Accepted Manuscript

The role of surfactants in wastewater treatment: impact, removal and future

techniques: A critical review

Matthew Palmer, Hazel Hatley

PII: S0043-1354(18)30754-1
DOI: 10.1016/j.watres.2018.09.039
Reference: WR 14089

To appear in: Water Research

Received Date: 7 June 2018

Revised Date: 20 September 2018
Accepted Date: 25 September 2018

Please cite this article as: Palmer, M., Hatley, H., The role of surfactants in wastewater treatment:
impact, removal and future techniques: A critical review, Water Research (2018), doi: https://
doi.org/10.1016/j.watres.2018.09.039.

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 ACCEPTED MANUSCRIPT
1 The role of surfactants in wastewater treatment: impact, removal and future techniques: A

2 critical review

3 Matthew Palmera, Hazel Hatleyb

4 a. Chemical Engineering Department, Loughborough University, LE11 3TU, UK,

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5 palmer.matthew76@gmail.com

6 b. Chemical Engineering Department, Loughborough University, LE11 3TU, UK,

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7 hhatley7@gmail.com

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8
9 Abstract

10
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Wastewater treatment has an important responsibility to react to changing consumer and
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11 industrial produced wastes that pose environmental challenges. Surfactants are one of these
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12 emerging contaminants. They are of interest because of their increasingly ubiquitous domestic

13 and industrial use and the difficulty their presence causes traditional treatment. In response to
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14 this developing area, this critical review considers research from a variety of technical
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15 backgrounds to provide an up to date overview of the impact of surfactants on the environment,

16 health and their removal. This found major concerns about surfactants on the environment and
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17 on health being corroborated in the past five years. Current research into removal focuses on
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18 existing biological and chemical wastewater treatment optimisation. Despite improvements being
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19 found to traditional biological methods using chemical pre-treatments there is a clear lack of

20 consensus regarding the ideal strategy. Drawbacks and potential solutions for a range of these

21 technologies, including Fenton reaction and aerobic degradation are discussed. In this field the

22 authors recommend an improved diversity in surfactants used for the research and addressing of

23 significant knowledge gaps. Novel methods, such as Carbon Nanotube (CNT) use are also

24 discussed. These methods, while showing promising results, will require continual research effort

25 to resolve present issues such as variable performance and environmental concerns. Larger scale
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26 work is also needed to validate the initial work done. Potential uses of surfactants to optimise

27 wastewater treatment, such as Surfactant Modified Zeolites (SMZs), are also discussed. This

28 review finds that surfactant removal from wastewater is a promising and challenging field that

29 warrants further investigation.

30

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31 Keywords: Surfactant; Wastewater; Fenton; Zeolite; Carbon Nanotube

32

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33 1. Introduction

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34 Treating emerging contaminants, such as surfactants, is one of the major challenges facing

35 wastewater treatment. Surfactants are a particularly challenging member of this group. This is

36
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because of the wide usage and range of surfactants and their negative impact both on the
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37 wastewater treatment process and more importantly on the environment.
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38 Surfactants (surface active agents) are amphiphilic molecules containing two distinct parts: a

39 hydrophilic group and a lipophilic group (Yuan et al., 2014) and can be broadly defined as
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40 compounds that alter the energy relationships at interfaces, often in terms of altering either the
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41 surface or interfacial tension (Glassman, 1948). When present in low concentrations, surfactants

reduce the amount of interfacial free energy required to alter the interfacial or surface area and
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42

43 promote the expansion of one of the interfaces within the system (Rosen, 1972), thereby
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44 improving the efficiency of numerous processes (Hoffmann, 1990). As a result, surfactants are
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45 widely used as wetting agents, detergents and emulsifying agents (Glassman, 1948) whilst other

46 surfactants, such as Quaternary Ammonium Compounds (QACs) have also been noted to

47 damage the outer membrane of gram-negative bacteria and so can be used as disinfectants

48 (McDonnell and Russell, 1999). The basic structure of a surfactant is shown as Fig.1.

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50

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51
52
53
54
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56 Fig. 1: The simplified structure of a surfactant, consisting of a hydrophilic group joined to a
57 hydrophobic/lipophilic group (Farn, 2006).
58 Surfactants use is extremely common and has been growing since the 1980s from the 1.7 million

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59 tons used in 1984 and the 9.3 million tons used in 1995 (Aboulhassan et al., 2006) to the 15.93

60 million tons used in 2014 and the expected 24.19 million tons used in 2022 (Market Wired,

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61 2017). Numerous industries utilise surfactants, notably the textile industry but also in the

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62 pharmaceutical, cosmetic, mining, oil recovery and paper industries (Patel et al., 1999;

63 Aboulhassan et al., 2006) although it should be noted that in 2014, homecare accounted for more

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64 than 40% of the global market (Market Wired, 2017).
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65 However, whilst the global market for surfactants is growing, there has also been increasing
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66 concern with regards to the harm surfactants cause to the environment, especially from

67 wastewater (Petrović et al.,2003; Bolong et al., 2009; Rebello et al., 2013) There are numerous
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68 papers published regarding the negative effect that surfactants had on the environment, wildlife
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69 and humans (HERA, 2002; HERA, 2013). Venhuis and Mehrvar (2004) report that Linear

70 Alkylbenzene Sulphonates (LAS) has been noted to, amongst other effects, damage fish gills,
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71 alter swimming patterns in the larvae of blue mussels and cause excess mucus secretion as well as
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72 (in the common goby) reduce respiration. Numerous other studies and reviews have reported on
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73 the toxicity of a variety of different surfactants (Lewis and Suprenant, 1983; Hall et al., 1989;

74 Liwarska-Bizukojc et al., 2005; Azizullah et al., 2012; Lechuga et al., 2016) as well as their

75 effect on the environment (Cserháti et al., 2002), mostly with a focus on a variety of aquatic

76 organisms. Acute toxicity tests show that there is a large range in LC50 values from species to

77 species and can range from 210 to 500,000 µg/L for non-ionic surfactants, 80 to 2,800,000 µg/L

78 for cationic surfactants and 110 to 92,000 µg/L for anionic surfactants (Lewis and Suprenant,

79 1982). Many of the surfactants tested were found to be toxic enough that they can be classified
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80 as very toxic, toxic and harmful according to European Union Directive 67/548/EEC (Lechuga

81 et al., 2016).

82 Other studies have noted that the surfactants can increase the amount of organic hydrocarbon

83 compounds that are solubilised into water sources or be sorbed into soils and sediments where it

84 could potentially become harmful to crops whilst also affecting the degradation of hydrophobic

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85 organic compounds (Ying, 2006). Further studies have noted that, whilst there can be a high

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86 amount of removal of some surfactants (more than 99% of LAS (Venhuis and Mehrvar, 2004)),

87 the remaining surfactant that ends up rivers and other water sources can bioaccumulate within

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88 certain species (Tolls et al., 2000), resulting in biotransformation of tissues. In addition to this, it

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89 has been shown that exposure to some surfactants (such as benzalkonium chlorides) can increase
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90 antibiotic resistance in microbes (Tandukar et al., 2013).

91 These concerns have, in Europe, led to much tighter regulation in terms of surfactant
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92 biodegradability and their phosphorous compounds and phosphates content (European

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93 Commission, 2000). In the USA, any surfactants that bypass sewage treatment have to meet
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94 specific criteria (EPA, 2016). Despite the increase in regulation, removal of surfactants from

95 wastewater is still a growing concern, especially considering the high toxicity and ubiquity of
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96 surfactants. This is reflected by a steady increase in the number of publications considering both

97 surfactants and wastewater treatment (Web of Science, 2017).

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98 However, it is worth noting to the reader that many of these publications do not consider

99 surfactants as their primary aim. In general, there is a lack of focus on surfactant challenges in

100 the wastewater treatment process despite the overall increase in publications seen in the

101 literature. A holistic overview of surfactant’s impact on the wastewater treatment process is

102 often missing from the literature addressing the subject.

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103 There is therefore a need for an up to date review of the topic. This review will consider the

104 breadth of current treatment methods used to remove commonly used anionic, cationic and non-

105 ionic surfactants, work in the literature to improve these techniques and novel removal attempts

106 and strategies to utilise surfactants in wastewater treatment. It is intended that this approach

107 motivates further research into promising areas found in this review to tackle this important

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108 emerging issue in wastewater engineering.

109 2. Current Treatment Methods

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110 2.1 Surfactant Types, Diversity and Occurrence in Wastewater

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111 Part of the challenge facing current treatment methods is that there are a wide variety of

112 surfactants with different characteristics. Within the surfactant market, there are three main

113
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categories of surfactant: anionic, cationic and non-ionic. Classification of a surfactant is normally
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114 done using the electrical charge on the hydrophilic part of the surfactant molecule. Anionic surfactants
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115 contain a negatively charged hydrophilic group such as a carboxyl or sulfonate whilst cationic

116 surfactants contain a positively charged hydrophilic group such as quaternary ammonium, or
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117 phosphonium (Glassman 1948). Non-ionic surfactants, on the other hand, have a non-ionised
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118 hydrophilic group such as polymerized ethylene oxide (Glassman, 1948). Anionic surfactants are the

119 most common and in 2009 accounted for around 60% of the world’s surfactant production whilst
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120 non-ionic surfactants accounted for 30% and amphoteric and cationic surfactants 10% (Aloui et
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121 al., 2009).

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122 Table 1: Summary of some of the most widely used classes of surfactant adopted from Ying

123 (2006).

124

Surfactant Surfactant Name Common Acronyms

Class

Anionic Linear alkyl benzene Sulphonates LAS

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Secondary alkane Sulphonates SAS

Alcohol ether sulphates AES

(Alkyl ethoxy) sulphates

Non-ionic Alkylphenol ethoxylates APE (or APEO)

Alcohol ethoxylates AE (or AEO

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Cationic Quaternary ammonium-based compounds QAC

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Alkyl trimethyl ammonium halides TMAC

Alkyl dimethyl ammonium halides DMAC

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125

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126 Surfactants also have the potential to be zwitterionic, with both negative and positive charges in
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127 the hydrophilic head (Gerola et al., 2017). An example is Cocamidopropyl betaine (Zhou et al.,

128 2017). This surfactant class is only just starting to attract attention in the literature from the
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129 treatment perspective, for example (Merkova et al., 2018). This review therefore focuses on the
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130 commonly researched surfactants outlined in Table 1. Other important emerging contaminants
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131 such as perfluorinated and organosilicone surfactants are also considered when possible,

132 although these are yet to attract significant attention in the literature from a removal perspective.
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133 Another potential challenge to removal methods could be the presence of multiple types of

134 surfactant in wastewater. A short literature review of surfactant occurrence and compositions in
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135 wastewaters highlights this issue and is presented in Table 2.

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136 Table 2: Surfactant classes, compositions and concentrations in wastewater samples from

137 different industrial sources (Mean values are presented).

Surfactant
Wastewater Classes of Surfactant
Concentrations Reference
Type surfactant compositions
(µg/L)

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Anionic LAS-C10, C11, C12, 261, 456, 520, 499
Industrial
Cationic C13
(Not
BAC-C12, C14 0.48, 0.16
specified) Zhu et al.

(2018)
LAS-C10, C11, C12,

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Anionic 203, 384, 386, 306
Domestic C13

Cationic BAC-C12, C14 0.65, 0.22

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Anionic LAS 4,230

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Cationic QACs 216
Multiple
Non-ionic nonylphenols 4.54 Clara et al.

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(Municipal,
nonylphenol 16.30 (2007)
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Textile) *
ethoxylates

octylphenol 0.360
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Kern et al.
Medical NA** Total Concentration 2,200
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(2013)
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BAC-C12, C14, C16, 2800, 1100, 27,

Kreuzinger
Medical Cationic C18 1.50
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et al. (2007)
DDAC-C10 210

ammonium
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Micro- Aboulhassan
Anionic nonylphenol ether 935,000
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electronic et al. (2006)

sulphate

Paper BACs 2.58

Cationic Kreuzinger
Production DDACs 0.33
et al.
BACs 2.06
Dairy Cationic (2007)***
DDACs 0.29

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138 *Clara et al. (2007) presented average values across the wastewater treatment plants surveyed.

139 ** Class of surfactant not highlighted in the paper. *** Composition dominated by BAC-

140 C12 in both cases.

141 The review of wastewater samples found that the highest concentrations in wastewaters were for

142 anionic surfactants. Cationic surfactants were also commonly found by researchers but at lower

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143 concentrations. Other classes, mainly cationic, were present in conjunction with anionic

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144 surfactants in some wastewaters, which may provide an additional complexity to their treatment.

145 Different wastewater sources also show significant variation between the surfactant

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146 compositions. A significant difference between wastewater types was seen for BACs in hospital

147 wastewater, a result that can be explained by BACs common use as a disinfectant agent.

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148 Crucially, concentrations also vary between wastewaters from similar sources as seen between

149 Kern et al.’s (2013) results and Kreuzinger et al.’s (2007) medical wastewater results. This
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150 means that ideal surfactant treatment needs to be suitable for a range of concentrations. Another

151 trend in the literature is a focus on specific surfactant classes by researchers, for example on the
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152 fate of QACs during sludge treatment (Li et al., 2014; Zhang et al., 2015). This means there is a
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153 relative lack of characterisations of wastewaters that focus on the presence of different classes of

154 surfactant. While there is work with this aim, most notably Clara et al. (2007), more up to date
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155 reviews that focus on wastewater characterisation are recommended to aid treatment
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156 development.
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157 2.2 Biological Treatments

158 A particularly common treatment method, especially for surfactants in domestic wastewater, is

159 for the surfactant to be treated in sewage waste water treatment. The effluent from this process is

160 usually returned to rivers or other water sources whilst the sludge is used as a soil fertiliser. The

161 biodegradation of the surfactant occurs as the microorganisms utilise the surfactant either as an

162 energy or nutrient source or by the co-metabolisation of the surfactant in the catabolic pathways

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163 (Mungray and Kumar, 2008). Mungray and Kumar (2008) also stated that the biodegradation

164 mechanism can be altered by factors such as the chemical structure of the surfactant and aerobic

165 or anaerobic conditions.

166 Aerobic degradation of surfactants has been investigated in numerous studies (Brunner et al.,

167 1988; Prats et al., 1997; González et al., 2007) and there a number of different species of

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168 bacteria capable of degrading a surfactant (van Ginkel, 1996). The strain Citrobacter braakii has

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169 been noted to degrade a wide variety of anionic surfactants (Aloui et al., 2009). Aerobic

170 degradation of the surfactant could be accomplished in a number of ways, from the use of

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171 activated sludge tanks to oxidation bonds to trickling filters. It is worth mentioning, however,

172 that the degradation method has a large impact on the removal efficiency of the surfactant.

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173 Numerous studies have shown that whilst activated sludge tanks can achieve removal

174 efficiencies of between 98.9 – 99.9% for LAS, a trickling filter has a much wider range of
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175 removal efficiencies of between 89.1 – 99.1% (Mungray and Kumar, 2008), whilst for
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176 alkylphenol ethoxylates the removal efficiency was more in the region of 90% (González et al.,
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177 2007). It should be noted that these efficiencies can be reduced when physico-chemical processes

178 occur simultaneously with biological process such as in the case of the surfactant being sorbed
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179 into the sludge particles, thus leading to it being withheld from aerobic degradation

180 (Mantzavinos et al., 2001). Caution should be taken when comparing removal efficiencies
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181 between different treatment methods. There is often a significant lack of consensus in the
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182 literature regarding quantification of a “good” removal efficiency.

183 Whilst aerobic degradation of surfactants has seen significant use, both historically and

184 currently, the same cannot be said for anaerobic degradation of surfactants. Indeed, for a

185 significant portion of history it was believed that it was not in fact possible to degrade

186 surfactants anaerobically at all (De Wolf and Feijtel, 1998). Since the 1990s, however, there

187 have been papers showing anaerobic feasibility. In these studies, it has been shown that there are
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188 numerous different mechanisms by which anaerobic degradation can take place although it

189 should be considered that most of the studies used LAS. These mechanisms include; sulphur

190 limited conditions (Denger and Cook, 1999), thermophilic upflow in an anaerobic sludge blanket

191 reactor (Mogensen and Ahring, 2002), inoculation from an aerobic environment (Angelidaki et

192 al., 2000), using an acidogenic reactor inoculated with Pseudomonas aeruginosa (Almendariz et

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193 al., 2001), after improving its bioavailability (Haggensen et al., 2002) and in an upflow

194 anaerobic sludge reactor under normal conditions (Sanz et al., 2003). There have been numerous

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195 successful upflow anaerobic sludge reactors operated in India (Mungray and Kumar, 2008).

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196 It is worth noting the anaerobic degradation method has a significant impact on the removal

efficiency of the surfactant. Depending on the method, LAS removal under anaerobic conditions

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197 AN
198 typically has a removal efficiency of between 40 – 85% (Haggensen et al., 2002; Mogensen and

199 Ahring, 2002). There are other papers stating that whilst it is possible to degrade surfactants
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200 anaerobically it is extremely difficult to do (Feitkenhauer and Meyer, 2002; Gavala and Ahring,

201 2002). It has also been shown that the surfactants disrupt certain digesters owing their high
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202 toxicity to some methogenic bacteria (Tanaka and Ichikawa, 1993).

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203 In the authors’ view biodegradation provides a reasonably efficient method of removing some
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204 surfactants within the existing infrastructural framework. However, there are also numerous

205 limitations that make it unsuitable as a sole treatment method for surfactants in waste water. The
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206 main disadvantage is that it requires a low surfactant concentration. This is because at levels
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207 above 1,000,000 µg/L, the surfactant depolarises the bacterial cell wall and therefore destroys

208 structure and function (Aloui et al., 2009). The concentration of surfactant at which this occurs

209 depends on the specific surfactant but values in the region of 50,000 µg/L for LAS degrading

210 under aerobic conditions are quoted in literature (Mantzavinos et al., 2001; Abu-Hassan et al.,

211 2005). Quaternary ammonium salts, on the other hand, are only degradable if fed into the waste

212 water treatment plant steadily and at low concentrations in the order of 15,000 µg/L (Gerike et

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213 al., 1978). Even below these concentrations it has been noted that a large portion of this

214 surfactant can be sorbed into the sludge, preventing it from being degraded (Abu-Hassan et al.,

215 2005).

216 High surfactant concentrations have also been noted to lead to significant foaming problems in

217 many reactors (both aerobic and anaerobic) due to the intense agitation and aeration required by

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218 the culture medium (Varley et al., 2004; Wang et al., 2008). This issue means that that

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219 biodegradation is not always a suitable method for being the sole treatment of surfactants, a

220 view that Tanaka and Ichikawa (1993) also expressed. Another issue are the concerns posed by

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221 the metabolites produced when some surfactants are degraded. These metabolites can often resist

further biodegradation, resulting in them being released into water sources where they can

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222 AN
223 mimic the forms of hormones (Petrović et al., 2003), preventing the complete mineralisation of

224 the surfactant.

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225 Another issue is that, whilst there are data that show certain surfactants can be biodegraded
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226 sufficiently, even completely (Giolando et al., 1995), there are also data suggesting that some
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227 surfactants have an extremely low biodegradability (Charles et al., 1996). This variability poses

228 feasibility issues. A final consideration with regards to the biological methods currently
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229 available for surfactant treatment is that the method can be extremely costly, as well as taking a

230 significant amount of time (Önder et al., 2007).

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231 2.3 Combined Chemical and Biological Treatments

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232 The fact that biodegradation cannot treat wastewater where there is a high concentration of

233 surfactant is a significant problem, especially with industrial waste water. The textile industry in

234 particular uses extremely high concentrations of surfactants (Arslan-Alaton et al., 2007) which

235 can cause significant issues with regards to treating the waste water produced. Despite this, it is

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236 often not considered economically feasible to remove biorecalcitrant surfactants from use (Lin et

237 al., 1999).

238 One of the methods by which the problems elucidated above can be mitigated is by utilising a

239 chemical pre-treatment before the waste water enters the treatment plant (Aloui et al. 2009). The

240 aim of chemical pre-treatment of the biorecalcitrant compounds is to convert them to products

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241 which can be more easily biodegraded using biological processes and not to completely

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242 mineralise them (Adams and Kuzhikannil, 2000). These pre-treatment methods usually fall into

243 numerous categories of which one of the more commonly researched is the use of Advanced

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244 Oxidation Processes (AOPs).

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245
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246

247 Fig.2. A schematic of an industrial plant for pollutant removal using Fenton’s reaction, adopted
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248 from Li et al. (2018).

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249 AOPs typically involve the addition or creation of a highly oxidising species to degrade the
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250 organic matter (Amat et al., 2004) and are usually either classified as homogeneous or

251 heterogeneous, depending on the state of the reactive phase, or according to the method by
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252 which the hydroxyl radical is generated (Babuponnusami and Muthukumar, 2014). This

253 category consists of a wide range of processes of which the most utilised is Fenton’s reaction
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254 (shown in Fig. 2).

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255 Fenton’s reaction utilises a mixture of hydrogen peroxide (H2O2) and ferrous irons (typically

256 Fe2+ although Fe3+ has been utilised on occasion), often from iron sulphate (FeSO4), to

257 decompose the hydrogen peroxide to water and oxygen (Pignatello, 1992; Wang et al., 2008).

258 Hydroxyl radicals then attack the surfactant (Babuponnusami and Muthukumar, 2014). Many

259 studies focus on the pH where a value of roughly 3 is usually considered to be optimal (Kitis et

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260 al., 1999; Babuponnusami and Muthukumar, 2014). Numerous other studies determined optimal

261 operating conditions, such as initial concentration of ferrous ions and hydrogen peroxide but

262 these are affected by the type of surfactant being degraded (Kitis et al., 1999; Wang, et al.,

263 2008). The method also usually takes only around 40 to 50 minutes to achieve desired surfactant

264 removal (Kitis et al., 1999; Babuponnusami and Muthukumar, 2014).

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265 Despite these positive findings, there have also been concerns raised over the turbidity and the

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266 removal of the dissolved iron after the process has been completed (Lin et al., 1999). Chemical

267 coagulation has been proposed as a solution and studies show that this can reduce the amount of

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268 dissolved iron from 5000 µg/L to below 2000 µg/L (Lin et al., 1999). This process is industrially

269 scaled as seen in Fig 2.

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270 Due to the success of Fenton’s reaction, other variations have been proposed such as electro-

271 Fenton (Panizza et al., 2013) although it is not widely used. Photo-Fenton, on the other hand,
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272 sees significantly more widespread use. The reaction utilises irradiation caused by either UV or
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273 visible light to increase the degradation of the surfactant (Amat et al., 2004) in a photocatalytic
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274 reaction. The method has seen some success and has been shown to work for alcohol ethoxylates

275 (Brand et al., 2000) as well as seen the proposal for the use of chromium(III) ions for use in the
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276 tannery industry (Amat et al., 2004). Photo-Fenton is sometimes considered to be more efficient

277 than the conventional Fenton reaction (Brand et al., 2000).

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278 Other photocatalytic AOP pre-treatment methods are common and have been the focus of
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279 numerous studies since the 1980s. The main premise of the treatment is the utilisation of a

280 catalyst to absorb the solar light (both visible and UV) (Amat et al., 2004). One subset of

281 catalysts used are solar sensitizers such as 2,4,6-triphenylpyrylium (Amat et al., 2004).

282 However, aside from Fenton’s reagent (hydrogen peroxide), the other most popular catalyst is

283 the heterogeneous titanium dioxide (TiO2), a semi-conductor catalyst (Zhang et al., 2001) that

284 has been thoroughly investigated (Hidaka and Zhao, 1992; Rao and Dube, 1996; Horikoshi et
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285 al., 2002). Although the catalyst has had some success in degrading surfactants, optimisation of

286 the catalysts is often required. This is because the use of solid supports for the catalyst can cause

287 numerous issues such as reducing surface areas, decreasing adsorption of the surfactant and

288 imposing mass transfer limitations (Horikoshi et al., 2002).

289 A final AOP that is also researched is ozonation which can be used either with hydrogen peroxide

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290 or UV to increase the biodegradation of the surfactant (Kitis et al., 1999; Venhuis and Mehrvar,

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291 2004). However, whilst the method has been shown to aid the degradation of many surfactants,

292 this is highly dependent on the oxidant dosage used (Kitis et al., 1999). The process has also

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293 been known to inhibit bacterial growth (Beltran et al., 2000).

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294 Other AOPs are worth mentioning, despite their uncommon use. Foam fractionation utilises
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295 bubbles created by a sparger to collect the surfactant, letting the liquid drain away with the aid of

296 gravity (Tharapiwattananon et al., 1996). Electrochemically generated coagulants utilise iron or
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297 aluminium ions that form flocs which float to the surface, taking the surfactants with them
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298 (Ciorba et al., 2002). Foam fractionation has been noted to work better for cationic surfactants
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299 than anionic surfactants (Tharapiwattananon et al., 1996).

300 Whilst the AOPs described above are commonly used, in particular Fenton’s and the
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301 photocatalytic reactions, it must also be considered that they will often only work for reasonably

302 low concentrations of surfactants (up to 100,000 µg/L) (Abu-Hassan et al., 2005) and that they
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303 are highly complex processes as well as being expensive treatments (Arena et al., 2015). The
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304 latter point is in particular related to the ozonation and photocatalytic treatments which are

305 sometimes held to be significantly more expensive than Fenton’s reaction (Lin et al., 1999). It is

306 therefore concluded with regards to AOPs that Fenton’s reaction is the most suitable method for

307 industrial use. Further improvements made to the system configuration and quantum efficiency of

308 photoreactors could reduce the costs associated with the use of titanium dioxide as a

309 photocatalyst.
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310 AOPs are considered highly versatile due to the fact that there are a number of different ways to

311 produce hydroxyl radicals (Babuponnusami and Muthukumar, 2014). They are, however, not the

312 only chemical pre-treatment method available.

313 Of particular, although not widespread, interest is the use of wet air oxidation (WAO). WAO

314 uses a high temperature, highly pressurised gaseous oxygen source to oxidise the surfactant

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315 (Mantzavinos et al., 1999). WAO has been used to treat concentrations of LAS up to 1,600,000

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316 µg/L (Abu-Hassan et al., 2005). Certain studies have also suggested that the use of a catalyst

317 could result in milder WAO operating conditions and shorter residence times (Mantzavinos et

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318 al., 1999; Abu-Hassan et al., 2005). However, whilst there have been successes in using this pre-

319 treatment method there have also been concerns raised that, overall, LAS biodegrades better

320
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without the treatment (Venhuis and Mehrvar, 2004).
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321 A final pre-treatment method that is sometimes considered is the use of ultrasound or sonication.
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322 This method has met with some success (Arena et al., 2015). It is not widely used however, as it

323 relies on the surfactant concentration being far below that of the critical micellar concentration
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324 as the micelles protect the organic tails of the surfactant, reducing the efficiency of the process
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325 (Vinodgopal et al., 2001).

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326 In considering the use of a chemical pre-treatment before biodegradation of a surfactant, it

327 should be noted that the process can be extremely complex and costly. It is therefore our
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328 recommendation that the process is used minimally, a view that is consistent with the literature
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329 (Adams and Kuzhikannil, 2000). It should also be noted that, whilst anionic and non-ionic

330 surfactants are heavily studied, the same cannot be said for cationic surfactants where there is a

331 significant gap within the literature (Olmez-Hanci, et al., 2011).

332 2.4 Chemical Treatments

333 The characteristic foaming of surfactants in oxygenated water causes operational difficulties to

334 biological and combined treatments (Dhouib et al., 2003). In response to this, purely chemical
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335 methods were discussed in the literature. Coagulation-flocculation surfactant treatment was

336 proposed by Aboulhassan et al. (2006). The use of traditional ferrous chlorides showed

337 promisingly high levels of surfactant removal (99%) for microelectronic wastewater at small

338 scale. However, as with the other techniques discussed, there is ambiguity in the literature. More

339 recently, Kaleta and Elektorowicz (2013) found poor removal rates for anionic surfactants using

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340 the same coagulant. They found certain enhancements, such as Activated Carbon (AC) addition

341 or polyelectrolyte based removal, made the process more effective.

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342 Mohan (2014) proposed the use of so called naturalised coagulants such as pectin. Treatment

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343 times of 24h showed good removal rates and utilised the secondary AC suggested by Kaleta and

344 Elektorowicz (2013). Ochoa-herrera and Sierra-Alvarez (2008) showed that AC powder had

345
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higher affinity for surfactants than both the standard zeolite and anaerobic sludge especially at
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346 high concentrations. Bindes and Franco Jr. (2014) presented adsorption mechanisms for anionic
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347 surfactant. The results imply that the technology is suitable for application.

348 AC is a well researched adsorbent for adsorption of surfactants (Wu and Pendleton, 2001;
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349 González-Garcia et al., 2004; Saleh, 2006). Adsorption is a popular physico-chemical method
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350 for surfactant removal, including evidence of perfluoro-carboxybetain removal by this method
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351 (Pabon and Corpart, 2002). Other adsorbents, including polymeric resins (García-Delgado et al.,

352 1992), zeolite (Kawai and Tsutsumi, 1995), silica (Goloub et al., 1996) and alumina (Pham et
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353 al., 2015) have been studied as well. However, these traditional adsorbents could pose
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354 environmental issues in larger scale surfactant removal (Abd El-Lateef et al., 2018). This is an

355 issue that Abd El-Lateef et al. (2018) addressed recently by developing zero-valent iron

356 nanoparticles for surfactant adsorption. This study considered both cationic and anionic

357 surfactants, a promising development as consideration of more than one type of surfactant class

358 is often absent in the literature. However, further work is needed to corroborate the optimal

359 adsorbent for large scale surfactant removal.

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360 Uptake of these chemical and physico-chemical methods are hindered by the prevalence of

361 biological treatments. However, the positive results shown by upstream and downstream

362 chemical processes could positively impact development. Research into combining systems

363 from the combined technologies with downstream processing such as AC technology is

364 therefore recommended.

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365 As with all research in this area, more work into surfactants other than anionic is needed

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366 considering the general lack of interest in cationic surfactants.

367 2.5 Areas for Improvement

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368 Based on the technologies reviewed, there are numerous treatment methods for surfactants

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369 available currently within the waste water industry. However, there are still significant concerns
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370 with regards to their efficacy. There are also few overarching literature reviews into current

371 usage of the technologies and so an apparent lack of a clear consensus amongst the scientific
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372 community regarding the best techniques to be used. This can be seen in the lack of comparable
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373 data between treatment methods. Improving the general availability of cost data for each of the
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374 processes as well as developing standardised tests for each of the treatment methods would

375 greatly improve comparability of the treatment methods.

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376 There is also a lack of information with regards to cationic surfactants as well as for other, less

377 widely used surfactants such as zwitterionic and non-ionic, something that has changed little
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378 over the last 10 years. Emerging classes such as perfluorinated and organosilicone surfactants
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379 should also be considered. Existing methods can partially deal with surfactant use but there

380 appears to be significant scope for improvement. In response to these challenges, increasing

381 attention is being seen in the literature for developing new techniques for surfactant removal.

382 The next section of this review therefore analyses proposals for novel surfactant removal

383 techniques. .

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384 3. Novel Treatment Methods

385 A potential strategy for future surfactant removal could be to promote novel techniques more

386 suited to dealing with surfactants. This section therefore reviews the cutting edge of surfactant

387 removal techniques to provide an up to date position of these technologies.

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388 3.1 Carbon Nanotube (CNT) Treatment

389 Ever since their discovery by Iijima (1991), CNTs have been researched for a wide variety of

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390 purposes from catalysis (Serp et al., 2003), drug delivery (Liu et al., 2009) and numerous others

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391 (Baughman et al., 2002). In the wastewater treatment context, CNTs could be used as a

392 nanomaterial for adsorption based treatment processes (Burakov et al. 2018) as a replacement

393

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for traditional materials such as AC, zeolite and kaolin (Gupta and Saleh, 2013; Bankole et al.,
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394 2017). As an example, the adsorption mechanism for anionic and cationic surfactants onto CNTs

395 is shown in Fig.3.

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396
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397 Fig. 3: Surfactant adsorption mechanisms on functionalised single walled CNTs (SWCNT-
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398 COOH); a) adsorption interaction between anionic surfactant adsorbate and CNT adsorbent

399 and b) cationic surfactant adsorbate interaction. Adopted from López-López et al. (2016).
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400 The technology has received significant attention for use in wastewater treatment owing to the
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401 technology’s large adsorption surface area and ability to adsorb a range of challenging materials
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402 that are of interest to the wastewater treatment industry (Qu et al., 2013, Lu and Chiu, 2006; Gao

403 et al., 2016; Younis et al., 2014).

404 One of these materials could be surfactants. Surfactants can be used to disperse CNTs (Vaisman et

405 al., 2006) and to stabilise CNTs in aqueous solutions (Vo and Papavassilou, 2017). Both

406 techniques rely on the adsorption mechanics of surfactant to CNTs shown in Fig.3. Gao et al.

407 (2016) therefore proposed CNTs for the removal of surfactants from water. Multi walled CNTs

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408 (MWCNTs) were used because of the relatively lower cost. The results show high removal

409 efficiencies for certain surfactants. The paper provides a promising scientific foundation for the

410 application of MWCNTs to surfactant removal but there are issues. The study was limited to

411 simple surfactant solutions which is very unlikely in industrial wastewater based on the

412 compositions found in Table 2.

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413 To the authors’ knowledge Gao et al.’s investigation is the only major investigation into this

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414 application of CNT technology. This is despite the established precedent of surfactant

415 adsorption using CNTs and feasibility demonstrated by Gao et al.’s (2016) work. The remainder

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416 of this section therefore analyses the challenges associated with the technology that may explain

this relative lack of research. Immediately, CNT’s high material cost compared to the other

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417 AN
418 available adsorbent materials discussed in section 2.4 to is a hindrance to adoption in water

419 treatment (Ihsanullah et al., 2016a). This is an issue that will become less pertinent as CNT
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420 production continues to increase and drive the cost down. In the authors’ opinion, there are four

421 technological issues that present a challenge for using CNTs in wastewater treatment; removal
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422 inconsistency, CNT aggregation, desorption and environmental impact.

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423 3.1.1 Removal Efficiency Inconsistencies

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424 Gao et al.’s (2016) results showed higher removal efficiencies for Triton X-100 (TX-100)

425 surfactants compared to the other surfactants. Interestingly, studies have even shown variation in
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426 the CNT removal performance of Triton based surfactants. Bai et al. (2010) found adsorption
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427 capacities of 330.6 – 737.3 mmol/kg for a range of TX based surfactants. They concluded that

428 the hydrophilic chain length of the surfactant greatly impacted the adsorption capacity. This is a

429 conclusion that Gao et al. (2016) reached as well, citing specific interaction mechanisms, that

430 are altered in different surfactants, that other authors have investigated in depth elsewhere (Yang

431 et al., 2008 and Pan and Xing, 2008).

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432 The variable adsorption capacity has been mitigated in other water treatment CNT applications by

433 surface modification and pH change (Ihsanullah et al., 2016b). Ihsanullah et al. (2016a)

434 presented detailed information about the wide range of CNT modifications shown in the

435 literature specifically for heavy metal removal. There are two conclusions that can be made from

436 the review and associated work. Optimisation of CNT adsorption performance has been studied

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437 and there are numerous viable strategies to improve performance of raw CNTs. These include

438 doping (Ji et al., 2012), oxidisation (Tofighy and Mohammadi, 2011) and increasing initial

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439 concentration of target ion (Li et al., 2005). The impact of this final change is shown in the

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440 improvement in lead removal between Li et al. (2002) and Li et al. (2005). This also raises an

441 important consideration, that the inconsistency is less of an issue than the effectiveness of

442
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removal. Similar work seen to modify CNTs for heavy metal removal for the interactions of
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443 desired surfactants with the CNTs could therefore solve this problem. This development would

444 allow for tailored surfactant removal if demonstrated in a more realistic system.
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445 3.1.2 Aggregation

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446 Another issue that Gao et al. (2016) found was the aggregation of CNTs found at lower
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447 surfactant treatment concentrations. This issue has been reported using CNTs in aqueous

448 solutions. Koh and Cheng (2014) concluded that this aggregation mechanism was driven by
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449 electrostatic forces. Solutions to this problem would therefore need to be chemical based. Han et
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450 al. (2015) proposed a bioinspired solution that limited aggregation effectively. However, both
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451 solutions were investigated for polymer disperse solutions where the aggregation could be

452 controlled in the product assembly. This is less feasible in the water treatment context. A more

453 viable solution could be to incorporate CNTs into membrane filtration. This has been shown to

454 be a viable application of CNT technology (Das et al., 2014). Das et al.’s application was for

455 desalination and further work is needed before this suggestion could be applied to surfactant

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456 removal. This is especially true considering the complex relationship surfactants have with

457 filtration that is discussed in section 4.2.

458 3.1.3 Desorption

459 One advantage of the adsorption approach for water treatment is material recycling that offsets

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460 the cost of water treatment. This can be achieved from desorption processing downstream

461 (Shang et al., 2016). A key property of CNTs in this application is therefore desorption capacity.

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462 CNT desorption mechanisms have been studied in the literature although there appears to be a

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463 gap in the literature relating to surfactant desorption. Desorption for various molecules has been

464 proven to be feasible for CNTs by parameter alterations such as pH change (Engel and Chefetz,

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465 2016), electric current (Paul et al., 2015), temperature and shear (Vo and Papavassiliou, 2017).
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466 These studies did not concern surfactant adsorption however. These studies do show that the

467 desorption strategy is viable and that similar work to address surfactant would potentially yield
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468 promising results.

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469 3.1.4 Environmental Impact

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470 The increased production and use of CNTs has led to concern about the impact on the

471 environment and human health of CNTs (Liné et al., 2017), especially in aquatic environments.
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472 Girardello et al. (2015) used a Hirudo medicinalis model to test the toxicity of MWCNTs in
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473 living organisms. Their results show the potential for adverse effects of CNTs on aquatic
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474 systems. The effect of CNT on the environment is still a young research field and the effects are

475 not properly understood. Liné et al. (2017) showed that there is a lack of consensus on the

476 toxicity of the nanomaterial on plants in the literature for example. That review called urgently

477 for an increased research attention to this problem. This is a view these authors share as it is

478 difficult to recommend the development of CNTs for surfactant treatment until that information is

479 known. The other issues (3.1.1 to 3.1.3) have been shown mitigatable in other CNT systems. It is

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480 therefore the authors’ opinion that research effort to advance the technology will facilitate CNTs

481 as an effective future treatment technology provided environmental safety is demonstrated.

482 3.2 Magnetic Removal Techniques

483 Another potential future surfactant treatment is magnetic removal. Compared to CNT

484 adsorption, this technology simplifies downstream processing by using filters and presently

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485 could therefore be more cost effective. This is a research area that has gained attention in

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486 multiple industries that Yavuz et al. (2009) reviewed for a general understanding. Ambashta and

487 Sillanpää (2010) reviewed magnetic technology in wastewater and water treatment in great depth

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488 and showed industrial adoption of the technology. Magnetic removal of contaminants such as;

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489 Arsenic (Mayo et al., 2007), red textile dye (Iram et al., 2010), radioactive pollutants (Ambashta
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490 and Sillanpää, 2010) and metallic contaminants (Oliveira et al., 2004) have been demonstrated.

491 Magnetic filtration is a feasible process and has been shown in numerous ways (Tsouris et al.,
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492 2006; Rossier et al., 2012; Ying et al., 2000). An example of how this could work is shown in

493 Fig.4.
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494
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495
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496

497
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498
AC

499

500

501

502 Fig.4. A magnetic filtration process (a) seeding process for magnetic filtration schematic

503 adopted from Ying et al. (2000) and (b) magnetic filter adopted from Rossier et al. (2012).

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504 Borghi et al. (2011) proposed the use of similar magnetic techniques shown in the figure for

505 surfactant removal. They compared commercially available iron oxides and found high cationic

506 removal rates (90%) at acceptable filtration times. This technology could feasibly be used to

507 adsorb surfactants alongside other contaminants, a feature that CNTs may not offer due to

508 contamination concerns. The development of magnetic surfactants, the authors recommend

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509 Brown et al. (2015) for more information, could also further improve the removal efficiency of

510 the technology.

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511 However, the surfactant abatement during magnetic filtration found by Borghi et al. (2011)

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512 varied significantly for the other classes of surfactants investigated, including anionic and non-

513 ionic surfactants. This removal inconsistency between classes of surfactant may explain the lack

514
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of follow up work to this paper. The lack of further investigation causes concern. Compared to
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515 CNTs, this technology could provide a quicker short-term enhancement. It is certainly a feasible
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516 suggestion where magnetic technologies are already used although no studies have shown the

517 interaction of complex surfactant containing systems. A potential reason could be the lack of
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518 agreement in the literature about the best adsorbent for use here. Research in the area has
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519 generally focused on using either powdered adsorbents such as iron oxide (Borghi et al., 2011),

520 zeolite based systems (Oliveira et al., 2004) or even MWCNT held magnetic oxide particles (Qu
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521 et al., 2008a). This lack of clear consensus is challenging this aspect of the technology. A clearer
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522 consensus needs to be found in the academic community before future work can tackle the
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523 concerns the authors would raise about this technology. Overall both technologies considered are

524 promising but face challenges to replace existing treatment practices.

525 4. Novel Uses of Surfactants in the Water Treatment Process

526 Despite the many negative challenges their presence can cause in water treatment, surfactants

527 could prove useful in improving existing wastewater treatment processes. This field is gaining

528 increasing attention in the literature. There is therefore a need to consider recent developments to

529 provide a balanced overview. The aim is to provide the authors’ opinion on the progress of
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530 development by focussing on two key developments and their feasibility considering the

531 potential risk of surfactant pollution. The first development to be investigated is the potential for

532 improving the performance of zeolites, an increasingly important element of wastewater

533 treatment.

534 4.1 Surfactant Modified Zeolites (SMZs)

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535 Natural zeolites have been used as low cost, abundant and efficient adsorbent material for

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536 wastewater treatment (Lai et al., 2003; Wang and Peng, 2010) including Ammonium ion

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537 removal (Nguyen and Tanner, 1998), heavy metal cations (Erdem et al., 2004; Jorfi et al., 2017)

538 and hydrocarbons (Torabian et al., 2010). For a review on this technology, Wang and Peng

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539 (2010) cover the subject in excellent depth. Zeolites have one major disadvantage as a
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540 wastewater adsorption material, owing to their surface chemistry, natural zeolites can only

541 remove cationic pollutants (Reeve and Fallowfield, 2017). This is an issue as many pollutants of
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542 interest, for example viruses and bacteria can only be absorbed by SMZs (Schulze-Makuch et
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543 al., 2002).

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544 Surfactant Modified Zeolites (SMZs) use a surfactant such as Hexadecyltrimethylammonium

545 (HDTMA) to alter the surface chemistry of the zeolite (Naghash and Nezamzadeh-Ejhieh,
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546 2015). This surface charge change allows adsorption of pollutants, such as viruses and bacteria,

547 that raw zeolites cannot capture. Bowman (2003) discussed the potential applications of these
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548 HDTMA-SMZs for removing contaminants from water. Recently this approach has been
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549 examined for use in larger scale water treatment. Naghash and Nezamzadeh-Ejhieh (2015)

550 focused on phosphate removal in industrial systems. Modification using surfactants increased

551 phosphate removal by 90% at a phosphate concentration of 100 mmol/L. The HDTMA-SMZ

552 performed optimally and stably across the parameters (water pH, contact time, temperature and

553 phosphate concentration). Interestingly this paper considers the performance of another

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554 surfactant, Hexadecylpyridinium (HDP) for zeolite modification. This HDP-SMZ performed

555 worse than the HDTMA-SMZ, although better than natural zeolite, throughout the investigation.

556 These results justify both an increased interest in SMZs recently and the general trend of the

557 literature to investigate HDTMA-SMZs. Hailu et al. (2017) investigated the preparation of

558 HDTMA-SMZs for organic and inorganic pollutants. Acid blue dye and Cr (VI) pollutants were

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559 effectively removed over a 24h period. A similar parameter investigation to Naghash and

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560 Nezamzadeh Ejhieh (2015) revealed different optimal conditions to the high pH system in that

561 paper. Hailu et al. (2017) suggested that their chosen dye becomes anionic (like the phosphate

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562 ion) in acidic conditions. This impact on performance is verified by the results in the Naghash

and Nezamzadeh paper and raises an important issue. In industrial reality, there will be

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563 AN
564 numerous competing pollutants. These results raise the possibility of varying removal efficiency

565 by SMZs in application. For example, if both phosphate ions and chromate ions are in a solution,
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566 selective adsorption would occur based on the different optimal conditions found in the paper. So

567 far, the studies on HDTMA-SMZs have focussed on proof of concept and have not attempted to
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568 improve the removal efficiency across the pH range.

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569 A potential solution to this problem is to tailor SMZs to their target application. Several other
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570 surfactant choices for SMZs were discussed by Apreutesei et al. (2008) and have been shown

571 feasible for specific removal purposes. Table 3 presents examples of research into different
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572 SMZs. While divergent, the use of different SMZs for specific targets is viable.
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573 Table 3: Different Surfactant Modified Zeolite Adsorption Strategies.

Surfactant Contaminant(s) Adsorbed Reference(s)

HDTMA Cr, Phosphate, Ammonium, Bacteria, Naghash and Nezamzadeh, (2015)

BTEX*, Arsenic Apreutesei et al. (2008),

Torabian et al. (2010)

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HDP Phosphate Naghash and Nezamzadeh, (2015)

CPB Nitrate Zhan et al. (2011)

HTAB Textile Wastewater Colour Ozdemir et al. (2009)

CTAB Reactive Black Dye Karadag et al. (2007)

574 *Benzene, toluene, ethylbenzene and xylene Mixtures.

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575 Another capability issue with using SMZs is the leaching of HDTMA into the environment an

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576 issue that a recent review of zeolite technology in water remediation by Reeve and Fallowfield

577 (2018). This review concluded that the desorption is a significant issue warranting further

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578 research. Reeve and Fallowfield (2017) found that HDTMA is non-monotonically toxic towards

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579 the F-RNA bacteriophage MS2. This conclusion means that the highest toxicity of HDTMA is
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580 not at its highest concentration for this bacteriophage. This could be a problem as the stability of

581 HDTMA binding during aquatic application has been questioned. At the low concentrations
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582 associated with surfactant desorption, the desorption could prove environmentally harmful

583 considering the toxicity and concentration relationship proposed by Reeve and Fallowfield.
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584 Those authors therefore investigated the impact of HDTMA on soil health. They found that for
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585 certain microflora there were no negative relationship was found. However, SMZs adversely

586 affected certain bacteria and future work to expand the scale of the work is recommended.
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587 As such, the studies considered on SMZs are presently limited in scale and pose feasibility
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588 issues. This means that as a technology, this use of surfactants cannot make an immediate
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589 impact on wastewater treatment. There are critical concerns that are beginning to be addressed

590 but a renewed Research and Development effort is needed before large scale adoption can occur.

591 This work needs to demonstrate the performance of SMZs on larger scale and the impact of their

592 use will have on the environment. In the author’s opinion, the positive results found for ion

593 removal performance across the range of technologies and articles considered show that SMZs

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594 have the potential to enhance the applicability of zeolite absorption and therefore improve

595 wastewater treatment.

596 4.2 Micellar Enhanced Ultra-Filtration (MEUF)

597 Another key process in the water treatment process is the use of ultrafiltration (UF) to remove

598 contaminants. This process is often necessary to remove secondary solid waste pollutants caused

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599 by other treatments upstream (Gao et al., 2018). Recently, there has been attention given to the

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600 potential of UF to recover key chemicals from the wastewater streams including nutrient recovery

601 for algal bioreactor growth (Sandefur et al., 2016), brackish water from textile wastewater

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602 (Erkanlı et al., 2017) and fluoride (Grzegorzek et al., 2017).

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603 However, ultrafiltration often fails to reject compounds in the low molecular weight range, such
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604 as phenol, a particularly harmful wastewater constituent from the olive oil industry (Victor-

605 Ortega et al., 2017). The use of surfactants can mitigate this issue. Adding surfactants in
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606 concentrations above the Critical Micellar Concentration (CMC) allows pollutants to be
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607 solubilised in the larger micelles and removed (Victor-Ortega et al., 2017). This technology has
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608 gained significant attention in the literature recently because of the enhanced performance

609 shown and mainly focuses on improving the performance of the technology (Huang et al., 2017;
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610 Grzegorzek et al., 2017; Tortora et al., 2018).

611 However, the major issue with the technology is the use of surfactants. Considering their impact
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612 on the environment, it is difficult to justify their use in this context. This is especially true
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613 considering the high concentrations needed for SDS CMC. There are potential mitigations to

614 these concerns. These approaches are summarised briefly in Table 4.

615 Table 4: Strategies for making Micellar Enhanced Ultra-Filtration more environmentally viable.

Strategy Lower CMC Environmental Reference

Impact Reduced

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Alternative Yes No Schwarze et al.

Surfactant e.g RO90 (2014)

BioSurfactant Yes Yes Verma and Sarkar

(2017)

Recovery No Yes Qu et al. (2008b)

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Modelling No Yes Rahmanian et al.

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(2011)

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Polymer Enhanced Yes Questionable Lam et al. (2018)

Ultrafiltration (PEUF)

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616 In the authors’ opinion, the use of biosurfactants in MEUF is the best strategy for reducing the
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617 impact of MEUF. However, there are major challenges facing this technology, most notably

618 the lack of large scale production of a compound such as Saponin used by Samal et al. (2017). As
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619 with the other treatments, a combination of technologies could be the best solution if
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620 economically feasible. Expansion of the PEUF technique could also be used to reduce the
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621 overall use of surfactants in this context. A continuation of the recent interest in this area is

622 therefore justified and recommended. A focus should be placed on ensuring that the
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623 environmental impact of the technology is maintained as low as feasible.

624 5. Conclusions
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625 This review has considered the overall role of surfactants in wastewater treatment. Current

626 biological, combined and chemical methods were reviewed and the work to improve these

627 techniques analysed. State of the art removal technologies and applications of surfactant

628 technologies in wastewater treatment were also discussed. This review has revealed a dynamic

629 and challenging field that could benefit from greater attention from the research community.

630

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631 A lack of clear consensus regarding multiple aspects of treatment, from best current method, to

632 materials used for novel methods to environmental impact was discovered. This is largely due to

633 the varying demands of different surfactants and a wealth of competing options. Several

634 optimisation strategies have been researched that merit further investigation. The novel

635 techniques are promising but renewed research effort is needed to tackle concerns over

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636 environmental impacts and performance inconsistencies. To aid this process, further

637 characterisation of multiple surfactant classes present in wastewater is required to enable

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638 tailored research into surfactant removal.

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639 Surfactants have also been shown to potentially play a key role in future contaminant removal.

640 Efforts need to be made however to alleviate the potential environmental impacts of this

641
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approach. Continuous research effort is therefore recommended to enhance surfactant removal
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642 through optimisation of current methods and development of new methods discussed in the paper

643 for new treatment plants.

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644 6. Acknowledgements
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645 The authors would like to thank Dr Anna Trybala for her assistance with proof reading.
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646 7. Funding

647 The authors did not receive any specific grant from funding agencies in the public, commercial
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648 or not-for-profit sectors.

649 8. Competing Interests

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650 The authors have no competing interests to declare.

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651 9. References

652 Abd El-Lateef, H.M., Khalaf Ali, M.M., Saleh, M.M., (2018), Adsorption and removal of

653 cationic and anionic surfactants using zero-valent iron nanoparticles, Journal of Molecular

654 Liquids, 268, 497-505. https://doi.org/10.1016/j.molliq.2018.07.093

655 Aboulhassan, M. A., Souabi, S., Yaacoubi, A., Baudu, M., (2006), Removal of surfactant from

656 industrial wastewaters by coagulation flocculation process, International Journal of

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657 Environmental Science & Technology, 3(4), 327–332. https://doi.org/10.1007/BF03325941

658 Abu-Hassan, M. A., Mantzavinos, D., Metcalfe, I. S., (2005), Wet air oxidation and ultrasound

659 for the removal of linear alkylbenzene sulfonates from wastewater: the beneficial role of

660 catalysis, Topics in Catalysis, 33(1–4), 141–148. https://doi.org/10.1007/s11244-005- 2520-6

661 Adams, C. D., Kuzhikannil, J. J., (2000), Effects of UV/H2O2 preoxidation on the aerobic

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662 biodegradability of quaternary amine surfactants, Water Research, 34(2), 668–672.

663 https://doi.org: 10.1016/S0043-1354(99)00186-4

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664 Almendariz, F. J., Meráz, M., Soberón, G., Monroy, O., (2001), Degradation of lineal

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665 alkylbenzene sulphonate (LAS) in an acidogenic reactor bioaugmented with a Pseudomonas

666 aeruginosa (M113) strain, Water Science and Technology, 44(4), 183–188.

667 https://doi.org/10.2166/wst.2001.0216
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668 Aloui, F., Kchaou, S., Sayadi, S., (2009), Physicochemical treatments of anionic surfactants

669 wastewater: Effect on aerobic biodegradability, Journal of Hazardous Materials. Elsevier,

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670 164(1), 353–359. https://doi.org/10.1016/J.JHAZMAT.2008.08.009

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671 Amat, A. M., Arques, A., Miranda, M. A., Seguí, S. (2004), Photo-fenton reaction for the
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672 abatement of commercial surfactants in a solar pilot plant, Solar Energy, 77(5), 559–566.

673 https://doi.org/10.1016/j.solener.2004.03.028
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674 Ambashta, R. D., Sillanpää, M., (2010), Water purification using magnetic assistance: A review,

675 Journal of Hazardous Materials, 180(1– 3), 38–49.

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676 https://doi.org/10.1016/j.jhazmat.2010.04.105
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677 Angelidaki, I., Mogensen, A. S., Ahring, B. K., (2000), Degradation of organic contaminants

678 found in organic waste, Biodegradation, 11(6), 377–383.

679 https://doi.org/10.1023/A:1011643014990

680

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681 Apreutesei, R.E., Catrinescu, C. Teodosiu, C., (2008), Surfactant-modified natural zeolites for

682 environmental applications in water purification, Environmental engineering and management

683 journal, 7, 149- 161. https://doi.org/10.30638/eemj.2008.025

684 Arena, F., Di Chio, R., Gumina, B., Spadaro, L. et al. (2015), Recent advances on wet air

685 oxidation catalysts for treatment of industrial wastewaters, Inorganica Chimica Acta. Elsevier

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686 B.V., 431, 101–109. https://doi.org/10.1016/j.ica.2014.12.017

687 Arslan-Alaton, I., Cokgor, E. U., Koban, B., (2007), Integrated photochemical and biological

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1103 Víctor-Ortega, M. D., Martins, R. C., Gando-Ferreira, L. M., Quinta-Ferreira, R. M., (2017),

1104 Recovery of phenolic compounds from wastewaters through micellar enhanced ultrafiltration.

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1108 Polydisperse Nonylphenol Ethoxylate in Aqueous Solution, The Journal of Physical Chemistry

1109 B, 105(16), 3338–3342. https://doi.org/10.1021/jp004178j

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1134 Chemical Engineering Science, 55(6), 1101– 1113. https://doi.org/10.1016/S0009-

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1142 Nd(III) from Aqueous Solutions Using Carbon Nanoparticles. American Journal of Analytical

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1157 Zhu, F.J., Ma, W., Xu, T.F., Ding, Y., et al. (2018). Removal characteristic of surfactants in

1158 typical industrial and domestic wastewater treatment plants in Northeast China. Ecotoxicology

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1160

1161

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1163

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Fig. 1: The simplified structure of a surfactant, consisting of a hydrophilic group joined to a

hydrophobic/lipophilic group (Farn, 2006).

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Fig.2. A schematic of an industrial plant for pollutant removal using Fenton’s reaction,

adopted from Li et al. (2018).

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Fig. 3: Surfactant adsorption mechanisms on functionalised single walled CNTs (SWCNT-

COOH); a) adsorption interaction between anionic surfactant adsorbate and CNT adsorbent

and b) cationic surfactant adsorbate interaction. Adopted from López-López et al. (2016).

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Fig.4: A magnetic filtration process (a) seeding process for magnetic filtration schematic

adopted from Ying et al. (2000) and (b) magnetic filter adopted from Rossier et al. (2012).

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Surfactant Surfactant Name Common Acronyms

Class

Anionic Linear alkyl benzene Sulphonates LAS

Secondary alkane Sulphonates SAS

Alcohol ether sulphates AES

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(Alkyl ethoxy) sulphates

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Non-ionic Alkylphenol ethoxylates APE (or APEO)

Alcohol ethoxylates AE (or AEO

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Cationic Quaternary ammonium-based compounds QAC

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Alkyl dimethyl ammonium halides DMAC
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Surfactant
Wastewater Classes of Surfactant
Concentrations Reference
Type surfactant compositions
(µg/L)

Anionic LAS-C10, C11, C12, 261, 456, 520, 499

Industrial
C13

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(Not
Cationic BAC-C12, C14 0.48, 0.16
specified) Zhu et al.

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(2018)
LAS-C10, C11, C12,

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Anionic 203, 384, 386, 306
Domestic C13

Cationic BAC-C12, C14 0.65, 0.22

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Anionic LAS 4,230

Cationic QACs 216

Multiple
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Non-ionic nonylphenols 4.54 Clara et al.

(Municipal,
nonylphenol 16.30 (2007)
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Textile) *
ethoxylates
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octylphenol 0.360

Kern et al.
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Medical NA** Total Concentration 2,200

(2013)
C

BAC-C12, C14, C16, 2800, 1100, 27,

Kreuzinger
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Medical Cationic C18 1.50

et al. (2007)
DDAC-C10 210

ammonium
Micro- Aboulhassan
Anionic nonylphenol ether 935,000
electronic et al. (2006)
sulphate

Paper Cationic BACs 2.58 Kreuzinger

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Production DDACs 0.33 et al.

BACs 2.06 (2007)***

Dairy Cationic
DDACs 0.29

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Surfactant Contaminant(s) Adsorbed Reference(s)

HDTMA Cr, Phosphate, Ammonium, Bacteria, Naghash and Nezamzadeh, (2015)

BTEX*, Arsenic Apreutesei et al. (2008),

Torabian et al. (2010)

HDP Phosphate Naghash and Nezamzadeh, (2015)

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CPB Nitrate Zhan et al. (2011)

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HTAB Textile Wastewater Colour Ozdemir et al. (2009)

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CTAB Reactive Black Dye Karadag et al. (2007)

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Strategy Lower CMC Environmental Reference

Impact Reduced

Alternative Yes No Schwarze et al.

Surfactant e.g RO90 (2014)

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BioSurfactant Yes Yes Verma and Sarkar

(2017)

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Recovery No Yes Qu et al. (2008)

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Modelling No Yes Rahmanian et al.

(2011)

Polymer Enhanced Yes

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Questionable Lam et al. (2018)
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Ultrafiltration (PEUF)
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Highlights
• Surfactants impact on wastewater treatment processes and environment presented.
• Critical analysis of existing treatment methods includes recommended
improvements.
• Novel surfactant removal technique analysis including development
recommendations.
• Analysis of the use of surfactants to enhance existing wastewater treatments.

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