Journal of Environmental Management 218 (2018) 165e180

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Journal of Environmental Management

journal homepage: www.elsevier.com/locate/jenvman

Research article

Pretreatment technologies for industrial effluents: Critical review on

bioenergy production and environmental concerns
Desika Prabakar a, Subha Suvetha K b, Varshini T. Manimudi a, Thangavel Mathimani c,
Gopalakrishnan Kumar d, Eldon R. Rene e, Arivalagan Pugazhendhi f, *
a
Centre for Biotechnology, Anna University, Guindy, Chennai, 600 025, Tamil Nadu, India
b
Amity Institute of Biotechnology, Amity University, Noida, Uttar Pradesh, 201 303, India
c
Agricultural and Food Engineering Department, Indian Institute of Technology, Kharagpur, West Bengal, 721302, India
d
School of Civil and Environmental Engineering, Yonsei University, Seoul, 03722, Republic of Korea
e
Department of Environmental Engineering and Water Technology, UNESCO-IHE Institute for Water Education, Westvest 7, 2601DA, Delft, The Netherlands
f
Innovative Green Product Synthesis and Renewable Environment Development Research Group, Faculty of Environment and Labour Safety, Ton Duc Thang
University, Ho Chi Minh City, Viet Nam

a r t i c l e i n f o a b s t r a c t

Article history: The implementation of different pretreatment techniques and technologies prior to effluent discharge is
Received 15 October 2017 a direct result of the inefficiency of several existing wastewater treatment methods. A majority of the
Received in revised form industrial sectors have known to cause severe negative effects on the environment. The five major
25 March 2018
polluting industries are the paper and pulp mills, coal manufacturing facilities, petrochemical, textile and
Accepted 31 March 2018
the pharmaceutical sectors. Pretreatment methods have been widely used in order to lower the toxicity
levels of effluents and comply with environmental standards. In this review, the possible environmental
benefits and concerns of adopting different pretreatment technologies for renewable energy production
Keywords:
Industrial effluents
and product/resource recovery has been reviewed and discussed.
Wastewater treatment © 2018 Elsevier Ltd. All rights reserved.
Pretreatment technologies
Renewable energy
Eco-friendly options. contents

1. Introduction pharmaceutical industry. The effluents generated by these in-

The rapid increase in the establishment of different industrial
sectors entails detrimental effects on the environment due to their
inability to meet the effluent discharge standards and regulations.
Several studies have reported the genotoxic effects of such efflu-
vium on all living forms. Consequently, the range of toxicity of
major industrial effluents was found to reach as high as 1012
revertant per liter (in Salmonella), which includes severe mutagenic
hazards. In order to mitigate such hazards, several pretreatment
methods have been adopted and proposed over the past few years.
Besides, among the numerous industrial establishments, five major
players have proven to inflict the highest level of hazard to both the
surroundings as well as all life forms (Tong et al., 2017; Shobana
et al., 2017). These include effluents from the paper and pulp in-
dustry, coal manufacturing facilities, petrochemical, textile and the
* Corresponding author.
E-mail address: arivalagan.pugazhendhi@tdt.edu.vn (A. Pugazhendhi).
dustries are highly toxic in nature. The complexity of the outflow
contaminants impedes the effects of effluents treatments to reduce
its toxicity and makes the treatment expensive. Therefore, proper
pretreatment method should be selected in order to achieve cost-
effective secondary treatment of the effluent. A thorough under-
standing of the pretreatment technologies used to treat these in-
dustrial effluents is particularly of high-priority to alleviate
environmental concerns.
With regard to the paper and pulp mill effluents, the fatality
induced to aquatic life forms owing to the disruption of carbohy-
drate metabolism, ion balance and biotransformation activity of
enzymes has been well documented in the literature. In order to
dilute such anomalies, several pretreatment methods for paper and
pulp industrial effluents have been recommended in the literature
(Kinnarinen et al., 2016; Kong et al., 2016; Shankar et al., 2014;
Yunqin et al., 2010). Among them, thermochemical precipitation,
advanced oxidation processes, adsorption, electrocoagulation and
enzymatic pretreatment have been tested at the laboratory scale
(Hakizimana et al., 2017; Koyama et al., 2017; Garg et al., 2005;

https://doi.org/10.1016/j.jenvman.2018.03.136
0301-4797/© 2018 Elsevier Ltd. All rights reserved.
166 D. Prabakar et al. / Journal of Environmental Management 218 (2018) 165e180
Shankar et al., 2014; Liu et al., 2011). The pretreated paper and pulp
discharge has also found application for biomethane production.
For instance, Baba et al. (2013) reported a 2.6-time increase in
methane yield using waste paper pretreated with rumen fluid.
However, in recent years, several studies have focused on inte-
grated pretreatment approaches, especially, by combining UV
pretreatment to existing techniques (Jaafarzadeh et al., 2016, 2017).
Another industrial effluent that can cause mutagenicity to even
the purest forms of water bodies is the petrochemical industry
(Siddique et al., 2017; Salehi et al., 2014). Several pretreatment
methods have been tested to mitigate the toxicity levels preceding
its environmental discharge. The most widely reported pretreat-
ment techniques for effluents from the petrochemical industry are
ozonation (Wu et al., 2017a; Kameswari et al., 2011; De los Santos
Ramos et al., 2009), coagulation (Wang et al., 2014; Verma et al.,
2010; Hakizimana et al., 2017), photocatalytic degradation (Saien
and Nejati, 2007), filtration (Salehi et al., 2014; Ko and Fan, 2010)
and adsorption (Shobana et al., 2017; Hakizimana et al., 2017).
Electrocoagulation as a pretreatment option was studied by Garg
et al. (2014) and it was found that under optimized conditions
(pH - 8.2, pretreatment time - 180 min, current density - 125 A/m2
and inter electrode distance - 1 cm), the chemical oxygen demand
(COD) removal was 66%. Another interesting pretreatment method,
i.e. the combination of fungi and bacteria for the degradation of 2-
naphthalensulphonic acid polymers (2-NSAPs) from petrochemical
wastewater (Gullotto et al., 2015), showed a COD removal of 62%.
It is noteworthy to mention that exploring the use of such
pretreated wastes for direct consumption in other fields is of
extreme interest for creating circular economy within different
industries. For instance, purified terephthalic acid wastewater has
been investigated for its ability to be used as a suitable substrate for
biohydrogen production (Zhu et al., 2010). Recently, a pretreatment
strategy that combines ultrasonication and microwaves to enhance
biomethane production was reported by Siddique et al. (2017). Li
et al. (2017a) adopted a one-step carbonization and ZnCl2 activa-
tion pretreatment to fabricate a novel polymer binder-free nano-
composite based electrode using waste activated biological sludge
from petrochemical industries and this product was reported to
have widespread applications in energy storage.
Moreover, the use of a wide range of chemicals and dyes in the
textile industry adds to the complex and variable characteristics of
its discharge, thereby necessitating the implementation of
adequate pretreatment strategies. Such complex industrial out-
flows usually interfere with the photosynthesis of plants and ma-
rine life forms (Ezechi et al., 2015) and also causes cancerous effects
on animals and humans (Almasian et al., 2015). Different pre-
treatment approaches have been tested for the removal of dyes
from aqueous solutions, namely electrochemical treatment (Basha
et al., 2012; Haque et al., 2015), coagulation and flocculation
(Hakizimana et al., 2017; Liang et al., 2014; Wei et al., 2015), pho-
tocatalytic oxidation (Kernazhitsky et al., 2015) and adsorption (Tan
et al., 2015).
Recently, advanced oxidation processes (AOP) that has the po-
tential to generate hydroxyl radicals have been shown to intensify
the decolourization of textile effluents (Jorfi et al., 2016). The
effective removal of the contaminants from wastewaters offers the
advantages of reusability and procurement of valuable elements
from such textile effluents (Koseoglu-Imer, 2013; Bhaskar Raju
et al., 2009).
Despite its inevitable role in energy generation, the coal in-
dustries have effectively implemented different pretreatment
methods for its effluents. One of the predominant emission from
coal manufacturing namely the fly ash, contains high amount of
heavy metals which necessitates pretreatment in order to prevent
its leaching into the groundwater (Blissett and Rowson, 2012; Chen
et al., 2008; Hsu et al., 2008). In this regard, the pretreatment of fly
ash with hydrogen peroxide and carbonation (Ecke et al., 2003) to
immobilize the heavy metals has been reported. Moreover, coal
gasification wastewater that is poorly biodegradable has also been
subjected to several pretreatments, among which the acid/alkali
method is most commonly used at the industrial scale (Koyama
et al., 2017; Lin et al., 2009). Additionally, the conversion of coal
industrial waste for an array of applications such as zeolite syn-
thesis (Iyer and Scott, 2001), CO2 capture (Arenillas et al., 2005) and
the manufacture of adsorbents (Hsu et al., 2008) have been
attributed to the selection of a suitable pretreatment method.
Current research shows a shift to the application of more integrated
approaches utilizing biologically pretreated coal gasification
wastewater for advanced wastewater treatment processes (Hou
et al., 2016; Xu et al., 2015).
The incremental uptake of drugs in recent times has often led to
bulk production of pharmaceuticals and as a consequence, an in-
crease in their proximity to aquatic life forms. Several toxicity
studies have reported the acute and chronic toxicity of wastewater
from the pharmaceutical industry to algae, fish, daphnia and bac-
teria. In order to overcome such ill effects, pretreatment methods
have been adopted to minimize the effects due to hazardous pol-
lutants from pharmaceutical industries. Some of the pretreatment
methods are Fenton oxidation, wet-air oxidation, coagulation/
flocculation and filtration (Hakizimana et al., 2017; Wang et al.,
2012; Tekin et al., 2006; Torres et al., 1997). Qiu et al. (2011) re-
ported wet air oxidation as a pretreatment for fosfomycin phar-
maceutical wastewater and recorded a 99.9% phosphate recovery
along with a surge in the biodegradability ratio, i.e. BOD5/COD from
0 to >0.5. Besides, cephalosporin bacterial residues have been
examined for its potential for biomethane production via thermo-
alkaline pretreatment (Li et al., 2017b). The results obtained from
that study proved the capacity of pretreated wastewater (6% NaOH
at 105
C for 15 min) for renewable energy generation owing to a
~255% increase in yield in comparison to that of the un-treated
waste.
The aim of this review is to provide a holistic view on the
beneficial aspects of pretreatment in five major industries, namely
the paper and pulp mills, coal manufacturing facilities, petro-
chemical, textile and the pharmaceutical industry. The argument
for such a preference are based on the aforementioned toxic effects
caused by the effluents of these highly polluting industries. More-
over, a comprehensive knowledge of the different pretreatment
methods is crucial in order to comply with effluent discharge
standards and at the same time to seek possible benefits by
enhancing its applicability. Anew, the characteristics of the pre-
treatment methods and its subsequent role in renewable energy
production have also been discussed with certain propositions for
large-scale implementation. Such an exclusive analysis over the
dominant industrial sectors will facilitate the integration of pre-
treatment technologies with conventional wastewater treatment
plants for resource recovery.
2. Importance of key industrial sectors
Several industrial establishments produce benefits for the so-
ciety, yet they also contribute to certain baleful effects. In this re-
gard, among the five selected industries, the products from the
paper and pulp industries contribute the most in our day to day
lives. The utilization of products from these industries is of personal
importance for the manufacture of vital commodities such as
newspapers and books. It is one of the key industry that consumes
large quantities of natural cellulosic resources and the manufacture
of pulp, paper and paper products ranks among the world's largest
industries (De los Santos Ramos et al., 2009). Secondly, energy
 D. Prabakar et al. / Journal of Environmental Management 218 (2018) 165e180 167

consumption is a major prerequisite in every industrial sector and  Biological oxygen demand (biodegradable organics)
the coal production facilities act as a principal source of power  Total suspended solids
production. Its major utilization is the result of its large-scale re-  Refractory organics (COD, TOC)
serves and its economic value (Shafiee and Topal, 2009). Thirdly,  Nitrogen
petrochemicals have become indispensable due to its multifaceted  Phosphorus
applications, especially pertaining to the manufacturing of plastics,  Heavy metals
which is used for packaging, insulation, molding, as well as in other  Dissolved inorganic solids
industries such as automobiles, fertilizers, etc. The textile industry  Oil and grease
is primarily concerned with the design and production of yarn,  Volatile organic compounds
cloth, clothing, and their distribution. Lastly, the industrial sector
that influences the health of all life forms is the pharmaceutical There is a huge demand to treat hazardous industrial waste or to
industry, featuring the design, development and manufacturing of effectively reuse, recycle and reclaim them for economic reasons,
drugs for the purpose of medication. eco-friendly use and the different pretreatment methods adopted
Despite these wide applications, the large amounts of liquid over the last few years have proved to adhere to such benefits and
wastes generated by these five industries are acclaimed to contain sometimes even beyond. A schematic representation of the green
high COD levels, toxic to human health and causes detrimental cycle exhibited by adopting different pretreatment methods is
effect on the environment. Thus, in order to eliminate these shown in Fig. 1.
negative impacts and to reduce the COD levels, it is essential to
design and develop hybrid wastewater treatment plants.
4. Classification of pretreatment technologies

3. Need for pretreatment of industrial effluents 4.1. Traditional methods

Industrial waste are regarded as the unwanted by-products that
remain after the production of desired products. Large quantities of
industrial waste are generated in the current/existing industrial
settings. The production of wastes is unavoidable to a certain extent
due to the increasing demand of the products produced from in-
dustries that are meant for commercial use (Baumga €rtner, 2003).
Majority of the industrial waste are hazardous as they contain
carcinogens and other toxic substances. Consequently, human
exposure to such hazardous wastes can cause headache, nausea,
skin irritation and also serious impairments such as neurological
dormancy, cancer, birth defects, and reproductive anomalies.
Moreover, such toxic wastes also result in insidious effects to the
environment, in the event of improper disposal and handling
practices. The toxic chemicals present in key industrial sectors are
outlined in Table 1.
However, at the industrial scale, a typical production plant or an
industry will face several challenges to eliminate such highly toxic
and radical pollutants, which are commonly prevalent in industrial
effluents. Inevitably, discharges from both industrial and com-
mercial sources can cause adverse negative effects on the quality of
water received by the water body. Furthermore, the disposal of
solid waste into landfills is of great concern as they occupy large
land area, making it unproductive with the increased possibility of
leaching of toxic substances, i.e. leachate, into the groundwater.
Thus, pretreatment of the wastewater prior to its discharge will
reduce the negative effects of industrial discharges.
An effective pretreatment for wastewater can be defined as that
process which eliminates or reduces the levels of important
physico-chemical parameters prior to its disposal.
The importance of pretreatment techniques lies in its capacity to
convert even harmful industrial discharge into a utilizable form in
various sectors. Over the years, a diverse range of approaches have
been studied of which certain methods remain crucial and long
established. In this regard, physical pretreatment methods have
been widely adapted at the laboratory and subsequently into an
industrial scale as well. For instance, in thermal treatment, the
destruction of the cell wall and cell membrane of the microor-
ganisms is achieved, thereby facilitating the release of intracellular
compounds. Ruffino et al. (2015) carried out a low temperature
(<100
C) thermal pretreatment on waste activated sludge for 3 h at
70
C and 90
C and reported an improved methane production by
21% and 31%, respectively, when compared to untreated waste.
Ultrasonication based on the principle of cavitation and hydroxyl
radical production is one of the most widely used physical pre-
treatment methods. Furthermore, it holds a more cost-effective
trait over its counterpart, i.e. ozonation, as evident from short
contact times of 2 and 1 min, and relatively high soluble COD of 85
and 97%, respectively, for the primary and the secondary sludge
(Kameswari et al., 2011). Moreover, biological pretreatment ap-
proaches have also greatly benefitted the wastewater treatment
processes with regards to enzymatic hydrolysis. In this case, the
cleavage of the bonds of substrate specific to the enzyme is ach-
ieved. Vallad~ao et al. (2007) tested enzymatic pretreatment and its
impact on the biodegradability of slaughterhouse effluents. The
results from that study indicated that the use of 0.1% solid enzy-
matic pool in hydrolysis increased the methane production rates
and decreased the processing time required. In another recent
study, Meng et al. (2017) hydrolyzed floatable grease, animal fat

Table 1
Toxic compounds present in five major industries namely petrochemical, textile, pharmaceutical, coal manufacture and paper and pulp industry.

S. Industrial Toxic components in the effluent References

No sector

1. Paper and pulp Dioxins, furans, chlorinated organics, dissolved colloidal organics, ligin, resin acids, phenols, sulfur compounds Ali and
Sreekrishnan, 2001
2. Coal Fly ash, polycyclic aromatic hydrocarbons (PAH), cyanides, silica, phenols, ammonia, nitrogen heterocyclic compounds Zhang et al., 2016
manufacturing
3. Petrochemical Phenols, heavy metals, nitrobenzene, organo- chlorines, aniline, acrylonitrile, chlorinated aliphatics, Liu et al., 2014
4. Textile Dyes, suspended solids, chlorinated aromatic hydrocarbons, surfactants, and heavy metals such as copper and chromium etc. Mahmoodi, 2015
5. Pharmaceutical Drug residues, organics and inorganics, degradable and non-biodegradables spent solvents, catalysts, additives, reactants and Chen et al., 2011
amounts of intermediates and products (amoxicillin), compounds with NH3-N concentration
168 D. Prabakar et al. / Journal of Environmental Management 218 (2018) 165e180
Fig. 1. A schematic representation of a closed system approach to avoid discharge into the environment using different pretreatment methods
and vegetable oil in food waste using lipases obtained from three
different sources. Under optimum process conditions (24 h and at
40e50
C), the biomethane production rate increased, while the
digestion time was reduced by ~10 days.
Moreover, chemical approaches of pretreatment such as the AOP
have also been frequently used to degrade a wide range of recal-
citrant organics present in wastewater. In AOP, hydroxyl radical, a
strong oxidizing agent is generated, which cleaves complex organic
compound into carbon dioxide, water and inorganic ions. Ponce-
Robles et al. (2017) treated cork boiling wastewater (CBW) by
combining different AOPs, i.e. nanofiltration and photo-Fenton
process, for the reuse of CBW. According to the authors, such
combination of AOPs resulted in high-quality permeate stream that
aided in reutilization of the cork boiling process. On a more
extended note, the Fenton's reagent which is an integral part of the
AOP comprises of a mixture of ferrous iron and hydrogen peroxide.
In the Fenton oxidation reaction, ferrous iron initiates and catalyzes
the decomposition of hydrogen peroxide, which subsequently
produces the hydroxyl radicals. Guzma n et al. (2016) proved that
photo-Fenton treatment along with natural solar radiation was a
unique and benefiting strategy for industrial applications in trop-
ical countries. The authors treated citrus fruit processing waste-
water through solar photo-Fenton treatment and different ozone-
based processes (O3, O3/OH, O3/UV, O3/H2O2 and O3/UV/H2O2).
When compared to ozone-based processes, solar photo-Fenton
treatment eliminated 76.9% and 53.3% of COD and dissolved
organic carbon (DOC), respectively. In addition, ozonation as a
pretreatment step, is relatively more common and its performance
depends on the formation of hydroxyl radicals along with alteration
of unsaturated bonds. Battimelli et al. (2010) studied the impact of
ozone pretreatment on molasses fermentation wastewater and
recommended that a dose of 0.5 ozone/g COD increased the
biodegradability by 33% without any toxicity on the biomass.
Another technique that is also used is the wet air oxidation (WAO)
in which the organic compounds are oxidized to carbon dioxide,
water and other inorganic components at high temperature and
pressure. It is usually enhanced by using catalysts and oxidants. As
an example, the overall degradation of an organic compound
(RCH3) into lower molecular weight compound R*, water, carbon
dioxide is shown below:
2RCH3 þ7½0 2R /2CO2 þ 3H2 O
Furthermore, pretreatment using radiation is highly recom-
mended owing to its ability to completely degrade non-
biodegradable organic compounds, thereby eliminating the chan-
ces of secondary pollution. Gamma radiation as a pretreatment
strategy for textile industrial discharges had shown good detoxi-
fying potentials. In a recent study, a combination of polyaluminum
chloride and cationic polyacrylamide was added to chemical metal
polishing wastewater (Pan et al., 2005). This increased the floc size,
which subsequently enhanced the permeate flux in membrane
filtration by inhibiting the fouling mechanism. Besides, with the
aim of avoiding fouling of membranes in wastewater treatment,
olive mill wastewater was subjected to a coagulation pretreatment
process (Stoller, 2009). Among the tested coagulants, it was
observed that aluminum sulphate was advantageous in contrast to
aluminum hydroxide due to its excellent fouling inhibition char-
acteristics. On the other hand, zero-valent iron (ZVI) has been
established as a strong reducing agent for the removal of organic
compounds from wastewater. Lee et al. (2009) reported that ZVI
pretreatment was effective for detoxifying iodine present in
wastewater from liquid crystal display manufacturing industry,
contributing to the flow of non-toxic products for subsequent
biological wastewater treatment. ZVI has also been used in com-
bination with Fenton oxidation for the treatment of 2, 4-
dinitroanisole containing wastewater and ~77% removal was re-
ported (Shen et al., 2013).
4.2. Hybrid methods
Classic pretreatment methods, usually practiced in a single step,
has evolved greatly over the years. Taking into account the
 D. Prabakar et al. / Journal of Environmental Management 218 (2018) 165e180
incremental effluent release from industries and the need to
eliminate them, a combined pretreatment approach was studied.
Recently, several studies have tested the efficiency of integrated
pretreatment methods for improving the efficiency of converting
effluents into valuable resources. For instance, Krishna et al. (2010)
investigated the electrochemical oxidation of distillery wastewater
using aluminum electrode. The authors reported a COD removal of
72.3% and the BOD5/COD ratio, which was originally 0.15, increased
to 0.68 within 120 min of electrolysis pretreatment. In this process,
the organic compounds are oxidized to CO2 and H2O in the pres-
ence of electricity. The reactions occurring at the anode and cath-
ode are shown in Fig. 2. The chlorine/hypochlorite acts as an
electrolyte and reacts with the organic molecules to remove the
COD. The Al3þ and OH in Al(OH)3 provides large surface area for
rapid adsorption of the soluble organic compounds (Krishna et al.,
2010). In another study, Ochando-Pulido et al. (2012) followed a
novel approach by combining Fenton-like oxidation, flocculation-
sedimentation and filtration through olive stones, for the treat-
ment of olive mill wastewater. The results from their study showed
high reductions of up to 94.1% COD and 99.8% total phenols
removal. Moreover, the adsorption using olive stones played a
beneficial role in lowering the iron concentration in the waste-
water, which would otherwise cause harmful effects to the mem-
branes. Zhao et al. (2012) reported a unique approach for the
removal of phosphate from synthetic wastewater through a syn-
ergy between open gradient superconducting magnetic separation
(OGMS) and high gradient superconducting magnetic separation
(HGMS) and reported a reduction in phosphate concentration from
0.5 to 0.01 mg/L.
Most clays are considered as nanoparticles. In the presence of
nanocomposites, the charged colloidal particles are neutralized and
the neutralized particles form large and dense aggregates that tend
to settle at the bottom faster. This exhibits the property of nano-
composites as a coagulant and flocculant, respectively. The prop-
erties of nanoparticles with a high surface area and high reactivity
Fig. 2. Electrochemical pretreatment of wastewater using aluminum electrode.
169
are advantageous to treat wastewater. Dendrimers, metal-
containing nanoparticles, zeolites and carbonaceous nano-
materials are commonly used as nanoparticles in pretreating
wastewater (Sulekha, 2016). Evidently, the results of these lab-scale
studies show that a combination of different pretreatment steps
could be more beneficial; yet, the economics of such a strategy
needs to be studied further before applying them in practice.
5. Salient characteristics of different pretreatment
technologies
The effects of various pretreatment methods on specific indus-
trial effluents are summarized in this section.
5.1. Biodegradability
The most commonly used wastewater treatment method in
practice is the use of biological treatment processes for industrial
wastewaters; however, the wastewater should have certain
physico-chemical and biological characteristics in order to facilitate
biological wastewater treatment. According to Chamarro et al.
(2001), it is mandatory to maintain a biodegradability index of
not less than 0.4. Taking this into consideration, a wide range of
pretreatment methods have been put forth to degrade specific
compounds. For this purpose, photo-Fenton oxidation, chemical-
oxidation, ZVI pretreatment, catalytic ozonation, etc, have been
applied (Mantzavinos and Psillakis, 2004; Perey et al., 2002; Li et al.,
2017a).
Sangave and Pandit (2006) tested hydrolysis using cellulase as a
pretreatment method for treating alcohol distillery spent wash,
followed by aerobic biological oxidation. The authors suggested
that the enzymatic pretreatment likely resulted in hydrolyzed
products, which were readily degradable by the microorganisms.
Consequently, a 2.3-fold increase in the oxidation rate established
the significance of pretreated spent wash. In another study, Fan and
Ma (2009) assessed the potential of Fe-Cu process alongside a cyclic
activated sludge system to improve the biodegradability of mixed
wastewater. Biodegradation estimates indicated a sharp increase in
the BOD5/COD ratio from a range of 0.13e0.18 to 0.28e0.34 thereby
favoring the subsequent biological treatment. The increase in the
BOD5/COD ratio was ascribed to many vital factors. One among
them was the elimination of biorefractory pollutants by strong
electron-drawing groups onto the surface of copper by Fe0 and
Fe(II), respectively.
Fenton-coagulation process was analyzed as a potential pre-
treatment for pesticide wastewater exhibiting high COD and
insufficient biodegradability (Chen et al., 2007). Under optimized
conditions, (H2O2 dosage - 97 mmol/L; Fe2þ dosage - 40 mmol/L;
pH - 3.0), an increase in the BOD5/COD ratio of the wastewater from
0.18 to 0.47 was observed. The mechanism of degrading phorate by
Fenton oxidation was a result of the mineralization of in-
termediates and breakage of P¼S double bond by OH∙ aggregating
sulphate and phosphate ions.
Furthermore, electrochemical techniques have been widely
explored to enhance the degradation of organics from wastewater.
Soloman et al. (2009) reported the improvement in the biode-
gradability index (0.11e0.46) after electrochemical pretreatment of
pulp and paper industry wastewater, under moderate conditions
(current density - 112.9 Am-2, pH - 7.3) and a short span of only
6.9 min. In another study, Hanafi et al. (2011) established the
favorable aspects of electrocoagulation pre-treatment of olive mill
wastewater and reported reduction efficiencies of 92.4%, 91.6% and
78.5%, for color, total phenolic content and COD, respectively.
Likewise, Gong et al. (2014) studied the change in biodegradability
with respect to pH, electrode area/wastewater volume (A/V) ratio,
170 D. Prabakar et al. / Journal of Environmental Management 218 (2018) 165e180
current density and inter-electrode distance using electro-
coagulation for the pretreatment of wastewater from the manu-
facture of wet-spun acrylic fibers. The degradation of aromatics and
straight-chain paraffins was found to increase the biodegradability
of the contaminants together with smaller inter-electrode dis-
tances (0.8 cm). The results from that study showed that, after
100 min of treatment, the BOD5/COD ratio which was initially at
0.25 increased to 0.35 at optimum A/V ratio of 0.28 cm1 and pH
5.0.
The mechanism of biodegradation of some of the widely used
pretreatment methods are summarized in Table 2. Evidently, recent
studies have also reported new approaches and mechanisms con-
cerning the different pretreatment strategies yielding satisfactory
outcomes. Xiong et al. (2017) reported a significant increase in the
BOD5/COD ratio from 0.19 to 0.56 as a result of a unique pretreat-
ment method comprising of a coagulation-flocculation treatment
combined with micro-scale Fe/Cu/O3 process for the degradation of
automobile coating wastewater. Conversely, Montusiewicz et al.
(2017) observed an extremely low increase in the BOD5/COD ratio
from 0.074 to 0.091 using hydrodynamic cavitation with the view of
enhancing the biodegradability of brewery spent grain. Hence, it
can be concluded that a more stringent analysis of the different
components present in the industrial wastewater is necessary in
order to determine the most appropriate choice of pretreatment.
5.2. Dewaterability
The widespread application of the activated sludge technology
demands strategies for its volume reduction and proper condi-
tioning (Chen and Yang, 2012; Feng et al., 2009). Several pretreat-
ment methods to enhance the sludge dewatering characteristics
have been reported in the literature, namely, the thermal method
(Zhou et al., 2015; Kuglarz et al., 2013), ultrasonication (Kameswari
et al., 2011; Huan et al., 2009), electrolysis (Ning et al., 2015; Yang
et al., 2017), microwave assisted irradiation (Kuglarz et al., 2013),
Fenton's reagent (Xing et al., 2017; Dai et al., 2017; Tony et al.,
2008), alkaline pretreatment (Koyama et al., 2017; Shao et al.,
2010), electrocoagulation (Gharibi et al., 2013), microwave-acid
pretreatment (Liu et al., 2016), chemical (acid/alkali) pretreat-
ment (Devlin et al., 2011; Yuan et al., 2011a, 2011b), and gamma
irradiation (Wu et al., 2017c), among others.
Shao et al. (2010) studied the influence of ultrasonication as a
pretreatment step on the sludge dewaterability characteristics. The
capillary suction time (CST) was normalized and applied to char-
acterize the sludge dewaterability. According to the authors, pre-
treatment followed by mesophilic anaerobic digestion displayed a
significant drop in CST from 44.4 to 11.1 (sec∙L)/g total suspended
Table 2
Few pretreatment methods recently studied for the enhancement of biodegradation and their mechanisms.
S. Pretreatment method Compounds/industrial wastewater
No analyzed
1. Catalytic wet oxidation (aminated Coking wastewater (phenols and N-
activated carbon) containing compounds)
2. Electrochemical Distillery wastewater
3. Electro-Fenton process Cosmetic industry wastewater- sodium
laurylether sulfate (SLES)
4. Coagulation/flocculation (FeCl3) Cheese whey wastewater
5. Ozone oxidation Oil field drilling wastewater
6. Photo-Fenton process Fe(II)/H2O2/ Paper mill wastewater
UV
7. Hydrolysis acidification Tannery wastewater
solids, indicating significant enhancement of sludge dewaterability.
Such a trait was attributed to the presence of proteins coupled with
the average molecular weight of loosely bound extracellular poly-
meric substances (EPS). The authors concluded that ultrasonication
pretreatment could likely alter the dispersion of organic matters in
the EPS matrix and the sludge flocs, ultimately facilitating sludge
dewaterability. Electrochemical methods for improved sludge
dewaterability was studied by Yuan et al. (2011a) and experimental
results showed an inverse relationship between electrolysis voltage
and sludge dewaterability. It was shown that at <20 V, positive
effects were observed, whereas, deterioration of sludge occurred
when the electrolysis voltage exceeded 30 V. In another study, Ning
et al. (2015) analyzed the dewaterability of textile dyeing sludge
when preceded by a micro-electrolysis treatment step. It was re-
ported that, in order to attain maximum sludge dewaterability, the
EPS concentration should be between 43 and 46 mg/L and the
sludge disintegration degree within a range of 4.2e4.9%.
On the other hand, Gao (2011) adopted a relatively new
approach by applying freezing as a pretreatment method; addi-
tionally, both individual as well as a combination of different
chemical treatments (acidification/basification) were tested.
Though the combined pretreatment strategies did not cause any
significant impact, freezing alone proved to be advantageous.
Firstly, it was effective in eliminating phosphorous from the sludge
particles and depicted a 2.5-fold increase in the phosphate con-
centration compared to other treatments tested. Accordingly,
freezing had directly contributed to increased floc size, as evident
from a 5 to 6-fold increase of the size of the particles 300 mm. This
ability to agglomerate small particles mitigates the adverse effects
of super colloidal particles and subsequently enhancing the sludge
dewaterability. In some cases, rapid sludge settling characteristics
can also be observed with about 90% of the sludge settling in less
than 10 min (Gao, 2011). Another non-conventional, yet relatively
less explored method is the explosive shockwave treatment pro-
posed by Chen and Yang (2012). The authors determined the op-
timum pretreatment conditions as 25 g explosive and 96.7%
original sludge water content.
Currently, most of the research is aimed at comprehending the
feasibility and efficiency of a combination of pretreatment methods
for enhanced sludge dewaterability. For instance, electrolysis inte-
grated with Fe(II)-activated persulfate oxidation to increase the
activated sludge dewaterability was studied by Zhen et al. (2013)
and it was inferred that the deterioration of tightly bound EPS
(TB-EPS), as well as the cells had contributed to enhanced dew-
aterability. In another recent study, Dai et al. (2017) reported the
efficiency of anaerobic mesophilic digestion integrated with Fen-
ton's reagent/lime and the potential of thermal-Fe(II) activated
Proposed reason for biodegradation Measured BOD5/COD after References
pretreatment
4-methylphenol was converted to lower 0.84 Xue et al.,
toxic compound, 4-HBZ 2017
Metal hydroxide formation; large surface 0.68 Krishna
area of flocs et al., 2010
Oxidation of Fe2þ leading to the formation 0.79 Aloui et al.,
of HO 2009
Formation of Fe(OH)3 ~0.90 GilPavas
et al., 2017
Change in molecular structure of pollutants 0.80 Wang et al.,
2004
Formation of OH radicals 0.70 Jamil et al.,
2011
Mineralization of dissolved organics 0.56 Wang et al.,
2014
 D. Prabakar et al. / Journal of Environmental Management 218 (2018) 165e180
ozone treatment to waste activated sludge. Xing et al. (2017) re-
ported a pretreatment method integrating Fenton's reagent with a
surfactant dodecyl dimethyl benzyl ammonium chloride. The re-
sults from that study showed a decrease in the bound water content
of the sludge from 3.15 to 1.08 g/g.
5.3. Renewable energy production
In recent times, an urge to fill in the void of the continually
exhausting fossil fuel reserves has increased. Energy is one of the
key factors in the modern technological world (Anburajan et al.,
2017). Among the substitutes explored, one of the promising
candidate for renewable energy production is ethanol and bio-
diesel. New gaseous alternatives namely biomethane and bio-
hydrogen also demonstrate a good potential to take over as
sustainable transportation fuels (Kumar et al., 2017; Saratale et al.,
2017). Although biogas production has increased within the
households, they mostly use animal manure as the primary feed-
stock. Since manure is not easily available in surplus amounts, its
dependence is usually restricted (Pang et al., 2008; Carrere et al.,
2009). To overcome the energy crisis and waste management is-
sues, an efficient technology like renewable energy usage is the
immediate need for the future (Veluchamy and Kalamdhad, 2017).
A detailed evaluation on the enhancements of biogas and bio-
hydrogen yields from the utilization of pretreated wastes and
wastewater as feedstock has been described in this section.
5.3.1. Biogas production
In field situations, the high organic load in industrial wastewater
and the presence of compounds that may be responsible for
inhibiting the biological activity (e.g. chromium and sulphide)
limits the full capitalization and potential in producing biomethane
at a low-cost despite the fact that it serves as an abundant source of
renewable energy (Ennouri et al., 2016). Pretreatment of substrates
is considered as the solution to overcome this negative aspect,
because it results in higher biomethane production within a short
span of time (Sivagurunathan et al., 2017). Ferrer et al. (2008) car-
ried out medium-temperature pretreatment (70
C) on both pri-
mary and secondary clarified wastewaters for enhanced biogas
production. The results showed a rise in biogas (methane) pro-
duction by up to 30%. Similarly, Carre re et al. (2009) analyzed the
effect of thermal pretreatment (70e190
C) on anaerobic digestion
of pig manure with an aim to maximize methane production. The
results from that study showed an increase in the methane po-
tential with increasing temperatures; yet, temperatures higher
than 135
C were required to obtain an exponential increase in the
methane potential. Likewise, Ennouri et al. (2016) studied thermal
pretreatment on waste activated sludge in order to enhance the
methane production and a temperature of 120
C was found to be
appropriate for pretreatment as evident from a high CH4 content of
63.8%. Alkali treatment for the anaerobic digestion of paper and
pulp wastes can also be considered as a pretreatment option to
improve the methane productivity (Lin et al., 2009). Under opti-
mized pretreatment conditions, the authors demonstrated an in-
crease in the methane yield, as high as 183%, when compared to
control experiments. This indicates the potential of alkali pre-
treatment for intensifying methane yields.
A comparative study on three pretreatment methods, namely
microwave treatment, ultrasonication and chemo-mechanical
treatment on pulp mill waste sludge was performed with an aim
to increase the methane yields (Saha et al., 2011). The results
showed that microwave pretreatment was the most advantageous
among the three treatments with ~90% increase in the yields
compared to controls. However, it was also revealed that pre-
treatment facilitated the thermophilic digestion on a relatively low
171
scale in contrast to that of a mesophilic process. More recently,
another study (Lizama et al., 2017) had investigated the effects of
ultrasonic pretreatment (USp) of waste activated sludge, in the
range of 5000e35000 kJ/kg total solids. In that study, anaerobic
digestion of raw and sonicated waste activated sludge was
compared with biochemical methane potential tests, and a biogas
production of 31% (219.5 mL/g VS) was observed at the highest USp
of 35000 kJ/kg total solids compared to that of the untreated sludge.
Recently, the effects of biological co-pretreatment on biogas pro-
duction from anaerobic co-digestion of food waste and waste
activated sludge were investigated by Zhang et al. (2017a). From a
practical view-point, these studies clearly demonstrate that bio-
methane production using organic wastes holds a sustainable
future based on their abundance in both developing and industri-
alized countries.
5.3.2. Biohydrogen production
Biohydrogen is a sustainable power source transporter due to its
beneficial properties such as high gravimetric vitality thickness and
clean burning, i.e. the absence of ozone-harming (carbon, sulfur or
nitrogen) emissions (Sivagurunathan et al., 2017; Boran et al.,
2012). In addition, the advances in biohydrogen generation tech-
nologies in the context of organic wastewater transformation could
fathom the issues identified with sustenance security, environ-
mental change and energy security from an economic standpoint
(Kumar et al., 2015, 2017; Saratale et al., 2017; Mohammadi et al.,
2011; Boran et al., 2012). The different industrial wastewaters and
their pretreatment methods used for renewable energy (bio-
methane and biohydrogen) production are shown in Table 3.
In that line of progressive research, Mohan et al. (2007) carried
out heat-shock (100
C, 2 h) and acid pretreatment (pH 3.0, 24 h) on
chemical wastewater for improved hydrogen production. The au-
thors reported that additional supplementation of glucose and
sewage wastewater positively influenced the hydrogen generation
rate and at an optimum pH of 6.0, the hydrogen yield was
1.25 mmol H2/g COD. In another study, it was also demonstrated
that biohydrogen production could be considerably enhanced by
co-culturing pure strains (Citrobacter freundii 01, Enterobacter aer-
ogenes E10 and Rhodopseudomonas palustris P2) to treat distillery
effluent (Vatsala et al., 2008). The average yield of hydrogen was
2.76 mol/mol glucose and the rate of hydrogen production was
estimated to be 0.53 kg/100 m3/h coupled with a high reduction of
BOD and COD within 40 h. Likewise, Hsiao et al. (2009) co-cultured
two isolated strains (i.e., Clostridium sporosphaeroides F52 and
C. pasteurianum F40) to generate biohydrogen using condensed
molasses fermentation soluble (CMS) as the substrate. In this co-
culture system of C. pasteurianum F40 and C. sporosphaeroides
F52, 12 to 220% increase in hydrogen production was obtained at
CMS concentrations ranging between 10 and 80 g COD/L. The in-
crease in hydrogen production was attributed to the ability of
C. sporosphaeroides F52 to convert monosodium glutamate into
hydrogen gas. Recently, Kumar et al. (2015) had examined the
outcomes of two important propositions using beverage industry
wastewater for biohydrogen production. An improvement in the
hydrogen yield was achieved by utilizing heat-pretreated sludge
(80
C, 30 min) together with the addition of tryptone and yeast
extract.
Hafez et al. (2009) performed pilot scale reactor studies and
tested the thermal pretreatment of corn-syrup waste at 37
C, a
hydraulic retention time (HRT) of 8 h and a solids retention time
(SRT) ranging from 2.2 to 2.5 days. The results showed that the
hydrogen production rate increased to 34 L H2/L$d from an initial
rate of 10 L H2/L$d, when the organic loading rate (OLR) was
increased from 26 to 81 g COD/L$d, and a maximum hydrogen yield
of 430 mL H2/g COD was obtained. However, third-generation
172 D. Prabakar et al. / Journal of Environmental Management 218 (2018) 165e180
Table 3
Various industrial wastewater and their pretreatment methods used for the production of biomethane and biohydrogen.
S. Type of Wastewater treated Pretreatment method
No
1. Corn syrup waste Thermal pretreatment
2. Pulp and paper sludge Biological method using mushroom compost
extracts (MCE)
3. Textile wastewater Activated carbon
4. Sunflower oil cake Dilute acid pretreatment
5. Algal strains (Chlorella & Nanochloropis) in Thermo e chemical
wastewater
6. Starch wastewater Dark photo fermentation
7. Waste activated sludge Hydrolyses & acidogenesis (Co-digestion)
technology of using algae thriving in pretreated wastewaters has
been considered as an alternate energy resource for the production
of biohydrogen. Radha and Murugesan (2017) used the marine
macroalgae Padina tetrastromatica for chemically (acid and alka-
line) pretreated sewage sludge and reported a maximum hydrogen
production of 78 ± 2.9 mL/0.05 g VS which demonstrated the effi-
ciency of using a chemical pretreatment approach. These pre-
treatment processes offer a dual advantage of hydrogen production
while concomitantly treating the wastewaters in a cost-effective
and sustainable manner.
5.3.3. Bioethanol production
In the near future, the demand for bioethanol will increase due
to its versatile characteristics as a non-renewable source of energy.
However, adhering to an approach of not depending on food-based
substrates but rather on industrial wastes, which reflect a rich
source of organic matter might prove to be advantageous in the
context of future renewable energy production (Sun and Cheng,
2005). Several industrial wastes have been exploited, one among
them is the olive mill wastewater (OMW) which comprises of a
mixture of soluble and insoluble carbohydrates capable of being
used by a wide range of microorganisms for fuel production. In a
study by Massadeh and Modallal (2008), ethanol production as
high as 14.2 g/L was attained subjective to the pretreatment of
OMW with P. sajor-caju (a “white rot” basidiomycete fungus). Ac-
cording to the results obtained, the bioconverted OMW by P. sajor-
caju appears to be a promising substrate for facilitating bioethanol
production. Besides, an investigation on the utilization of dextran
wastewater for ethanol production by Zymomonasmobilis was
performed by He et al. (2014). The authors tested a batch fermen-
tation system and after 24 h of fermentation, ~24e29 g/L of ethanol,
equating to 99% of the theoretical yield was observed, while a semi-
continuous system yielded ~28 g/L of ethanol, after 48 h
fermentation.
Further, a comparative study by Khoja et al. (2015) was carried
out to investigate the fermentative bioethanol production effi-
ciency of Zymomonas mobilis and Saccharomyces cerevisiae using
sugarcane molasses as the substrate. It was concluded that
S. cerevisiae produced 8.3% (v/v) bioethanol at a sugar concentration
of 14 g/100 mL with a fermentation efficiency of ~92%. In contrast,
Z. mobilis exhibited a slightly higher yield of 9.3% (v/v) bioethanol at
16 g/100 mL sugar and ~90% fermentation efficiency. Recently,
Bashiri et al. (2016) examined ethanol production using waste
sludge produced from anaerobic digestion. The waste sludge was
subjected to several pretreatments (mechanical, chemical, thermal,
and thermo-chemical) and the result indicated that the yield of
ethanol using alkaline pretreatment improved the ethanol pro-
duction by 43% compared to that of untreated sludge which
Methane yield increase Hydrogen production References
(in %) obtained
e 430 mL H2/g COD Hafez et al., 2009
134.2% increase that of e Yunqin et al.,
control 2010
e 1.37 mol H2/mol hexose Li et al., 2012a,b
50% yield e Monlau et al.,
2013
30% and 40% e Bohutskyi et al.,
respectively 2014
e 166.83 ± 27.79 mL H2/g Nasr et al., 2015
COD
24.6% increase than e Zhang et al.,
control 2017a
contributed to only 10% of the theoretical yield. The authors also
reported that, by removing the hydrolysate of alkaline treated
sludge, ~65% increase in ethanol production could be achieved and
the results demonstrate the competency of alkaline pretreatment
for industrial level applications.
Besides the advantages of biofuels, studies have also highlighted
the challenges in the large-scale production of biofuels. From a
practical view-point, two key factors involved in ethanol produc-
tion process are the cost of feed and the process energy re-
quirements. Hence, there exists the need to hone the traits of
different pretreatment approaches to develop cost-effective tech-
nology for sustainable ethanol production.
6. Pretreatment and types of industrial effluents
6.1. Pretreatment - paper and pulp effluents
The pulp and paper industry is one of the major taxpaying in-
dustries owing to the high rate of pollutants discharge to the
environment. This is also attributed to the fact that these industries
are the largest consumers of power and natural resources (De los
Santos Ramos et al., 2009; Garg et al., 2005). These industries are
known to consume large amount of fresh water for the production
of different products and the various unit operations also generates
large amount of wastewater. The wastewater generated from paper
and pulp industries contains lignin, polyphenols, cyanide, chlori-
nated organic compounds along with other aromatic compounds
(Jaafarzadeh et al., 2017). Due to the complex structure of the
contaminants, biodegradation of wastewater generated from these
industries is inefficient. The toxicity and complexity of contami-
nants make the treatment of wastewater highly priced and less
efficient. Hence, in order to bring down the cost and toxicity levels
of the wastewater stream and to avoid detrimental effects on the
environment as well as life forms, more effective and suitable
pretreatment methods need to be adopted.
More recently, wastewater treatment of contaminants from
paper and pulp industries using a UV/oxidant system was studied
by incorporating electrocoagulation (EC) as a pretreatment
method (Jaafarzadeh et al., 2016). As a sole chemical process was
not efficient to treat paper and pulp wastewater due to its
complex constituents, the integration of EC and a UV/oxidation
system was tested by the authors. Accordingly, the results
showed that the BOD5/COD ratio decreased after the stand-alone
EC step, while ECþUV/PMS raised the biodegradability to 0.46
although the COD removal was only 50%. Nevertheless, 100%
removal of total suspended solids (TSS) was obtained rendering
EC as an advantageous pretreatment method. In another study by
the same authors (Jaafarzadeh et al., 2017), a unique approach
 D. Prabakar et al. / Journal of Environmental Management 218 (2018) 165e180
including permanganate (PM) oxidation/coagulation as a pre-
treatment for electro-Fenton (EF) process and a subsequent sul-
fate radical (SR)-based process (Co3O4/peroxymonosulfate/UV)
was proposed. The sequence of PMþEFþSR yielded a COD
reduction of 96%, whereas the binary system of EF and PM
showed the highest biodegradability as seen from an increase in
the BOD5/COD ratio from 0.24 to 0.52. Moreover, phytotoxicity
analysis was carried out for the final effluent from PMþEFþSR to
estimate the toxic effect on several plant species, namely cress,
lettuce, tomato and radish and the germination index values of
44.7%, 61.4%, 73.1% and 70.2% showed that the treated effluents
were non-toxic for plant growth.
Zazouli et al. (2017) reported 92% COD removal together with
complete color removal (100%) when EC (Fe electrode) was used as
the pretreatment method for effluent from a paper recycling plant.
The authors concluded that the efficiency of the pretreated
wastewater increased with increasing pH, duration time and
applied voltage. Hence, irrespective of adopting an integrated
approach or an individual pretreatment strategy, both can yield
instrumental outcomes facilitating subsequent wastewater treat-
ment systems and established environmental standards. Never-
theless, the expense of attaining such favorable results from
adopting suitable pretreatment methods, indubitably needs to be
taken into account during scale-up for field applications.
6.2. Pretreatment - wastes from coal combustion
One of the largest players in the generation of power is the coal
industry. It is not only highly valued for its initiation of energy but it
is also beneficial in the construction sector by aiding cement pro-
duction. Yet, the solid and liquid wastes that ensue as a result of
mining and burning of coal causes adverse effects to the environ-
ment (Li et al., 2015). Of the very many harmful pollutants emitted
from coal mining, fly ash which is produced along with flue gas
during the combustion of coal is highly predominant. It is generally
disposed into landfills and ash ponds which in turn requires large
land area and renders the lands barren. With the view of effectively
reusing the fly ash, extensive studies have been conducted for the
implementation of an effective pretreatment method to boost its
reusability (Blissett and Rowson, 2012).
The pretreatment of fly ash alters its physical and chemical
properties and makes it beneficial for reutilization. The presence of
H2O2 oxidizes As (III) to As (V) and improves the quality of solidified
product by lowering the leachability of As and other contaminants.
Wdowin et al. (2014) had postulated that fly ash pretreated with
NaOH and water at 80
C for 36 h could be utilized for the synthesis
of high purity (81%) Na-P1 zeolite. Another novel pretreatment
strategy for fly ash with CaO was investigated by Dermatas and
Meng (2003). The authors evidently noticed that the increase in
pH formed calcium aluminosilicate hydrates, which has application
in immobilizing Pb, trivalent and hexavalent chromium.
Anew, wastewaters from industries availing coal are contami-
nated with high concentrations of ammonia, cyanides, phenolics
and polycyclic aromatic hydrocarbons. To effectively remove such
pollutants an advanced oxidation method portrays as a promising
pretreatment technology. In this regard, Monteagudo et al. (2004)
conducted experiments to eliminate cyanides present in thermo-
electric power station wastewater via ozonation at basic pH, ozone/
hydrogen peroxide, ozone/ultraviolet radiation and ozone/
hydrogen peroxide/ultraviolet radiation. In comparison to a com-
bination of ozonation with other pretreatment techniques, ozone
with hydrogen peroxide resulted in the highest cyanide degrada-
tion of 20.58  102 M. The other pretreatment method that has
been widely utilized for coal industry wastewater is adsorption (Li
et al., 2015).
173
Xu et al. (2015) conducted laboratory scale experiments on
biologically treated coal gasification wastewater (CGW). The au-
thors reported that the fusion of heterogeneous Fenton oxidation
(HFO) with an anoxic moving bed biofilm reactor (ANMBBR) and
biological aerated filter (BAF) along with FeOx/SBAC (sludge based
activated carbon) as the catalyst was effective in eliminating the
toxic substances from biologically treated CGW. Zhuang et al.
(2016) recommended a more efficient and cost-effective method
by integrating Fe3O4MNPs/RSAC (recycled rice straw was converted
into an activated carbon support for nano-scaled Fe3O4) as a cata-
lyst for Fenton oxidation pretreatment of real coal gasification
wastewater. The results from their study showed that, COD and
total phenols (TPh) removal efficiencies as high as 93% and 98%
could be achieved by integrating Fenton oxidation and the bio-
logical wastewater process.
Recently, Liu et al. (2017) utilized a biopolymeric flocculant
extracted from potato residues (BFPR) to eliminate coal fly ashes
from ash-flushing wastewater to enable its reuse. The results
demonstrated ~93% flocculating activity when only 8.3 mg/L of the
flocculant was added. Comparably, aluminum-based coagulants
have also been experimented for their ability to remove dissolved
species from coal seam water (Lin et al., 2017). Zhu et al. (2017)
examined a catalytic ozonation method using Nano-MgO as a
pretreatment step in order to enhance the biodegradability of coal
gasification wastewater. There was a significant increase in the
BOD5/COD ratio from 0.071 to 0.374 within 60 min of the catalytic
ozonation process and this increase was attributed to the nano-
MgO enhancement of ozone decomposition into hydroxyl radi-
cals. In practice, the toxicity of fly ash and coal industrial waste-
waters can also be reduced by using different pretreatment
methods. Such pretreated wastes have proven benefits for the
synthesis and recovery of essential industrial elements. However,
since majority of the studies have been carried out only at the
laboratory or pilot scale, venturing into research mimicking the
large-scale effects of such pretreatment methods would present a
more advantageous front by attenuating environmental concerns.
6.3. Pretreatments - petrochemical outlets
Terephthalic acid (TPA) wastewater contains toxic compounds
such as terephthalic acid, acetic acid and benzoic acid in decreasing
order of concentration. Pophali et al. (2007) had proposed an
anaerobic-aerobic treatment as a replacement to a two-stage acti-
vated sludge process (ASP). The pretreatment of TPA effluent using
an upflow anaerobic fixed film fixed bed reactor exhibited lower
levels of BOD (63%) and COD (62%) and rendered a high settling
sludge, unlike the two-stage ASP.
Verma et al. (2014) studied the kinetics of adsorption and
thermodynamic features of COD removal from acid pretreated TPA
wastewater by granular activated carbon (GAC). The filtrate
collected as a result of acid precipitation using 1N H2SO4 was used
for analysis and a higher COD reduction of 83% was achieved in
comparison to untreated effluent (64%), together with >99%
removal of benzoic acid and terephthalic acid, respectively. Like-
wise, electrochemical degradation for the removal of benzoic acid
(BA) and terephthalic acid (TPA) from acid pretreated (1N H2SO4)
synthetic binary solution of TPA wastewater was studied by
Sandhwar and Prasad (2017). The results showed that the Electro-
Fenton technique depicted higher removal efficiencies of 80% of
BA, 76% of TPA and 73% of COD, respectively, with lower energy
consumption (~20 kWh/kg COD removed) in comparison to the
electrochemical oxidation method (70%, 68% and 67% and ~31 kWh/
kg COD removed).
Furthermore, several studies have also reported coagulation-
flocculation as a pretreatment method to reduce the toxicity
174 D. Prabakar et al. / Journal of Environmental Management 218 (2018) 165e180
levels of petrochemical industry wastewater (Santo et al., 2012;
Wang et al., 2014). The effect of various coagulants as a pretreat-
ment for purified TPA wastewater was analyzed and the sludge
settling characteristics were determined (Verma et al., 2010). It was
found that ferric chloride was the most efficient, with a COD
removal of 75%, and the addition of cationic polyacrylamide pro-
duced sludge with good settling and filtration characteristics. In a
similar study, Zheng et al. (2014) tested the removal of acrylonitrile
from petrochemical discharge using three inorganic coagulants and
three polymer coagulants. It was found that a combination of pol-
yaluminum chloride and cationic polyacrylamide (PACþCPAM)
depicted turbidity removal efficiency as high as 91% at a dosage of
310e390 mg/L for the six individual coagulants considered. This
opens the possibility of exploring a combination of polymers with
conventional inorganic coagulants for the pretreatment of petro-
leum industry effluents.
Moreover, the existence of inorganic and organic materials in
petrochemical wastewater contributes to membrane fouling
(Lujan-Facundo et al., 2017; Romero-Dondiz et al., 2016). To over-
come this, the most commonly used membrane pretreatment
technologies (granulated activated carbon filtration (GAC), ultra-
filtration (UF), nanofiltration (NF) and GACþNF) were experi-
mented by the authors for its ability to provide suitable feed for
reverse osmosis (Benito-Alc azar et al., 2010). The results showed
that a combination of GACþNF did not incur significant changes as
depicted by the nearly similar silt density index (SDI) values of 0.5
for NF permeate and 0.7 for GACþNF permeate, respectively.
Similarly, Vincent Vela et al. (2014) tested the suitability of
coagulation-flocculation, microfiltration and ultrafiltration as pre-
treatment steps for reverse osmosis. The authors reported that the
coagulation-flocculation process integrated with UF achieved high
reduction levels of turbidity, suspended solids (SS) and COD. In a
recent study, a pilot scale micro-flocculation and dynas and filtra-
tion process was tested for the pretreatment of secondary effluents
and it was reported that hydrophobic neutrals and hydrophobic
acids could be removed from the dissolved organic matter, with SS
removal efficiencies as high as 51% (Wu et al., 2017b).
The AOP is another widely studied pretreatment method for
petrochemical effluents. A combined Fenton oxidation process and
a composite magnetic nanoparticle catalyst was tested by
Kakavandi and Babaei (2016), wherein the magnetic nanoparticle
was coated onto activated carbon and in the presence of H2O2 and
its influence on the Fenton reaction for COD reduction (~65%) from
petrochemical wastewater was analyzed. Sponza and Oztekin
(2010a) tested the application of ultrasonication as a pretreat-
ment method for petrochemical effluents. After 150 min of soni-
cation, 97% total poly aromatic hydrocarbon (PAH) removal was
obtained and the use of titanium dioxide and ferric ions did not
have any influence on PAH removal. The authors also studied the
effects of NaCl administration on the degradation of seven PAHs
commonly present in petrochemical industry wastewater (Sponza
and Oztekin, 2010b). The results showed an increase in the
removal efficiency of all the PAHs from 72-78% to 97e99% when the
NaCl concentration was increased from 1.5 to 12 g/L. The same
authors had also analyzed the effect of ultrasonic irradiation on the
treatment of PAHs from a petrochemical industry wastewater
(Sponza and Oztekin, 2011). Accordingly, a maximum removal of
98% at 60
C in the absence of DO, N2(g) and TiO2 was observed. In
all cases, the mechanism of removal was attributed to OH and
pyrolysis for less hydrophobic and more hydrophobic PAHs.
A comprehensive list of various pretreatment methods tested
for the treatment of petrochemical wastes is shown in Table 4.
These include photocatalytic degradation, thermolysis, ozonation
as well as the combination of one or two pretreatment methods
(Babaei and Ghanbari, 2016; Zhou et al., 2015; Punzi et al., 2015).
For instance, Ramteke and Gogate (2015) had coupled Fenton and
ultrasound methods under stirring conditions for the treatment of
wastewater containing benzene, toluene, naphthalene and o-
xylene. The biodegradability index showed a slight increase from
0.17 to ~0.39, within 40 min of treatment. More recently, bio-
methane generation from petrochemical wastewater was per-
formed with the incorporation of both ultrasonic and microwave
pretreatment (Siddique et al., 2017). It was found that the ultrasonic
and microwave sludge pretreatments raised the methane yields by
25% and 53%, respectively. Thus, the advantages of pretreating
petrochemical wastes and the ability to increase methane yields,
i.e. under optimized process conditions, unveil their potential for
renewable energy production in industrial situations.
6.4. Pretreatments - textile industrial effluents
The main challenge in treating the textile effluent is the decol-
ourization of the wastewater. Various strategies for pretreating the
effluents from textile industry have been reported in the literature.
Punzi et al. (2015) biologically treated textile effluents by ozonation
which effectively reduced the COD, UV absorbance and also the
toxicity, specifically towards Artemiasalina and Vibrio fischeri,
respectively. This method also reduced the mutagenicity after long
exposure to ozone.
Similarly, the impact of ozonation on the toxicity and biode-
gradability of industrial textile wastewater was studied by Pa zdzior
et al. (2017). Tests were conducted using two reactor configurations
namely, the sequencing batch reactor (SBR) and the horizontal
continuous flow bioreactor (HCFB), among which the latter
demonstrated higher toxicity reduction of 98%. In another study
using ozonation as the pretreatment step for solutions containing
the azo dye Reactive Orange 16 (RO16), 97% color removal and a
COD reduction of 93% was achieved (Castro et al., 2017). Coagula-
tion/flocculation (C-F) as a pretreatment method was studied by
Golob et al. (2005) for the decolourization of residual dye bath ef-
fluents using reactive and acid dyes. It was found that a combina-
tion of Al2(SO4)3 and a cationic organic flocculant was effective for
the complete decolourization and reduction of total organic carbon
(TOC), COD, AOX, BOD and anionic surfactants.
Textile wastewaters are generated at high temperatures and the
presence of complex dyes renders them amenable to decolouriza-
tion under anaerobic conditions. A recent study by Verma et al.
(2015) proposed an effective strategy to overcome the issue by
using an upflow anaerobic sludge blanket (UASB) reactor as a
pretreatment step, resulting in 95% COD removal and 100% decol-
ourization. Wu et al. (2017b) reported that starch-graft-poly[(2-
methacryloyloxyethyl) trimethyl ammonium chloride] STC-g-
PDMC (a starch-based flocculant) with cationic branches had an
upper hand over starch-3-chloro-2-hydroxypropyl trimethyl
ammonium chloride (STC-CTA) and polyaluminum chloride (PAC)
owing to the efficient charge neutralization and bridging floccula-
tion effects of STC-g-PDMC. GilPavas et al. (2017) studied the
combination of C-F pretreatment and AOP (Fenton or Photo-
Fenton) and reported a 74% COD removal when C-F was used in
combination with the Fenton reagent and an even higher COD
removal of 87% was achieved when C-F was followed by a photo-
Fenton's process.
Furthermore, biological pretreatment of the effluents has been
extensively studied using different fungal strains. The white rot
fungi Pleurotus eryngii (Hadibarata et al., 2013), Coriolopsis sp. (Chen
and Yien Ting, 2015a) and Penicillium simplicissimum (Chen and
Yien Ting, 2015b) showed good degradation of naphthalene and
triphenylmethane dyes (Crystal Violet, CV), Methyl Violet (MV),
Cotton Blue (CB), Malachite Green (MG), respectively. However, it is
noteworthy to mention that the application of pretreated textile
 D. Prabakar et al. / Journal of Environmental Management 218 (2018) 165e180 175

Table 4
Various pretreatment methods used over the years pertaining to petrochemical effluents treatment.

S. Pretreatment method Type of petrochemical effluent treated References

No

1. Ozonation and biological activated carbon advanced treatment Phenol, benzoic acid, aminobenzoic acid and acrylonitrile butadiene styrene Lin et al., 2001
system (ABS)
2. Electro-Fenton process Organic acids, epoxidized soybean oil, poly-vinyl-alcohol and hexamethylene Ting et al., 2007
tetramine
3. Continuous sedimentation, demulsification and flotation Super viscous oil refinery wastewater Chen et al., 2007
separation
4. Photo-degradation Petroleum hydrocarbons, dichloromethane, dichloroethane, t-butyl methyl Stepnowski et al.,
ether 2002
5. Oxidation by H2O2 Petrochemical wastewater Siddique et al., 2014
6. Electrochemical method using three-dimensional electrode Heavy oil refinery wastewater Wei et al., 2010
reactor
7. Polyelectrolyte-modified ordered nanoporous carbon Aromatic compounds present in purified terephthalic acid wastewater Anbia and Salehi,
(sorption) 2012
8. White rot fungus Pleurotusostreatus 2-naphthalenesulfonic acid polymers Palli et al., 2014
9. Coagulation-flocculation Wastewater reused by reverse osmosis in a petrochemical circulating cooling Wang et al., 2014
water system
10. Hydrolysis acidification anoxiceoxic (A/O) process Mixed wastewater from a petrochemical industrial park Wu et al., 2016
11. Combined application of fungi and bacteria 2-naphthalensulphonic acid polymers Gullotto et al., 2015
12. Electro-coagulation process Purified terephthalic acid wastewater Garg et al., 2014
13. Anaerobic biofilm reactor and nitrification reactor Acrylonitrile wastewater Dong et al., 2017
14. Fe2þ-BAF and ozonation Organic micro pollutants and phosphorus removal in petrochemical secondary Wu et al., 2017a
effluent
15. Catalytic ozonation using synthesized carbon impregnated by High saline petrochemical wastewater Ahmadi et al., 2017
iron oxide

wastewaters are not restricted only to the reduction of toxicity but
it finds advantages in other fields as well. In this context, an
interesting application for the reutilization of textile waste sludge
for producing concrete blocks with a lime-based pretreatment step
was reported by Zhan and Poon (2015). The results of that study
showed that the lime-based pretreatment process could diminish
the ammonia concentration in the sludge and ultimately enhance
the compressive strength and volume stability of the concrete
blocks. Hence, delving into studies to explore the practical appli-
cation of pretreated textile wastewater could aid in reducing
environmental concerns with an added edge.
6.5. Pretreatments - pharmaceutical industrial effluents
The presence of pharmaceutical residues degrades the quality of
water environment and more importantly has fatal effects on living
organisms. The main reason for the prevalence of toxic pollutants in
the environment can be ascribed to the inefficiency of the con-
ventional wastewater treatment plants (Wang and Wang, 2016).
Hence, the use of proper pretreatment methods for pharmaceutical
wastewater might yield beneficial outcomes.
Fenton oxidation as a pretreatment method has been tested for
the refinement of coking wastewater, a common effluent from the
pharmaceutical industries that is rich in pyridine and quinoline
(two predominant N-heterocyclic aromatic compounds). A study
by Adishkumar et al. (2012) showed effective biodegradability of a
solar-photon pretreatment of pharmaceutical wastewater. After
optimization of the pretreatment step (pH - 3.0, H2O2 - 5 g/L, Fe2þ -
1 g/L and irradiation time - 60 min) followed by SBR operation, high
COD removal of 98% and an increase in the BOD5/COD ratio from
0.015 to 0.54 was achieved. Xue et al. (2017) proposed the inte-
gration of magnetically immobilized cells of strain JB(strain JB) and
an Electro-Fenton process and showed that the integrated
approach improved the breakdown of phenol, pyridine, and qui-
nolone, respectively. According to the authors, high removal rates
for phenol (92%), pyridine (80%), quinoline (77%), and COD (76%)
was obtained and with an increase in the treatment cycles, com-
plete degradation of the contaminants was achieved. In another
recent study, Zhang et al. (2017b) tested Fenton iron mud (mud rich
in Fe3þ ion) as the main raw material of cathodic-anodic-
electrolysis ceramic granular fillers (ICMF) in a continuous
reactor, to pretreat oxytetracycline (OTC) wastewater. This system
showed a higher stability and good removal efficiency of TOC (80%)
and OTC (98%) under optimal conditions (pH - 3.0, HRT - 4 h,
anaerobic). According to the authors, even after 60 days of opera-
tion, the TOC removal efficiency was stable and the ICMF did not
become hard.
Ozonation is the most contemplated oxidation process that has
demonstrated high removal efficiencies for pharmaceutical resi-
dues (Espejo et al., 2014). A recent study by Almomani et al. (2016)
adopted ozonation as a pretreatment step and it was demonstrated
that the efficiency of oxidizing the antibiotics, estrogens, and
neutral pharmaceuticals present in the discharge was directly
proportional to the ozone dosage. The results showed that, within
1 min, DOC reductions of 40%, 33%, and 23% could be achieved at an
ozone dosage of 2.05 for antibiotics, 1.11 for estrogens, and 1.30 mg
O3/mg DOC for neutral pharmaceuticals, respectively. In another
study by Khan et al. (2016), the effectiveness of using a catalyst for
the photodegradation of real pharmaceutical wastewater was
tested. Among the three catalysts (titanium dioxide, zinc oxide, and
TiO2/H2O2) tested in that study, maximum degradation (45%) was
achieved by the combined use of TiO2 and H2O2. This provides a
platform to study several combinations of catalysts which is likely
to promote the degradation of toxic elements.

Alvarez-Gallego et al. (2015) pretreated a highly polluted
fermentation broth by wet air oxidation to enhance its biode-
gradability and reduce the toxicity levels. It was observed that the
DOC was reduced by 63 and 80%, at 240 and 280
C, respectively.
Besides, the biodegradability of the sample broth increased from 63
to 88% together with the reduction in toxicity that was evident from
the Vibrio fischeri tests. However, the fact that the treatments were
carried out using diluted substrates (2% v/v) might affect the
viability of wet air oxidation for full-scale applications.
An interesting study on the pretreatment of tetracycline
wastewater (TET-WW) by reformed sintering ferric-carbon ce-
ramics (SFC) and sintering-free ferric-carbon ceramics (SFFC) based
176 D. Prabakar et al. / Journal of Environmental Management 218 (2018) 165e180
on coal ash and scrap iron was presented by Yang et al. (2017).
According to the results obtained from that study, SFC and SFFC
significantly enhanced the biodegradability of TET effluents using
micro-electrolysis reactors. In a recent study, Jin et al. (2017) treated
pyridine wastewater that consisted mainly of 4,40 -diamino-2,20 -
disulfonic acid (DSD acid) industrial iron sludge using cathodic-
anodic-electrolysis packing (CAEP) in a column reactor. The au-
thors tested the reduction of TOC and pyridine under the influence
of different pH, HRT, air-liquid ratio (A/L) and initial concentration
of pyridine. The removal of TOC and pyridine were 50% and 58%,
respectively, at the optimal experimental conditions (pH - 3.0, HRT
- 8 h, A/L - 2). Moreover, the CAEP was stable and the packing was
not hardened even after 3 months of reactor operation.
In addition, the dissolved organic nitrogen (DON) as a surrogate
of dissolved organic matter (DOM) demands recognition, especially
when dealing with pharmaceutical wastes. Hu et al. (2017) studied
the reduction of DON and its effects on the N-nitrosodimethyl-
amine formation potential (NDMA FP) during the treatment of
pharmaceutical wastewater and its subsequent impact on the acute
toxicity of DOM in a full-scale hydrolysis/acidification þ anaerobic/
Fig. 3. Proposed outline of wastewater treatment plant incorporated with pretreatment method in an individual or integrated route.
anoxic/aerobic þ moving bed biofilm reactor (MBBR) process.
Although the maximum DON removal was only 68%, analyzing the
DON levels in pharmaceutical wastewater is vital owing to its in-
fluence on the reduction of DOM. Evidently, the composition of
pharmaceutical wastewater is complex encompassing high con-
centrations of organic matter, microbial toxicity, high salt content
and is extremely difficult to degrade. In addition, since most of the
pharmaceutical industries adhere to a batch mode of operation
there exists a concoction of several substances in the discharge
which demands advanced treatment methods for removal. Hence,
through the rational use of various methods, one could effectively
improve the quality of pharmaceutical wastewater effluents.
7. Scope and suggestions
At the industrial scale, the pretreatment of industrial effluents
has opened up a new arena which equates to solving problems
related to waste disposal as well as resource depletion. For process
scale-up, integration and intensification, it is important to explore
certain aspects prior to delving into large-scale implementation of
 D. Prabakar et al. / Journal of Environmental Management 218 (2018) 165e180
any selected pretreatment technology. Primary focus should be
placed on eliminating the trace amounts of secondary pollutants
that might have been generated as a result of the pretreatment step.
Moreover, setting up reactors with built-in pretreatment technol-
ogies would contribute to high efficiency at low costs. On a more
extended note, the design of a wastewater plant receiving wastes
from several industries (via interlinking systems) would reduce the
costs involved in construction of multiple individual pretreatment
units. A suggested wastewater treatment plant outline comprising
of treating complex wastes from various industries with benefits of
energy generation has been shown in Fig. 3. In addition, such an
approach adds to an augmented renewable energy generation
(such as biohydrogen and biomethane) which can be directly
injected into existing power grids.
8. Conclusion
The potential benefits of using different pretreatment technol-
ogies is evident from their numerous applications. However, in
order to transcend from the laboratory to the industrial scale, the
optimization of process parameters is of significant importance.
Besides, it can be deduced that certain discrepancies might arise
despite the incorporation of pretreatment methods for the refine-
ment of wastewater. This could be addressed by prior under-
standing of the nature of the effluent and its characteristics.
Thereby, a battery of tests with several combinations of pretreat-
ment approaches needs to be conducted prior to scale up. More-
over, apart from the advantages offered by pretreatment
technologies in bioenergy generation, it is essential to fine-tune the
process of production to achieve zero liquid discharge. It is there-
fore suggested that a shift in focus from greener industrial effluents
such as agricultural sectors, towards the core industries such as
paper and pulp mills, coal manufacturing units, petrochemical,
textile and the pharmaceutical industries would positively
diminish the thriving environmental concerns.
Acknowledgments
This work was supported by the Korea Research Fellowship
Program through the National Research Foundation of Korea (NRF)
funded by the Ministry of Science and ICT (Grant No:
2016H1D3A1908953).
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