317temperature [11].

3183.6.1. Langmuir isotherm

319 The Langmuir adsorption model is proposed based on the following assumptions [18]: (a) the

320adsorptive sites are identical (i.e., equal size and shape), (b) the number of vacant sites is fixed,

321(c) each site can occupy one molecule (monolayer adsorption), and (d) a constant amount of heat

322energy is released during adsorption. The non-linear form of the Langmuir model is expressed by

323Eq. (7).

Qo K L C e
324 qe  (7)
1  K LCe

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325

326where, KL is the Langmuir constant describing the affinity of binding sites towards the sorbate (L

327mg-1), Qo is the amount of adsorbed species per unit mass of adsorbent that forms a complete

328monolayer on the surface bound, i.e., also known as monolayer adsorption capacity (mg g -1), and

329Ce is the adsorbate concentration at equilibrium (mg L-1).

330 Fig. 4c shows the regression plot of q e versus Ce, which resulted in the curve of Langmuir

331isotherm fitted to the sorption data. The high coefficient of determination (R2: 0.937) indicated

332that the adsorption equilibrium constant (KL) of 0.53 L mg-1 was appropriate for describing the

333adsorption isotherm of chlorothalonil onto CAC. In addition, the adsorption sites formed a

334homogenous distribution, and no side interaction undertakes between the adsorbed molecules.

335The adsorption capacity causing complete monolayer coverage of chlorothalonil at the outer

336surface of CAC was 192 mg g -1. As listed in Table 1, the powdered activated carbon prepared

337from Casuarinas wood could provide a higher adsorption performance than several carbon-based

338sorbents reported in the literature.

339 A separation factor in Eq. (8) was proposed to represent the type of the Langmuir isotherm.

1
340 RL  (8)
1  K L  Co

341

342where, RL is the separation factor describing the isotherm shape; i.e., linear isotherm at R L = 1,

343irreversible at RL = 0, favorable isotherm at RL between 0 and 1, and unfavorable at RL > 1.

344 In the current study, the calculated RL was 0.2, indicating that adsorption of chlorothalonil

345onto the prepared activated carbon was favorable.

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346 3.6.2. Freundlich isotherm

347 Freundlich isotherm is an empirical model employed to describe the non-ideal and

348heterogeneous adsorption process [21]. Freundlich isotherm can be expressed in the linear form

349of Eq. (9).

1
350 ln  qe   ln K F   ln Ce  (9)
n

351

352where, KF is the Freundlich constant (or distribution coefficient) describing the adsorption

353capacity of CAC ((mg g-1) (L mg-1)1/n), and 1/n is a constant that depicts the favorability of

354adsorption; i.e., favorable isotherm at 0 < 1/n < 1, irreversible at 1/n = 0, and unfavorable (or

355cooperative adsorption) at 1/n > 1.

356 Fig. 4d displays the regression plot of ln(qe) vs. ln(Ce), which obtained a slope of (1/n) and an

357intercept of ln(KF). The 1/n was 0.184 (i.e., lower than 1), implying that chlorothalonil was

358favorably adsorbed onto CAC. The 1/n of 0.184 referred that 18.4% of the active adsorption sites

359retained same energy level [8]. This result was lower than the “1/n” of 0.300 for Pellet-600,

3600.375 for GAC-F400, and 0.624 for ACF-10 obtained during the adsorption of Cr(VI) onto

361chemically activated carbon materials [11], as well as, 1/n = 0.450 for the removal of

362perfluorooctanoic acid by a powdered activated carbon [20]. The smaller the “1/n”, the more

363effective the adsorbent and the higher sturdy the adsorption strength. Additionally, the

364heterogeneity of solid surfaces increases when the value of “1/n” decreases [9].

3653.7. Quadratic model application

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366 A pure-quadratic model, Eq. (2), was performed to evaluate the effects of experimental

367factors on the uptake capacity of CAC material. The results in Table 2 indicated that the R 2

368between the actual and predicted results was 0.912. The high R2-value ensured a satisfactory

369agreement of the quadratic model to the experimental data. Accordingly, the percentage of

370variation in the response explained by the model was 91%; however, the proposed model could

371not describe 9% of variations in the data. Further, the adjusted-R2 was computed to determine the

372percentage of variation explained by the independent variables that affected the model output

373[13]. It was found that the adjusted-R2 of 0.904 was close to the R 2-value, which indicated that

374the independent variables were important and no data overfitting occurred.

375 The linear and quadratic effects of each independent variable on the uptake capacity of CAC

376were determined by t-test, as listed in Table 2. The quadratic effect of pH and the linear

377influence of Co were found to be significant (p < 0.05). This result indicated that the plot of

378uptake capacity versus each of pH and Co resulted in quadratic concave and linear up curves,

379respectively. Moreover, the effect of CAC dosage on the uptake capacity was non-significant (p

380> 0.05), whereas the reaction time exhibited both linear and quadratic influences (p < 0.05). This

381trend indicated that the plot of the uptake capacity against each of CAC dosage and contact time

382caused flat and quadratic-linear concave up curves, respectively.

383 A response surface methodology was employed to fit the adsorption data and display the

384curve type of a single predictor. The example in Fig. 5 showed that at pH 7, Co 240 mg L-1, CAC

385dosage 0.50 g L-1, and contact time 20 min, the expected uptake capacity was 90 mg g-1. This

386result was close the actual value of 94 mg g -1, suggesting that the developed model could be used

387to predict the uptake capacity at certain independent variables.

3883.8. ANN results

35 18
36
3893.8.1. Estimation of ANN output

390 The output of a feed-forward neural network with one hidden layer can be calculated from

391Eq. (10).

^ m  k  
392 Y  f o W j  f h  Wij . X i  b j   bo  (10)
 j 1  i 1  

393

394where, Ŷ is the simulated output value, k and m are the numbers of input neurons (i.e., k = 4) and

395hidden neurons (i.e., m = 5), respectively, W ij is the weight of connection between ith input and jth

396hidden neuron, Wj is the weight of connection between jth hidden neuron and output neuron, bj

397and bo are the biases of hidden and output layers, respectively, and f h and fo are the transfer

398functions of hidden and output layers, respectively.

399 The application of Eq. (10) can be illustrated as follows:

400 Each element of the input vector (P4 × 1) was connected to each neuron in the hidden layer

401through a weight matrix (W5 × 4). The inputs were weighted and summed up (ΣW5 × 4 P4 × 1), and

402then a bias (b5 × 1) was added. The resulted net input (u5 × 1 = ΣW5 × 4 P4 × 1 + b5 × 1) was transformed

403to the output layer through “tansig” transfer function.

404 Each neuron of the hidden layer vector (u5 × 1) was connected to the single neuron in the

405output layer through a weight matrix (W1 × 5). The inputs were weighted and summed up (ΣW 1 × 5

406u5 × 1), and then a bias (b1 × 1) was added. The resulted net input (Ŷ 1 × 1= ΣW1 × 5 u5 × 1 + b1 × 1) was

407converted to the output layer through “purlin” transfer function.

4083.8.2. ANN training and validation

37 19
38
409 The training and validation procedures were used to calculate the optimum weights (W 5 × 4

410and W1 × 5) and biases (b5 × 1 and b1 × 1) providing the minimum MSE [29]. The plot in Fig. 1b

411depicts the MSE versus the iteration number for training, validation and test curves. After epoch

412number 0, the MSE of training started to decrease gradually until epoch number 6. This trend did

413not recognize any major problem with the network training because the MSE was minimized. On

414the contrary, after epoch number 0, the MSE of the validation set typically initiated to increase,

415indicating that the network started to over-fit the data [17]. The test curve also increased after

416epoch number 0, demonstrating that the validation and test behaviors were identical. This result

417revealed that the best validation performance was 33.9 at epoch number 0. At this point, the

418adjustable weights and biases were determined (Table S1).

419 The training step is terminated if the magnitude of the gradient of performance becomes less

420than 1e-5, or if the number of successive iterations that the validation performance fails to

421decrease reaches 6.0, whichever occurs first [17]. As displayed in Fig. 1c, the training process

422was finished at epoch = 6, where the magnitude of the gradient of performance was 7.86 (i.e.,

423higher than 1e-5), and the number of validation checks was equal to 6. This observation

424indicated that the training step stopped because the number of validation checks reached 6,

425regardless the gradient of performance.

4263.8.3. ANN regression plot

427 The regression analysis of ANN depicted the R 2 value between network outputs and

428corresponding targets (Fig. S2). The training, validation, and test plots indicated a good fit with

429R2 values of 0.983, 0.977, and 0.985, respectively. The overall R 2 value considering the

430aforementioned steps was 0.982, showing the model reliability. This performance revealed that

43198.2% of the variations in the uptake capacity were explained by the independent variables;

39 20
40
432however, 1.8% of the total variability in the response was not defined by the ANN model. After

433training, validation, and test, the developed ANN model can be used to predict responses using

434new input data. It should be noticed that the ANN model provided higher accuracy than the

435quadratic model in predicting the uptake capacity, indicating that it could be recognized as a

436powerful predictive tool for the adsorption process.

4373.8.4. Sensitivity analysis

438 Sensitivity analysis was employed to determine: (a) the relative importance (RI) of each

439input variable, and (b) the input factor that provided the highest impact on the ANN output. This

440step was conducted using the “Weights method”, which partitions the hidden-output connection

441weights of every hidden neuron into constituents linked to each input neuron [14].

442 For each hidden neuron j, the absolute value of W ij is divided by the sum of the absolute

443value of Wij of all input neurons. This step can be described by Eq. (11).

444 For j = 1 to m

445 For i = 1 to k

Wij
Qij 
446 k (11)
W
i 1
ij

447

448 For each input neuron i, the sum of the Q ij for each hidden neuron “j” is divided by the sum

449for each hidden node “j” of the sum for every input neuron “i” of Qij. The RI of all output

450weights for a certain input factor is then estimated by Eq. (12).

41 21
42
451 For i = 1 to k

Q
j 1
ij

452 RI (%)  m k
 100 (12)
 Q
j 1 i 1
ij

453

454 The results in Fig. 1d indicated that the solution pH was the highest contributed factor with

455an RI of 54%. The pH of the medium provided the major effect on adsorption performance as it

456impacts both the surface characteristics of activated carbon and the ionization/dissociation of

457adsorbate molecules [26]. This result was followed by Co (RI: 24%) and reaction time (RI: 19%).

458However, the influence of the CAC dosage was the least. This observation was in agreement

459with that obtained from the t-test (Table 2), which indicated that the adsorbent dosage had no

460significant effect on the model output and its relationship with the uptake capacity resulted in a

461flat curve.

4623.9. Cost estimation

463 Despite the success of the adsorption process in the removal of pesticide pollutants, there is a

464lack of studies that dealt with the economic aspects. In this section, real wastewater samples

465were collected from Chema pesticides Co, at Nubareia City, Egypt. The company produced a

466daily discharge of 100 m3 containing chlorothalonil concentration of 250 ± 50 mg L-1. Batch tests

467were conducted based on the optimum environmental condition of pH: 7, and adsorbent dosage:

4680.75 g L-1, as obtained previously. The contact time was selected as 40 min because the design

469criteria of a large-scale treatment facility entail shorter contact time, which can decrease the

43 22
44
470sizing of units. The total cost of the adsorption process (TC) was estimated by considering the

471amortization cost of the investment (AC) and operating cost (OC); i.e., TC = AC + OC.

4723.9.1. Amortization cost of investment (AC)

473 The AC was assumed as the sum of the installation (construction) items and the required

474mechanical and electrical facilities [31]. The total treated volume describes the number of

475batches conducted for a particular working duration. Hence, the treatment unit capacity (V c, in

476m3) can be computed based on the ratio of the working hours per day (t w: assuming 8 h d-1) to the

477treatment time in each batch (tt: assuming 40 min), as seen in Eq. (13).

Vt tt
478 Vc   (13)
D tw

479

480where, Vt is the total treated volume on a yearly basis (m3 yr-1), and D is the number of operating

481days (i.e., 300 d yr-1).

482 The amortization of investment per m3 of wastewater was calculated by Eq. (14) [6].

C p  Vc
483 AC  (14)
L  Vt

484

485where, Cp is the cost per cubic meter of the treatment unit (i.e., assumed as 10000 $ m -3 based on

486quotes from local contractors), and L is the lifecycle of the adsorption unit (assuming 10 yr).

487 The AC per year (ACannual) was estimated by Eq. (15).

45 23
46
  1  i  L i 
488 AC annual  AC  
 (15)
  1  i  L
 1 

489

490where i is annual interest rate (assuming of 4%).

491 Based on the yearly wastewater discharge of 36500 m3, the units volume could be

492approximately 10 m3 resulting in AC of 0.34 $ m-3. This value was equivalent to 29% of the TC.

4933.9.2. Operating cost (OC)

494 The OC included the adsorbent material with a lifespan of 2 yr, water and chemicals supply,

495and energy consumption. The labour expenses were not involved in this study for simplification

496because the adsorption process does not require intensive manpower.

497 The costs of adsorbent and utilized chemicals, namely C reactant, were calculated from the

498dosage (Ci in kg m-3) multiplied by the unit price (Pi in $ kg-1). Based on a cost survey from local

499suppliers and administrative databases in the period of 2012–2016, the P i of CAC material

500(including the collection of raw material, cleaning, and activation) and chemicals were 0.6–0.7

501and 0.40–0.45 $ kg-1, respectively.

502 The energy cost (EC, in $ m -3) was calculated by Eq. (16), based on the power required for

503mixing, drying, and equipment operation.

E  PE  t w  D
504 EC  (16)
Vt

505

506where, E is the consumed power (kW), PE is the unit price of power energy (i.e., 0.24 $ kWh-1).

47 24
48
507 Maintenance cost was assumed as 2% of the AC [31]. Hence, the total operating cost

508including consumed materials, power, and maintenance was calculated by Eq. (17)

2
509 OC  Creac tan t  EC  AC (17)
100

510

511 Results showed that the reagent cost was Creactant = 0.70 $ m-3, corresponding to 59.2% of TC.

512In addition, the reactant cost was higher than the energy cost and the resulting OC was 0.84 $ m -

5133. Similarly, Alalm et al. [6] found that the variation of OC was mainly depended on the dosage

514and type of chemicals in a solar TiO 2 photocatalysis and solar photo-Fenton employed for the

515treatment of pesticides industry wastewater. Thus, the total cost including amortization and

516operating costs was estimated as 1.18 $ m-3. In addition, the chlorothalonil concentration in the

517treated effluent was not detected, suggesting a removal efficiency of approximately 100%. This

518result indicated that CAC could be used as a low-cost and efficient material for the adsorption of

519chlorothalonil. However, further studies should be conducted using a large-scale application for

520the adsorption process under a continuous mode of operation; i.e., and that will be the focus of

521our future work.

5224. Conclusions

523 Casuarina wood was found to be a promising raw material for developing activated carbon

524that can be used for the adsorption of chlorothalonil ion from aqueous solutions. The adsorbent

525material contained multiple functional groups such as ketones, esters, alkenes, aromatic, alcohol,

526hydroxyl, and carboxyl, suggesting a chemically heterogeneous surface. The optimum pH value

527was 7, which achieved adsorption capacity of 187 mg g-1 at Co: 480 mg L-1, adsorbent dosage: 0.5

49 25
50
528g L-1, and equilibrium time: 40 min. The pseudo-second-order equation provided a reliable

529description of the adsorption kinetics, signifying that the rate-limiting step could be

530chemisorption. Langmuir model described the isotherm study with a monolayer adsorption

531capacity of 192 mg g-1, and Freundlich isotherm indicated that chlorothalonil was favorably

532adsorbed onto the CAC material. The plot of adsorption capacity against every experimental

533factor demonstrated that pH, Co, adsorbent dosage, and contact time caused quadratic-concave,

534linear-up, flat, and quadratic-linear concave up curves, respectively. An ANN of 4–5–1 was a

535powerful predictive tool for the adsorption process (R 2: 0.982), and the sensitivity analysis

536indicated that the relative importance of each experimental factor was: pH (54%) > C o (24%) >

537reaction time (19%) > adsorbent dosage (3%). An economic estimation (i.e., AC and OC) of an

538adsorption unit subjected to 100 m3 d-1 of wastewater containing chlorothalonil of 250 ± 50 mg

539L-1 could cost 1.18 $ m-3.

540Acknowledgement

541 The authors gratefully acknowledge the financial support from Science and Technology

542Development Fund (STDF).

543References

544[1] WHO. The WHO Recommended Classification of Pesticides by Hazard and Guidelines to

545Classification. Geneva, Switzerland: World Health Organization; 2009.

546[2] Chaves A, Shea D, Danehower D. Analysis of chlorothalonil and degradation products in soil

547and water by GC/MS and LC/MS. Chemosphere 2008;71:629–38.

548[3] Gar Alalm M. The performance of electro-Fenton oxidation in the removal of pesticides from

549wastewater using stainless steel electrodes. Int Proc Chem Biol Environ Eng 2016;98:9–14.

51 26
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550[4] Cox C. Fungicide fact sheet: chlorothalonil. J Pestic Reform 1997;17:14–20

551[5] Kwon JW, Armbrust KL. Degradation of chlorothalonil in irradiated water/sediment systems.

552J Agr Food Chem 2006;54:3651–7.

553[6] Alalm MG, Tawfik A, Ookawara S. Comparison of solar TiO 2 photocatalysis and solar

554photo-Fenton for treatment of pesticides industry wastewater: operational conditions, kinetics,

555and costs. J Water Process Eng 2015;8:55–63.

556[7] Alalm MG, Tawfik A, Ookawara S. Combined solar advanced oxidation and PAC adsorption

557for removal of pesticides from industrial wastewater. J Mater Environ Sci 2015;6:800–9.

558[8] Kumar A, Prasad B, Mishra IM. Adsorptive removal of acrylonitrile by commercial grade

559activated carbon: kinetics, equilibrium and thermodynamics. J Hazard Mater 2008;152:589–600.

560[9] El Nemr A, Abdelwahab O, El-Sikaily A, Khaled A. Removal of direct blue-86 from aqueous

561solution by new activated carbon developed from orange peel. J Hazard Mater 2009;161:102–10.

562[10] Kumar A, Prasad B, Mishra IM. Isotherm and kinetics study for acrylic acid removal using

563powdered activated carbon. J Hazard Mater 2010;176:774–83.

564[11] Yue Z, Bender SE, Wang J, Economy J. Removal of chromium Cr (VI) by low-cost

565chemically activated carbon materials from water. J Hazard Mater 2009;166:74–8.

566[12] Alalm MG, Tawfik A, Ookawara S. Solar photocatalytic degradation of phenol by TiO 2/AC

567prepared by temperature impregnation method. Desalin Water Treat 2016;57:835–44.

568[13] Ateia M, Nasr M, Ikeda A, Okada H, Fujii M, Natsuike M, et al. Nonlinear relationship of

569near-bed velocity and growth of riverbed periphyton. Water 2016;8:461.

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570[14] Gevrey M, Dimopoulos L, Lek S. Review and comparison of methods to study the

571contribution of variables in artificial neural network models. Ecol Model 2003;160:249–64.

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573purpose using artificial neural network. Egypt J Aquat Res 2014;40:111–5.

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575for predicting the impact of rolling dynamic compaction using dynamic cone penetrometer test

576results. J Rock Mech Geotec Eng 2017;9:340–9.

577[17] Nasr M, Mahmoud AED, Fawzy M, Radwan A. Artificial intelligence modeling of

578cadmium (II) biosorption using rice straw. Appl Water Sci 2017;7:823–31.

579[18] Mittal A, Kaur D, Malviya A, Mittal J, Gupta VK. Adsorption studies on the removal of

580coloring agent phenol red from wastewater using waste materials as adsorbents. J Colloid Interf

581Sci 2009;337:345–54.

582[19] Gupta VK, Gupta B, Rastogi A, Agarwal S, Nayak A. A comparative investigation on

583adsorption performances of mesoporous activated carbon prepared from waste rubber tire and

584activated carbon for a hazardous azo dye-Acid Blue 113. J Hazard Mater 2011;186:891–901.

585[20] Qu Y, Zhang C, Li F, Bo X, Liu G, Zhou Q. Equilibrium and kinetics study on the

586adsorption of perfluorooctanoic acid from aqueous solution onto powdered activated carbon. J

587Hazard Mater 2009;169:146–52.

588[21] Hameed BH, Salman JM, Ahmad AL. Adsorption isotherm and kinetic modeling of 2,4-D

589pesticide on activated carbon derived from date stones. J Hazard Mater 2009;163:121–6.

55 28
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590[22] Mittal A, Mittal J, Malviya A, Kaur D, Gupta VK. Decoloration treatment of a hazardous

591triarylmethane dye, Light Green SF (Yellowish) by waste material adsorbents. J Colloid Interf

592Sci 2010;342:518–27.

593[23] Nasr MS, Moustafa MAE, Seif HAE, El Kobrosy G. Application of Artificial Neural

594Network (ANN) for the prediction of EL-AGAMY wastewater treatment plant performance-

595EGYPT. Alexandria Eng J. 2012;51:37–43.

596[24] Ioannidou OA, Zabaniotou AA, Stavropoulos GG, Islam MA, Albanis TA. Preparation of

597activated carbons from agricultural residues for pesticide adsorption. Chemosphere

5982010;80:1328–36.

599[25] Gupta VK, Saleh TA. Sorption of pollutants by porous carbon, carbon nanotubes and

600fullerene – an overview. Environ Sci Pollut Res 2013;20:2828–43.

601[26] Rahim AA, Garba ZN. Efficient adsorption of 4-chloroguiacol from aqueous solution using

602optimal activated carbon: equilibrium isotherms and kinetics modeling. J Assoc Arab Univ Basic

603Appl Sci 2016;21:17–23.

604[27] Behnamfard A, Salarirad MM. Equilibrium and kinetic studies on free cyanide adsorption

605from aqueous solution by activated carbon. J Hazard Mater 2009;170:127–33.

606[28] Gupta VK, Agarwal S, Saleh TA. Synthesis and characterization of alumina-coated carbon

607nanotubes and their application for lead removal. J Hazard Mater 2011;185:17–23.

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609adsorption of phenol and resorcinol from water environment using some carbonaceous

610adsorbents. J Hazard Mater 2011;188:67–77.

57 29
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611[30] Derylo-Marczewska A, Blachnio M, Marczewski AW, Swiatkowski A, Buczek B.

612Adsorption of chlorophenoxy pesticides on activated carbon with gradually removed external

613particle layers. Chem Eng J 2017;308:408–18.

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615estimation for degradation of phenol by solar photo-Fenton process. Appl Water Sci 2017;7:375–

61682.

617

618

59 30
60
619Table 1

620Comparison of the maximum adsorption capacity of pesticides and toxic substances onto carbon-

621based adsorbents. AC: Activated carbon, and PAC: Powdered activated carbon.

Carbon-based adsorbent Toxic element Qo (mg g-1) Reference

AC 4-Chloroguiacol 499 [26]
AC from date stones 2,4-D pesticide 238 [21]
PAC Chlorpyrifos 200 [7]
AC from casuarina charcoal Chlorothalonil pesticide 192 This study
PAC Acrylonitrile 52 [8]
AC Cyanide 48 [27]
PAC Acrylic acid 36 [10]
AC from orange peel Direct blue-86 34 [9]
PAC Lambda Cyhalothrin 23 [7]
PAC Perfluorooctanoic acid 17 [20]
AC from waste rubber tire Azo dye—Acid Blue 113 9.2 [19]
PAC Diazinon 8.1 [7]
622

623

624

625

61 31
62
626Table 2

627t statistics and p-values for coefficients of the pure-quadratic regression model. In which, X 1: pH,

628X2: initial chlorothalonil concentration, X3: CAC dosage, and X4: contact time. The significant

629levels at the 95% level (p < 0.05) were considered to have a greater impact on the response. The

630model accuracy at R2: 0.912, and adj-R2: 0.904.

Factor Regression

coefficient Std Error t Ratio Prob > |t| Effect

β0: 71.65 53.36 1.343 0.183 Non-Significant
X1 β1: 7.56 5.74 1.316 0.192 Non-Significant
X2 β2: 0.36 0.06 6.224 0.000 Significant
X3 β3: -208.1 151.1 -1.376 0.172 Non-Significant
X4 Β4: 2.41 0.44 5.460 0.000 Significant
(X1)2 β11: -1.22 0.44 -2.776 0.007 Significant
(X2)2 β22: 0.000 0.00 -1.199 0.234 Non-Significant
(X3)2 β33: 51.653 102.45 0.504 0.615 Non-Significant
(X4)2 β44: -0.028 0.01 -4.215 0.000 Significant
631

632

633

634

635

636

63 32
64
 b5î 1 b1î 1
(a) (b)
5

Initial pH 1
6
Chlorothalonil
concentration 2
Adsorption
7 10
capacity
CAC dosage 3 Output layer node
8 (n = 10)
Reaction time 4
9
Input layer nodes
(k = 1, 2…, 4)
Hidden layer nodes
(m = 5, 6…, 9)

(c) (d)
Relative importance
CAC dosage
3.1% Reaction
time 18.9%

Initial pH
Chlorothalonil 54.2%
conc. 23.8%

637

638Fig. 1. Artificial neural network for the prediction of the uptake capacity of CAC: (a) ANN

639structure of 4–5–1, (b) validation performance, (c) training parameters, and (d) relative

640importance of each input using the connection weights.

641

642

643

644

645

646

65 33
66
 (a) (b)

Transmittance (%)
Wavenumber (cm-1)

647

648Fig. 2. Characterization of the prepared CAC: (a) SEM image, and (b) FTIR.

649

650

651

652

653

654

655

656

657

658

659

660

67 34
68
 (a) 200 (b) 200
180 180

Adsorption capacity (mg g-1)

Adsorption capacity (mg g-1)

160 160
140 140
120 120
100 100
80 80
60 60
40 40
20 20
0 0
2.0 3.5 5.0 6.5 8.0 9.5 11.0 0 10 20 30 40 50 60
Initial pH Contact time (min)
60 mg L⁻¹ 120 mg L⁻¹ 240 mg L⁻¹
60 mg L⁻¹ 240 mg L⁻¹ 480 mg L⁻¹
360 mg L⁻¹ 480 mg L⁻¹
(c) 200
180
Adsorption capacity (mg g-1)

160
140
120
100
80
60
40
20
0
0 10 20 30 40 50 60
Contact time (min)

0.50 g L⁻¹ 0.75 g L⁻¹ 1.00 g L⁻¹

661

662Fig. 3. Effect of experimental factors on the uptake capacity of CAC: (a) initial pH, (b) initial

663chlorothalonil concentration, and (c) CAC dosage.

664

665

666

667

668

669

69 35
70
 (a) 6 Pseudo-First-Order (b) 190 Pseudo-Second-Order
5 185
4 180
ln(qe – qt) = -0.1166t + 5.3863
ln(qe - qt) (mg g-1)

qt (mg g-1)
R² = 0.9931 175
3 105.3t
170 qt 
2 1  0.5474t
165
1 160 R² = 0.8529
0 155
0 10 20 30 40 50 60 150
-1
0 10 20 30 40 50 60
-2
t (min) t (min)

(c) 200 Langmuir Isotherm (d) 4.6 Freundlich Isotherm

4.4
150 4.2

ln(qe) (mg g-1)

102.0Ce
qe (mg g-1)

qe  4.0
100 1  0.531Ce 3.8
R² = 0.9372 3.6 ln(qe) = 0.1844ln(Ce) + 3.5486
50 3.4 R² = 0.9408
3.2
0 3.0
0 20 40 60 80 -2 0 2 4 6
Ce (mg L-1) ln(Ce) (mg L-1)
670

671Fig. 4. Kinetics and isotherm studies of chlorothalonil adsorption at qe,exp. = 187.1 mg g-1: (a)

672Linear form of pseudo-first-order model (qe,calc.: 218.4 mg g-1; k1: 0.117 min-1; R2: 0.993), (b)

673Non-linear equation of pseudo-second-order model (qe,calc.: 192.3 mg g-1; k2: 0.003 g mg-1 min-1;

674R2: 0.853), (c) Non-linear model of Langmuir isotherm (Qo: 192.0 mg g-1; KL: 0.531 L mg-1; R2:

6750.937), and (d) Freundlich isotherm (KF: 34.8 mg1-1/n L1/n g-1; 1/n: 0.184; R2: 0.941).

676

677

678

679

680

681

71 36
72
682

683Fig. 5. Response surface methodology for describing the correlation between experimental

684factors and the uptake capacity of CAC.

685

686

687

688

689

73 37
74
690Supplementary materials

691Table S1

692Weights and threshold levels of the designed ANN model.

Hidden layer Weight from node i in input layer to node j in hidden layer for the matrix W5 × 4 Hidden layer
k=1 k=2 k=3 k=4
node threshold (b5 × 1)
m=5 -3.17 -8.64 1.48 0.56 -5.922
m=6 -3.16 -0.86 -4.21 2.06 -1.688
m=7 -7.25 1.90 0.37 3.04 -1.294
m=8 -2.94 1.62 0.10 0.71 -0.746
m=9 -1.584 -1.981 1.249 -0.033 0.702

Output layer Weight from node j in hidden layer to node k in output layer for the matrix W1×5 Output layer
m=5 m=6 m=7 m=8 m=9
node threshold (b1 × 1)
n = 10 -0.09 0.35 -0.23 0.70 -0.47 -0.304
693

694

75 38
76
695

696

697Fig. S1. Chemical structure of chlorothalonil (2,4,5,6-tetrachloroisophthalonitrile).

698

699

700

701

702

703

704

705

706

707

708

77 39
78
709

2 2
Training: R =0.983 Validation: R =0.977

150 150
Output = 0.99×Target + 0.46

Output = 1×Target + 2
100 100

50 50

50 100 150 50 100 150

Target Target

2 2
Test: R =0.985 All: R =0.982

150 150
Output = 0.98×Target + 0.72
Output = 0.98×Target + -2

100 100

50 50

50 100 150 50 100 150

Target Target
710

711Fig. S2. Regression plot of training, validation, and test procedures for the prediction of CAC

712uptake capacity using 4–5–1 ANN. The dashed line expresses the perfect fit, where the model

713outputs are equal to the targets. The solid line signifies the best-fit linear regression that indicates

714the ANN performance. The total number of data sets is 96.

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