Water Research 135 (2018) 262e277

Contents lists available at ScienceDirect

Water Research
journal homepage: www.elsevier.com/locate/watres

A review of bio-based materials for oil spill treatment

Bhairavi Doshi a, *, Mika Sillanpa
€a€ a, b, Simo Kalliola a
a
Laboratory of Green Chemistry, Lappeenranta University of Technology, Sammonkatu 12, Mikkeli, 50130, Finland
b
Department of Civil and Environmental Engineering, Florida International University, Miami, FL, 33174, USA

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

Article history: Being cost-effective, synthetic materials were initially used abundantly for the removal of oil. Gradually,
Available online 15 February 2018 however, awareness of the use of dispersants like Corexit, which makes water resources more toxic than
oil, has changed the scenario for the treatment of spilled oil. The removal of spilled oil from water re-
Keywords: sources is still a very topical issue. An eco-friendly and sustainable approach towards the environment
Oil spill has introduced many low-cost, non-toxic and biodegradable materials along with different biomasses to
Sorbent
make micro-to nano-sized materials, membranes, sponges/aerogel, etc. for the removal and recovery of
Particle
oil from water resources. Additionally, the reusability of these materials after the recovery of oils has
Surfactant
Aerogel
added one more step towards sustainability. This review comprises the work conducted by various re-
Gelator searchers in the field of the removal and recovery of spilled oils using various biomasses and polymers,
Separator either in the form of sorbents or separators.
© 2018 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND
license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 262
2. Statistical trend of sorbents used in oil spill response . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
3. Materials for oil removal, dispersion and biodegradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264
3.1. Biomass sorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264
3.2. Particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
3.3. Surfactants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 267
4. Materials for oil recovery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 269
4.1. Conventional sorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 269
4.2. Separators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 270
4.3. Aerogels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 271
4.4. Gelators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 273
5. Outlook and challenges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 274
6. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 275
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 275
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 275

1. Introduction from industry, dumping, or oil spills (NOAA, 2017a). An oil spill is
the accidental or intentional discharge of petroleum hydrocarbons
Currently, the challenge is to clean water resources, which are into the environment, especially the marine ecosystem. An oil spill
being polluted by oil either in the form of routine shipping, run-offs on water can be transported by wind and current, and the
distributed oil either evaporates or forms a surface slick, disperses
in water, or submerges and accumulates in the sediments (Reddy
et al., 2002; Liu et al., 2012). Additionally, temperature, salinity,
* Corresponding author.
E-mail address: Bhairavi.doshi@lut.fi (B. Doshi).
and waves also increase oil transportation and weathering rates.

https://doi.org/10.1016/j.watres.2018.02.034
0043-1354/© 2018 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
 B. Doshi et al. / Water Research 135 (2018) 262e277
Moreover, oil spill from tankers such as Exxon Valdex in 1987 (11
million gallons) (Carson et al., 2003) and Deep Horizon in 2010 (4.9
million barrels) (Brody et al., 2010) were marked as the greatest
disasters for the marine environment. Since most oils float on the
water surface, seabirds and marine animals are mainly affected
(Barron, 2012), and other creatures and terrestrial animals are
harmed if the oil comes ashore (Brody et al., 2010). Such spilled oils
also affect humans through inhalation, skin and eye irritation.
Many researchers have reviewed the aspects and impacts of these
spills on the ecosystem over time (Jernelo €v, 2010; Henkel et al.,
2012; Chang et al., 2014) and developed various methods and
chemicals for oil spill response (Michel et al., 1992; ITOPF, 2014a).
However, the spill intensity and location determine the clean-up
technology that needs to be applied.
Oil spill treatment methods can be classified as physical/me-
chanical, chemical, or biological (EPA, 2017). Physical/mechanical
methods include booms that are stationary floating devices to
prevent the movement of the oil slick. Using high-temperature
booms enables the burning of the oil in-situ (Evans et al., 2001;
Fingas, 2011; IOGP, 2016). Skimmers are stationary or mobile de-
vices, that were used to remove floating and/or emulsified oil from
the water surface (Michel et al., 1992). Hydrophobic meshes that
repel water but allow oil to pass through can be utilized in skim-
mers for enhanced oil recovery. Chemical methods include dis-
persants (IPIECA, 2001; ITOPF, 2014b; Graham et al., 2016) sprayed
on the oil spill to break it up into small droplets (NOAA, 2017b). In
addition, sorbent materials may be used in small-scale oil spills.
Biological methods include the addition of microbes and/or nutri-
ents and/or oxygen to stimulate bacterial growth and the resultant
biodegradation of the spilled oil (Azubuike et al., 2016). However,
physiochemical methods have limitations in terms of crude oil
clean-up, so recently biological methods have held sway (Das and
Preethy, 2011; Dave and Ghaly, 2011). However, the selection of
sorbent materials is dependent on the nature of the spilled oil (Teas
et al., 2001).
The rate at which oil can be treated in open waters depends on
the treatment method. Dispersants applied from aircrafts are the
fastest, followed by skimming and in-situ burning (Graham et al.,
2016). In addition, environmental conditions affect the perfor-
mance of the treatment methods, such as wind, currents, waves, oil
viscosity, and sensitivity to debris. The costs of different oil spill
treatment methods from the least to most expensive are as follows:
in-situ burning, dispersants, mechanical recovery, and manual
cleanup. Despite cost efficiency, in-situ burning generates many
particulates and carbon dioxide in the environment (Mullin and
Champ, 2003). Choosing the oil spill treatment method becomes
an optimization task by minimizing both the environmental impact
and cost of operation. Local jurisdiction also affects costs, due to
possible fines based on the amount of spilled oil, which limits the
oil spill. However, some treatment methods leave the oil in the
environment, so it may still cause damage to the ecosystem. It was
therefore suggested to impose fines based only on the amount of oil
left in the environment. In other words, recovering the spilled oil
would decrease the amount of the fine. This kind of jurisdiction
could make recovery methods more economically viable, depend-
ing on the scale of the fine and the oil spill scenario (Prendergast
and Gschwend, 2014).
Most of the materials reviewed in this paper aim to either
recover spilled oil or enhance the biodegradation of the oil. The best
solution in the case of an oil spill depends on numerous factors, and
the optimal solution from environmental and economic points of
view might be a combination of several different methods. There-
fore, instead of classifying oil spill treatment methods based on
technical aspects, solution-based classification of oil recovery or oil
biodegradation is proposed. In the case of an oil spill, either the oil
263
must be left in the environment for biodegradation or it can be
recovered from the environment, and to achieve this there are
different technical methods and materials. Scheme 1 shows this
classification.
Existing dispersants/chemical herders are chemically stable, but
non-biodegradable so remain longer in the marine environment.
There is therefore a growing demand for green, facile and eco-
friendly, low-cost sorbents from biopolymers for the treatment of
oil spills and chemical leaks. In past few years, advanced materials
such as aerogels, foam membranes, inorganic meshes, and surface-
modified fabrics have been used extensively for the separation of
oil-water mixtures. Meanwhile, the increasing population rate has
increased the rate of food consumption, resulting in massive
amounts of bio-waste globally. For this reason, the wise way is to
use such easily biodegradable bio-waste or biomass to produce
low-cost sorbents with higher oil sorption capacity that are simple
to scale up for the cleanup of an oil spill, rather than hazardous
chemicals. This review addresses the potential and
environmentally-friendly bio-based materials in the form of sor-
bents, particles, gelators, surfactants and separators for oil spill
treatment. These kinds of bio-based materials have recently been
the subject of increasing interest in oil spill treatment applications,
and reviews have been published on specific materials or methods
(Sabir, 2015; Ifelebuegu and Johnson, 2017). The different materials
and methods for oil spill treatment are suitable for different kind of
conditions. For sustainable and effective oil spill treatment, bio-
based materials must be studied extensively, since one material is
unlikely to be suitable in all possible oil spill scenarios. Additionally,
local legislation has also affected the economic view of the mate-
rials, and method design must be considered. Legislation is subject
to changes due to increased environmental awareness, which has a
direct impact on oil spill treatment methods, so the utilization of
bio-based materials in different kind of oil spill treatment methods
and materials must be extensively studied and researched, in
response to different kinds of oil spill scenarios and possible future
legislation. This review highlights a wide range of different bio-
based oil spill treatment materials and methods along with their
strengths and weaknesses.
2. Statistical trend of sorbents used in oil spill response
The statistical trends based on the Scopus database of various
sorbents studied extensively in the past ten years are given below
(Fig. 1). This implies that more research is being conducted using
these materials as oil sorbents. Statistical data shows a continual
increment in the use of nanoparticles and aerogel for oil spill
treatment in the past few years.
Scheme 1. Oil spill treatment methods based on the oil recovery or oil dispersion.
264 B. Doshi et al. / Water Research 135 (2018) 262e277

600
materials such as lotus leaves are superhydrophobic but super-
hydrophobicity can be also introduced into an otherwise non-
500 superhydrophobic material by increasing the roughness of the
Annual publica ons

surface and decreasing the surface energy. An ideal sorbent for oil
400 aerogels sorption has high porosity and surface area, and is selective to oil.
300
sorbents For oil spill treatment applications, the sorbent should also be
gelators mechanically and chemically stable, recyclable, environmentally-
200 nanopar cles friendly, and have low density and good buoyancy properties
surfactants (Gupta and Tai, 2016).
100 Natural products, such as cotton, kapok, rice straw, etc. are
separators
abundant, low-cost, biodegradable, and non-toxic materials and
0
2007 2009 2011 2013 2015 2017 therefore ideal for oil sorption in oil spill treatment (Refer Table 1).
Year The downsides of such materials are poor hydrophobicity, buoy-
ancy, and sorption capacity (Maleki, 2016). There were a variety of
different kind of modifications to natural sorbent materials re-
Fig. 1. Annual publications including words “oil” AND “spill” AND “material” extracted ported in literature, which enhanced the properties of the materials
from Scopus.
such as hydrophobicity and sorption capacity. Ideally, the modifi-
cation should be minimal and should keep the good properties of
the native material while enhancing weaker properties i.e.
3. Materials for oil removal, dispersion and biodegradation
enhancing oil sorption and buoyancy while not altering the
biocompatibility of the materials. Moreover, the sorption capacity
3.1. Biomass sorbents
of the oleophilic sorbents prepared via bulk polymerization mainly
depends on the size and molecular weight of the polymer used.
In adsorption, sorbate molecules accumulate on the surface of
Increasing size from monomer to macromonomer increases the
the sorbent. In the case of oil adsorption, the oil molecules need to
cross-linked structure, but in turn decreases the swelling capacity
diffuse onto the sorbent surface, the oil molecules then entrapped
by blocking the penetration of organic solvents into polymer
in the sorbent due to capillary effects, and finally the oil droplets
network. On the other hand, the increasing molecular weight of the
agglomerate in the pores of the sorbent. Oil consists mainly of non-
dendric structure macromonomer also increase the hydrophobicity
polar hydrocarbons and their adsorption is attributed to physical
of the sorbent (Kizil and Sonmez, 2017).
non-covalent interactions such as van der Waals forces (Wahi et al.,
Cheaper and readily biodegradable plant biomass such as kapok
2013). However, for fibrous sorbent, only adsorption and capillary
fiber, cattail fiber, Salvinia sp., wood chip, rice husk, coconut husk
action processes take place. In this paper, the term ‘oil sorption’ is
and bagasse are used as inserts to remove oil from the storm water
used instead of oil adsorption, absorption, separation, or removal,
runoff of gas station effluent, with 70% greater oil removal capacity
since all these terms are used in literature when discussing oil
compared to synthetic polymer fiber sorbent, due to the presence
sorption on various materials. The differences have not usually
of ample void spaces in their loose fiber structure and hydropho-
been discussed in literature and one of the terms is used without
bicity (Khan et al., 2004). The bio-waste of rice (rice husk) contains
further rationalization. Therefore, to avoid confusion, in this paper
a large amount of silica. The pyrolysis of rice husk causes the
‘oil sorption’ refers to oil removal using sorbents.
decomposition of organic material and the breaking of bonds be-
Surface chemistry and morphology determine the wettability of
tween the silicon and organic material present in it. This enhances
the surface, which closely relates to the adsorption of oils. Water
the hydrophobicity of rice husk, which leads to the purification of
contact angle is used to measure wettability. If the contact angle of
crude oil (Vlaev et al., 2011). The adsorption of the oils shows a
a water droplet on a flat surface is less than 90
, it is characterized
direct dependency on granulometric composition i.e. weight ratio
as hydrophilic, if the contact angle is between 90
and 150
, it is
of C/SiO2 along with the bulk density, surface morphology and
characterized as hydrophobic, and if the contact angle is over 150
,
oleophilicity of the sorbent. However, an inverse dependency of
it is characterized as superhydrophobic (Fig. 2). Similar measure-
sorbent bulk density on the height of penetration of the oil in it
ments can be done for different kinds of oils, and the solid material
exists (Angelova et al., 2011). Moreover, alkaline treatment of rice
can be characterized as oleophilic, oleophobic, or superoleophobic,
husk produces lignocellulosic sorbent material by removing its
respectively. The hydrophobicity of the sorbent prevents water
silica, which enhances the adsorption capacity of the diesel. Such
sorption and therefore enhances the oil sorption capacity due to the
adsorbed oil along with the sorbent can be used as a solid fuel
lack of competition between water and oil molecules. Natural

Fig. 2. Wettability of water on the flat surface of the sorbent.

 B. Doshi et al. / Water Research 135 (2018) 262e277 265

Table 1
Biomass-based sorbent used for the degradation and removal of oils.

Sorbent Method Oils Sorption Capacity/ Ref.

Removal

Rice Husks White Ash (Pyrolysis) Diesel 5.02 g/g (Vlaev et al., 2011)
Crude Oil 6.22 g/g
Black Ash (Pyrolysis under N2 or inert atmosphere) Diesel 2.78 g/g
Crude Oil 2.98 g/g
Rice Husks Pyrolysis (Carbonized) at 480
C Gasoline 3.7 kg/kg (Angelova et al., 2011)
Diesel 5.5 kg/kg
Light crude oil 6.0 kg/kg
Motor oil 7.5 kg/kg
Heavy Crude oil 9.2 kg/kg
Rice Husks Alkaline treatment Marine diesel 19 g/g (Bazargan et al., 2014)


Silkworm cocoon waste Drying (110 C), Cutting, and Milling Motor oil 42e52 g/g (51%) (Moriwaki et al., 2009)
Vegetable oil 37e60 g/g (54%)
Banana skins Drying (sunlight and 70
C), crushing and Sieving Crude oil 5e7 g/g (Alaa El-Din et al., Article-In-Press)
Potato peel Drying (70
C) and Crushing Waste lubricating oil 2.15 g/g (Tontiwachwuthikul et al., 2016)
Luffa (an agricultural Cutting, Sieving, washing and drying (105
) Diesel Oil >85% (Abdelwahab, 2014)
waste) Heavy Crude Oil >50%
M.Rouxii (32.7% Chitosan) Shaking flask method, Autoclave and drying Mineral oil 77.2 mg/g (77%) (Srinivasan and Viraraghavan,
Vegetable oil 95.5 mg/g (93%) 2010)
Cutting Oil 84 mg/g (84%)
A.Coerulea (10.4% Chitosan) Mineral oil 72%
Vegetable oil 91%
Cutting Oil 80%
Hybrid peel waste (Banana Hybridization of peels with NaOH and drying at 70
C Lubricant oil 38% (Abdullah et al., 2016)
skins + orange peel) Petrol oil 32%
Walnut shells Media Mineral Oil 0.56 g/g (Srinivasan and Viraraghavan,
Vegetable oil 0.58 g/g 2008)
DoALL Bright-Edge 0.74 g/g
Oil

(Bazargan et al., 2014). Another low-cost sorbent obtained from
silkworm cocoon waste removes 30% more motor oil and vegetable
oil from marine water than natural wool fibers (Moriwaki et al.,
2009). Various fruit peels such as banana and orange, being rich
in cellulosic content, can remove heavy oil more effectively than
lighter oils (Abdullah et al., 2016; Alaa El-Din et al., Article-In-
Press). Similarly, Tontiwachwuthikul et al. show the effectiveness of
potato peel in the remediation of water from a waste-lubricating oil
spill (Tontiwachwuthikul et al., 2016). Cellulosic materials, being
fluffy and possessing low bulk density, show higher uptake of
marine fuel with less treatment. Macroporous agricultural waste
called Luffa with low bulk density removed more than 50% of crude
oil from water with good reusability (Abdelwahab, 2014).
3.2. Particles
Particle behavior in the presence of oil and water mainly
depends on its functional characteristics together with size and
porosity, which either undergoes emulsion and/or adsorption. In an
emulsion system, small-volume fraction is classified as dispersed
phase (oil) and larger as continuous phase (aqueous/water).
Strongly hydrophilic particles get wetted only by water and remain
dispersed in the aqueous phase of the emulsion whereas strongly
hydrophobic particles remain in the oil due to being wetted only by
the oil phase. The particle needs to be amphiphilic in order to
adsorb at the interface. Oil-in-water (o/w) emulsion is favorable
when the three-phased contact angle (CA) between the oil, solid
and water is < 90
, whereas water-in-oil (w/o) emulsion when CA
is > 90
(Aveyard et al., 2003). Moreover, adsorption-free energy is
at maximum when the CA is z 90
i.e. the particle is equally wetted
by both the aqueous and oil phases. In this case, other factors such
as the wettability of the particles, inter-particle interactions, etc.
must be considered, knowing the type of emulsion. Emulsions are
therefore stable, if particle adsorption and droplet stabilization by

Fig. 3. Oil dispersion/degradation using different types of particles.

266 B. Doshi et al. / Water Research 135 (2018) 262e277

those particles resist destabilization phenomena such as coagula-
tion and coalescence (Chevalier and Bolzinger, 2013). However, Lam
et al. in their work emphasized that stable emulsion has also been
observed with contact angles 20e120
(Lam et al., 2014). However,
the oil/water emulsion system separates, if the interfacial tension
(IFT) between these two phases increases. Moreover, interfacial
area had direct influence on resulting droplet size depending on
particle dosage, i.e. a lower number of particles creates a small
interfacial area and larger droplets, whereas a higher number of
particles forms fine emulsion with smaller droplets. Fig. 3 shows
the pictorial form of particles used in the destabilization of oils.
Generally, raw natural sorbents have excellent adsorption ca-
pacity, biodegradability and non-toxicity in comparison with syn-
thetic sorbents, but their low hydrophobicity increases water
uptake and lowers oil sorption capacity. Many researchers are
therefore working on the enhancement of oil sorption affinity
through various modifications or the addition of hydrophobic
moieties to these natural sorbents, as the functional group prop-
erties play a significant role in the adsorption of oils (Refer Table 2).
The addition of a hydrophobic chain on the biopolymer enhances
the tensile properties and thermal stability of the polymers (Amri
et al., 2011) and forms more stable emulsion due to its amphiphi-
licity (Doshi et al., 2018). However, by increasing the hydropho-
bicity, the particles get wetter in oil than in water, and form w/o
instead of o/w emulsion (Andresen and Stenius, 2007). On the
contrary, the formation of stable emulsions is feasible by switching
the pH rather than hydrophobic modification (Liu et al., 2012).
Pickering emulsions are emulsions stabilized by solid particles,
with similar properties to classical emulsions stabilized by surfac-
tant, which can be either o/w-, w/o- or multiple emulsions
(Chevalier and Bolzinger, 2013). Cellulose nanocrystals (CNC) ob-
tained using a deep eutectic solvent (DES) of choline chloride with
oxalic acid dihydrate, form emulsified creaming with marine diesel
through Pickering emulsions, which in the case of oil spill can be
easily skimmed (Laitinen et al., 2017a). Such particles forming
Pickering emulsions, are irreversibly adsorbed at the oil-water
interface and require high energy for desorption compared to
conventional surfactants. So, particles that carry thermo-
responsive polymers (copolymers) are used as stabilizers for o/w
Pickering emulsion, and the emulsions are destabilized by simple

Table 2
Different particles used in the formation of emulsions, removal and recovery of oils.

Particles Method Hydrophobic modification Oil Type of Emulsion/ Ref.

Adsorption capacity/
Recovery

Chitin Powder form Toluene 1.6 mg/g (Mohamed and

Chitosan 2.2 mg/g Ouki, 2011)
Chitosan Grafting using free radical n-butyl acrylate Gasoil ~45% (Mohy Eldin et al.,
polymerization Mobil-1 oil ~60% 2011)
Light crude oil ~75%
Heavy Crude oil ~80%
Oil palm leaves Blending and mixing Lauric acid Crude Oil 1.2 g/g (Sidik et al., 2012)
Carboxymethyl chitosan Partial monochloroacetic acid Marine Diesel Winsor o/w micro (Doshi et al., 2017)
(Micro-sized) Carboxymethylation (partial) Diesel emulsion (<100 mm)
Neste 2T oil
H-Oleoyl-Carboxymethyl chitosan Carboxymethylation and Oleoyl chloride Wastewater of oil >95% residual oil (Sun et al., 2010)
acylation extraction adsorption
Sodium salt of oleoyl carboxymethyl Carboxymethylation and Oleoyl chloride Marine Diesel o/w emulsion (Doshi et al., 2018)
chitosan acylation (30 mm);
(Micro-sized) 75e85% oil recovered
by CaCl2
Chitosan Microspheres Carboxymethylation and Sodium tripolyphosphate Oil in water effluents90% removal (Grem et al., 2013)
cross-linking of oil industry
Chitosan-silica hybrid (Nano-sized) Sol-gel encapsulation Tetraethyl orthosilicate, 3- Toluene, cyclohexane, >90% removal (Soares et al.,
(triethoxysilyl)propyl n-heptane, Chloroform 2017)
isocyanate
Cellulose nanocrystals (Nano-sized) Deep Eutectic Solvents Choline chloride and oxalic Marine Diesel Pickering Emulsion (Laitinen et al.,
acid dihydrate (<10 mm) 2017a)
Bifunctionalized cellulose (Nano-sized) Oxidation and Amination n-butylamine Marine Diesel o/w emulsion (<20 mm) (Ojala et al., 2016)
Blends of poly (vinyl alcohol) Emulsion polymerization Toluene 48.7 g/g (Fouad et al., 2016)
nanoparticles with chitosan or starch Kerosene 39.3 g/g
(Nano-sized) Hydraulic oil 22.7 g/g (Oil absorption)
Electrospun Polyvinyl Chloride/ Electrospinning Motor oil 146 g/g (Zhu et al., 2011)
Polystyrene Fibers (Nanofibers) peanut oil 119 g/g
diesel 38 g/g (Oil sorption)
Eugenol-Based Polymeric microspheres Suspension Polymerization Chloroform ~81 g/g (Deng et al., 2015)
and self-crosslinking Toluene ~75 g/g
Gasoline ~5 g/g
Diesel 31.7 g/g
Kerosene 33.8 g/g
Peanut Oil ~32 g/g (Oil absorption;
5 cycles)
Cellulose nanofibril and polyvinyl Emulsification and Freeze Span-80 Crude oil 54e140 g/g (Oil (Zhai et al., 2016)
alcohol (Aerogel microspheres) Drying absorption)
Polyvinylpyrrolidone-coated magnetite Hydrothermal Method MC252 oil ~100% (Magnetic oil (Mirshahghassemi
nanoparticles (Nano-Sized) sorption and and Lead, 2015)
separation)
Polystyrene coated magnetic hollow Hydrothermal synthesis lubricating oil ~100% (Magnetic oil (Chen et al., 2013)
Fe3O4 nanoparticles (Nano-Sized) and emulsion sorption and
polymerization separation)
 B. Doshi et al. / Water Research 135 (2018) 262e277
heating (Zoppe et al., 2012). Cellulose consists of long chains of
poly-b-(1 / 4)-D-glucosyl residues and these chains unite to form
long thread-like fibers known as microfibrils. Due to the hydro-
philic nature of fibrillated and micro-fibrillated cellulose (MFC),
wettability in water is more than that in oil, to form o/w emulsion.
Bifunctionalized cellulose rod-like nanocrystals (<120 nm in
length) obtained by oxidation of cellulose with sodium periodate
and chlorite followed by amination with n-butylamine, were
effectively used to stabilized oil-in-water (o/w) emulsion of up to
3.5% sea water salinity (Ojala et al., 2016).
Hydrophilic carboxymethyl chitosan (CMC) obtained from crab
shells destabilized Marine Diesel, Diesel and Marine-2T oil into
small droplets of <100 mm at sea water alkalinity and salinity (Doshi
et al., 2017). In a similar way, our previous work (Kalliola et al.,
2016) reflects the applicability of Caþ2 cross-linked CMC nano-
particles to stabilize dodecane in o/w emulsions. However, chitosan
flakes have superior adsorption properties to chitosan powder for
oil (Barros et al., 2014). Chitosan microspheres produced by ionic
gelation of chitosan with sodium tripolyphosphate (STP) separated
90% of the oil from oil industry effluents using packed columns
(Grem et al., 2013). On the other hand, polymeric microspheres
derived from eugenol suspension polymerization and self-
crosslinking showed higher adsorption of chloroform and toluene
than gasoline, diesel, and kerosene, as these lighter oils consists of
longer molecular chains, which adsorb on the surfaces of micro-
spheres and block further adsorption of small molecules (Deng
et al., 2015). Aerogel microspheres obtained from polyvinyl
alcohol (PVA) and cellulose nanofibril (CNF) exhibit outstanding oil/
solvent absorption capacities for floating oil cleanup (Zhai et al.,
2016).
Recently nano-particles and polymer-based blends have
appeared with better surface functionality and biodegradability in
comparison to other sorbents used for oil removal, along with
simple recovery and reusability (Fouad et al., 2016). Similarly,
another technique to produce continuous fibers ranging from
nanometers to micrometers in diameter is Electrospinning. Wang
et al. recently reviewed nanofibrous materials obtained by elec-
trospinning for oil/water separation (Wang et al., 2016). Nanofibers
obtained from polyvinyl chloride (PVC) and polystyrene through
blending electrospinning process, showed 5e9 times higher sorp-
tion capacity than commercial polypropylene for motor oil, peanut
oil and diesel, respectively, because of high porosity (Zhu et al.,
2011). For oil sorption, an appropriate size void is mandatory, and
can be determined by the viscosity and gravity of the oil, fiber
roughness and diameter together with the interfacial force be-
tween oil and water.
Nowadays, the removal of oil by magnetism is attracting
attention, as oil or emulsified oil can be easily separated from water
by an external magnetic field. In short, the adsorbed oil and par-
ticles are easily removed by the external magnetic field, once the
magnetic particles are completely wetted by the oil. Magnetic
hybrid nanoparticles in the absence and presence of chitosan
(Fe3O4@SiO2/SiChitosan) were applied on the water surface con-
taining non-polar solvents, and chitosan-grafted nanoparticles
were more effective due to the high surface-to-volume ratio and
reduced particle dimensions (Soares et al., 2017). Quaternized
chitosan (QC) coated with magnetic nanoparticles (MNP) was also
reported (Zhang et al., 2017) with excellent oil-water separation at
different pHs, without showing significant difference in separation
up to 8 cycles compared to that of MNP coated with silica and 3-
aminopropyltriethoxysilane (APTES). This observed behavior was
due to the positive surface charge of QC-coated MNP at various pH
levels, enabling adsorption onto the negatively-charged oil droplets
via electrostatic attraction. Gomes de Souza et al. demonstrated the
high chemical affinity of magnetic material with a polymer matrix
267
for the removal of oil from the water surface (Gomes de Souza et al.,
2010). Polymer-coated nanoparticles showed effective separation
of oil from oil-water mixture (Mirshahghassemi and Lead, 2015),
but the presence of natural organic macromolecules reduced the
nanoparticles-oil interactions governed by the hydrophobic effect
of the polymer coating, which led to a decrease in oil removal
(Mirshahghassemi et al., 2016). Moreover, scale-up of these mag-
netic particles is easy and cheap with high sorption capacity
(Mirshahghassemi et al., 2017).
Generally, if the particle is small enough (5 nm - 52 mm (Lam
et al., 2014)) and can be wetted by both aqueous and oil phase, it
can adsorb at the oil-water interface and stabilize emulsions, also
called Pickering emulsions. For particulate adsorbents, neither of
these criteria is usually fulfilled, since oil adsorbents are normally
prepared as hydrophobic and cannot be wetted by the aqueous
phase. Moreover, the particle size is usually larger since separation
of the adsorbent from the aqueous phase is not convenient for
particles of near nano size, unless the particles have suitable
magnetic properties and can be separated using magnets. Addi-
tionally, adsorbent particles usually exhibit surface roughness and
porosity to increase the surface area of the adsorbent. Surface
roughness is found to decrease the stability of Pickering emulsions
(Lam et al., 2014; Dickinson, 2017), so is not a desirable property.
The particles used in oil spill response can act either as a surfactant,
dispersing agent, emulsifying agent, herding agent, or coating
materials.
3.3. Surfactants
Surfactants (surface-active molecules) are amphiphilic com-
pounds, which reduce oil-water interfacial tension by orienting the
interaction of hydrophilic groups with the water phase and the
hydrophobic groups with oil, and depressing coalescence by
forming stable micro-emulsions. Such microemulsions occur
spontaneously, and mainly depend on surfactant type and struc-
ture. For example, if the surfactant is ionic along with a single hy-
drocarbon chain, microemulsion formation takes place in the
presence of co-surfactant and/or electrolyte whereas, for non-ionic
and double chain ionics surfactants, co-surfactant is not required
(Eastoe, 2003). Winsor proposed four types of microemulsions
(Winsor, 1947) as mentioned in Fig. 4. Watcharasing et al. demon-
strated the removal of motor oil from Winsor type III micro-
emulsions using the froth floatation process, a surfactant-based
separation process (Watcharasing et al., 2009).
Surfactants are mainly present in the dispersants that break the
Fig. 4. Classification of Winsor’s microemulsions, where the orange layer indicates the
oil phase, the blue layer the water phase and the dotted one the microemulsion layer.
268 B. Doshi et al. / Water Research 135 (2018) 262e277

oil slick into smaller droplets, and can move easily into the water
column. Dispersion effectiveness is the percentage of an oil slick
treated with a given dispersant under a stated set of mixing con-
ditions. Dispersants Corexit 9527 and Corexit 9500A comprising
anionic surfactant dioctyl sodium sulfosuccinate (DOSS) were
widely used for the Deepwater Horizon oil spill response (Belore
et al., 2009). Herding agents are surface-active molecules which,
when added along the periphery of an oil spill slick, contract and
thicken the slicks or push them together for easy burning or
collection (MAREX, 2016). However, existing chemical dispersants/
herders are chemically stable, but are non-biodegradable and stay
longer in the marine environment (Gray et al., 2014; Place et al.,
2016), so current research focuses more on developing eco-
friendly biodegradable green dispersing/herding agents for the
cleanup of oil spills from water, as summarized in Table 3.
Muhammad et al. showed the Eggshell modified by surfactant
for the effective removal of crude oil from water (Muhammad et al.,
2015). Bio-based surfactants obtained from biological sources are
favored due to their biodegradability and lesser environmental
risks. Hydroxylated soya bean Lecithin reduces the rigidity of the
fatty acid chains with dense surfactant packing at the oil-water
interface, which shows that hydrophilicity improves the interfa-
cial coverage by resisting the coalescence of the droplets (Nyankson
et al., 2016). Blends obtained from the food-grade amphiphilies
such as Lecithin and Tween 80 (60:40) in the presence of ethanol as
a solvent turn out to be an effective emulsifier for oil spills (Athas
et al., 2014). Similarly, replacing some ethanol with co-solvents
such as octane or octanol enhances dispersion effectiveness, sug-
gesting that hydrophobic solvents strengthen dispersant-oil
miscibility (Riehm et al., 2015). Moreover, oil-into-water emulsifi-
cation reveals rapid leaching of surfactants from oil into water,
which lowers dispersant effectiveness such as Tween-80-rich dis-
persants, whereas water-into-oil emulsification indicates stabili-
zation of surfactants in the oil by increasing the dispersant
effectiveness such as Lecithin-rich dispersants. Hence, Tween-80-
rich dispersants exhibit lower dispersion effectiveness than
lecithin-rich dispersants (Riehm et al., 2017). In a future perspec-
tive, such mixtures can be used in Corexit compounds rather than
DOSS. Recently, Wang et al. showed that the presence of Xantham
Gum additive in chemical dispersant 9500A through a synergistic
mechanism enhances dispersion effectiveness, droplet stability and
the biodegradation of crude oil (Wang et al., 2017). Plant-based
herding agents’ (phytol) tend to hydrolyze quickly after herding
compared to commercial siliconeebased herders (Gupta et al.,
2015). Even though, silicone-based herders are effective in spilled
oil thickening, but they exist in the marine environment due to
slow biodegradability.
Edwards et al. showed the reduced toxicity of bio-surfactants
over synthetic surfactants used in oil spill treatment (Edwards
et al., 2003). Bio-surfactants, the surface-active amphiphilies pro-
duced from the micro-organisms, require a culture medium with a
hydrophobic and hydrophilic carbon source, and have enhance
bioavailability of inaccessible substrates with survival under low
moisture conditions. In such bio-surfactants, the hydrophobic

Table 3
Surfactant-based materials used in oil spill treatment.

Dispersants/ Surfactants Method/Solvent Oil Surface Dispersant Conclusions Ref.

Herding agents tension/ to oil ratio
Interfacial (DOR)
tension
(mN/m)

A branched alcohol Froth floatation process Motor oil Winsor Type III (Watcharasing
propoxylate sulfate, microemulsion (0.5 wt% C14 et al., 2009)
sodium salt (C14 e15(PO)5SO4Na and 5 wt%
e15(PO)5SO4Na) NaCl, have maximum oil
removal
Modified Eggshell Hexadecyl-trimenthyl- Mixing with HDTMA-Br solution, Crude oil 8.24:1 6.493 mg/g oil removal (Muhammad
ammonium-bromide washing and drying et al., 2015)
(HDTMA-Br)
Food-Grade Soya bean lecithin Blending of surfactants (40/60) in Louisiana 0.05 1:10 60/40 wt ratio of L/T acts as (Athas et al.,
Amphiphiles (Zwitterionic) and Tween ethanol sweet crude effective o/w emulsifier 2014)
80 (Nonionic) oil
Food-grade Lecithin and Tween 80 Blending of surfactants in ethanol Crude Oil 0.08 1:25 v/vAddition of cosolvents (Riehm et al.,
surfactants (60:40 to 80:20) with cosolvent like octane or improves the dispersion 2015)
octanol effectiveness
Food-Grade Lecithin and Tween 80 Blending of surfactants in ethanol Crude Oil, 0.03e0.4 1.25e10% Tween rich dispersant forms (Riehm et al.,
Amphiphiles Isooctane dispersant o/w emulsions and Lecithin- 2017)
rich dispersant forms w/o
emulsion
9500A þ Xanthum Tween 80 (48%), bis (2- 1-(2-butoxy-1-methylethoxy) Crude Oil IFT increases Dispersion Efficiency >50% (Wang et al.,
Gum (XG) ethylhexyl) propanol (17%) with with reduction of chemical 2017)
sulfosuccinate sodium addition of dispersant dosage
salt (35%) þ Xanthum XG to 9500A
Gum
Plant-based small- Branched chain of Esterification with cation (1- Crude oil retraction oil slicks ~500% (Gupta et al.,
moleculephytol Isoprene units methylimidazolium/pyridinium) (5
C), 700% (20
C) and 2500% 2015)
(35
C)
Microbial Surfactin Genetically-modified strains of Crude Oil 27.4 1:96 Salinity increases the toxicity (Marti et al.,
biosurfactants fatty acyl-glutamate (FA- Bacillus subtilis on 2% glucose and 27.2 1:12 of surfactants 2014)
Glu) mineral salts media in shake-
flasks and bioreactors
Octyl Octyl aldehyde Carboxymethylation, acylation Waxy Crude 35 Dispersion efficiency is 90% (Anon., 2012)
carboxymethyl and reduction oil and and 53%
chitosan Fresh
asphaltenic
oil
 B. Doshi et al. / Water Research 135 (2018) 262e277 269

Fig. 5. Classification of surfactants for oil spill treatment.

moiety can be either protein, peptide or fatty acids with 10e18
carbon atoms chain, whereas hydrophilic moiety comprises hy-
droxyl, carboxylate, ester or phosphate groups. Silva et al. reviewed
the potentiality of bio-surfactants in the oil industry and the
bioremediation of oil spills (Silva et al., 2014). However, bio-
surfactant production from agro-industrial wastes must be studied
more, due to its lower production costs.
For oil spill remediation, emulsifying agents, which disperse oil
slicks into smaller droplets and boost oil biodegradation by mi-
crobes, are widely used. Another way towards sustainability is
microbes, which degrade oil and ingest oil droplets as a part of their
natural diet. This reveals that such microbes produce their own
surfactants, known as biological compounds, which consist of
sugars, amino acids, and lipids. These compounds are classified into
two groups, biosurfactants which have low molecular weight
compounds (Rhamnolipids and surfactin produced by Pseudomonas
aeruginosa and Bacillus subtilis) and bioemulsifiers comprising
high molecular weight compounds (Emulsan and alasan produced
by Acinetobacter radioresistens and Acinetobacter venetianus
recombination activating gene). Hence, the alternative green way to
clean marine oil spill is bioremediation through such biological
compounds (Refer Fig. 5). R. Mohanram et al. found that some
biosurfactant- and bioemulsifiers produce bacteria from the oil-
polluted water of the Mumbai harbor (Mohanram et al., 2016).
Some examples include iturins, esperine, mycosubtilin and sur-
factin, which are cyclic lipopeptides produced by the Bacillus spe-
cies. Rongsayamanonta et al. synthesized a solvent-free dispersant
for crude oil spills using lipopeptides from Bacillus sp. GY19, based
on hydrophilic-lipophilic deviation concept (Rongsayamanonta
et al., 2017).
4. Materials for oil recovery
4.1. Conventional sorbents
The use of sorbents in oil spill treatment allows the recovery of
the oil and reuse of sorbent material, which is considered
environmentally-friendly and economical (Al-Majed et al., 2012).
There are different kinds of oil recovery methods reported in
literature (see Table 4), such as vacuum filtration (Wang et al.,
2013), distillation (Yang et al., 2014), and extraction (Feng et al.,
2017). Mechanical and chemical stability are important for the
reuse of the materials. Mechanical pressure during the mechanical
recovery of oil may cause deformations in the pore structure of the

Table 4
Conventional sorbent used for the removal and recovery of oils.

Raw material Synthesis Oil adsorption Recovery Recovery cycles Ref.

(g/g) method

Kapok fibers Polybutylmethacrylate 65e82 Vacuum 6 (Diesel, soybean oil, crude oil, 150NS, 20cst) (Wang et al., 2013)
Silica nanoparticles filtration
Lignin Organogel 2e4 Distillation 5 (Gasoline) (Yang et al., 2014)
Ambient drying (70
C)
Liquidambar Pyrolysis 2e3 Extraction >10 (Paraffin and turpentine oil) (Feng et al., 2017)
formosana (ethanol or
hexane)
Drying 60
C
Kapok fibers SiO2 nanoparticles 40e85 Vacuum 8 (Diesel and soybean oil) (Wang et al., 2012)
Silanization filtration
Cellulose foam Drop-casting stearic acid and graphite 9-24 (v/v) Squeezing 15 (Paraffin and motor oil) (Calcagnile et al.,
particles 2017)
Heat treatment at 100
C
Kapok fibers Fe3O4 nanoparticles and 24e51 Vacuum 16 (Toluene, gasoline, and diesel) (Wang et al., 2016)
Dopamine modification filtration
Drying 60
C
Cotton SiO2 nanoparticle and 25e50 Squeezing 10 (n-hexane and chloroform) (Liu et al., 2014)
Octadecyltrichlorosilane modification Vacuum
filtration
Poly (lactic acid) Vacuum 40
C 3.5e5 Squeezing 5 (Hexane, diesel, gasoline, vegetable oil, and (Xue et al., 2013)
Dioxane and ethanol solvents Vacuum petroleum ether)
distillation
270 B. Doshi et al. / Water Research 135 (2018) 262e277

material and result in decreased oil sorption capacity. In addition,
the material should be stable against elevated temperature and
solvents during oil recovery by distillation and/or extraction.
Superhydrophobic dissocyanate-modified lignin xerogel was
prepared by the formation of organogel in THF followed by ambient
pressure drying, with 75.1% porosity and a borderline water contact
angle of 146.4
. The sorption capacity of various oils was 2e5 g/g.
When absorbing gasoline, the material was recyclable by distilla-
tion at 70
C for five cycles with no decrease in performance (Yang
et al., 2014). Wang et al. studied hydrophobically-modified Kapok
fibers with polymerized butylmetacrylate (PBMA) and silica
nanoparticles, as an oil sorbent. The PBMA and silica nanoparticle
coating on the fiber enhanced the oil sorption due to increased
nano- and micro-scale roughness on the surface and the low sur-
face energy of PBMA. The prepared material had high and selective
oil sorption from a mixture of various oils (approximately 65e90 g/
g), and could be reused at least six times by vacuum filtration. After
six cycles, the sorption capacity reduced by approximately 6e10%
(Wang et al., 2013). In another study, Wang et al. prepared super-
hydrophobic and oleophilic Kapok fibers by coating them with
silica nanoparticles and silanization. The materials showed high
sorption of various oils (40e85 g/g), was reusable for at least eight
cycles and oil was recovered by vacuum filtration. The sorption
capacity decreased slightly depending on the oil type (Wang et al.,
2012). Cotton with superhydrophobic and superoleophilic proper-
ties was prepared by the attachment of silica nanoparticles on the
surface of cotton and subsequent octadecyltrichlorosilane modifi-
cation, to introduce hydrophobicity into the material with a water
contact angle of 156
. The materials showed high and selective oil
sorption (26e50 g/g) of various oils, with ten times the reusability
and almost constant sorption capacity (Calcagnile et al., 2017).
4.2. Separators
Conventional techniques such as gravitational separation,
skimming and flotation are more feasible for oil/water mixtures but
steeped down for oil/water emulsions due to micro- and nanosized
droplets. To overcome such limitation, superhydrophobic and
superoleophilic separators like mesh and/or membranes have been
developed (refer Table 5), with a smaller pore size than emulsions.
Fig. 6 shows the selective separation of oil and water depending on
the wettability of the mesh and the density of the oil. Mesh
membranes with selective surface wettability can attract either of
the phases from the oil/water mixture through effective gravity
filtration (Yu et al., 2016). Moreover, the surface chemical compo-
sition also determines the intermolecular forces at their interfaces,
which is enhanced through surface roughness. A mixture of waste
potato residue and polyurethane-coated stainless steel mesh shows
dual characteristics i.e. superhydrophilic and superoleophilic, and
separates oil and water mixtures through prewetting depending on
their respective densities (Li et al., 2016). However, fibrous tunicate
cellulose nanocrystal (TCNC)-based superhydrophilic and under-
water oleophilic membrane separate surfactant-stabilized oil-in-
water emulsions depending on their porosity (Cheng et al., 2017).
Chitosan-based film is stable in alkaline medium, but the pro-
tonation of the amino groups makes them sensitive in acidic con-
ditions and, to overcome this, amino groups were blocked through
cross-linking agent. However, the completely cross-linked film

Table 5
Separators used in the separation of oil and water.

Membrane/Separator Method Wettability/Water Oil Phase in water Medium Separation No. of Ref.
Contact Angle/ Stability Efficiency cycles/
Underwater (%) Reusability
hydrophobicity

Stainless Steel (SS) with Waste potato Spraying 152
± 1.3
Light or heavy oil >96.5% 40 cycles, (Li et al., 2016)
residues and polyurethane Kerosene 98.0% Excellent
Nylon filer membrane covered by TCNC Facile dip-coating process 171
Toluene, Isooctane, n- Acidic 99.59% 10 cycles (Cheng et al.,
155
hexane, Chloroform, Saline 99.99% 2017)
157
Individual emulsion in Alkaline 99.99%
175.9
water 93.33%
(Underwater Rejection
superoleophilic)
Copper mesh coated with Immersing >150
Hexane pH >99.0% 30 times (Zhang et al.,
CS-PVA-GA (1e13) 2013)
Stainless Steel (SS) coated with CS-SiO2- Spraying 150
e159
Gasoline Acidic >99.0% 20 cycles (Liu et al.,
GA composite Rapeseed oil Saline 2016)
Petroleum Ether Alkaline
Toluene
Bean Oil
Stainless Steel (SS) with CTS-PFO/SiO2 Gun Spraying 157
± 1
Hexadecane >99.0% Simple (Yang et al.,
recyclability 2014)
Cellulose membrane coated with block Reversible addition- 160
± 4
Crude oil and water Saline >99% Excellent (Kollarigowda
co-polymer of silane and myrcene fragmentation chain emulsion et al., 2017)
monomers transfer (RAFT)
polymerization
Foam membrane from Agarose, Gelatin Blending þ Lyophilization 0
(Superhydrophilic) Crude oil, Hexane, >97% pure 4-5 cycles (Chaudhary
and Genipin Toluene, water et al., 2014)
Oil spill wastewater
Aerogel membrane from Chitosan, Blending þ Lyophilization Superhydrophilic Bio-diesel, >99% pure (Chaudhary
Agarose, and Genipin Oil spill wastewater water et al., 2016)
Cellulose acetate/Polyimide fibrous Electrospinning þ In-situ ~160
Dichloromethane pH 99.73% 10 cycles (Ma et al.,
membrane modified with fluorinated polymerization (1e13) 2017)
polybenzoxazine and silica
nanoparticles
Stainless Steel mesh coated with ZnO and Hydrothermal method 151
e158
n-hexane, Paraffin Oil, >94% 10 cycles (Wang et al.,
polydimethylsiloxane Vegetable Oil, Motor Oil, 2015)
Crude Oil
 B. Doshi et al. / Water Research 135 (2018) 262e277 271

Fig. 6. Selective separation of oil and water from mixture or emulsion using separators.

tends to be brittle, so the mixing of chitosan with polyvinyl alcohol PUS after the removal of oil is simple with easy scale-up (Wang
(PVA) prior to cross-linking makes the film tougher. CS/PVA-coated et al., 2015).
mesh through glutaraldehyde crosslinking also improves the sta-
bility of separation under acidic conditions (Zhang et al., 2013). The
4.3. Aerogels
superhydrophilicity of the chitosan composite-coated metallic
mesh shows the effective separation of various oils from oil-water
Aerogel is a gel in which the continuous liquid phase has been
mixture by blocking the oil on the surface of the mesh with high
replaced by air resulting in a solid porous material. The typical
stability in harsh environments (Liu et al., 2016). Similarly, hierar-
characteristics of an aerogel are high porosity (~99%), high surface
chical rough structures can be obtained by introducing SiO2
area (>100 m2/g), and low density (~10 mg/ml). These character-
nanoparticles to chitosan (CTS) and sodium perfluororooctanoate
istics are ideal for oil sorption applications allowing for rapid
(PFO) nanocomposite prior to coating, which leads the reorgani-
sorption and flotation on water. Aerogels for oil sorption have been
zation of fluorinated moieties to make a hydrophilic subsurface for
the subject of intensive research in recent years. Aerogels can be
the water to penetrate through it (Yang et al., 2014). However, hy-
prepared using inorganic materials, synthetic organic materials,
drophilic and underwater superoleophobic materials mesh proved
and natural biomaterials (Al-Majed et al., 2012), such as silica
superior to hydrophobic and oleophilic materials due to a reduction
(Wang et al., 2012), graphene (Hu et al., 2014; Kabiri et al., 2014; Li
in external fouling and water barrier capacity. Antifouling cellulose
et al., 2014), and nanocellulose (Laitinen et al., 2017b), respectively.
membrane obtained through reversible addition-fragmentation
However, in this review we shall concentrate on aerogels derived
chain transfer technique (RAFT) possesses a fibrillary structure,
from bio-based sources. A good number of the reported aerogels
which captures the oil easily without any structural disruption
are prepared from nanocellulose, which Liu et al. have recently
during filtration, and myrcene blocks the foul odor of thiol mole-
reviewed (Liu et al., 2017). The reported oil absorbency values in
cules from water (Kollarigowda et al., 2017).
literature are based on large variety of different oils, so the absor-
One of the eco-friendly ways to separate oil from water is to
bency in Table 6 is reported on a scale between the minimum and
generate bio-based membrane through replacement of the metallic
maximum values. It has, however, been noted by multiple authors
mesh substrate. A bio-based foam membrane obtained by blending
that the density of the oil affects the mass absorbency value giving
agarose and gelatin along with genipin cross-linker results in a
higher values for higher density oils. The use of volume-based ab-
lamellar structure, where superhydrophilic agarose micropore is
sorbency has been proposed but not yet been widely applied.
surrounded by gelation walls through hydrogen bonding. This al-
The main benefit of aerogels/sorbents for oil spill-treatment is
lows the aggregated water to pass through the pores by breaking
the recovery of the oil and the recyclability of the sorbent material.
the water molecular film from the oily wastewater and leaving
Several different kinds of recovery methods have been reported,
behind oil, and the oil-fouled membrane is completely biodegraded
such as extraction (Meng et al., 2015), distillation (Cheng et al.,
in soil over a period of one month (Chaudhary et al., 2014). The
2017), and mechanical squeezing (Jin et al., 2015). Combustion
porosity of such aerogel membrane is enhanced by replacing
has also been reported as a way to recover the absorbent but not
gelatin with chitosan, where thin-layered agarose is surrounded by
the oil (Bi et al., 2013). Squeezing might be the most
chitosan walls with inter-walled, cross-linked genipin, which en-
environmentally-friendly way to recover the oil, followed by
hances the recovery of high-quality water from oil spills
distillation and extraction. Extraction might be the least
(Chaudhary et al., 2016). Similarly, transforming surface to hydro-
environmentally-friendly of the three techniques due to the addi-
phobic enhances the selectivity of oil over water. In order to achieve
tion of organic solvents to produce a mixture of oil and the solvent
a superhydrophobic and superoleophilic surface, the polyimide/
that is then removed. The mixture usually needs to be distilled to
cellulose acetate fibrous membrane was coated with fluorinated
separate the oil and solvent so that the solvent may be recycled. The
polybenzoxazine along with silica nanoparticles, showing water
sorbent also needs to be dried. Fig. 7 shows the functioning of
repellence by the air pockets of the membrane (Ma et al., 2017). A
aerogel for the removal and recovery of oil from the spilled area.
porous unmanned ship (PUS) with a low water adhesion force on
The preparation of an aerogel usually involves freeze-drying a
the mesh surface infiltrates the oil through the porous mesh
gel containing the bio-based material dispersed in water (Cheng
without any artificial operation, which can protect humans from
et al., 2017; Tripathi et al., 2017). Many natural raw materials
toxic oil spills. However, water wettability can change the super-
such as cellulose are amphiphilic, so the prepared sorbents absorb
hydrophobic behavior of PUS to hydrophobic. The recycling of the
both water and oil unless the sorbent is modified to be
272 B. Doshi et al. / Water Research 135 (2018) 262e277

Table 6
Aerogels for removal and recovery of oils.

Raw materials Synthesis Oil sorption (g/g) Recovery method Recovery cycles Ref.

Cellulose Hydrophobic modification 70e200 Mechanical 30 (Laitinen et al.,

(recycled waste fibers) Freeze-drying 2017b)
Cellulose microfiber Freeze-drying 50-86 (normalized by oil Extraction 10 (constant (Meng et al., 2015)
Pyrolysis density) absorbency)
Cotton Freeze-drying 40e100 Distillation 5 (Cheng et al., 2017)
Cotton/cellulose
(paper waste)
Waste newspaper Dissolution, Gelation. Solvent Exchange, 16 Squeezing 5 (Jin et al., 2015)
Freeze drying
Raw cotton Pyrolysis 50e190 Distillation 5 (constant (Bi et al., 2013)
Combustion or absorbency)
Mechanical
Cellulose acetate Freeze-frying 15e30 Mechanical 10 (Tripathi et al.,
2017)
Rice straw cellulose Freeze-drying 135e356 Distillation 6 (Jiang and Hsieh,
(nanofiber) Hydrophobic modification (CVD 2014)
Waste newspaper Freeze-drying 29e51 Distillation 5 (Han et al., 2016)
Pyrolysis
Glucose Hydrothermal carbonization 50e140 Distillation 10 (constant (Wu et al., 2014)
Freeze-drying absorbency)
Pyrolysis
Chitosan and silica Sol-gel method 14e30 Evaporation 10 (Ma et al., 2015)
Freeze drying
Bamboo pulp fibers Freeze-drying 50e150 Distillation 5 (Yuan et al., 2017)
Pyrolysis Extraction
Cellulose nanofibers Hydrophobic modification 80e190 Mechanical 10 (constant (Sai et al., 2015)
Freeze-drying Extraction absorbency)
Freeze-drying
Cellulose nanofibers Freeze drying and Atomic layer deposition 20-40 (normalized by oil Extraction or Combustion 10 (constant (Korhonen et al.,
density) absorbency) 2011)
Cellulose fibers Solvent exchange 25e27 Extraction 5 (constant (FunChin et al.,
Fe2O3 nanoparticles cCO2 Drying absorbency) 2014)
Lettuce Hydro-thermal carbonization 3e11 Oil pumped through the Continuous (Wang et al., 2016)
Freeze-drying material
Hydrophobic modification
Cellulose nanofibers Freeze-drying 88e228 Mechanical 30 (Wang et al., 2015)
Hydrophobic modification (CVD)
Winter melon Hydrothermal carbonization 16e50 Distillation 5 (constant (Li et al., 2014)
Freeze-drying absorbency)
Pyrolysis

mechanical degradation of the materials due to mechanical stress

Fig. 7. Oil recovery using aerogels.
hydrophobic. Hydrophobicity was achieved by introducing hydro-
phobic moieties on the surface of the sorbent. According to litera-
ture, this has been achieved by chemical modifications (Jiang and
Hsieh, 2014; Laitinen et al., 2017b) or pyrolysis (Bi et al., 2013;
Han et al., 2016). In non-pyrolyzed aerogels, mechanical and
distillation methods to recover the oil tend to decrease absorbency
during multiple recycles of the material. This is attributed to
caused by squeezing and capillary forces from the evaporating
liquid at an increased temperature (Cheng et al., 2017). Freeze-
drying combined with pyrolysis is an environmentally-friendly
way to prepare hydrophobic aerogels due to the lack of added
chemicals or reagents. In addition, pyrolysis usually increases the
mechanical, chemical and temperature durability of the materials
compared to non-pyrolyzed aerogels, indicated by the more
consistent performance in multiple use of the material (Table 6),
and induces hydrophobicity due to the formation of saturated
carbon moieties. The downside of pyrolysis is the high temperature
(up to at least 1450
C) reported in literature (Wu et al., 2014), so
high energy is required for the process. Freeze-drying is also an
energy-intensive process due to low temperatures and high vac-
uum. Moreover, the sublimation of water is slow and the scale-up of
the freeze-drying process to industrial scale is not a trivial task.
Cervin et al. produced aerogels by air and oven-drying foams were
stabilized by surface-modified nanofibrillated cellulose. The aero-
gel produced had high porosity (98%) and low density (30 mg/ml)
and mechanical properties comparable to aerogels prepared by
freeze-drying (Cervin et al., 2013). This kind of strategy to produce
aerogels for oil spill treatment could be an interesting alternative to
freeze-drying. Nonetheless, the production of a sufficient amount
of aerogel sorbents may prove to be difficult for use in the treat-
ment of large oil spills. In general, aerogels have higher production
costs (Maleki, 2016) than other sorbents. In addition, the aerogels
 B. Doshi et al. / Water Research 135 (2018) 262e277 273

are usually brittle (Maleki, 2016), which is a drawback since the
mechanical properties are important for the reuse of the materials
and oil recovery. Lack of mechanical strength may degrade the
materials and decrease sorption capacity. Ma et al. prepared
Chitosan-silica composite aerogel, whose mechanical strength was
enhanced through an increasing concentration of chitosan (Ma
et al., 2015).
Wu et al. prepared a carbon nanofiber aerogel and applied it to
oil recovery from oil-water mixture. Carbonaceous nanofibers
synthesized through the hydrothermal carbonization method from
glucose followed by freeze-drying and pyrolysis at 1450
C
possessed low density (10 mg/ml), high porosity (>99%), good
mechanical strength, and large specific surface area (547 m2/g).
This material was also hydrophobic (water contact angle 135.8
)
and superoleophilic (oil contact angle 0
) resulting in high selec-
tivity to oils, and it showed high absorbency (50e140 g/g) of variety
of oils. The material was also recyclable with stable performance
over ten cycles, as demonstrated by the recovery of n-hexane by
distillation at 69
C (Wu et al., 2014). Yuan et al. prepared carbon
aerogel from bamboo pulp fibers using the freeze-drying and py-
rolysis (up to 800
C) method. This material showed low density
(5.65 mg/ml), hydrophobicity (water contact angle 135.9
), large
specific surface area (379.39 m2/g), high sorption capacity
(50e150 g/g) of a variety of oils, and was reusable over five cycles
with constant performance. Two different recovery methods were
employed: evaporation at an elevated temperature, and extraction
with cyclohexane followed by evaporation at an elevated temper-
ature to remove residual organics (Yuan et al., 2017). Bi et al. py-
rolyzed (800
C) raw cotton to prepare a carbon aerogel. The
prepared material had low density (12 mg/ml), hydrophobicity due
to pyrolysis and loss of functional groups, and high sorption ca-
pacity (50e190 g/g) for a variety of oils. Oil could be recycled by
distillation, combustion, or the squeezing for five cycles. Distillation
and combustion did not decrease the absorbance of the material in
the subsequent cycles, but squeezing reduced the absorbance after
the first cycle, after which the absorbance remained constant (Bi
et al., 2013).
Cellulose diacetate cross-linked with 1,2,4,5-
benzenetetracarboxylic acid (PMDA) in acetone, to form a gel fol-
lowed by solvent-exchange to water and freeze-drying. The resul-
ted aerogels were subjected to chemical vapor deposition (CVD)
with trichloro-octylsilane (TCOS) to introduce hydrophobicity and
oleophilicity. The prepared material showed low density (4.3 mg/
ml) and highly porosity (99.7%). The highest kerosene oil uptake
was 111.8 g/g aerogel. The aerogel could be recycled and the oil
recovered ten times by mechanical compression, with a 40%
reduction in the original value (Tripathi et al., 2017). Cellulose
nanofibril aerogel was prepared from recycled waste fibers using
deep-eutectic solvents (choline chloride-urea) for pre-treatment,
and freeze-drying. Silylation was used to introduce hydrophobici-
ty into the materials. The materials have low density (2.9 mg/ml),
high porosity (99.81%) and hydrophobicity, and high sorption ca-
pacity for a variety of oils (70e200 g/g). Oil was recovered by me-
chanical squeezing and the absorbency decreased linearly to
approximately 70e80% of the original value during 30 cycles
(Laitinen et al., 2017b). Cellulose nanofibers forming an aerogel
were modified by silanization followed by freeze-drying. The ma-
terials have low density (<6.8 mg/ml), high specific surface area
(>169.1 m2/g), high porosity (>99.6%), and high absorbency of a
variety of oils (80e190 g/g), together with hydrophobicity and
oleophilicity. Recovery of the oil was achieved by a combination of
compression (>90% of the oil was recovered), extraction with tert-
butanol to remove residue oil and swell the aerogel, and freeze-
drying to recover the aerogel. The recovered aerogel was reusable
ten times with constant absorbency of diesel (approximately 120 g/
g) (Sai et al., 2015). Hydrophobic nanocellulose aerogel with oleo-
philic coating absorb a variety of organic solvents and oil, but TiO2
deposition through atomic layer deposition techniques is very
expensive (Korhonen et al., 2011), so FunChin et al. introduced a
cost-effective technique through magnetic cellulose aerogel coated
with TiO2, which sorbs oil up to 28 times its own weight, and can be
easily regenerated by immersing in ethanol (FunChin et al., 2014).
4.4. Gelators
Low-molecular weight phase-selective organogelators have
been proposed for oil spill treatment applications. The gelator is a
supramolecular instead of polymeric and is insoluble in water,
leaving the water phase unchanged. The gel formed via non-
covalent interactions between the gelator molecules allows them
to self-assemble reversibly into polymeric solid-like networks. This
fiber-like network is capable of immobilizing a large volume of
liquid (usually 99% in ideal conditions) due to capillary forces.
There are several phase-selective gelation processes reported in
literature, where the gelator can be dissolved into the oil by heating
and then cooling to form the gel, or the gelator can be dissolved in

Table 7
Gelators used for the removal and recovery of oils.

Raw material Gelator concentration Gelation Co-solvent Temperature Oil recovery Reusable Ref.
rate (
C) gelator

Galactose 50 mg/ml 0-45 min THF (250 mg/mL) 25 Vacuum Multiple (Mukherjee and
(Diesel) distillation times Mukhopadhyay, 2013)
Mannitol 0.75 wt% (Diesel) 15- Diesel (12 wt%, 80
C) 25 Distillation (Prathap and Sureshan,
30 min 2012)
Xylitol 1.8e2.1 wt% 2 min Warm toluene (10%) 25 Distillation >5 (Raju et al., 2017)
SRN
(Crude oil) Not reported
specifically
N-Acetyl 20 mg/mL 1-3 min THF (80 mg/mL) 0e25 Distillation Multiple (Narayana et al., 2017)
glucoseamine (Diesel and petrol) times
Mannitol 5%wt/v 0-60min Ethanol 25 Vacuum At least (Jadhav et al., 2010)
Sorbitol (Diesel) distillation once
D-Glucose 1 wt% ~60min None (powder) 25 Distillation Multiple (Vibhute et al., 2016)
(Crude oil) times
Lauric acid (LA) 240 mg/mL DES (Pump <1min N-metylacetamide (NMA) (DES 1:2, 25 (Cui et al., 2017)
oil) LA:NMA, LA ~50 wt%)
N-Acetyl 20 mg/mL 45s THF (160 mg/mL) 0e25 Distillation 3 (Mukherjee et al., 2014)
glucosamine (Diesel)
274 B. Doshi et al. / Water Research 135 (2018) 262e277
an oil-soluble or water-soluble solvent, or the oil that is being
gelated can be applied to the oil to form the gel, or dried gel
(xerogel) can be directly applied to the oil. The gels are responsive
to a number of external stimuli such as pH, temperature, and light,
due to the non-covalent interactions which, when applied, reverse
the gelation. In their review, Okesola & Smith compiled the ideal
properties of organogelators for oil spill treatment: feasible and
scalable synthesis, rapid gelation without solvents or temperature
change, recoverable oil, reusable gelator, environmentally-friendly
gelator derived from bio-resources, stable gels at natural temper-
atures, high mechanical strength of the gel (Okseloa and Smith,
2016).
Recently, many gelators have been prepared from sugars and
sugar derivatives, such as galactose (Mukherjee and
Mukhopadhyay, 2013), mannitol (Prathap and Sureshan, 2012),
xylitol (Raju et al., 2017), and N-acetyl glucosamine (Narayana et al.,
2017), through organic synthesis methods usually involving organic
solvents and petroleum-derived chemicals to introduce suitable
functional groups and allow oil gelation. The initial gelation is
usually quick and happens in few seconds but the strengthening of
the gel takes several minutes to over 1 h (Table 7). The mechanical
properties of the gel are important for their removal from the water
surface, and further handling for the recovery of the oil and gelator.
The oil can be recovered by distillation and in some cases the
gelator can be reused multiple times (Mukherjee and
Mukhopadhyay, 2013; Narayana et al., 2017). The reusability of
the gelator depends on the temperature stability of the gelator as
well as the type of oil. Some oil types require high temperatures to
evaporate, which might be challenging if the gelator is
temperature-sensitive. Many of the reported gelators require a co-
solvent, such as THF (Mukherjee and Mukhopadhyay, 2013),
toluene (Raju et al., 2017), or ethanol (Jadhav et al., 2010), in which
the gelator is dissolved (~10% w/v) prior to application. Often the
gelator solution needs to be heated for sufficient dissolution of the
gelator. Fig. 8 shows the behavior of gelators for oil spill response.
For example, a gelator was synthesized from xylitol and benz-
aldehyde. Derivatives using 1-phenylethanone and 1-phenyl-1-
propanone instead of benzaldehyde were also synthesized, but
these derivatives performed worse than benzaldehyde derivative
due to the increased hydrophobicity. The gelator was dissolved
(10%) in toluene by gentle heating, and the gelator solution was
added to crude oil on top of sea water and phase-selective gelation
was observed within 2 min. The gelated crude oil was recovered
with 53% efficiency up to a boiling point of 350
C (Raju et al., 2017).
The use of a co-solvent is obviously a drawback considering a
Fig. 8. Oil recovery using gelators.
real-life application due to the high amount of potentially hazard-
ous co-solvent discharged into the environment and the lack of
control over the temperature in the environment. Therefore, gela-
tors applied in powder form would be a superior option. The lack of
co-solvent makes the diffusion of the gelator in the oil phase
slower, resulting in slower and uneven distribution of the gelator
and leading to insufficient mechanical properties of the gel.
Vibhute et al. synthesized an organogelator from D-Glucose that
could be applied as a fine powder on benzene, diesel, and crude oil
to form a gel in the presence of sea water. They studied alkyl 4,6-O-
benzylidene-glycopyranoside, which is known as gelate non-polar
solvents but it is not phase-selective, presumably due to partial
water solubility. The gelation properties are attributed to benzyli-
dene group and diol motifs. Among five different alkyl 4,6-O-ben-
zylidene-glycopyranoside derivatives, the authors found that the
derivative with an additional phenyl group showed promising
performance, which was attributed to increased PeP interactions.
This derivative was studied for oil gelation on sea water. The
amount of applied gelator was 1% (w/v) and was enough to form a
rigid gel in 1 h, which could be skimmed off the water surface. The
oil could be separated by distillation and the gelator could be
reused multiple times (Vibhute et al., 2016).
The problem with the co-solvent was also addressed using a
two-component deep eutectic solvent (DES) system where the
solid gelator and solid co-solvent produce a mixture with a
significantly lower melting point than the pure components alone
(Cui et al., 2017). Lauric acid and N-methylacetaminde were mixed
to prepare a DES, and it was applied to oil gelation. Lauric acid
forms a gel with the oil phase while the N-methylacetamide dis-
solves in water. The components are biodegradable and the prep-
aration of the DES only requires mixing of the components. The
solvent in this case is less toxic than many other co-solvents re-
ported in literature. Also, less co-solvent is required since the
concentration of the gelator in the co-solvent is approximately
50 wt%.
5. Outlook and challenges
The greatest challenge with the sorbents are their effectiveness
with respect to increase in oil and emulsion density, changes in
emulsion viscosity due to evaporation and emulsification over a
period of time.
 Traditional sorbents derived from bio-based waste materials are
generally cost-effective and environmentally-friendly due to
their abundance and biological origin. Also, the possibility to
recover the oil and reuse the sorbent is definitely a desirable
attribute of the sorbents from environmental and economical
points of view. The downsides of these materials are low hy-
drophobicity that results in low oil sorption capacity, and
buoyancy properties. These properties can be enhanced by
modification of these materials, which may result in decreased
biocompatibility of the material. Simple, effective, and
environmentally-friendly modifications to bio-based sorbent
materials could increase their potential in oil spill treatment.
 Hydrophilic and hydrophobic particles can make stable emul-
sions when the wettability of particles (organic as well as
inorganic) is partial with CA 20e120
. The surface area and
porosity of microspheres rules over nanosized particles in the
sorption of oil. However, the dispersion rate of nano-particles is
higher, to form stable emulsions.
 Pickering emulsions stabilized by particles are more stable
against coalescence rather than the surfactant-stabilized
emulsions. Highly dispersed oil in a water column with
hydrocarbon-habituated microbes can enhance the
 B. Doshi et al. / Water Research 135 (2018) 262e277
biodegradation of the oil. Even though the bio-surfactants are
biodegradable and less toxic than chemical surfactants, the
scale-up production cost is higher. One way to minimize the cost
is selectivity of the low-cost substrate and another is to produce
such surfactants from vegetable oils, dairy and distillery waste.
 Aerogels are ideal sorbent materials due to high surface area and
low density resulting in high sorption capacity and good buoy-
ancy properties. However, aerogels share some of the same
disadvantages as traditional sorbents as they are derived from
biomaterials that are usually amphiphilic and require some form
of additional modification to introduce hydrophobicity. Other-
wise, synthesis of aerogels can be very environmental-friendly,
where biomaterial is dispersed in water, freeze-dried, and py-
rolyzed, without any added reagents to form a hydrophobic
aerogel sorbent. On the other hand, aerogel preparation may be
difficult on account of high cost and the scale-up of the aerogel
production. Therefore, aerogels may not be a feasible alternative
for the treatment of large oil spills. The development of more
convenient preparation methods could make aerogels a more
practical option for oil spill treatment. A less studied method to
prepare aerogels is air-drying of foams stabilized by nanoscale
biomaterials, which is an interesting alternative to freeze-
drying.
 Sugar-based gelators are effective at immobilizing the oil at the
water surface for mechanical removal, and the oil can be
recovered and the gelator can be reused. However, the gelators
were derived from sugars, and the synthesis usually involves
organic solvents and petroleum-derived chemicals. Also, most
of the gelators reported in literature require a co-solvent to
dissolve them prior to addition into the oil. Recently, fine
powder gelators have been reported, which can eliminate the
need for co-solvent. The use of DES in dissolving the gelators, an
interesting alternative to co-solvents, can reduce the amount of
required solvent and utilize more environmentally-friendly
solvents. Green synthesis of efficient gelators as powders
proves to be effective at controlling oil spills and oil removal.
 Oil and water separation from their mixtures through separators
is solely a gravity-driven process, and mainly depends on their
density difference together with the porosity and wettability of
the separator. Generally, coated or sprayed surface materials
show lack of long-term stability and reusability of the mem-
brane, in comparison to covalently grafted hydrophobic poly-
mer. However, the spray coating process increases the surface
roughness by favoring the amplification of surface wettability.
The wetting properties of the separators are switchable be-
tween hydrophilic and hydrophobic states by surface modifi-
cation with hydrophilic or hydrophobic materials. Moreover,
hydrophilic and underwater superoleophobic material separa-
tors are superior to hydrophobic and oleophilic materials due to
the reduction in external fouling and water barrier capacity. Bio-
based foam/membranes are biodegradable, but the production
and scale-up cost is more than that of mesh, due to the
lyophilization.
6. Conclusions
In general, when the booms and skimmers are ineffective in
rough seas, dispersants composed of surfactants could be the best
option for oil spill response. However, for an Arctic oil spill, in-situ
burning is preferable. In a cold ecosystem, prevention of an oil spill
is environmentally and economically preferable to costly land
remediation. The two major things of any sorbent affecting the
sorption of oils are its physical characteristics and hydrophobic
properties in terms of oil selectivity. From an environmental point
275
of view, the removal of the oil from the environment is always the
best solution, but economical aspects may restrict the methods
available for oil spill-treatment. Both sorbents and gelators can be
used to immobilize the oil by different mechanisms for easier
removal from the water surface, the oil can be recovered and the
sorbent/gelator can be reused. Although, the collection of the
immobilized oil is slow and labor-intensive, resulting in high costs,
the recovery of the oil and the reusability of the materials increase
the environmental friendliness and could decrease the cost of the
methods. In comparison to other sorbents, the scale-up cost of
magnetic particles along with the recovery of oil could be cheaper.
The different bio-based sorbents discussed in this review paper
have threefold benefits in treating oily wastewater: a steep
reduction in oil content from water, reutilization of waste and re-
covery of oil. Effective materials from bio-based resources can be
prepared but this often requires significant and costly modification
of the native materials. The future challenge and prospective is to
produce effective materials with minimal, feasible, and
environmentally-friendly modifications while still retaining the
desirable properties of the native bio-based materials such as
biodegradability and non-toxicity.
Acknowledgement
This work was funded by the Academy of Finland (decision
number 283200) and EU Structural Funds.
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