Accepted Manuscript

Adsorption of organic contaminants by graphene nanosheets: A review

Gamze Ersan, Onur G. Apul, Francois Perreault, Tanju Karanfil

PII: S0043-1354(17)30663-2
DOI: 10.1016/j.watres.2017.08.010
Reference: WR 13133

To appear in: Water Research

Received Date: 22 April 2017

Revised Date: 12 July 2017
Accepted Date: 4 August 2017

Please cite this article as: Ersan, G., Apul, O.G., Perreault, F., Karanfil, T., Adsorption of organic
contaminants by graphene nanosheets: A review, Water Research (2017), doi: 10.1016/
j.watres.2017.08.010.

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Adsorbate Properties
Background Solution Chemistry

Molecular size 5
4
Geometrical configuration
4 16 studies 8
pH Hydrophobicity
Ionic strength Aromaticity

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Presence of NOM 26 studies Polarity
8
Presence of Surfactant
Substituent groups 14
Temperature 5

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8 8

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GNS Properties Type of GNSs

Morphological
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characterization
-Sheet dimensions
-Particle thickness
-Surface area Graphene
-Pore volume 18 studies 26 GOs
40 studies 22
-Pore size distribution

Surface chemical
properties
-Surface charge
-Surface chemistry
-Purity
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1 Adsorption of organic contaminants by graphene nanosheets: A review

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4

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5 Gamze Ersana, Onur G. Apulb,c, Francois Perreaultc, and Tanju Karanfila

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7 Department of Environmental Engineering and Earth Sciences, Clemson University, Anderson,

8 SC 29625, USA

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9 Department of Civil and Environmental Engineering, University of Massachusetts Lowell,

10 Lowell, MA 01854, USA

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11 School of Sustainable Engineering and the Built Environment, Arizona State University, Tempe,
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12 AZ 85287-3005, USA
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16 Submitted to Water Research

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19 *Corresponding author: email: tkaranf@clemson.edu; phone: +1-864-656-1005; fax: +1-864-656-0672

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21 ABSTRACT

22 Graphene nanosheets (GNS) such as graphenes and graphene oxides (GOs) have been

23 widely investigated as next-generation adsorbents in both water and wastewater treatment

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24 processes due to their unique physicochemical properties and their affinity towards different

25 classes of organic contaminants (OCs). In the last five years, more than 40 articles investigating

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26 adsorption of different classes of OCs by graphene and GO were published in peer-reviewed

27 journals. Adsorption mechanisms were controlled by molecular properties of OCs (e.g., aromatic

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28 vs aliphatic, molecular size and hydrophobicity), characteristics of adsorbents (e.g., surface area,

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29 pore size distribution, and surface functional groups), and background solution properties (e.g.,
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30 pH, ionic strength, surfactants, NOM, and temperature). This literature survey includes: (i) a

31 summary of adsorption of OCs by GNS, (ii) a comprehensive discussion of the mechanisms and
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32 factors controlling the adsorption of OCs by GNS and a comparison of their adsorption behaviors

33 with those of CNT. This literature survey also identifies future research needs and challenges on
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34 the adsorption of OCs by GNS.

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36
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37 Keywords: Graphene, Graphene Oxide, Organic Contaminants, Adsorption,

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44 Contents

45 1. Introduction .................................................................................................................. 4
46 2. Overview of graphene based adsorption studies .......................................................... 5
47 3. The characterization of GNS ........................................................................................ 7
48 4. Adsorption of OCs by GNS ........................................................................................ 11

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49 4.1. OC adsorption mechanisms by GNS ....................................................................... 11
50 4.2. The effect of GNS properties on adsorption of OCs ............................................ 16

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51 4.3. The effect of OC properties .................................................................................. 19
52 4.4. The effect of background solution properties....................................................... 24

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53 4.4.1. The effect of pH ................................................................................................... 24
54 4.4.2. The effect of ionic strength .................................................................................. 28
55 4.4.3. The effect of natural organic matter (NOM) ........................................................ 29
56
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5. Comparison of GNS with CNT and GAC.................................................................. 33
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57 6. Future research needs and conclusions ...................................................................... 36
58 Acknowledgement .......................................................................................................... 38
References ....................................................................................................................... 39
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62 1. Introduction

63 Graphene nanosheets (GNS) are two-dimensional carbon nanomaterials with a single

64 layer of sp2-hybridized carbon atoms arranged in six-membered rings. The extended honeycomb

65 lattice of GNS is the basic building block of other important allotropes; it can be stacked to form

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66 3-D graphite, rolled to form 1-D carbon nanotubes (CNT), and wrapped to form 0-D fullerenes

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67 (Allen et al., 2010). The unique structure and outstanding physicochemical properties of GNS

68 have attracted tremendous attention from researchers, who are exploring the applications of GNS

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69 in several fields of technology, from electronic systems to biomedical devices (Huang et al.,

70 2011; Wassei and Kaner, 2013; Perreault et al., 2015). As a result, graphene-based materials are

71
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rapidly becoming to be the most patented form of carbon nanomaterials (Zurutuza and Marinelli,
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72 2014).
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73 In the environmental field, GNS and graphene based materials have been explored as

74 next-generation adsorbents in water and wastewater treatment due to their highly hydrophobic
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75 surface, open-up layer morphology, and high adsorption affinity towards different organic
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76 contaminants (OCs) (Björk et al., 2010; Roos et al., 2011; Zhao et al., 2011a,b,c; Apul et al.,

77 2013; Ji et al., 2013; Wang et al., 2014; Beless et al., 2014a; Ersan et al., 2016), organic dyes
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78 (Ramesha et al., 2011; Zhang et al., 2011; Sharma and Das, 2013) and metallic ions (Chandra et

al., 2010; Zhao et al., 2011). Graphene oxide (GO), the oxidized form of graphene, exhibits a
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80 lower surface hydrophobicity, and different adsorption mechanisms compared to GNS (Apul et

81 al., 2013; Zhou et al., 2015; Ersan et al., 2016).

82 The use of GNS for the adsorption of various classes of OCs (i.e., polycyclic aromatic

83 hydrocarbons (PAHs), halogenated aliphatic, pharmaceuticals and personal care products

84 (PPCPs), plasticizers, pesticide, dyestuff, and polychlorinated biphenyls (PCBs)) has been

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85 reported in the literature. The adsorption of OCs by GNS is controlled by multiple factors related

86 to the physicochemical properties of OCs and GNS as well as the background water chemistry.

87 The relative contribution of each mechanism to the overall adsorption is of major importance to

88 predict OCs adsorption by GNS, and previous studies have reported some mechanisms more

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89 predominant than others (Wang et al., 2014; Beless et al., 2014a; Apul et al., 2015; Ersan et al.,

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90 2016). However, quantifying the individual contributions of the various mechanisms to overall

91 adsorption has yet to be thoroughly elucidated.

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92 The role of GNS in the fate, transformation, and toxicity of OCs in the aquatic

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93 environment have also been investigated in the past decade. Research have shown that the
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94 adsorption of OCs onto GNS altered their cellular uptake and mobility in natural systems

95 (Sanchez et al., 2012; Jastrzebska et al., 2012; Hu and Zhou, 2013; Bussy et al., 2013; Bianco,
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96 2013; Zhao et al., 2014b). One recent review documented the negative environmental impacts of

97 GNS with the cellular uptake and mobility of OCs (Zhao et al., 2014b). Thus, it is of critical
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98 importance to understand the adsorption of OCs by GNS to adequately assess these

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99 environmental impacts.

The main aims of this study were to conduct a comprehensive review of peer-reviewed
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101 articles regarding the adsorption of OCs by GNS, and to identify the future research needs and
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102 challenges. We first discuss the main properties of GNS relevant to environmental applications.
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103 Then, we examine the mechanisms and factors controlling adsorption of OCs by GNS and

104 compare their adsorption behavior with those of CNT.

105 2. Overview of graphene based adsorption studies

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106 The majority of the GNS studies have focused on three major areas: (i) the synthesis and

107 functionalization of GNS for various applications, (ii) the adsorption of organic and inorganic

108 compounds on GNS for environmental applications and implications, and (iii) the environmental

109 behavior of GNS (such as dispersion, toxicity and transformation) in aquatic systems. Among

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110 these, this review only focuses on studies of the adsorption of OCs by GNS, which have been

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111 rapidly growing in recent years (Table S1). Only a limited number of reviews have been

112 undertaken to address the use of graphene based materials for the adsorption of OCs (Wang et

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113 al., 2013; Yu et al., 2015a; Perreault et al., 2015; Cincinelli et al., 2015). However, a detailed

114 analysis of the mechanisms of OCs adsorption by GNS and the major parameters influencing

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adsorption still need to be realized. Understanding the adsorption of OCs by GNS is essential to
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116 accurately assess the use of GNS for OCs removal.

The literature compiled in Table S1 includes the adsorption of OCs for a wide range of
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118 graphene, GO, reduced GO (rGO), and composite materials combining various types of metal,
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119 metal oxide, or silica nanoparticles (Li et al., 2011; Apul et al., 2013; Wang et al., 2014; Zhou et
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120 al., 2015; Ersan et al., 2016). Specifically, the adsorption of more than 40 OCs by graphene (e.g.,

121 Li et al., 2011; Apul et al., 2013; Wang et al., 2014a; Zhou et al., 2015; Ersan et al., 2016) and
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122 more than 50 OCs by GOs are listed. The OCs investigated include PAHs (Zhao et al., 2011a;

123 Apul et al., 2013; Pei et al., 2013; Ji et al., 2013; Yang et al., 2013; Zhang et al., 2013b; Zhao et
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124 al., 2014ba; Wang et al., 2014a-b; Yan et al., 2015; Ersan et al., 2016; Wang et al., 2016),
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125 halogenated aliphatic hydrocarbons (Zhou et al., 2015; Ersan et al., 2016), PPCPs (Wu et al.,

126 2011; Ji et al., 2013; Liu et al., 2014; Cai and Casanova et al., 2014; Kyzas et al., 2015; Nam et

127 al., 2015; Yan et al., 2015; Moussavi et al., 2016), antibiotics and drugs (Gao et al., 2012;

128 Ghadim et al., 2013; Cai and Casanova et al., 2014; Zhu et al., 2015; Liu et al., 2016; Zhao et al.,

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129 2011b), endocrine disrupting chemicals (EDCs), (Xu et al., 2012; Liu et al., 2014; Cai and

130 Casanova et al., 2014; Jin et al., 2015), hormones (Cai and Casanova et al., 2014; Jiang et al.,

131 2016), plasticizers (Wu et al., 2011; Wang et al., 2014b), pesticides (Wu et al., 2011; Zhao et al.,

132 2011a-b; Pei et al., 2013; Ji et al., 2013; Yang et al., 2013; Cai and Casanova, 2014; Wang et al.,

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133 2014b; Chen and Chen, 2015; Yan et al., 2015), herbicides (Wang et al., 2014b), dyestuff

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134 (Ramesha et al., 2011; Zhang et al., 2011; Liu et al., 2012; Sharma and Das, 2013; Li et al.,

135 2013; Pei et al., 2013 Ji et al., 2013; Yang et al., 2013; Sharma et al., 2014; Chen and Chen,

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136 2015; Yan et al., 2015), phenolic contaminants (Li et al., 2012; Apul et al., 2013), brominated

137 flame retardants (BFRs) (Zhang et al., 2013b) and PCBs (Beless et al., 2014). In addition, the

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structure and main properties of graphene-based nanomaterials are shown in Table 1. In this
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139 review, we only focused on two main types of GNS as graphene and GO. A meteor rain chart

was developed to gain an insight on the most common trends for OCs adsorption by graphene
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141 and GO in Figure 1. It is evident that two aromatic contaminants, phenanthrene and naphthalene,
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142 have been the most frequently studied. For GO, the dye methylene blue was frequently used as a
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143 model OC. The meteor rain chart also shows that most of the research to date has focused on the

144 adsorption of OCs within 100-300 g/mol molecular weight.

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145 3. The characterization of GNS

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146 The adsorption of OCs by carbonaceous adsorbents is affected by both adsorbent

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147 morphology and surface chemistry. Two types of GNS, graphene and GOs, have been the subject

148 of several adsorption studies (Table S1). Specifically, in 37 articles reviewed, twenty two

149 graphene and forty GOs were used as adsorbents, respectively. Some studies have also used

150 different types of GNS such as sulfonated, colloidal and magnetic GNS.

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151 To correlate the physicochemical properties of GNS with OCs adsorption, the

152 morphology and surface chemistry of the adsorbents need to be thoroughly characterized. The

153 morphological characterization includes sheet dimensions, particle thickness (i.e. number of

154 layers, wrinkle, folds and 3D arrangement of graphene sheets), surface area (SSA), pore volume

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155 (PV), and pore size distribution (PSD). On the other hand, the important chemical properties

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156 include surface charge and polarity, surface chemistry, and purity of the product. A brief

157 overview of the principal techniques used for GNS characterization is provided below.

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158 The SSA, PV and PSD of adsorbents are most commonly determined by physisorption

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159 analysis in the gas phase (nitrogen gas adsorption at 77K). The Brunauer-Emmett-Teller (BET)
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160 equation is used to calculate the SSA, while the total PV is obtained from the adsorbed volume

161 of nitrogen near the saturation point (P/P0 = 0.99). The reported mean SSA of graphene and GO
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162 in previous adsorption studies were 576 and 624 m2/g, respectively (Table S1), which is

163 generally lower than the SSA of activated carbon (AC) (Yang and Xing, 2009; Chin et al., 2007;
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164 Liao et al., 2008). The measured BET surface areas of graphene and GO are much smaller than
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165 the theoretical value of 2630 m2/g for the monolayer carbon structure of GNS (Chae et al., 2004,

166 Stoller et al., 2008). This can be attributed to the aggregation and bundle formation of GNS,
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167 which results in much lower measurable surface area values. (Ramesha et al., 2011; Wu et al.,

2011, Zhou et al., 2015, Ersan et al., 2016).

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169 The PV and PSD of adsorbents have also been determined from nitrogen isotherms

170 through the Density Functional Theory (DFT) model. Generally, the reported total PV of

171 graphene is 2-3 times greater than for CNT and 2-6 times greater than GO and GAC (Beless et

172 al., 2014; Zhou et al., 2015, Ersan et al., 2016). The higher PV value of graphene (>3 cm3/g) may

173 be attributed to its less compact aggregated structure compared to other adsorbents, which might

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174 lead to the incarceration of space within its `house-of-cards` structure (Zhou et al., 2015).

175 Regarding the PSD of the adsorbents, graphene exhibited a series of meso- and macropores,

176 while GO was dominated by micro- and mesopores (Zhou et al., 2015, Ersan et al., 2016, Liu et

177 al., 2016). The lacking macropores might be ascribed to a tighter aggregation of GO because of

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178 hydrogen bonding between oxygen containing functional groups in the graphene bundle (Apul et

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179 al., 2013; Zhou et al., 2015, Ersan et al., 2016).

180 The morphological characteristics of GNS can be characterized by scanning electron

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181 microscopy (SEM), transmission electron microscopy (TEM), and atomic force microscopy

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182 (AFM). The structure, shape, and surface of GNS can be visualized by SEM, while the thickness
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183 of the sheets can be obtained by AFM imaging. Measuring the sheet thickness can theoretically

184 lead to the quantification of the number of layers in GNS, with a single layer of carbon atoms
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185 being 0.34 nm in thickness (Jin et al., 2015). However, the preferential adsorption of a thin layer

186 of water on GNS makes it difficult to obtain this theoretical thickness under ambient conditions.
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187 TEM imaging is useful to determine the morphological feature of GNS and to elucidate the
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188 number of GNS layers, wrinkle, folds and 3D arrangement of graphene sheets (Dong and Chen,

189 2010; Wang et al., 2014a; 2016). It has been shown that the edges of the GNS layers always fold
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190 back, permitting a cross- sectional view of the films. Observation of these edges by TEM

provides an accurate method for determining the number of layers at multiple locations on the
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192 films.

193 Approximately 80% of the GNS used in adsorption studies were subject to some form of

194 pretreatment for purification or functionalization (Table S1). Chemical oxidation in acidic

195 solutions, using the methods developed by Brodie, Staudenmaier, or Hummers and Offeman, is

196 the most common treatment used (Brodie, 1859; Staudenmair, 1898; Hummer and Offeman,

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197 1958). These oxidation procedures are used to generate GO from bulk graphite. The produced

198 GO can then be re-reduced by thermal treatment, chemical method, plasma, or microwaves (Cao

199 et al., 2012; Zhang et al., 2010a; Cardinali et al., 2011, Zhu et al., 2010).

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200 Oxidation can also result in a change of the surface polarity of reduced graphene (Wu et

201 al., 2011; Zhao et al., 2011a; Pei et al., 2013). These different procedures lead to changes in the

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202 functional groups present on GNS, either at the side-layers or at the defect sites within the sheets

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203 through the covalent and non-covalent attachment of functional groups. Non-covalent

204 functionalization might be more beneficial since it has not been shown to alter the pore texture of

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205 carbon nanomaterials (Datsyuk et al., 2008; Ma et al., 2011; Apul and Karanfil, 2015). The most
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206 common type of functionalization entails the introduction of oxygen containing functional

207 groups on the GNS surface during the oxidation of graphite to GO. The amount and form of
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208 oxygen containing functional groups (e.g. -OH, O=COH, -COOH, and C=O) depends on the

209 type of oxidation technique and acid used (Wu et al., 2011; Zhao et al., 2011). The surface
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210 composition of GNS can be characterized by X-Ray photoelectron spectroscopy (XPS), Fourier
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211 Transform Infrared Spectroscopy (FT-IR), and elemental analysis. Raman spectroscopy is also

212 used to characterize the structure and quality of GNS, especially in identifying structural
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213 changes, such as defects and (dis)ordered structures (Chen and Chen, 2015, Jiang et al., 2016).
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214 The addition of oxygen containing functional groups decreases the surface
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215 hydrophobicity, and increases the dispersion of GO in water. The presence of oxygen containing

216 functional groups can also bond water clusters on the surface and inhibit the adsorption of OCs;

217 GO generally exhibits a lower OC adsorption than graphene (Apul et al., 2013, Beless et al.,

218 2014; Ersan et al., 2016). The adsorption of OCs on GNS is also affected by pH, exhibiting

219 lower adsorption capacity at low pH levels (Zhao et al., 2011b; Wang et al., 2013). The behavior
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220 of GNS in aquatic systems is controlled by its point of zero charge (pHpzc), which can be

221 measured by zeta potential analysis (Dastgheib, et al., 2004). At pH values above the pHpzc, the

222 net charge on the GNS surface is negative due to the deprotonation of carboxyl and hydroxyl

223 groups. As a result, the electrostatic interactions with positively charged OCs become more

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224 favorable. In contrast, at pH below the pHpzc, the net charge on the GNS surface becomes

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225 positive and electrostatic repulsion between OCs and graphene surfaces of the same charge

226 increases (Zhao et al., 2011b; Wang et al., 2013.

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227 4. Adsorption of OCs by GNS

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228 4.1. OC adsorption mechanisms by GNS
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229 The adsorption interactions between adsorbate-adsorbate, adsorbent-solvent, and

230 adsorbate-solvent are typically described as physical, chemical, and electrostatic interactions
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231 (Summers and Roberts 1988a. 1988b; Weber et al., 1991; Radovic et al., 1997; Karanfil and

232 Kilduff, 1999; Moreno-Castilla, 2004). The underlying mechanisms involved in the adsorption of
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233 OCs on the GNS surface have been reported by Mishra and Ramaprabhu, (2011); Apul et al.,
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234 (2013a); Ji et al., (2013); Wang et al., (2014); Beless et al., (2014); Chen and Chen., (2015);
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235 Zhou et al., (2015), and Ersan et al., (2016b). Briefly, various molecular-level interactions, which

236 include hydrophobic, π-π, π-π electron donor-acceptor (π-π EDA), van der Waals, electrostatic
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237 (Coulomb force), Lewis acid-base, and hydrogen bonding interactions are the causative factors
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238 behind the adsorption of OCs by GNS. These interactions can act in concert with varying relative

239 contributions for the adsorption of OCs by GNS. They are affected by the physicochemical

240 properties of adsorbents, the characteristics of adsorbates and the background solution chemistry.

241 Hydrophobic interaction is one of the most important adsorption mechanisms for

242 hydrophobic and nonpolar OCs onto graphene and rGO (e.g., Apul et al., 2013; Ersan et al.,
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243 2015b). Adsorption affinities of different adsorbates have been independently reported in many

244 studies as correlating quite closely with their hydrophobicity regardless of the GNS properties

245 (Yang et al., 2006; Wang et al., 2008; 2009; Yang and Xing, 2007). The octanol-water

246 distribution coefficient (KOW), the hexadecane-water distribution coefficient (KHW), and the

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247 aqueous solubility (Cw) of the OC molecule have been used to determine the intensity of the

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248 hydrophobic interactions (Apul et al. 2013, Beless et al., 2014, Liu et al., 2014; Wang et al.,

249 2014b, Jin et al., 2015, Nam et al., 2015, Ersan et al., 2016). Of these three parameters, KOW has

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250 been the most commonly used to describe hydrophobicity for nonpolar OCs. However, KOW is

251 unsuitable to normalize adsorption coefficients for polar OCs due to the possible interaction

252
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between -OH of octanol with polar OCs (Chen et al., 2002). As a result, the KHW with its greater
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253 accuracy is often used to normalize the adsorption coefficient for polar OCs.

There are four types of π bonding, specifically π−π, n−π, cation−π, and anion−π bonding.
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255 The π−π bonding occurs between C=C double bonds or benzene rings of adsorbed OC molecules
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256 and benzene rings on GNS surface. The n−π interactions occur between GNS electron depleted
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257 sites and n-electron donors of OCs containing oxygen (e.g., 1-naphthol) or nitrogen (e.g., 1-

258 naphthylamine) with lone electron pairs (Yang et al., 2013). The cation−π bonds form between
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259 the GNS π−electrons and quickly protonated amino groups (e.g., tetracycline) (Gao et al., 2012).

260 Conversely, the GNS surface can act as an electron acceptor for anion (e.g., F−, Cl−, Br−)
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261 adsorption; the anion−π bonding was found to be unexpectedly strong using a computational
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262 method based on the DFT (Shi et al., 2012). Of these four, the π-π interaction is the most

263 important adsorption mechanism for the interactions between OCs and GNS (Li et al., 2011; Wu

264 et al., 2011; Sharma and Das, 2013; Zhao et al., 2011a; Li et al., 2012; Gao et al., 2012; Li et al.,

265 2013). Wu et al. (2011) reported that each carbon atom on the GNS sheet had a π-electron orbit

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266 perpendicular to GNS surface. The OCs containing π electrons (such as C=C double bonds or

267 benzene rings) can form π-π bonds with GNS (Apul et al., 2015). For each carbon atom on the

268 GNS surface, three of the four outer electrons strongly bonded with its neighboring atoms by σ

269 orbitals with each carbon atom having a single π electron orbiting perpendicular to the GNS

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270 surface (Li et al., 2011). For example, cationic red X-GRL containing π electrons can also form

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271 π-π bonds with GNS, which permits their easy adsorption. Different from other carbon-based

272 materials, the advantage of GNS is the strong bonding between OC molecules and open-up layer

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273 graphene surface through π-π interaction (Cai, et al., 2014; Ersan et al., 2016). Overall, GNS is a

274 promising adsorbent for the removal of OCs containing C=C double bonds or benzene rings.

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In addition to π-π interaction, π-π electron donor–acceptor (EDA) interaction is a primary
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276 adsorption-enhancement mechanism for OCs with either strong π-electron-donating (e.g.,

polycyclic aromatic hydrocarbons and amino- and hydroxyl-substituted aromatics) or

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278 withdrawing ability (e.g., nitroaromatics and sulfonamide and tetracycline antibiotics) because of
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279 the interactions of OC molecules with π-electron-depleted or rich regions on the GNS surface.
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280 The π-energy level of individual OCs can sensitively affect the π-π EDA interaction between

281 OCs and carbonaceous adsorbents (Yang et al., 2010; Ji et al., 2010b; Chen and Chen, 2015). Ji
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282 et al. (2013) reported that the substitution with a strong electron donating, –OH group or –NH2

283 group enhanced the π electron density of aromatic rings on naphthalene. The strong π-π EDA
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284 interaction was likely to occur for the adsorption of the two substituted naphthalene. A recent
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285 study has demonstrated that diclofenac has two separate benzene rings and differs

286 sulfamethoxazole (one benzene ring). However, both exhibit similar π energies in their chemical

287 structures (Nam et al., 2015). Although molecular modeling predicted the electron affinity for

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288 aromatic rings between the OCs and GO qualitatively, the π energies of the OCs suggested no

289 significant association between the π-π EDA interactions with the OC adsorption.

290 The van der Waals forces, also known as London forces, are weak interactions caused by

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291 momentary changes in electron density in OC molecules. Their interaction includes either the

292 attraction or repulsion between OC molecules and the GNS surface, as well as other

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293 intermolecular interactions. Though van der Waals forces are weak compared to chemical bonds

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294 (covalent and ionic), their long-range nature and collective effect can be important depending on

295 the structure of OC molecules and their interactions with adsorbent surfaces (Atwood and Steed,

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296 2004; Lawley, 2009; Jortner, 2009; Zeng, 2013). In the absence of π-π EDA interaction, the van
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297 der Waals interactions are the dominant contributor to the overall attractions of many molecules.

298 These interactions are proportional to either the product of the polarizability or the dipole
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299 moment of the OCs and carbonaceous adsorbents (Zhou et al., 2015).
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300 The presence of a charged functional group on OC molecules can result in the adsorption
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301 of these molecules by GNS through electrostatic interaction, or Coulomb force (Li et al., 2011;

302 Zhang et al., 2011; 2013a; Ramesha et al., 2011; Sharma and Das, 2013; Li et al., 2013). Li et al.
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303 (2011) reported the adsorption of the cationic dye methylene blue was primarily due to the

304 electrostatic interactions with negatively charged GO sheets. Sharma and Das, (2013) also
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305 postulated that, using Diffuse Reflectance Infrared Fourier Transform (DRIFT) spectra analysis,
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306 electrostatic interaction occurred between carboxyl (–COOH) groups of GO sheets and

307 positively charged nitrogen moieties of cationic methylene green. According to Ramesha et al.,

308 (2011), the adsorption of anionic rhodamine B and Orange G dyes was not favorable at the pH

309 range of 6 and 10. As the carboxyl (–COOH) group in both anionic dyes was negatively charged,

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310 electrostatic repulsion was possibly important between GO sheets and anionic dye molecules

311 (Ramesha et al., 2011).

312 Lewis acid-base interactions also play an important role in the adsorption of OCs on

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313 GNS, particularly for GO, which is abundant in acidic groups. For example, Ji et al., (2013)

314 reported the inhibited adsorption of 1-naphthylamine, when the pH was below the pKa (3.9), was

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315 a result of the protonation of most of the 1-naphthylamine molecules. Trends observed in the

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316 higher pH range (7.0–10.5) between graphene and GO were consistent with the mechanism of

317 Lewis acid–base interaction. At high pH, some of the Lewis acid sites (e.g., –COOH, –OH) of

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318 GNS were ionized; as a result, the Lewis acid–base interaction was weakened. This effect was
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319 more profound for GO, which contained much greater numbers of acidic functional groups.

320 Hydrogen bonding interaction plays an important role when the OC molecules and GNS
M

321 involved in the adsorption contain functional groups such as hydroxyl, carboxyl and amines.

322 (Perreault et al., 2015). However, Pei et al., (2013) reported that hydrogen bonding was not
D

323 likely the primary cause of the enhanced adsorption for both hydroxyl (–OH) group on OCs
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324 (2,4,6-trichlorophenol and 2-napthol) and O-containing groups of GNS at high pH due to

325 ionization, which should have greatly inhibited the hydrogen-bonding effect. Hydrogen bonding
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326 can have a strong effect on the OC adsorption at a neutral pH due to water cluster formation
C

327 around polar groups, like those found on GO (Ersan et al., 2016). As such, the more hydrophilic
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328 GO is expected to exhibit a lower adsorption affinity to hydrophobic OCs compared to graphene.

329 There are other potential interactions based upon theoretical analysis (Zhao et al., 2014b).

330 For instance, although there are no current reports on the formation of covalent bonds, this

331 interaction may occur between GO and OCs containing functional groups such as −OH,

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332 −COOH, and −NH2. The formation of covalent bonds has been reported for CNT and OCs (e.g.,

333 L-phenylalanine, 1-naphthylamine and tylosin) (Piao et al., 2008; Chen et al., 2008).

334 Overall, hydrophobic, electrostatic, π-π, π-π EDA, dispersion (van der Waals), Lewis

335 acid-base interactions, and hydrogen bonding with oxygen bearing impurities (e.g. carboxyl

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336 functional groups) are important adsorption mechanisms, depending on properties of OCs and

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337 graphene materials. The adsorption capacity of the same OC molecule may differ on rGO and

338 GO. Similarly, the presence or absence of functional groups (–NH2, –OH, –COOH) in the OC

SC
339 molecule will influence the mechanism and efficiency of the adsorption process. Therefore,

340 describing OC adsorption by GNS requires a good characterization of both the adsorbent and

341
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OCs properties as well as careful consideration of multiple adsorption mechanisms.
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342 4.2.The effect of GNS properties on adsorption of OCs
M

343 Of the array of the techniques available for the characterization of GNS, a few

344 physicochemical properties of GNS (i.e. the SSA, PSD, surface charge and chemistry) have been
D

345 most commonly used to determine the adsorption of OCs. In recent years, researchers have also
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346 reported other properties of GNS such as wrinkle, folds and 3D arrangement of graphene can
EP

347 impact the OC adsorption (Wang et al., 2014; 2016).

348 SSA was an important but not exclusive factor in designation of the adsorption capacities
C

349 of graphene based adsorbents (e.g., Yang et al., 2006; Lin and Xing, 2008a; Pan et al., 2008;
AC

350 Yang and Xing, 2009; Chen et al., 2009). Li et al. (2013) reported CNT had larger SSA than GO;

351 however, GO adsorbed more methylene blue dye. This was attributed to the unique open-up

352 layer structure of GO. Zhou et al., (2015) observed that GAC and SWCNT exhibited higher

353 uptake for the aliphatic OCs than graphene and rGO. After normalized with SSA and micropore

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354 volumes of all adsorbents, the adsorption of aliphatic OCs by GAC and SWCNT were still

355 higher than those of graphene and rGO. This result showed that SSA and micropore volume

356 difference did not show an impact on the adsorption capacity difference.

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357 PSD is one of the important properties of adsorbents for controlling the adsorption. PSD

358 determines the fraction of total PV that can be accessed by OCs (Apul et al., 2013). If adsorbent

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359 pores are too small, the size exclusion will limit the adsorption of OCs. On the other hand, the

SC
360 micropore-filling has been determined as a central mechanism behind the adsorption of low

361 molecular weight OCs by porous adsorbents (Karanfil and Kilduff, 1999; Li et al., 2002;

U
362 Karanfil and Dastgheib, 2004; Bandosz, 2006). Since there are plenty of high-energy sites
AN
363 available in micropore regions, adsorbent will interact with OC molecules through multiple

364 contact points, and this interaction becomes stronger as the adsorbate and adsorbent dimensions
M

365 get closer to each other.

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366 In addition to SSA, PSD and PV, the oxygen functional groups of adsorbents also affect
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367 the interactions between OCs and adsorbents. Two opposing factors play roles in adsorption in

368 the presence of oxygen functional groups on graphenes and GOs: (i) an increase in adsorption
EP

369 from the polarity of surface oxides that increase the dispersal of these adsorbents in water; and

370 (ii) a decrease in adsorption from the formation of water clusters around oxygen-containing
C

371 functional groups. Previous studies have found that oxygen containing functional groups can
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372 decrease the surface hydrophobicity and increase the dispersion of GO in water. The presence of

373 oxygen-containing functional groups contributes to OCs adsorption, while creating water clusters

374 on GO sheets thereby reducing the number of available adsorption sites (Apul et al., 2013; Zhou

375 et al., 2015 and Ersan et al., 2016). The GO exhibited a lower OC uptake compared to graphene,

376 indicating the importance of water cluster formation over a decrease in the adsorption sites in the
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377 adsorption of nonpolar aromatic and aliphatic OCs. Conversely, some studies found that GO had

378 similar or weaker polar OCs uptake than graphene. This was attributed to more polar surface of

379 GO as suggested by its high oxygen content (>%10). The high surface oxygen content of GO can

380 also enable a strong hydrogen bonding and Lewis acid base interactions with hydroxyl- and

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381 amino-substituted OCs (Wang et al., 2014b; Yang and Xing 2009). Thus far, only a limited

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382 number of studies have been conducted to systematically compare adsorptive interactions

383 between GNS and OCs with significantly different physicochemical properties (i.e., polarity,

SC
384 functional groups). The significant variance in GNS size, morphology, and impurity (metallic

385 and oxygen containing groups) can further enhance the intricacies of the adsorptive properties of

386
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GNS to OCs. This discrepancy reveals the need for additional research to more thoroughly
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387 elucidate the molecular interaction of GNS and OCs with different graphene properties.

Moreover, the surface charge on graphene was created to elicit more adsorption sites (Zhao et al.,
M

388

389 2011; Wang et al., 2014). Ramesha et al. (2011) pointed out that one important advantage of
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390 exfoliated GO was to maintain a high negative charge density in a wide range of pH, allowing an
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391 ion exchange with either metal cations or positively charged OC molecules.

392 Recently, researchers have been using different treatment methods, such as thermally
EP

393 treating with KOH, to increase the graphene active sites for OC adsorption. As a result, graphene

394 sheets form wrinkles and folds which are the genuine structures of graphene minimizing the total
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395 free energy and keep stability. Wang et al., (2014a) reported that the high adsorption affinities of
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396 PAHs onto graphene are dominated by π−π interactions with flat graphene surface and sieving

397 effect of the groove regions formed by wrinkles on GNS surfaces. On the other hand, when the

398 groove regions disappear, the carboxyl groups attached to the edge of GO altered its adsorptive

399 properties by limiting the π−π interactions on polar nanosheet surfaces. Chen and Chen (2015)

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400 showed that the wrinkles and holes within graphene have more active sites with a stronger

401 adsorption affinity to OC molecules, compared to the flat surface. Similarly, Wang et al., (2016)

402 examined the relationship between surface morphology of graphene and its adsorption

403 performance toward p-nitrotoluene, naphthalene and phenanthrene molecules. The adsorption of

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404 OCs by activated graphene with KOH etching was greatly enhanced compared to pristine

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405 graphene. Overall, there is still a limited number of studies on the relationship between graphene

406 morphology and active adsorption sites for OCs.

SC
407 Having an open-up flat-layer structure nearly doubles the number of potential adsorption

408 sites compared to single-walled CNT. This makes GNS an ideal platform for inducing the π−π

409
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interaction and hydrophobic effect with OCs (Zhao et al., 2011b; Wang et al., 2016). However,
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410 perfect two-dimensional (2D) nanostructures of graphene tend to rearrange into a three-

dimensional (3D) graphene structure for stability; wrinkles are formed on free-standing graphene
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411

412 sheets and are prone to restack together. Restacking is attributed to strong van der Waals forces
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413 between each layer of graphene (Wang et al., 2014). Aggregation of GNS may cause
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414 obstructions of adsorption sites (Yang et al., 2014; Shen et al., 2015). For GNS, the three main

415 adsorption sites are the longitudinally-parallel external surface, the open-up layer, and the
EP

416 interstitial channels (Figure 2). Adsorption of OCs by GNS is possible from either open-up

417 surface GNS or through some bundle structure large enough for OC molecules to make contact
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418 with GNS surface. To date, researchers have examined the role of functional groups and/or
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419 composites on GNS on the availability of adsorption sites and the overall adsorption mechanisms

420 of OCs by GNS. However, further research is still needed to understand the impact of GNS

421 aggregation in water on the adsorption of OC molecules.

422 4.3.The effect of OC properties

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423 Adsorbate properties, including molecular size, geometrical configuration (e.g. planarity,

424 ring structure), hydrophobicity, aromaticity, polarity, and substituent groups have been

425 investigated to determine their influence upon GNS adsorption (Table S2). The physicochemical

426 properties of OCs are known to affect the adsorption as much as those of adsorbents (Ania et al.,

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427 2008).

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428 The geometrical configurations of OCs exhibit a significant effect on their interaction

429 with GNS because of the open-up surface and interstitial channel of the GNS surface. Apul et al,

SC
430 (2013a) reported that hydrophobicity was not the only factor influencing the adsorption, and the

431 planar versus nonplanar molecular structure of phenanthrene and biphenyl molecules also

432
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affected the adsorption. The longitudinally-parallel external surface, the open-up layer and the
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433 interstitial channels can provide more favorable adsorption sites to planar molecules than to non-

planar molecules based on the π-π contact. A limited number of studies have examined and
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434

435 reported the effect of molecular configuration and size on the OC adsorption. Further research is
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436 warranted to confirm and extend the findings to include larger and more complex aliphatic and
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437 aromatic molecules.

438 The hydrophobicity of OCs is an important driving force for the adsorption of both
EP

439 hydrophobic and nonpolar OCs by GNS from aqueous solutions. This is understandable

440 considering the strong nonpolarity and hydrophobicity of GNS. In general, the adsorption of OCs
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441 by GNS increases with a decrease in their solubility and/or an increase in their hydrophobicity.
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442 Further, several studies have reported the adsorption affinities of different adsorbates to GNS

443 were correlated well with hydrophobicity of the OC molecule and GNS (Apul et al., 2013; Ji et

444 al., 2013; Wang et al., 2014; 2016; Chen and Chen, 2015; Zhou et al., 2015; Ersan et al., 2016).

445 However, Liu et al. (2014) found that after Kow normalization, the adsorption isotherms of the

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446 three PPCPs (ketoprofen, carbamazepine and bisphenol A) onto graphene and rGO were in the

447 order of bisphenol A > carbamazepine > ketoprofen, which followed the reverse order of their

448 hydrophobicity. This result showed that hydrophobic interaction exhibits no significant role due

449 to low oxygen contents of graphene, rGO1 and rGO2. Similarly, Ji et al., (2013) concluded that

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450 the order of adsorption affinity among the naphthalene, tylosin, 2-naphthol, 1-naphthylamine on

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451 graphene and GO correlated poorly with the hydrophobicity of OC molecules. Of the Cw and

452 KOW values of the four adsorbates studied, naphthalene was found to be the most hydrophobic

SC
453 compound, with the lowest Cw value, and its KOW value is similar to that of tylosin and

454 considerably higher than those of 2-naphthol and 1-naphthylamine. The adsorption of

455
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naphthalene exhibited the weakest or lowest affinity, while the least hydrophobic compound (1-
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456 naphthylamine) exhibited the highest adsorption affinity on graphene and GO. The surface

defects of carbonaceous adsorbents can result in significant delocalization of the π electrons

M

457

458 (McDermott and McCreery, 1994; Fagan et al., 2004; Robinson et al., 2006), and this effect is
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459 more profound for GO due to their oxygen containing functional groups. Conversely, Zhou et al.,
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460 (2015) determined that the adsorption isotherms were normalized according to their solubilities.

461 After the Cw normalization, the separation in the adsorption isotherms on both graphene and rGO
EP

462 were greatly reduced with the isotherms failing to converge on a single line. This indicates the

463 hydrophobicity of the aliphatic OCs was an important driving force but not the only controlling
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464 factors. Overall, these reports demonstrate that the hydrophobicity itself may not adequately
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465 explain the adsorption affinity of different classes of OCs on GNS. Indeed, other attractive forces

466 may also contribute to the overall intermolecular interaction between OC molecules and the GNS

467 surface.

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468 In addition to the molecular structure and the hydrophobicity of OCs, several studies have

469 been undertaken to determine the importance of aromaticity (the number of aromatic rings and

470 their spatial arrangement) on the interaction between aromatics and GNS (Zhao et al., 2011a; b;

471 2014a; Apul et al., 2013; Pei et al., 2013; Zhang et al., 2013b; Liu et al., 2014; Ersan et al., 2016;

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472 Wang et al., 2014a; b; 2016). Here, the π−π dispersion is hypothesized as the major interaction

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473 between the adsorption of aromatic OC molecules on the electronic polarized surface of GNS

474 (Apul et al., 2013, Pei et al., 2013; Zhang et al., 2013b; Wang et al., 2014b; Ersan et al., 2016).

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475 The interaction would be enhanced with increasing number of aromatic rings (Pei et al., 2013).

476 Zhang et al., (2013b) concluded that tetrabromobisphenol A (with two aromatic rings) could be

477
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adsorbed on GO by π−π electron and hydrophobic interactions. Apul et al., (2013a) attributed
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478 higher adsorption affinity of phenanthrene than biphenyl on GNS to stronger π-π interaction

between phenanthrene molecules and GNS surface due to increase in the number of aromatic
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479

480 rings. Similarly, Wang et al., (2014b) observed a higher adsorption affinity of 1-naphthol (with
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481 two benzene rings) than 2-4 dichlorophenol (with a single benzene ring) to GNS, which was
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482 attributed to the higher π−π interaction between 1-naphthol and the GNS surface. In addition, the

483 adsorption of OC molecules is a noncovalent functionalization involving π-stacking interactions

EP

484 with a correspondingly weak binding energy. The π–π bonding interaction between OC

485 molecules and GNS are affected by either the relative position of the benzene ring or the C=C
C

486 double bond of OC molecules to the hexagons on the GNS surface (Pan et al., 2008). Wu et al.,
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487 (2011) demonstrated that the adsorption rate of p-toluenesulfonic acid, 1-naphthalenesulfonic

488 acid and methyl blue on GNS is faster than acrylonitrile, since p-toluenesulfonic acid, 1-

489 naphthalenesulfonic acid and methyl blue with benzene ring can be more “fit” there position with

490 GNS than acrylonitrile with C=C double bond.

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491 The electronic polarizability of aromatic rings on GNS may also considerably alter the

492 adsorption of OCs on GNS. Wang et al., (2014b) reported that the polar OCs exhibited strong

493 adsorption affinities to GO. Besides, GO, CNT, and C60 are often showed different adsorption

494 affinities for the tested polar and nonpolar OCs, which can be ascribed to the differences in their

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495 morphology and surface polarizability. Increases in surface oxygen functionalities of GO can

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496 allow polar interactions between polar OC molecules and GO, such as strong H-bonding of OC

497 molecules.

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498 In addition, substituent groups on the OCs may also affect the adsorption mechanism of

499 GNS. Ji et al. (2013) reported the naphthalene (two fused aromatic rings) was π electron-rich,

500
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and the substitution with a strong electron-donating like -OH group of –NH2 group further
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501 enhanced the π electron density of the aromatic rings, indicating that the strength of adsorption

affinity followed the order of the π- electron-donor ability of the solute: 1-naphthylamine > 2-
M

502

503 naphtho > naphthalene. Regarding the adsorption mechanisms of aliphatic OCs, Zhou et al.,
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504 (2015) concluded that the highly polarizable GNS play an amphoteric role in attracting both π
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505 electron-withdrawing (e.g., NO2 and -Cl) and donating (e.g., -OH) substituents to the surface,

506 with the chlorine groups on the trichloroethylene, tetrachloroethylene and 1,1 dichloroethylene
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507 serving as π electron acceptors to enlarge the π electron-withdrawing ability of the carbon double

508 bonds of these OCs. Promoting adsorption interaction between the OCs and adsorbents through
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509 π-π EDA complex, and thus adsorption affinities of three OCs by graphene and rGO was
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510 enhanced with increasing number of -Cl substituent. The comparison of different OCs revealed

511 that, in addition to hydrophobicity, the number of substituent groups on aliphatic OCs also

512 influences their adsorption behaviors. Pei et al. (2013) conducted that demonstrated that the

513 2,4,6-trichlorophenol and 2-naphthol structures had more hydroxyl groups on their individual

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514 molecular structure compared to the molecular structures of 1,2,4-trichlorobenzene and

515 naphthalene, while their similar adsorption capacity on the GNS indicated no substantial

516 contribution of the hydroxyl group to the overall adsorption of 2,4,6-trichlorophenol and 2-

517 naphthol. These results are consistent with those of Zhao et al., (2011) who observed a similar

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518 adsorption capacity of naphthalene and 1-naphthol on sulfonated GNS. Unlike graphene, the

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519 strong adsorption of hydroxyl-substituted 2-naphthol and 2,4,6-trichlorophenol indicated an

520 adsorption reaction that was related to the presence of hydroxyl group. It is well known that GO

SC
521 has less π-electron and more oxygen containing groups on its surface. The hydroxyl groups of 2-

522 naphthol and 2,4,6-trichlorophenol may interact with oxygen containing groups on GO through

523
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H-bonding (Pei et al., 2013). Moreover, Wang et al., (2014b) studied the adsorption of eight
AN
524 aromatics or substituted aromatics with different physicochemical properties by colloidal GOs.

The result demonstrated that the high surface oxygen content of GOs enables strong hydrogen
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525

526 bonding and Lewis acid-base interactions with hydroxyl- and amino-substituted aromatics.
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527 4.4.The effect of background solution properties

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528 Recent peer-reviewed publications indicate background solution chemistry can affect the
EP

529 adsorption of OCs by GNS (Table S3). While the effects of pH, ionic strength, and presence of

530 NOM were discussed in this manuscript, the information regarding surfactant and temperature
C

531 are provided in SI section (Text S1).

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532 4.4.1. The effect of pH

533 The pH of background solution is one of the major factors influencing the adsorption of

534 OCs by GNS. The effect depends on the ionizability and EDA ability of OCs, and the

535 protonation/deprotonation of functional groups on the active sites of GNS surface. With

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536 increases in pH, enhanced dissociation of ionizable OCs would increase their hydrophilicity and

537 consequently decreasing their adsorption by GNS. In addition, increased pH generally leads to

538 enhanced deprotonation of the oxygen groups on the GNS and formation of water cluster on

539 these groups, blocking access to the GNS surface and interfering with the EDA complex between

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540 OCs and carbonyl sites on GNS, thereby decreasing the adsorption. Ramesha et al. (2011)

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541 observed that the adsorption capacities of exfoliated graphene oxide (EGO) and GO for cationic

542 methylene blue and methyl violet dyes increased with increasing pH. On the other hand, the

SC
543 adsorption capacity of EGO and GO for anionic rhodamine B dye decreased with

544 the increase in pH due to the presence of the acidic carboxyl groups creating a negative charge

545
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density on the dye. Gupta et al. (2004) also reported a similar variance in pH for the adsorption
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546 of methylene blue and rhodamine B organic dyes on red mud. The effect of pH on the only three

aliphatic OCs (tetrachloroethylene, trichloroethylene and 1,2-dibromo-3-chloropropane)

M

547

548 adsorption by GNS was investigated in the literature (Zhou et al., 2015). The authors pointed out
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549 that the change in pH did not impact the adsorption of these three aliphatic OCs on graphene and
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550 GO (except for 1,2-dibromo-3-chloropropane under pH 11), owing to the nonionic contaminants

551 examined. Further research is needed to understand the adsorption of ionic/nonionic halogenated
EP

552 aliphatic OCs by GNS under varying levels of pH.

553 The enhanced dissociation of functional groups from ionizable OCs is also thought to
C

554 hinder the formation of hydrogen bonds between functionalized carbonaceous surface and
AC

555 dissolved OCs, which may reduce the adsorption (Zhang et al., 2010b; Li et al., 2013; Liu et al.,

556 2014; Yu et al., 2015a). Pei et al. (2013) evaluated the adsorption of structurally similar nonionic

557 1,2,4-trichlorobenzene and naphthalene, 2-naphthol and 2,4,6-trichlorophenol, which contain

558 nonpolar hydroxyl groups, under different pH conditions. The results showed that the adsorption

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559 of 1,2,4-trichlorobenzene and naphthalene on graphene and GO were almost independent of

560 solution pH over the investigated pH range because both molecules are nonionic. However, a

561 slight decrease was observed in the adsorption of 2,4,6-trichlorophenol on graphene and GO

562 decreased between pH values from 2 to 6 followed by a rapid decreased at pH > 6. Further, a

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563 significant increase over a pH range of 8–9.2 was observed with the adsorption of 2-naphthol on

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564 GNS. It was apparent from the pKa value of 2,4,6-trichlorophenol (6.15) and 2-naphthol (9.51),

565 that a higher content of neutral 2,4,6-trichlorophenol caused a greater adsorption of 2,4,6-

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566 trichlorophenol at a low pH. An increase in the solution pH increased the fraction of negatively

567 charged 2,4,6-trichlorophenol species, hindering GO adsorption through the electrostatic

568
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repulsion of anionic 2,4,6-trichlorophenol with negatively charged surfaces of graphene. For
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569 adsorption of 2-naphthol, the predominant fraction of 2-naphthol was in anion form at pH above

9.51. The high adsorption capacity of 2-naphthol at higher pH suggested that specific adsorption
M

570

571 enhancement interaction can occur to counterbalance electrostatic repulsion between anionic 2-
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572 naphthol and GNS surface (Zhao et al., 2011b; Wu et al., 2011). Ji et al., (2013) also reported
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573 similar findings for naphthalene and 2-napthol adsorption by graphene and GO under varying pH

574 values. They determined the primary effect of pH on the adsorption of naphthalene was likely
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575 affecting the protonation/deprotonation transition of the acidic oxygen containing functional

576 groups (e.g., –OH and –COOH) on the surface of the adsorbents, subsequently affecting the
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577 surface hydrophobicity (possibly the π-electron density of the GNS surfaces). The different
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578 responses to the pH effect between graphene and GO were likely related to the differences in

579 both the types and amount surface acidic groups between these adsorbents.

580 Yan et al., (2015) found that the adsorption behavior of the GOs for both nitrobenzene

581 and chlorobenzene exhibited pH independence. However, the cationic amino groups on aniline

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582 bonded efficiently via electrostatic interactions with the anionic functional groups of GO (Gao et

583 al., 2009). Both hydrophilic and hydrophobic interactions are involved in aniline adsorption,

584 differing from nitrobenzene and chlorobenzene, because aniline contains cationic −NH3+ groups

585 which have good water solubility and hydrogen bonding. The existing GAC and CNT literature

PT
586 indicates the possibility of controlling either adsorption of ionic or nonionic OCs through a

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587 combination of (i) hydrogen bonding interaction between the –OH group of OCs and oxygen

588 containing groups on GNS, (ii) the direct anion-π interaction between –OH or –O (n-electron

SC
589 donor) groups of OCs and electron-depleted sites (π-electron acceptor) of GNS, (iii) the π-π EDA

590 interaction between the aromatic ring(s) of OCs and GNS surface, (iv) van der Waals forces, and

591
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(v) a Coulombic attraction and/or repulsion between OCs and GNS, depending on pH (Li et al.,
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592 2013). There is, however, no consensus regarding the effect of the adsorption of ionizable OCs

onto GNS. Systematic investigations are still needed to elucidate the interactions between the
M

593

594 ionizable OC molecules and GNS surfaces for all other factors.
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595 Furthermore, the electrostatic interaction can also play an important role in OCs
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596 adsorption by GNS with change in solution pH, owing to changing both charge of OCs and GNS

597 surface. Several research groups have reported an increase in pH has a positive influence on
EP

598 adsorption of positively charged OCs due to electrostatic attraction (Li et al., 2011; Zhang et al.,

599 2013a; b; Sharma and Das, 2013; Zhang et al., 2011; Li et al., 2012; 2013). On the other hand,
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600 Gao et al., (2012) observed opposite effect of solution pH on the tetracycline antibiotics
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601 adsorption. The adsorption capacities of tetracycline on GO decreased with the increase in pH.

602 Increasing pH facilitated the deprotonation of the groups, including charged polar/ionizable

603 groups (especially amino and enol groups) on tetracycline molecule and carboxyl groups on GO.

604 As a result, the electron acceptor ability of these moieties was weakened with the increase in the

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605 pH of the background solution, which in turn suppressed both the cation-π bonding and π-π

606 stacking with GO. Further, the π-π EDA interaction and cation-π bonding has been hypothesized

607 as the causative effect behind the adsorption of tetracycline on CNT and graphite (Ji et al., 2009).

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608 4.4.2. The effect of ionic strength

609 The effect of ionic strength also has an influence on the adsorption of OCs by GNS (Liu

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610 et al., 2014; Jiang et al., 2016). Ionic salts are known actors in a variety of mechanisms,

SC
611 particularly those interactions with OC molecules in solution and on the adsorbent surface, and

612 in the change of the adsorbent surface charge (Zhang et al., 2010a; b; Apul and Karanfil, 2015).

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613 Thus far, two distinct effects are known to characterize the ionic strength in OC adsorption from
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614 carbonaceous adsorbents (Zhang et al., 2010a; b; Zhou et al., 2015; Jiang et al., 2016): (i) the

615 effect of ionic salts on adsorption capacity can vary according to the electrostatic nature and
M

616 configuration of the OCs and the activity coefficient of hydrophobic OCs, decreasing their

617 solubility (from a “salting out” effect), which is favorable for OC adsorption, and (ii) the
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618 increase in salt ions can exert a “squeeze-out” effect on carbonaceous adsorbents, which is
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619 unfavorable for OC adsorption. Specifically, the ions may penetrate into the diffuse double layer
EP

620 surrounding the GNS surfaces and repel the interaction between the GNS, thus promoting the

621 formation (i.e. squeezing-out) of a more compact aggregation structure (Zhou et al., 2015; Jiang
C

622 et al., 2016). Positive salt cations could also neutralize the negative charge of both adsorbents
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623 and OCs, thus decreasing the electrostatic repulsion between them and moving adsorbents

624 towards the OC molecule (Fontecha-Camara et al., 2007).

625 According to Gao et al. (2012), the adsorption capacities of tetracycline antibiotics

626 decrease with the increase in Na+ concentration due to an electrostatic screening effect. The

627 increase in ionic strength can reduce the electrostatic interactions between the charged amino
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628 group of tetracycline and deprotonated carboxyl groups of GO. The cation-π bonding can also be

629 weakened because of electronic screening of the surface charge sites by Na+. A similar

630 observation was also found in study conducted by Liu et al., (2014) . The adsorption capacity of

631 GO for ketoprofen increased with increasing ionic strength (from 0 to 20 mM). In another study,

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632 Liu et al., (2016) emphasized that the uptake of 17b-Estradiol by GO improved in the presence of

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633 NaCl (< 0.001 M). This result clearly stated that the salting-out effect was consistently greater

634 than the squeezing-out effect. However, when the NaCl concentration was >0.001 M, the

SC
635 adsorption capacity slightly decreased, and was related to the decreasing salting-out effect. In

636 contrast, Zhang et al. (2011) reported that high ionic strength had no effect on the adsorption of

637
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methylene blue by GO. Zhou et al. (2015) also pointed out that increasing ionic strength had
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638 negligible effect on adsorption of the aliphatic OCs by both graphene and rGO. The results of

both analyses determined that i) either the salting-out effect on the adsorption of these aliphatic
M

639

640 OCs and organic dye was equivalent to that of the squeezing-out effect or ii) both the salting and
D

641 squeezing-out effect were too weak to affect the adsorption of the OCs on GNS. Despite these
TE

642 intriguing results, only a limited number of studies have been undertaken to determine the impact

643 of ionic strength on limited classes of OCs adsorption by graphene and GO (Gao et al., 2012; Liu
EP

644 et al., 2014; Zhou et al., 2015; Jiang et al., 2016).

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645 4.4.3. The effect of natural organic matter (NOM)

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646 The influence of NOM on OCs adsorption by GNS have been investigated in limited

647 studies, which demonstrate that NOM reduces the adsorption capacity of GNS and GOs for

648 aromatic OCs (Apul et al., 2013; Ersan et al., 2016), pharmaceuticals and personal care products

649 (PPCPs) (Liu et al., 2014; 2016; Zhu et al., 2015; Jiang et al., 2016), and halogenated aliphatic

650 OCs (Zhou et al., 2015; Ersan et al., 2016). Besides, there has been only one critical review
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 ACCEPTED MANUSCRIPT

651 report examining the effect of NOM on OCs adsorption by GNS according to the environmental

652 fate, toxicity and transform of GNS (Zhao et al., 2014b). From an environmental perspective, the

653 strong interaction between GNS and OCs may bring high environmental toxicity and risks. With

654 the rapid increase in commercial GNS production, considerable GNS release into the aquatic

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655 environment has occurred during the environmental applications and/or the waste disposal of

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656 GNS containing products (Zhao et al., 2014b), increasing the environmental risks due to the

657 toxicity of GNS. Further, the presence of ubiquitous contaminants in the aquatic environment,

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658 and the interaction between GNS and OCs may change the fate, transport and toxicity of both

659 GNS and OCs. More importantly, the relationship between the NOM properties and the

660
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associated GNS adsorption performance is not yet fully understood. NOM may exhibit two
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661 opposite effects on the adsorption of OCs by GNS: (i) decreases the adsorption sites through

competition and pore interstice/blockage, and (ii) increases the adsorption sites from a superior
M

662

663 dispensability (Apul et al., 2013; Zhou et al., 2015 and Ersan et al., 2016). As shown in Figure 3,
D

664 both of the graphene and GO bundles and their available adsorption sites are evident in the
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665 presence of NOM molecules. The NOM molecules interact with the GNS surface via

666 hydrophobic forces and π–π dispersion effect, and with any available surface functional groups
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667 (such as –OH, -COOH, =O) via hydrogen bonding and electrostatic interaction. The exact

668 dispersion mechanism of GNS in NOM solutions may depend upon such NOM characteristics as
C

669 aromaticity, charge density, size and configuration of GNS and OCs. However, limited number
AC

670 of studies has been examined the effect of NOM on the adsorption of OCs by GNS. Therefore,

671 there is still a need to further understand the adsorption of OCs by NOM preloaded GNS, which

672 are able to modify the GNS surface. The available data have emphasized that the molecular

673 structure (planarity, flexibility, hydrophobicity) and/or adsorbent type (specific surface area, pore

30
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674 volume, pore size distribution and oxygen functional groups) greatly affect the adsorption

675 behavior of OCs by graphene and GO under NOM preloading conditions. Further, the adsorption

676 of biphenyl molecules (nonplanar and flexible structure) was more affected from the NOM

677 preloading of graphenes and GO, as compared to planar and rigid phenanthrene molecules (Apul

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678 et al., 2013). On the other hand, the uptake of hydrophobic phenanthrene molecules (logKow:

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679 4.68) was less affected than hydrophilic trichloroethylene molecules (logKow: 2.42) onto the

680 NOM preloaded graphene and GO (Ersan et al. 2016b). This was attributed to the stronger

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681 hydrophobic interactions and π-π bonding between the graphene surface and phenanthrene

682 molecules instead of NOM.

683
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The presence of electron withdrawing groups (-Cl) on the trichloroethylene molecule
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684 would be expected to increase the interactions of the OCs with carbon surfaces having high

electron density (Brooks et al., 2012). Finally, Zhou et al., (2015) studied that six different
M

685

686 halogenated aliphatic OCs adsorption by graphene and rGO under NOM preloading conditions.
D

687 The NOM effect on adsorption capacity of GNS were stronger than rGO, which indicate
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688 electrostatic repulsion of negatively charged NOM molecules by the rGO surface. While the

689 adsorption of all halogenated aliphatic compounds decreased under NOM preloading conditions,
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690 no clear trends were observed for each OC according to the Rm values (KF (NOM)/KF (DDW)), with

691 no correlation of the Rm values with the OC properties (e.g., solubility, molecular size and
C

692 polarizability). Clearly, these physicochemical properties of the selected halogenated aliphatic
AC

693 OCs exhibited very little change in the effects of the various NOMs on GNS adsorption.

694 Furthermore, the effect of NOM on the adsorption of OCs was generally smaller on GO

695 than graphene and other carbon nanomaterials, a difference attributed to a larger polar surface of

696 GO as indicated by its high oxygen content. Apul et al. (2013) determined that the polarity of

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697 surface oxides results in a better dispersion of GO in water, thus reducing the effect of NOM on

698 OC uptake. The electrical repulsion between NOM and GO reduced NOM coating on the GO

699 surface. Although, humic acid (HA) is a suppressant of PPCPs (ketoprofen, carbamazepine and

700 bisphenol A) adsorption to CNT and rGOs, the impacts on the rGOs were lower than those on

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701 CNT (Liu et al., 2014). Zhou et al., (2015) also observed a minimal effect of NOM preloading on

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702 the adsorption capacities of GO for six aliphatic OCs (tetrachloroethylene, trichloroethylene, 1,1-

703 dichloroethylene, 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane and 1,2-dibromo-3-

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704 chloropropane), which was attributed to a low level of NOM coating on the GO surface from the

705 electrostatic repulsion between negatively charged NOM molecules and GO. Finally, Liu et al.,

706
U
(2016) and Ersan et al., (2016b) observed a lower level of NOM inhibition upon sulfapyridine,
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707 sulfathiazole, thrichloroethylene and phenantherene adsorption for GOs compared with CNT and

GNS, which is possibly due to a higher oxygen contents of the GOs.

M

708

709 The adsorption capacity of OCs on GNS has been reported to depend more on the
D

710 physicochemical properties and molecular structures of OCs and characteristics of GNS than the
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711 NOM type (Apul et al., 2013; Zhu et al., 2015; Ersan et al., 2016). According to the Ersan et al.,

712 (2016b), the impact of different NOM types on the OCs adsorption isotherms of all preloaded
EP

713 adsorbents did not depend on the select NOM's characteristics (hydrophobic vs hydrophilic and

714 isolated vs reservoir water). The difference in the NOM aromaticity, indicated with the
C

715 difference in SUVA254 values, was not a predominant factor on OCs adsorption at similar DOC
AC

716 concentration of NOM solutions (3 ± 0.4 mg/L DOC). However, the structural characteristics

717 cannot fully explain the impact of NOM between different GNS and OCs. The different physico-

718 chemical properties of OCs (i.e., solubility, hydrophobicity, molecular size and polarizability),

32
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719 GNS (i.e., size, morphology and impurity), and NOM (i.e., aromatic content, DOC levels) should

720 be tested in the future.

721 5. Comparison of GNS with CNT and GAC

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722 Given the comparative novel nature of GNS, studies have also been undertaken to

723 investigate the interaction between GNS, CNT and GAC-OCs (Apul et al., 2013; Li et al., 2013;

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724 Yang et al., 2013; Zhao et al., 2014a; Liu et al., 2014; 2016; Beless et al., 2014; Zhou et al.,

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725 2015; Zhu et al., 2015; Ersan et al., 2016). The structural and chemical differences of GNS from

726 CNT and GAC may cause distinct interactions of GNS with OCs. As indicated in Figure 2, GNS

U
727 are composed of several two-dimensional graphene sheets, possessing open-up layered structure
AN
728 for OC molecules adsorption. Further, GNS layers are prone to restack due to strong van der

729 Waals forces, and thus may form interconnected pores within the aggregates, when compared
M

730 with CNT. Although it carries similar surface characteristics with CNT and GAC, graphene

731 exhibits significant differences in pore structure and aggregation behavior. Thus, the adsorption
D

732 behavior of OCs on graphene, GO, CNT and GAC is quite different and depends on the
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733 physicochemical properties of the adsorbents (e.g., specific surface area, pore size distribution
EP

734 and surface chemistry). Li et al., (2013) reported that adsorption capacity of methylene blue by

735 AC was higher than CNT and GO. This might be related to the higher surface area of AC. After
C

736 the adsorption capacity of methylene blue was normalized by the BET surface area of
AC

737 adsorbents, the adsorption capacity followed an order of GO > CNT > AC indicating that

738 adsorption of methylene blue onto carbonaceous materials was not only to the large surface area

739 but also to π-π EDA and electrostatic attraction between positively charged dye ions and

740 negatively charged adsorbents. Supporting this concept, Zhao et al., (2014a) concluded that

741 MWCNT had higher adsorption capacity after normalizing with surface area and micropore
33
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742 volume, compared to GNS. A possible explanation is that GNS possessed more oxygen

743 containing functional groups than MWCNT as indicated by the elemental oxygen composition of

744 these two materials (6.3% vs 0.1%). Liu et al., (2014) examined the adsorption of the three

745 PPCPs (ketoprofen, carbamazepine,and bisphenol A) by SWCNT, MWCNT, graphite, rGO1,

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746 rGO2 and GNS. According to their results, GNS, especially rGOs, possessed high adsorption

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747 capacity for the three PPCPs. The adsorption capacities were further compared with ACs, which

748 showed Q0/Asurf values of rGOs were much higher than that of ACs even though AC has the

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749 largest surface area.

750 The differences of OCs uptake by GNS, CNT and GAC not only depends on the

751
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physicochemical properties of the adsorbents but also on the OC characteristics (e.g.,
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752 hydrophobicity, molecular size and substituent groups). When the compared adsorption

behaviors of phenanthrene and biphenyl onto GNS, CNT and GAC, two microporous adsorbents
M

753

754 (SWCNT and GAC) showed the highest biphenyl uptake after surface area and oxygen content
D

755 normalization. This was attributed to better filling of micropores by biphenyl molecules (flexible
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756 and non-planar). These findings represented the factors controlling OC adsorption by GNS in

757 DDW are similar to those of GAC and CNT (Apul et al., 2013). In addition, Beless et al., (2014)
EP

758 reported the effect of molecular planarity had a greater effect on eleven PCB congeners

759 adsorption to the AC, charcoal, CNT, graphene and GO, such that the planar congeners form
C

760 stronger bonds with CNT, graphene, and GO, compared to AC and charcoal. These findings may
AC

761 be related to the planar congener molecules being better aligned on the GNS and CNT surfaces.

762 Previous studies have reported a decline in planarity effect with increasing chlorination,

763 demonstrating that the effect eventually became negligible, possibly impacted by the hexa-

764 homologue group (Jonker and Koelmans, 2002; Koelmans et al., 2009; Jantunen, et al., 2010).

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765 However, Beless et al., 2014 emphasized that the adsorption of eleven polychlorinated biphenyl

766 congeners increased due to increased planarity in the hexahomologue group, which might be

767 related with affinity between the planar congeners and the GNS surface outweighing the

768 deterrence via steric hindrance. In a similar study, Zhou et al., (2015) investigated six different

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769 halogenated aliphatic OCs adsorption by graphene, GO and SWCNT. In terms of their

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770 adsorption capacities, GNS did not exhibit a major advantage over SWCNT for the adsorption of

771 aliphatic OCs, indicating aliphatic compounds do not benefit from planarity of graphenes as

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772 much.

773 The impact of NOM on the adsorption of OCs was found to be smaller on GNS than

774
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CNT and GAC, which is thought to be due to a lower hindrance of aromatic and/or aliphatic OC
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775 molecules to adsorption sites on sheet-like GNS (Apul et al., 2013; Liu et al., 2014; 2016; Zhu et

al., 2015; Zhou et al., 2015; Ersan et al., 2016). This difference was attributed to the total pore
M

776

777 volumes and surface structure of GNS. Ersan et al., (2016b) concluded that among GNS, CNT
D

778 and GAC, GO was generally least effected from the NOM preloading for phenantherene,
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779 whereas there was not observed any trend of NOM competition with a specific adsorbent for

780 trichloroethylene. They further determined that NOM preloading for adsorption of
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781 trichloroethylene had the most effect upon SWCNT with no trend at all evident for

782 phenanthrene. Multiple factors can effect on the adsorption of OCs by GNS with varying relative
C

783 contributions, simultaneously. Therefore, the competitive mechanisms between NOM and OCs
AC

784 were controlled by not only NOM, but also the molecular properties of OCs and characteristics

785 of adsorbent. Moreover, of the three background solution properties (pH, ionic strength and

786 presence of NOM), NOM showed the most influential effect on the adsorption of OCs, while pH

787 and ionic strength had negligible effects (Zhang et al., 2010a; Zhou et al., 2015). Further

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788 research is still needed to examine the adsorption of ionic/nonionic aromatic and/or aliphatic

789 OCs by GNS and CNT under varying pH and ionic strength levels, simultaneously.

790 6. Future research needs and conclusions

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791 The physicochemical properties and characteristics of OCs, GNS and background

792 solution chemistry play an important role on the adsorption of OCs by GNS. The

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793 physicochemical properties of OCs (e.g., molecular size, geometrical configuration,

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794 hydrophobicity, aromaticity, polarity, and substituent groups), the characteristics of GNS (e.g.,

795 SSA, PSD, PV, surface charge and chemistry), and the aggregation state of GNS in water can

U
796 alter highly, depending on background water properties (e.g., pH, ionic strength, NOM type, and
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797 temperature). In that each of these individual parameters may influence the adsorption

798 mechanisms. Further research is still needed to understand the adsorption of different OC classes
M

799 (e.g., aromatic vs. aliphatic, ionic vs. nonionic) by GNS under varying environmental conditions.

800 Determining the contributions of each mechanism to overall adsorption remains a

D

801 challenging task. Understanding the influence and role of individual mechanisms including
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802 hydrophobic, electrostatic, other diverse π and dispersion (van der Waals), hydrogen bonding,
EP

803 and Lewis acid-base interactions needs further investigation. The molecular configuration

804 including size, aromaticity, and substituent groups of OC are all possible contributors to
C

805 adsorption of OCs by GNS. Research needs to be undertaken to gain further insights about
AC

806 adsorption affinity of different classes of OCs on GNS. Furthermore, competitive adsorption

807 among different classes of OCs should be investigated.

808 The unique structure of graphene-based material causes different adsorption behaviors as

809 compared with those of CNT and GAC. Due to the strong van der Waals forces along the ‘house-

810 of-cards’ bundle structure, GNS layers are prone to restack, decreasing their surface areas and
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811 the adsorption capacity for OCs. However, adsorption capacity of OCs may be reconstituted by

812 increasing the dispersion of bundled GNS structures with different modification techniques,

813 preventing restacking by forming 3D arrangements, wrinkles, and folds. Potential approaches

814 should be developed for producing new GNS or GNS-based materials with higher OC capacity.

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815 Approximately 40 peer-reviewed journal articles have been published on the adsorption

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816 of OCs by graphene and GOs. In this review paper, we discussed the investigations regarding the

817 adsorption of OCs by 22 graphenes and 40 GOs. A systematic evaluation was undertaken to

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818 examine the key adsorption mechanisms and advantages/disadvantages of applying GNS as

819 adsorbents. Overall results showed that the adsorption mechanisms were not only controlled by

820
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characteristics of GNS but also the molecular properties of OCs and the background solution
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821 composition. The SSA, PV, PSD, surface charge and chemistry of GNS have been found to be

influential parameters for adsorption of OCs. However, these parameters were not the only
M

822

823 factors determining adsorption capacities. The predominant driving force that repels OCs from
D

824 water onto the GNS surface is hydrophobic forces. The π-π interaction was found to be the major
TE

825 attractive force between OCs molecules and the electron rich graphitic surface of GNS. In terms

826 of GNS surface chemistry, the lower uptake of OCs by GO compared to GNS indicates the
EP

827 importance of water cluster formation on OC adsorption. The pristine graphene has hydrophobic

828 surface and presents high adsorption to aromatic OCs due to strong π-π interaction, while GO
C

829 have several acidic functional groups, exhibiting high adsorption for basic OCs.
AC

830 The presence of NOM, in general, has been reported to decrease the adsorption of OCs

831 by GNS. However, the inhibition effect on GO is lower than on CNT due to polarity of surface

832 oxides improving the GO dispersion in water. This dispersion in turn reduces the effect of NOM

833 on the OCs uptake with the presence of oxygen functional group decreasing the NOM coating on

37
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834 the GO surface. Further studies are also needed on the influence of pH, ionic strength and

835 temperature. Indeed the combined effect of both the pH and ionic strength may greatly depend

836 upon the ionizability and EDA ability of OCs, and the protonation/deprotonation of functional

837 groups on GNS surface. Neither pH nor ionic strength exhibited a significant difference on

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838 nonionic OC adsorption by GNS.

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839 Overall, the laboratory studies have offered a good insight to adsorption mechanisms of

840 OCs by GNS. The greatest challenge lies in understanding the adsorption mechanisms of

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841 different classes of OCs and/or competition among different OCs by GNS within complex

842 natural water systems. In addition, the GNS adsorption database for the OCs is much smaller

843
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than both the ACs and CNTs. Reporting more data in the literature for OC adsorption by GNS
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844 and GO with extensive characterization information can be helpful in future for developing

predictive adsorption models.

M

845

846
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847 Acknowledgement
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848 This work was supported by a research grant from the National Science Foundation (CBET
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849 0967425). It was not subjected to the peer and policy review of the agency and therefore does not

850 necessarily reflect those views.

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851
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1257 Zeng H. 2013. Polymer Adhesion, Friction, and Lubrication; Wiley: Hoboken, NJ.

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1259 layered graphene sheets on a large scale using chemical exfoliation, Carbon 48, 2367–
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1261 Zhang, Y., Ali, S. F., Dervishi, E., Xu, Y., Li, Z., Casciano, D., Biris, A. S., 2010b. Cytotoxicity
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1262 effects of graphene and single-wall carbon nanotubes in neural phaeochromocytoma-

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1264 Zhang, W. J., Zhou, C. J., Zhou, W. C., Lei, A. H., Zhang, Q. L., Wan, Q., Zou, B. S., 2011. Fast
1265 and considerable adsorption of methylene blue dye onto graphene oxide. Environmental
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1267 Zhang, C., Wu, L., Cai, D., Zhang, C., Wang, N., Zhang, J., Wu, Z., 2013a. Adsorption of
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1271 Zhang, Y., Tang, Y., Li, S., Yu, S., 2013b. Sorption and removal of tetrabromobisphenol A from
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1273 Zhao, G. X., Li, J. X., Wang, X. K., 2011a. Kinetic and thermodynamic study of 1-naphthol
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1276 Zhao, G., Jiang, L., He, Y., Li, J., Dong, H., Wang, X., Hu, W., 2011b. Sulfonated graphene for

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1 Table 1. Structure and properties of the most commonly used graphene based nanomaterials for environmental application

Properties Graphene Sulfonated Graphene Graphene Oxide Reduced Graphene

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(sGNS) (GO) Oxide (rGO)

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Structure

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Surface

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Area 132-1556 520 4-771 128-497
(m2/g)

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Oxygen
contents 0.8-5 N.R. 10.4-54.4 17.5-31.3

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• Graphite exfolation • Prereduction of GO • Oxidation and • Reduction of GO
Synthesis • Chemical vapor and then post- exfolation of

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deposition reduction with graphite

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SO3H
Cost $10-240/1g N.R. $97-250/1g $97-700/1g
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References Liu et al., 2014; Ersan et al., Zhao et al., 2011a;b Cai and Casanova, Jin et al., 2015; Zhou et
2016 2014; Ersan et al., 2016 al., 2015
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*N.R.: Not reported. The range of surface area and oxygen contents of GNS were obtained from Table S1.Cost of given graphene based nanomaterials was collected from
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3 Figure 1. Meteor rain chart of the literature review detailing the adsorption data of OCs by (a) GNS and (b) GO

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6 *The summary of adsorption of OCs by GNS/GO in the literature was displayed in the figures through a semi-quantitative numerical simulation;
7 **The size of each circle represents the number of studies in the literature

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11 Figure 2. Schematic illustration of the GNS and CNT bundles and their adsorption sites

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12

13

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External grooves
14 Inner cavities
Open-up surface

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Interstitial
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Interstitial channels
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Longitudinally-parallel Outermost
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external surface surface

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29

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30 Figure 3. Schematic representation of (a) GNS and (b) GOs bundles and their adsorption sites in the presence of NOM

31 (a)

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32 polarity of surface oxides
NOM OCs

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33 OC

34

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site better dispersion

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competition
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38 electrical repulsion

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39 pore/interstice
blockage
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Highlights

• 40 articles investigating adsorption of OCs by GNSs were comprehensively

examined.

• Graphene sheet structure is advantageous for reducing NOM competition .

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• Oxygen content of graphene sheets change the dispersion state.

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• Background water properties alter the adsorption of OCs by GNSs.

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