Water Science and Technology

Effective removal of an alkaline dye in water using raw shrimp-waste and its activated
charcoals
--Manuscript Draft--

Manuscript Number:

Full Title: Effective removal of an alkaline dye in water using raw shrimp-waste and its activated
charcoals

Short Title: Removal of alkaline dyes by shrimp waste

Article Type: Research Paper

Section/Category: Physico-Chemical Treatment for Wastewater

Keywords: Shrimp waste, activated charcoal, sorption isotherms, emerging pollutants, crystal
violet, sorption kinetics

Corresponding Author: john rojas, PhD

Universidad de Antioquia
Medellin, antioquia COLOMBIA

Corresponding Author Secondary

Information:

Corresponding Author's Institution: Universidad de Antioquia

Corresponding Author's Secondary

Institution:

First Author: john rojas, PhD

First Author Secondary Information:

Order of Authors: john rojas, PhD

David Suarez, MsC

Javier Silva, PhD

ricardo Torres, PhD

Alfredo Moreno, BsC

Order of Authors Secondary Information:

Manuscript Region of Origin: COLOMBIA

Abstract: crystal violet (CV). Activation was conducted with phosphoric acid at a 1:2 and 1:3
ratios. Activated charcoals were more porous and had a more roughly surface
containing mainly C, O, Ca and P since the initial N content of waste disappeared. All
adsorbents exhibited a pseudo-second order of adsorption kinetics. Further, the
activation created acidic moieties and reduced the point of zero charge. Further, the
best fit was obtained by the Freundlich isotherm, suggesting a heterogeneous
adsorption process. An endothermic and spontaneous physisorption was responsible
for the sorption phenomena in most adsorbents. The high removal of CV was attributed
to the high ionization capacity of the adsorbent along with the external surface area
and microporosity. Further, hydrogen bonding, electrostatic interactions and -
interactions were the main type of forces responsible for CV adsorption. Shrimp waste
as the starting material for the production of activated charcoals represents an
interesting option since this material is highly economical and widely available.
Therefore, it is possible to deal with two environmental problems: (i) the reuse of
shrimp waste, and (ii) the removal of water pollutants such as an alkaline dye.

Suggested Reviewers: Md Juned Ahmed

Nacional'nyj issledovatel'skij universitet Moskovskij institut elektronnoj tehniki Fakul'tet
institut Ekonomiki upravlenia i prava
md_a2002@rediffmail.com
Expert in activated charcoal

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 Hailing Wang
Nanjing Tech University
wanghailing@njtech.edu.cn
Expert in dye removal

Rupam Kataki
Latvijas Universitate
rupamkataki@gmail.com
Expert in dye removal from activated charcoals

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Manuscript Click here to access/download;Manuscript;adsorbent
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1
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6 1 Effective removal of an alkaline dye in water using raw shrimp-
7
8 2 waste and its activated charcoals
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10 3
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4 Removal of alkaline dyes by shrimp waste
12
13 5 J. Rojas*a, D. Suarez a, J. Silva-Agredob, R.A. Torres-Palmab*, A. Moreno a
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15 6
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17 7
18
19 8 a
Department of Food, College of Pharmaceutical and Food Sciences, University of Antioquia, Medellín, Columbia,
20 9 street 67 # 53-108, lab 5-108, Medellín, Colombia.
21 10
22 11 b
Grupo de Investigación en Remediación Ambiental y Biocatálisis (GIRAB), Instituto de Química, Facultad de
23 12 Ciencias Exactas y Naturales, Universidad de Antioquia UdeA, Calle 70 No. 52-21, Medellín, Colombia.
24 13
25
26 14 Corresponding author: *jhon.rojas@udea.edu.co (Tel: +44(0)1223334786)
27 15 *ricardo.torres@udea.edu.co (Tel: +57 4 219 56 69; Fax: +57 4 219 56 66)
28
29
16 ABSTRACT
30
31
32 17 Shrimp waste and its charcoal derivatives were evaluated for the removal of the alkaline dye
33
34 18 crystal violet (CV). Activation was conducted with phosphoric acid at a 1:2 and 1:3 ratios.
35
36 19 Activated charcoals were more porous and had a more roughly surface containing mainly C, O,
37
38 20 Ca and P since the initial N content of waste disappeared. All adsorbents exhibited a pseudo-
39
21 second order of adsorption kinetics. Further, the activation created acidic moieties and reduced
40
41 22 the point of zero charge. Further, the best fit was obtained by the Freundlich isotherm, suggesting
42
43 23 a heterogeneous adsorption process. An endothermic and spontaneous physisorption was
44
45 24 responsible for the sorption phenomena in most adsorbents. The high removal of CV was
46
47 25 attributed to the high ionization capacity of the adsorbent along with the external surface area and
48
49 26 microporosity. Further, hydrogen bonding, electrostatic interactions and - interactions were the
50
51
27 main type of forces responsible for CV adsorption. Shrimp waste as the starting material for the
52 28 production of activated charcoals represents an interesting option since this material is highly
53
54 29 economical and widely available. Therefore, it is possible to deal with two environmental
55
56 30 problems: (i) the reuse of shrimp waste, and (ii) the removal of water pollutants such as an
57
58 31 alkaline dye.
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62 1
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4 32 Keywords: Shrimp waste, activated charcoal, sorption isotherms, emerging pollutants, crystal
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6 33 violet, sorption kinetics
7
8 34 INTRODUCTION
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11 35 Different types of dyes are used in various applications such as textiles, ceramics, printing and
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13 36 paper production. However, their residues are poorly disposed, generating risks to public health
14
15 37 and the environment. It is estimated that around fourteen thousand metric tons of textile dyes are
16
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38 thrown into the environment each year, causing a serious damage to the environment (Daneshvar
18 39 et al. 2014). A special case corresponds to the alkaline dyes. For instance, crystal violet (CV) is
19
20 40 highly harmful to human health, causing eye irritation and cornea damage upon contact with the
21
22 41 eyes. Further, CV ingestion generates nausea, vomiting, respiratory distress, diarrhea, and
23
24 42 abdominal pain (Otero, et al. 2003). CV also prevents the penetration of sunlight into the water
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26 43 stream, reducing both the photosynthetic activity and the dissolution of oxygen (Nelson & Hites
27
44 1980). The high residence time of CV in water is due to its resistance to physical, chemical and
28
29 45 biological degradation, making it highly harmful for aquatic organisms, since just 1 ppm inhibits
30
31 46 the photosynthesis of aquatic plants (Adegoke & Bello 2015).
32
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34 47 Different technologies have been reported in the literature to remove dies. However, the
35
36 48 adsorption-based systems are one of the most attractive alternatives due to their easy
37
49 implementation and short application time. Therefore, many adsorption materials have been
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39 50 studied for removing dies. Carbon nanotubes and graphene are among the preferred adsorbents
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41 51 for removing pollutants from waters (Xu et al. 2018). Nevertheless, the use of these adsorbents is
42
43 52 inconvenient due to their high production costs. On the contrary, low cost and environmentally
44
45 53 friendly activated charcoals can be prepared from feedstock such as coconut shells and palm
46
47 54 seeds (Hu et al. 2001) achieving a high carbon content and low amount of ash (González 2018).
48
55 Likewise, minerals and lignite could also originate activated charcoals.
49
50 56
51
52 57 Activated charcoal is a material whose main component is carbon, considered
53
54 58 macroscopically an amorphous material which is an allotropic form of graphite. Activated
55
56 59 charcoal has a high surface area, microporous structure and surface chemistry, mainly composed
57
58 60 of carboxylic, phenolic, ketone, quinone, hydroquinone and aldehyde moieties. The adsorption
59 61 properties depend on the precursor material and the activation method (Asimbaya, et al. 2015).
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62 2
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4 62 The physical or thermal activation can be carried out in presence of water vapor, CO2 or air.
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6 63 Conversely, the chemical activation require low temperatures and an activation agent which
7 64 inhibit the production of volatile substances during the process.
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9 65
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11 66 Annually, the world production of crustacean waste ranges from 6 to 8 million tons, being
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13 67 China, Indonesia, Thailand and India the countries with the highest production rate resulting in a
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15 68 large quantity of shrimp and crabs waste (Cheba et al. 2018). Thus, the conversion of shrimp
16
17 69 waste into activated charcoals will decrease the waste disposal, making these materials a value-
18 70 added product with potential applications in polluted water treatment.
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21 71 Some attempts have been conducted for the adsorption of dyes with shrimp waste. For
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23 72 example, shell waste was extracted from Penaeus indicus to adsorb the acid blue anionic dye 25
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25 73 (Daneshvar et al. 2014). This adsorption was favored at acidic pH and small particle size. In
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27 74 another study, the removal of mixtures of two dyes (Direct red 80 and direct blue 71) was
28 75 evaluated using shell waste from two different species of shrimp (Aristaeomorpha foliacea and
29
30 76 Aristeus antennatus) obtaining a removal greater than 90% (Fabbricino & Pontoni 2016).
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32 77 Another study reported a biochar obtained from shrimp waste for the adsorption of methylene
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34 78 blue, especially favored at alkaline pH (Liu et al. 2018). Therefore, the goal of this study is to
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36 79 assess the sorption power of shrimp waste, its pyrolyzed material and its activated charcoals by
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38 80 phosphoric acid for the removal of an alkaline dye (crystal violet) as compared to a commercial
39 81 activated charcoal.
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42 82 METHODS
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44 83
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46 84 Isolation and treatment of shrimp waste
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48 85 Shrimp waste was collected from the coast of Tumaco (Columbia), dried in an oven (Memmert,
49 86 Germany) at 150 °C for 30 minutes and milled in a cutting mill (Willey Arthur Thomas Co,
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51 87 Philadelphia, USA). Subsequently, it was depigmented with sodium hypochlorite (15% w/v) for
52
53 88 5 days, neutralized with 1.0 M HCl, filtered under vacuum, dried at 100 °C and passed through #
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55 89 200 mesh (75 μm) sieve. This material was subjected to successive washes with distilled water in
56
57 90 a 1.0 L beaker, followed by sonication at 40 °C for 30 minutes (Elmasonic E 15H, Elma GmbH
58
59
91 & Co, Germany) and occasional stirring. The resulting powder was labeled as shrimp waste
60 92 (SW).
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62 3
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4 93
5
6 94 Pyrolysis of shrimp waste
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95
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9 96 Approximately, 187 g of SW was submitted to pyrolysis at 500°C in an electric muffle (KSY-6D-
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11 97 16B, Electric Furnace Factory, France) coupled to a nitrogen pumping at a rate 2.9 °C/min for 2h.
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13 98 Subsequently, the carbonized material was passed through a # 200 (75 m) sieved and labeled as
14
15 99 the charred material (CM).
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17 100
18
19
101 Activation of shrimp waste and charred material with phosphoric acid
20 102
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22 103 The same conditions described in the pyrolysis process were employed, except for a heating time
23
24 104 of 1h. The SW-to-phosphoric acid ratio of 1:2 was employed. Activated adsorbents were
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26 105 neutralized with 0.1N KOH in order to eliminate the residual acid, followed by washings with
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28 106 distilled water and a final vacuum filtration. Subsequently, the material was tray-dried in an oven
29
107 at 100 °C for 48 h and passed through #200 mesh. This material was named as AC1. In a separate
30
31 108 experimental condition the same procedure was conducted using the CM material as precursor at
32
33 109 1:3 adsorbent: acid ratio employing the same activator. This sample was labeled as AC2.
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35 110
36
37 111 Physicochemical characterization of adsorbents
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39 112 The moisture content was determined using a moisture balance (OHAUS, MB200, U.S.A.), at
40
113 100 °C for 5 min. Bulk density (ρbulk) was obtained on 2 g sample and measuring the volume
41
42 114 using a 10 mL graduated glass cylinder (BrecKnell Model MBS-300, Fairmont, USA). True
43
44 115 density (true) was determined by gas pycnometry using a Helium pycnometer (Micromeritics,
45
46 116 reference AccuPyC II 1340, Norcross, U.S.A). Porosity was obtained from the equation:
47
48 117
49
50 118 ε = [1- (ρbulk / ρtrue)] x 100% (1)
51 119
52
53 120 The Specific surface area (SBET) was found using a sorption system (ASAP 2020 PLUS,
54
55 121 Norcross, USA) at relative pressures ranging from 0.02 to 0.25. The samples were degassed for
56
57 122 240 minutes at 350 °C under vacuum conditions. The pH and conductivity measurements were
58
59 123 made using a combo digital pH meter and conductivity meter (EC600, Extech Instruments,
60
61 124 Massachusetts, U.S.A.) at room temperature of a 5% adsorbent dispersion.
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4 125
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6 126 Morphology and elemental analysis (SEM/EDX)
7 127 They were performed using a Scanning Electron Microscope (SEM, Joel 6490LV, Peabody, MA,
8
9 128 U.S.A.) at an accelerated voltage of 20 kV. The sample was fixed to aluminum sample holders
10
11 129 with adhesive tape and coated with a 5 nm gold layer using a vacuum chamber (Desk IV, Denton
12
13 130 Vacuum, Moorestown, NJ, USA) operated at 50 mm Hg for 10 minutes, 300 W and Ar
14
15 131 atmosphere. The X-rays were detected by linear surface scanning for 90 s at an acceleration of 15
16
17 132 kV and 10 mm depth of field.
18 133
19
20 134 Determination of functional groups (Boehm titration)
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22 135 Approximately, 0.1 g of each adsorbent was mixed separately with 10 mL of 0.1M NaOH, 0.05
23
24 136 M Na2CO3 and 0.05 M NaHCO3 solutions to titrate the acidic groups. Conversely, 0.1 M HCl
25
26 137 was used in turn to titrate alkaline sites. The solutions were then stirred for 24 h. Subsequently, 5
27
28
138 mL aliquots were taken, filtered with a 0.45 μm filter. Further, the hydroxyl and carbonates
29 139 groups were titrated with 0.1 M HCl using phenolphthalein and bromocresol green as indicators,
30
31 140 respectively. Conversely, acidic groups were titrated with 0.05M NaOH using phenolphthalein as
32
33 141 indicator (Boehm 2002).
34
35 142
36
37 143 Determination of the Zero Point Charge (PZC)
38
39
144 Approximately, 10 mg of each adsorbent was dispersed in 10 mL of different aqueous solutions
40 145 having different pH values (1, 2, 3, 5, 6, 8, 10 and 12). The subsequent zeta potential readings
41
42 146 were made on a ZetaSizer (Nano-ZS90 nano Series, Malvern Instruments Ltd., UK) at 633 nm.
43
44 147 The quantifications were performed in triplicate at 25 °C. The samples were analyzed between 12
45
46 148 to 16 cycles and 4 mV.
47
48 149
49
150 Fourier-Transform Infrared characterization (FT-IR)
50
51 151 It was carried out in a FT-IR spectrophotometer (IRAffinity-1, Shimadzu Corporation, Kyoto,
52
53 152 Japan), in a range between 4000 and 400 cm-1, 16 scans and a resolution of 4 cm-1. The samples
54
55 153 were mixed with KBr in an agate mortar and compressed to pellets using a single tablet press
56
57 154 (060804 Compac, Idemec, Itagüí, Columbia).
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59 155
60 156
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 1
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4 157 Adsorption study and adsorption kinetics
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6 158
7 159 Approximately, 20 mg of each adsorbent was weighed and 50 mL of a CV solution (3.0x10-5 M)
8
9 160 was added and stirred with a magnet for 20 minutes at 30 rpm. Samples were then centrifuged at
10
11 161 1550 rpm for 30 minutes (Precision Scientific CO Ref. 10-T-5, Chicago, USA), passed through a
12
13 162 0.45 μm filter, followed by absorbance measurements at 590 nm using a UV/VIS
14
15 163 spectrophotometer (Mettler Toledo UV5 LabX® ready, Switzerland). The kinetic study was
16
17 164 conducted by mixing 50 mL of 3 x 10-5 M solution with 10 mg of each adsorbent at 30 rpm and
18 165 the absorbance measurements was taken at 1, 2, 4, 7, 10, 15, 20, 30 and 60 min. A negative
19
20 166 control was carried out with no CV and subjected to the same experimental conditions. The
21
22 167 amount of CV adsorbed was calculated from:
23
24 168
25
26 169 Adsorption = 100*(C0-Ce)/C0 (2)
27
28
170
29 171 Where, C0, and Ce correspond to the initial and equilibrium CV concentration (mg/L),
30
31 172 respectively.
32
33 173
34
35 174 The adsorption data was adjusted to the pseudo-first (Lagergren) and pseudo-second order
36
37 175 models. The kinetics of pseudo-first order postulates that the speed of occupation of the
38
39
176 adsorption sites is proportional to the number of vacant sites as follows:
40 177
41
42 178 ln (qe - qt) = ln qe - k1t (3)
43
44 179
45
46 180 Where, qe is the amount of adsorbate removed at equilibrium (mg/g), qt corresponds to
47
48 181 the amount of adsorbate removed (mg/g) at time t (min) and k1 is the pseudo-first order
49
182 equilibrium constant (1/min). In contrast, the pseudo-second order adsorption kinetics assumes
50
51 183 that the occupation speed of the adsorption sites is proportional to the square of unoccupied
52
53 184 active adsorption sites as follows:
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55 185
56
57 186 t/qt = 1/(k2 qe2) + t/qe (4)
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59 187
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4 188 Where, k2 corresponds to the pseudo-second order adsorption constant (mg/g/min).
5
6 189 Likewise, the intra-particle diffusion model was determined using the following equation:
7
190
8
9 191 𝑞𝑡 = 𝑘𝑖𝑑 𝑡1/2 + 𝐶 (5)
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11 192
12
13 193 Where, 𝑞𝑡 (mg g-1) is the amount of pollutant adsorbed at time 𝑡, 𝑘𝑖𝑑 is the intra-particle
14
15 194 rate constant (mg g-1 min-1/2), while 𝐶 is a constant that indicates the thickness of the boundary
16
17 195 layer. Thus, a larger intercept means a greater effect of the boundary layer.
18
19
196 The activation energy was determined following the same procedure at three
20
21 197 temperatures (25, 40 and 70 ºC), using a heating mantle (Gehaka, MS7-H550-S, São Paulo,
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23 198 Brazil). The non-linear fitting was accomplished using the Statgraphics® Centurion XVI
24
25 199 software.
26
27 200
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29 201 Adsorption models
30 202 25 mL of CV at the 3.34 x 10-5, 1.67 x 10-5, 8.34 x 10-6, 3.34 x 10-6, 1.67 x 10-6 and 6.68 x 10-7 M
31
32 203 concentrations were employed with 20 mg of adsorbent for 60 minutes and 30 rpm followed by
33
34 204 settling for 60 minutes. Samples were then centrifuged at 1550 rpm for 15 minutes and filtered at
35
36 205 0.45 μm before each absorbance reading. Tests were carried out at medium pH and room
37
38 206 temperature. The adsorption data were adjusted to the Langmuir, Langmuir-like, Freundlich and
39
40 207 Tempkin models.
41 208
42
43 209 RESULTS AND DISCUSSION
44
45
46 210 Production and characterization of adsorbents
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48 211 Table 1 lists the physical properties and elemental composition of the adsorbents. The SW
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50 212 submitted to a direct charring rendered a lowest yield due to pyrolysis of residual low molecular
51 213 weight sugars, peptides and amine compounds. It is also expected that pyrolysis release gases
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53 214 such as CO, CO2, H2O, H2 and CH4 (Bastidas et al. 2010). Phosphoric acid is an activator that
54
55 215 affects the total porosity of the samples. A high adsorbent to phosphoric acid ratio (1:3) rendered
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57 216 a lower porosity as compared to the SW treated at a 1:2 ratio. Previous attempts (not reported in
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59 217 this study) to produce activated charcoals using other activated agents such as NaOH and ZnCl2
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218 failed giving rise to a massive degradation of the SW and very low yields (<40%). Moreover, the
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4 219 pyrolysis and activation processes increased the true density of the adsorbents, but this was not
5
6 220 reflected in major increase of bulk density. For this reason, pyrolysis did not lead to a great
7 221 increase in total porosity (Table 1).
8
9 222
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11 223 The process of pyrolysis increased the total alkalinity of SW due to the reduction of surface
12
13 224 phenol groups (Table 1). This fact was reflected in the resulting elevated pH value, especially for
14
15 225 the CM sample which showed the highest pH value. Further, the pyrolysis process caused a
16
17 226 reduction of carbon and triggered a complete disappearance of N, probably due to the formation
18 227 of volatile compounds such as NO, NO2 and N2O5 (Wang et al. 2018). In fact, a temperature of
19
20 228 500°C, and H3PO4 activation promoted the evolution of H and O from the precursors materials as
21
22 229 H2O or H2 more than CO, CO2 or hydrocarbons (Lin et al. 2013), leading to a reduction of
23
24 230 oxygen. Interestingly, the activation with phosphoric acid caused a major increase in the content
25
26 231 of phosphorous probably in the form of phosphate moieties. Upon activation, the carbon content
27
28
232 slightly increased, whereas the oxygen content was reduced. These changes are certainly related
29 233 to breaking of the least stable chemical bonds present in the adsorbents, promoting the removal of
30
31 234 heteroatoms as gaseous or liquid compounds and consequently, for the rearrangement of the
32
33 235 carbon structure. Interestingly, the content of calcium remained unchanged probably as CaCO3
34
35 236 and CaO. On the other hand, CAC had the largest amount of carbon, and the lowest content of
36
37 237 oxygen, calcium and phosphorous as compared to the shrimp-based adsorbents (SBA).
38
39
238
40 239
41
42
43 240 The Boehm titration quantifies functional groups on the surface of each adsorbent based on a
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45 241 selective neutralization using a series of alkalis and acids. The results from the Boehm analysis
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47 242 suggested that acidic moieties predominated on the surface of all adsorbents (Table 2). A more
48
49
243 detailed analysis revealed that SW was initially an alkaline material which increased in alkalinity
50 244 upon pyrolysis (i.e., CM) due to the CaCO3 transformation to CaO. However, a subsequent
51
52 245 activation with H3PO4 removed any trace of alkaline moieties and increased the content of phenol
53
54 246 moieties, especially when the starting material was CM. Further, upon chemical activation the pH
55
56 247 decreased and conductivity increased. In contrast, CAC exhibited a mixture of phenol and
57
58 248 alkaline moieties at a 4:1 ratio, but this adsorbent was not as acidic as the activated materials.
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4 249 Except CAC, the moisture content of the adsorbents was lower than 10%, probably explained by
5
6 250 the lower surface area as compared to CAC.
7 251
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9 252
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11 253 Pyrolysis of SW in the presence of H3PO4 (AC1) induced the formation of gases such as
12
13 254 water vapor, carbon oxides, CH4 and H2 and contributed to the formation of pores as reflected in
14
15 255 the increase of the surface area. Conversely, the lower surface area of CM is explained by the
16
17 256 presence of heteroatoms such as O, and Ca which are necessary for the formation of volatile
18 257 compounds. Particularly, the high content of N in the SW eased the formation of a porous
19
20 258 structure, while volatile gases such as NO2 were formed resulting in a product with a complete
21
22 259 absence of this element. Thus, the activated adsorbent produced from CM had the lowest specific
23
24 260 surface area.
25
26 261
27
28
262 The high CV adsorption ability might be explained by two major factors: (a) the high
29 263 content of acidic phenol groups and (b) a high SBET. In fact, the pyrolyzed product showed
30
31 264 approximately one half of SW SBET, hence it exhibited a lower CV adsorption. Moreover, the
32
33 265 functionalization of the surface especially with carboxyl and phosphate moieties is essential for
34
35 266 enhancing the adsorption capability. The low adsorption of CV by CM was also corroborated by
36
37 267 the low PZC values. The PZC is the pH value where the net surface charge in the adsorbent
38
39
268 particle is neutral. The lower the PZC value, the wider the pH range for the removal of a cationic
40 269 adsorbate such as CV. Therefore, the adsorbent in acidic pH has a negative surface charge and it
41
42 270 is expected to be attracted to the positive charges of CV by electrostatic attractions. Thus, at a pH
43
44 271 higher than the PZC the adsorbent is able to remove cationic compounds by electrostatic
45
46 272 interactions with the negative surface charges of the adsorbents. Further, adsorbents that did not
47
48 273 go through a chemical activation process (SW and CM) showed PZC values larger than 2.0 and
49
274 for this reason; they showed a low ability for having electrostatic interactions with CV. In fact,
50
51 275 the increase in the CV adsorption by AC1 and AC2 suggests an improvement in the specific
52
53 276 surface area and the type of electrostatic interactions (Table 2).
54
55 277 At neutral pH, the chemical structure of CV (pKa1= 5.31; pKa2= 8.64) is partially ionized.
56
57 278 Thus, the adsorption process is influenced by the surface charge of the activated charcoals. This
58
59 279 suggests that CV adsorption on the activated charcoals is a physical process, where the hydrogen
60
61
280 bonds and - interactions seems to prevail. On the other hand, the adsorption process is also
62 9
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4 281 associated with the porosity and surface area of the adsorbent material. Therefore, the low
5
6 282 adsorption with CM in distilled water is related to the low SBET. Conversely, CV adsorption on
7 283 the activated materials was more influenced by the incorporation of acidic groups inside the
8
9 284 surface. Therefore, phosphoric acid rendered a higher SBET than pyrolysis resulting in a higher
10
11 285 CV adsorption. Thus, the CM let the activating agent to enter directly inside the material
12
13 286 promoting a better microporosity and surface area development resulting in a better CV
14
15 287 adsorption.
16
17 288 The morphological features of the particles are shown in Figure 1. As compared to the
18 289 raw SW, CM had a rougher surface, and upon phosphoric acid treatment the surface becomes
19
20 290 more eroded and rougher having big holes and cavities with presence of lumps of small size. In
21
22 291 contrast, the CAC shows both rough and smooth surfaces. However, upon activation of SW and
23
24 292 CM the carbon and phosphorous content increased. The development of porosity is attributed to
25
26 293 the activating agent effect which breaks the C-O-C and C-C bonds of hydrochar and eases the
27
28
294 release of gas. Even though SW showed a smooth surface it showed a reasonable high CV
29 295 removal due to the innate high surface area and combined acidic and alkaline moieties. The CM
30
31 296 although showed a high porosity (81.82%) exhibited crystalline particles. On the surface, some
32
33 297 chunks of CaCO3 are observed which decreased the surface area.
34
35
36 298
37
38
299 FT-IR characterization
39 300 Figure 2 depicts the FT-IR spectra of the adsorbents. SW shows bands at 3400 cm-1 and 3255 cm-
40
1
41 301 attributed to OH and NH2 stretching, respectively. Further, the bands at 2900 cm-1, 2918 cm-1
42
43 302 and 2850 cm-1 are due to CH symmetric stretching. On the other hand, the signal at 1652 cm -1 is
44
45 303 attributed to C=O stretching from the N-acetylglucosamine subunits of chitin. Further, the signal
46
47 304 at 1560 cm-1 is attributed to the deformation in plane of the secondary amide of the acetylamine
48
49
305 group. Other bands at 1423 cm-1 and 1311 cm-1 are due to the CH deformation and flexion of
50 306 CH2. Bands at 1064 cm-1, 870 cm-1, 713 cm-1 corresponds to COC ring stretching (chitin ring),
51
52 307 glycosidic bond stretching, and -OH out-of-plane stretching, respectively. The bands between
53
54 308 400-700 cm-1 are due to C-C stretching. The pyrolysis process confirmed the elimination of
55
56 309 proteins since the signal at 1560 cm-1 disappeared. Further, the bands at 1419 cm-1 and 1056 cm-1
57
58 310 strengthened due to the CH deformation and C-O-C ring stretching vibrations, respectively(Hesas
59
311 et al. 2013).
60
61
62 10
63
64
65
 1
2
3
4 312
5
6 313 In general, activation with phosphoric acid produced changes in the bands between 900-
7 314 1400 cm-1 due to vibrations of the C-H bond and loss of oxygen on the surface of the materials.
8
9 315 Further, the emerging band at 1100 cm-1 is attributed to the emerging phosphate group.
10
11 316 Moreover, bands around the region of 1050-1070 cm-1 decreased upon activation of SW.
12
13 317 However, these bands completely disappeared when the pyrolyzed sample was activated with
14
15 318 phosphoric acid and a new band at 1100 cm-1 appeared. Further, a small signal at 1625-1641 cm-1
16
17 319 emerged due to the C=O stretching possibly corresponding to the ketones, aldehydes, lactones or
18 320 carboxylic acids formed during combustion (Yakout & Sharaf 2016). Likewise, activated
19
20 321 charcoals showed a wide band around 3300 cm-1 corresponding to the stretching vibration of -OH
21
22 322 due to the presence of carboxylic, phenolic and alcohol groups in the adsorbents. This signal is
23
24 323 very small in magnitude in the activated charcoals due to the action of phosphoric acid. This
25
26 324 agrees with the decrease of O in the activated materials as reported in the elemental analysis
27
28
325 (Table 1). Furthermore, the activated charcoals showed an ansence of bands at 2920 cm-1
29 326 attributed to C–H stretching of aliphatic carbon. They also showed a strong band at ~900 cm-1
30
31 327 due to the glycoside bend stretching. Further, the peak at 1630 cm−1 corresponds to aromatic C=C
32
33 328 and suggest the existence of aromatic rings in the carbonized charcoals.
34
35
36 329 On the other hand, the CAC shows bands at 3420 cm-1 due to OH stretching, adsorbed water,
37
38 330 or hydrogen bonds interaction of OH groups of alcohols and phenols. The signals at 2918 cm-1
39 331 and 2848 cm-1 are attributed to symmetric stretching of CH. The band at 1620 cm-1 can be
40
41 332 attributed to C=O and C-O stretching of phenolic esters, carboxylic acids or conjugated ketone
42
43 333 structures.
44
45 334
46
47 335
48
49
336 Adsorption kinetics and adsorption isotherms
50
51 337 There was a better fit to the pseudo-second order kinetics (r2> 0.99). The resulting parameters of
52
53 338 these models are shown in Table 3 where the theoretical results of equilibrium concentration (qe)
54
55 339 calculated by the pseudo-second order model were closer to the experimental values. In contrast,
56
57 340 the pseudo-first-order and intra-particle diffusion models did not show a good fit to the
58
59
341 experimental data. For a solid-liquid adsorption process, the solute transfer is usually controlled
60 342 by either external mass transfer, intra-particle diffusion or both (Xie et al. 2011). Results
61
62 11
63
64
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 1
2
3
4 343 suggested that one step occurred during the adsorption process attributed to the diffusion of the
5
6 344 adsorbate through the solution to the external surface of the adsorbent.
7
8 345
9
10 346 On the other hand, the adsorption isotherms show that SW, CM and AC1 presented a very
11
12 347 good fitting to the Langmuir-like and Freundlich models (Table 4). The first one implies that the
13
14 348 removal of CV in these materials follows the assumptions (i) the active adsorption sites are
15
16 349 energetically homogeneous, (ii) there is no interaction of the CV adhered to the adjacent
17
350 adsorption sites, (iii) there is a monolayer formation of CV on the adsorbent surface and, (iv) the
18
19 351 formation of non-polar interactions between the non-polar CV sites and the adsorbent surface,
20
21 352 resulting in loss of water structure around the non-polar CV sites, generating also hydrophobic
22
23 353 bonds with the adsorbent (VanDer Kamp et al. 2005). The essential characteristics of the
24
25 354 Langmuir isotherm can be expressed by a dimensionless equilibrium parameter, also known as
26
27 355 the separation factor (RL) which rendered values closed to 1 (𝑅𝐿 ~1) indicating a linear adsorption.
28 356 Conversely, CAC and AC2 only showed better fitting to the Freundlich model. This indicates that
29
30 357 the adsorption sites in the CAC and AC2 are energetically heterogeneous with the formation of
31
32 358 several layers of adsorbate on their surface. Thus, sites having a higher energy are occupied first,
33
34 359 as well as the possible formation of CV multilayers adsorbed on the surface of the adsorbent.
35
36 360 This might be due to the double exposure of these materials. Conversely, the Temkin model did
37
38 361 not show a good fit to the data indicating that the adsorption energy does not decrease linearly as
39 362 the surface is covered by the adsorbate.
40
41 363
42
43 364
44
45 365 The Freundlich model for SW, CM in distilled water reported a maximum adsorption
46
47 366 capacity of 9.6 mg g-1 and 3.9 mg g-1, respectively, whereas the same model predicts for AC1,
48
49
367 AC2 and CAC an adsorption capacity of ~17 and 82 and 5x107, mg g- 1respectively. In fact, the
50 368 commercial material showed the largest value due to its largest SBET. Interestingly, the adsorption
51
52 369 capacity in SW was higher than those reported using materials such as activated charcoal fiber
53
54 370 cloths (4.15 mg g-1) (Fallou et al. 2016), sediment river (0.03 mg g-1) (Zhao et al. 2014), and
55
56 371 chitin modified with Kraft lignin (0.27 mg g-1) (Żółtowska-Aksamitowska et al. 2018).
57
58
59
372 Ea was calculated from of the pseudo-second-order k2 constant. The Ea is defined as the
60 373 minimum energy needed for adsorption to take place. It is accepted that when this value is lower
61
62 12
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65
 1
2
3
4 374 than17.6 kJ/mol the process is named as physisorption, whereas higher values are characteristics
5
6 375 of chemisorption (Chakraborty et al. 2011). In addition, these energies are positive, suggesting an
7 376 endothermic adsorption process. On the other hand, SW, AC1, AC2 showed an increase in the
8
9 377 value of the rate constant (K2) as the temperature increased promoting the interaction forces
10
11 378 between the surface functional groups of these adsorbents and the pollutant. This phenomenon is
12
13 379 explained by the increase in the interaction forces between the adsorbate and adsorbent at high
14
15 380 temperatures since diffusion is an endothermic process. Further, the increase in temperature also
16
17 381 increases the rate at which the particles move, thereby increasing the number of collisions and
18 382 thus favoring the adsorption process. Further, a lower Ea value also implied a lower PZC value
19
20 383 and a larger ionization degree allowing for a rapid and spontaneous physisorption process. A rise
21
22 384 in the temperature is known to increase the diffusion rate of the adsorbate across the external
23
24 385 boundary layer and within the pores. Interestingly, the high Ea value of CM suggest a
25
26 386 chemisorption process although further thermodynamics studies need to be conducted to
27
28
387 corroborate these findings.
29 388
30
31 389 Adsorption mechanism
32
33 390 The adsorbent power of adsorbents activated by phosphoric acid is attributed to their
34
35 391 complex surfaces, being composed of hydrophobic regions (basal carbon surface) and a wide
36
37 392 variety of polar regions containing oxygen functional groups. Thus, CV can be specifically
38
39
393 adsorbed with a particular functional group on the surface or not specifically on the surface of the
40 394 basal carbon. Non-specific interactions can also occur due to loss of water structuring after
41
42 395 adsorption around the non-polar absorption sites by hydrophobic bonds. As the energy applied to
43
44 396 the system increases, the structuring of the hydrogen bonds formed will break down, becoming a
45
46 397 similar phenomenon when the temperature of the water increases breaking hydrogen bonds due to
47
48 398 the increase in molecular movement. Furthermore, the energy of the hydrogen bonds is
49
399 significantly lower (approximately 1 to 2 kJ/mol for weak hydrogen bonds) with respect to other
50
51 400 types of bonds such as weak covalent bonds (155 kJ/mol) (Markovitch & Agmon 2007). On the
52
53 401 other hand, CAC it is expected that the polar parts of the molecule interact with the polar
54
55 402 functional groups via hydrogen bonds, Keesom forces, Debye forces or ion-ion interactions.
56
57 403 However, the hydrophobic portions of the molecule interact with the basal surface via the
58
59 404 hydrophobic bond, which is a distinctly entropic process.
60 405
61
62 13
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 1
2
3
4 406 CONCLUSIONS
5
6
407 Shrimp waste, pyrolyzed and activated charcoals were successful adsorbents for CV. Further, it is
7
8 408 not necessary to carry out pyrolysis prior to chemical activation in order to get a high adsorption
9
10 409 efficiency saving processing costs. The temperature treatment and activation with phosphoric acid
11
12 410 caused the formation of mainly acidic moieties (phosphate) on the surface and the disappearance of N.
13
14 411 The low PZC proved that it is not required to have an alkaline media in order to have a sufficient
15
412 ionization state so that the electrostatic attractions with CV take place. The adsorption of CV mainly
16
17 413 occurred by hydrogen bonds, electrostatic interactions and - interactions. The thermodynamic values of
18
19 414 𝐸𝑎 confirmed an endothermic physisorption process. Activated charcoals prepared from SW had high
20
21 415 carbon content and a significant SBET. These adsorbents can be a viable alternative to produce
22
23 416 industrial filters for the removal of basic dyes in wastewater treatment plants of textile industries. They
24
417 contribute to the solution of two environmental issues: (i) the removal of water pollutants, and (ii) the
25
26 418 reuse of these abundant agroindustry wastes.
27
28
29 419 ACKNOWLEDGEMENTS
30
31 420 The authors are grateful to Colciencias for providing the financial resources for the execution of
32
33
34 421 this study through the Grant No. 111571551545 and contract No. 036-2016. Authors thank CODI
35
36 422 for their sustainability strategy 2018-2019 of University of Antioquia.
37
38
39
40
423 REFERENCES
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42 424 Adegoke, K.A. & Bello, O.S. 2015 Dye sequestration using agricultural wastes as adsorbents. Water
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428 Bastidas, M., Buelvas, L., Marquez, M. & Rodríguez, K. 2010 Producción de Carbón Activado a partir de
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5 441 wastewater. Journal of Environmental Chemical Engineering 4, 4100–4106.
6 442 Fallou, H., Cimetiere, N., Giraudet, S., Wolbert, D. & Cloirec, P. 2016. Adsorption of pharmaceuticals
7 443 onto activated carbon fiber cloths - Modeling and extrapolation of adsorption isotherms at very low
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454 activated carbons produced from NaOH-pretreated rice husks. Bioresource Technology 136, 437–
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35 468 activated carbon developed from Trapa natans husk. ScienceChina Chemistry 54, 835–843.
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471 mechanism. Chemosphere 195, 351–364.
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41 473 CO reaction on Fe-Co binary metal oxides over activated semi-coke supports. Royal Society of
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44 476 acid activation of olive stones. Arabian Journal of Chemistry 9, S1155–S1162.
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479 Żółtowska-Aksamitowska, S., Bartczak, P., Zembrzuska, J. & Jesionowski, T. 2018 Removal of
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49 480 hazardous non-steroidal anti-inflammatory drugs from aqueous solutions by biosorbent based on
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51 482
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Figure

List of Figures

Figure 1. Surface characteristics of the adsorbents

Figure 2. FT-IR spectra showing the effect of pyrolysis and chemical activation on shrimp
waste
 CAC SW CM

AC1 AC2
Figure 1. Surface characteristics of the adsorbents
 SW CM AC1 AC2 CAC

3900 3400 2900 2400 1900 1400 900 400

Wavenumber (cm-1)

Figure 2. FT-IR spectra showing the effect of pyrolysis and chemical activation on shrimp
waste
Table

1
2
3
4 List of Tables
5
6
7
8
9 Table 1. Physical properties and elemental analysis of the adsorbents
10
11 Table 2. Relationship between moieties, physical properties and CV adsorption
12
13
Table 3. Adsorption kinetic parameters of CV
14
15
16 Table 4. Sorption and thermodynamic parameters for CV with several adsorbents
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
 1
2
3
4 Table 1. Physical properties and elemental analysis of the adsorbents
5
6
7 Element SW CM AC1 AC2 CAC
8 C 59.6 53.1 59.4 69.8 84.0
9
10 O 32.7 34.6 29.7 23.5 15.3
11 Ca 16.7 19.9 10.4 10.3 0.3
12
P 1.5 1.9 7.3 3.3 0.8
13
14 N 15.9 0.00 0.00 0.00 0.00
15 Si 0.00 0.5 0.10 0.00 0.2
16 Element
K 0.00 0.00 0.94 1.03 0.05
17
18 Cl 0.23 0.20 0.00 0.00 0.04
19 Mg 0.35 0.56 0.12 0.09 0.00
20
Al 0.00 0.32 0.06 0.04 0.06
21
22 Na 0.00 0.26 0.00 0.00 0.00
23 Sn 0.99 0.00 0.00 0.00 0.00
24
25 Moisture 3.2 8.2 8.8
8.0 15.7
26 (%)
27 Porosity 75.9 81.8 81.9 77.0 80.0
28 (%)
29 Yield (%) 81.7 53.6 73.3 73.2 N/A
30 Property bulk 0.43 ± 0.47 ± 0.42 ± 0.49 ± .32 ±
31 (g/cm3) 0.02 0.02 0.02 0.01 0.02
32 n=3
33 true 1.79± 2.58± 2.32± 2.13± 1.59±
34 (g/cm3) 0.00 0.00 0.00 0.01 0.03
35
n=3
36
37
38 SW, raw shrimp waste; CM, charred material; AC1, charcoal activated with H 3PO4 using SW as precursor;
39
40 AC2, charcoal activated with H3PO4 using CM as precursor; CAC, commercial activated charcoal; bulk, bulk
41
42 density; true, true density.
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
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 1
2
3
4 Table 2. Relationship between moieties, physical properties and CV adsorption
5
6 Functional moieties (µmol/g)
7 Adsorption
8 Adsorbent Total acidity PZC Conductivity SBET
Total pH (%)
9 (carboxylic, lactones Phenols Lactones Carboxylic (mV) (µS/cm) (m²/g) n=3
10 alkalinity
11 and phenols)
12 95.3 B ±
13 SW 3960 3960 0 0 5850 2.5 8.0 69.5 97.6
14 0.0
15 84.8C ±
16 CM 2040 2040 0 0 9350 2.0 8.4 68.8 44.4
17 0.2
18
100.5 A
19 AC1 4760 4600 0 160 0 1.3 6.0 80.3 146.9
20 ± 0.0
21
22 100.6 A
AC2 4880 4880 0 0 0 1.1 7.2 85.5 83.3
23 ± 0.4
24
25 100.9 A ±
CAC 4320 4320 0 0 950 3.8 6.9 44.5 597.9
26 0.0
27
28 SW, raw shrimp waste; CM, charred material; AC1, charcoal activated with H 3PO4 using SW as precursor;
29 AC2, charcoal activated with H3PO4 using CM as precursor; CAC, commercial activated charcoal, SBET,
30
31 specific surface area.
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
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 1
2
3
4 Table 3. Adsorption kinetic parameters of CV
5
6
7
8 Adsorbent Parameter SW CM AC1 AC2 CAC
9 qe (exp) (mg/g) 38.41 19.76 48.42 36.98 47.37
10
Pseudo qe (theor) (mg/g) 21.05 5.69 26.52 18.13 30.60
11
12 1st Order k1 (1/min) 0.08 0.06 0.07 0.08 0.06
13 r2 0.94 0.57 0.94 0.91 0.99
14
15 qe (exp) (mg/g) 38.41 19.76 48.42 36.98 47.37
16 Pseudo qe (theor) (mg/g) 39.16 19.72 49.18 35.76 48.67
17 2nd 4 3 4 19
k2 (mg/g/min) 2.74 x 10 7.07 x 10 5.39 x 10 -9.20 x 10 3.33 x 104
18 Order
19 r2 1.00 1.00 1.00 0.99 0.99
20
Intra- Kid 0.25 0.11 0.26 0.23 0.26
21
22 particle C (mg g-1 min-1/2) 0.19 0.23 0.79 0.53 0.99
23 r2 0.95 0.79 0.65 0.77 0.55
24 diffusion
25 Qe, amount of CV removed at equilibrium; q t amount of CV removed; k1 pseudo-first order equilibrium
26 constant;k2, pseudo-second order adsorption constant; 𝑘𝑖𝑑 intra-particle rate constant (mg g-1 min-1/2); 𝐶,
27 thickness of the boundary layer.
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
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 1
2
3
4
5
6 Table 4. Sorption and thermodynamic parameters for CV with several adsorbents
7
8 Model Parameter SW CM AC1 AC2 CAC
9 K1 (mL/mg) 0.00 0.65 0.00 0.00 0.00
10 Langmuir K2 (mg/g) 5.57 x 104 10.00 1.17 x 105 1.21 x 105 1.95 x 105
11 r2 0.99 0.97 1.00 0.45 0.31
12 K1 (mL/mg) 0.20 0.46 0.00 0.00 0.00
13 K2 (mg/g) 59.34 9.96 4.43 x 104 1.92 x 104 1.29 x 104
14 Langmuir-like Khb (mg/g) -0.05 0.69 0.36 -4.72 -6.55
15 RL 1.00 0.99 1.00 1.00 1.00
16 r2 1.00 0.99 1.00 0.57 0.43
17 K (mg/g) 9.57 3.90 17.13 81.84 5.07 x 107
18 Freundlich P 0.87 0.39 0.94 3.86 11.84
19 r2 1.00 0.99 1.00 0.76 0.92
20 A (L/g) 20.35 1.93 x 102 88.95 6.48
21
22 Temkin B (J/mol) 3.24 0.93 2.44 6.25 No fitting
23 r2 0.80 0.85 0.69 0.41
24 Ea. (kJ/mol) 15.78 34.2 6.82 6.19 16.57
Arrhenius
25
26 r2 0.97 0.99 1.0 0.98 0.79
27
28
29 Ceq (mg/mL) is the concentration of the adsorbate at equilibrium, K1 (mL/mg) and K2 (mg/g) are affinity and capacity
constants of the adsorption sites, respectively KHB (mg/g) is the hydrophobic binding constant, which represents
30
hydrophobic bonds between the non-polar adsorbate sites and the surface of the adsorbent Where, qe is the Kf is the
31 maximum adsorption capacity constant (mg/g), Ceq (mg / mL) is the concentration of the adsorbate at equilibrium an p is
32 the affinity constant of the adsorbent. Where, A is the Temkin constant (L/g) and B is the heat of adsorption (J/mol).
33
34
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38
39
40
41
42
43
44
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Supplementary Material Click here to access/download;Supplementary
Material;suplementary materials.docx

Figure 1. Kinetic studies conducted at 3 temperatures (a) 25, (b), 40 and (c) 70°C

100

80
Adsorption (%)

60

40

20
EE CB CA2 CA4 CAC
0
0 10 20 30 40 50 60
Time (min)

100
90
80
70
Adsroption (%)

60
50
40
30
20
10
EE CB CA2 CA4 CAC
0
0 10 20 30 40 50 60
Time (min)
 100
90
80
70
Adsorption (%)

60
50
40
30
20
10
EE CB CA2 CA4 CAC
0
0 10 20 30 40 50 60
Time (min)
Table 1. Kinetic values at different temperatures

T (°C) SW CM AC1 AC2 CAC

25 0.00202 0.00837 0.00859 0.00475 0.05220
40 0.00242 0.00315 0.00983 0.00558 0.04270
70 0.00401 0.00132 0.02987 0.00664 0.02020