Journal of Petroleum Science and Engineering 122 (2014) 705–718

Contents lists available at ScienceDirect

Journal of Petroleum Science and Engineering

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

Nanotechnology-based remediation of petroleum impurities

from water
Boris I. Kharisov a, H.V. Rasika Dias b, Oxana V. Kharissova a,n
a
Universidad Autónoma de Nuevo León, Monterrey, Mexico
b
Department of Chemistry and Biochemistry, The University of Texas at Arlington, Arlington, TX 76019, USA

art ic l e i nf o a b s t r a c t

Article history: Nanotechnology-based methods for removal of oil in petroleum spills and its separation from water are
Received 12 March 2014 discussed in this review. Oil spills during petroleum extraction and processing and transport are often
Accepted 16 September 2014 inavoidable and could lead to events of different impact and magnitude from small contaminations of
Available online 28 September 2014
ground and sea water up to huge disasters. In addition to classic methods of oil removal, the “nano”-
Keywords: techniques are being currently developed, which use nano zero-valent iron (nZVI), carbon nanotubes,
nanomaterials sponges, aerogels and nanocomposites, metal and non-metal nanostructurized oxides, nitrides, salts, and
oil spills zeolites. Some of these nanomaterials can be prepared by “greener” methods at lower costs and without
remediation damage to the environment. These methods (except nZVI) are applied presently in small scale due to
nZVI
insufficient knowledge of their toxicity, lack of more detailed investigations or higher costs. Some of
titanium dioxide
these methods are still objects of academic laboratory studies. Simplicity of fabrication, decrease of costs,
peroxides
and commercial availability of applied nanomaterials and their precursors are main objectives of current
investigations.
& 2014 Elsevier B.V. All rights reserved.

1. Introduction emulsions, oil aggregates and lumps, in dissolved forms, sorbed by

Hundreds of compounds can be present in the oil; every crude
oil type contains 200–300 different compounds. About 50–98% of
the oil composition corresponds to hydrocarbons, which are
primarily alkanes (paraffins) (in the form of gases, liquids or solids,
possessing relatively low toxicity and are biodegradable); 5–6
atom-per-cycle cycloalkanes (naphthenes) (stable and very poorly
biodegradable); aromatic compounds (20–40% of the oil) such as
volatile compounds (benzene, toluene, xylene), bicyclic com-
pounds (naphthalene), tricyclic compounds (anthracene, phenan-
threne) and polycyclic compounds (pyrene). In addition to
hydrocarbons there are sulfur compounds reaching up to 10%,
and fatty acids and nitrogen compounds, as well as vanadium and
nickel.
During oil extraction and processing (especially in accidental
situations), barely separated water/oil/solid phase mixtures can
appear, representing serious problems for the environment. Oil
products entering the aquatic environment very soon change their
initial state. In the sea oil can be present in different migration
forms, such as surface films (slicks), water-in-oil and oil-in-water
n
Corresponding author.
E-mail address: bkhariss@hotmail.com (O.V. Kharissova).
suspensions and bottom sediments, or accumulated by the aquatic
organisms. In case of the cold environment, especially evaporation,
dissolution and biodegradation of oil are extremely slow. In
wintery conditions, cold water affects highly the oil viscosity,
making it very thick and sticky. It also contributes to forming of
the oil lumps. From one hand, ice can serve as a natural contain-
ment, preventing oil from spreading and allowing more time for
the response operations.
Many cases of water contamination from shale gas drilling
operations, which use high-volume hydraulic fracturing (HVHF),
exist: a number of problems, including spills, explosions, leaks,
and the seepage of contaminants into drinking water supplies,
have been documented around the country in conjunction with
shale gas extraction by HVHF (http://www.tcgasmap.org/default.
asp?metatags_Action ¼Find(‘PID’,‘8’)#WaterrContamination;
Thyne, 2008; Lustgarten, 2008, 2009a, 2009b; McConnell, 2009;
Rubinkam and Esch, 2010). Independent scientific studies that
indicate the absence of water contamination after gas extraction
operations using HVHF are needed. When drilling operations
fracture the shale, they do not have complete control over where
fractures will develop, so fracturing fluids and natural gas can
move in unexpected directions (http://www.tcgasmap.org/media/
HydraulicFracturing Predicting Difficulties Industry Source.pdf),
and may end up in aquifers and water wells.

http://dx.doi.org/10.1016/j.petrol.2014.09.013
0920-4105/& 2014 Elsevier B.V. All rights reserved.
706 B.I. Kharisov et al. / Journal of Petroleum Science and Engineering 122 (2014) 705–718
During drilling (http://teeic.anl.gov/er/oilgas/impact/drilldev/
index.cfm; (http://talkingpointsmemo.com/news/four_states_drilling_
contaminates_water) hydraulic fracturing (http://www.infowars.com/
water-pollution-in-four-states-linked-to-oil-and-gas-drilling/), com-
pletion, and stimulation processes (http://www.earthworksaction.
org/reform_governments/oil_gas_accountability_project), water with
contaminants (dissolved hydrocarbons, sand and metals) in pit sludge
may leach out of the soil or overflow the pit and contaminate nearby
soils, surface waters and groundwater. According to the reports of the
United States Environmental Protection Agency (http://www.epa.gov/
region1/superfund/sites/beede/contaminants.html), the contaminants
originated from oil include a series of aliphatic (methane) and
aromatic (benzene, toluene, ethylbenzene, xylenes, polycyclic aromatic
compounds) hydrocarbons, their mixtures (diesel fuel), H2S, metals
(Cr, Pb, Hg, V, Zn, etc.), nitrogen oxides (NOx), sulfur dioxide (SO2) and
volatile organic compounds, frequently potential carcinogens, explo-
sive, dangerous for respiratory, heart and central nervous system.
Their sources are generally venting of natural gas, drilling, working of
heavy equipment, pits, stimulation fluids, diesel and natural gas
exhaust. Radioactive contamination could also occur (Rucke). In case
of oil spills in the ocean, havoc to marine ecology (sea birds, mammals,
algae, coral, seagrass etc.) can be caused, beside the health hazards to
the human population located in nearby coastal zones. Moreover, the
economic loss suffered by oil companies resulting from oil-spillage is
enormous. Numerous solutions have been proposed for dealing with
the problem of oil spills. These include use of microorganisms to
digest the oil, mechanical means like skimmers, booms, pumps,
mechanical separators, etc., sorbents to remove oil from water through
adsorption and/or absorption and use of chemical dispersants like
detergents etc.
In this review, we present modern methods of elimination of
oil spills using nanotechnology-based techniques. The area of
nanomaterials applications for water cleanup and remediation
started to be actively developed only several years ago (see recent
book (Street et al., 2008) and fundamental reviews (Savage and
Diallo, 2005; Tratnyek and Johnson, 2006; Nanotechnology for Site
Remediation, 2008; Agarwal and Joshi, 2010; Rajan, 2011; Jain,
2012; Yunus et al., 2012; Matlochova et al., 2013; Dallas et al.,
2013; Bhattacharya et al., 2013; Prabhakar et al., 2013) in this field)
and represents a considerable interest to petroleum industries,
since the application of classic oil cleanup methods does not give
comprehensive results in water/soil purification and complete oil
elimination.
2. Overview on nanotechnology-based methods for the
cleanup of water contaminated with oil products
For pollutions in general, two main treatment routes are
known, adsorptive and reactive, both of which could be applied
in in situ and ex situ cleanup processes (Table 1). In case of oil-
contaminated water, conventional techniques are not frequently
adequate to solve the problem of massive oil spills. In recent years,
nanotechnology has emerged as a potential source of novel
solutions to many of the world's outstanding problems. Although
the application of nanotechnology (Mahajan, 2011) for oil spill
cleanup is still in its nascent stage, it offers great promise for the
future. In the last 5 years, there has been particularly growing
Table 1
Classification of remediation methods involving nanoparticles.
Type In situ
Adsorptive Sequestration of contaminants adding binding agents.
Reactive Reaction of a nanomaterial with target pollutant.
interest worldwide in exploring ways of finding suitable solutions
to clean up oil spills through use of nanomaterials (Fig. 1 and
Table 2). In particular, the nanoporous sorbents, namely thermally
exfoliated graphite oxide (TEGO), CF3-functionalized aerogels and
carbon nanotube sponges have outstanding oil absorption capa-
cities, among other adsorbents. Briefly, the description of nano-
materials for oil spill cleanup is as follows:
(1) Aerogels (hydrophobic aerogel, CF3-functionalized silica aero-
gel, aeroclays, etc.).
(2) Nanodispersants (micelles forming colloidal solution of bio-
based chemicals).
(3) Magnetic nanocomposites (iron oxide – nanoclays, Fe/C, iron
oxides/C, magnetic polymer nanocomposites).
(4) Membranes (on the basis of manganese oxide nanowires).
(5) Foams and meshes (superhydrophobic and superleophilic).
(6) Filters/pads (oil repellant/hydrophilic cotton filter, superhy-
drophobic and superleophilic filter paper).
(7) Carbon nanostructures (graphene worms, CNTs sponges, ver-
tically aligned CNT membranes, Recam).
(8) Nanostructured hydrophobic organoclays.
(9) Micro- and nano-TiO2 for photocatalytic decomposition.
An important requirement for the sorbent/membrane/filter
nanomaterial is its selectivity for a broad range of organic solvents
and oils to effectively separate oil and water and thus clean up the
oil spills. Conventional sorbents based on polypropylene, silicon-
coated glass fibers, raw cotton, etc. have a tendency to absorb both
water and organic solvents, whereas nanomaterials such as CNT
sponges, nanowire membranes, Recams, hydrophobic core-shell
magnetic Fe2O3@C nano-particles, etc. selectively absorb oil from
water–oil mixtures because of their unique combination of super-
hydrophobic and superoleophilic properties. An additional feature
of nanomaterials like CNT sponges and aerogels, Recams, Gigasorb
etc. is that they are robust, highly flexible and capable of with-
standing a number of large strain compressive cycles without
affecting their properties. These attributes are highly beneficial for
recovery of oil as well as regeneration and reuse of the material.
3. Aerogels
Earlier work on aerogels (Reynolds et al., 2001a) indicated an
importance of this material for water cleanup. Thus, aerogels
containing the CF3(CH)2-group (CF3-aerogel) were synthesized
using (CH3O)4Si and CF3(CH2)2Si(OCH3)3 in CH3OH by a NH4OH
catalyzed reaction followed by supercritical extraction with
CH3OH (Reynolds et al., 2001b). The aerogels were found to be
hydrophobic based on water absorption and sessile drop experi-
ments. Treating oil and salt-water mixtures showed that all CF3-
aerogels cleanly separated the oil from the water indicating that
CF3-aerogels can absorb oil much times their weight. Recent
results in this field are also encouraging. In particular, silica aerogel
granules were prepared by two step acid–base catalyzed sol–gel
process, involving ambient pressure drying of alcogels, were made
use for absorption and desorption studies of different organic
liquids (Parale et al., 2011). Four alkanes, four aromatic com-
pounds, four alcohols and three oils were used for absorption
Ex situ
Extraction of polluted solution, which is then treated with adsorbents.
Extraction of polluted solution, which is then treated with reactants.
 B.I. Kharisov et al. / Journal of Petroleum Science and Engineering 122 (2014) 705–718 707

Fig. 1. Oil absorption capacity of various candidate nanomaterials (different types of oils studied with each material: activated carbon – diesel oil, CNT sponge – various
organic solvents and oils, PU form – paraffinic and naphthenic oils, CF3 functionalized aerogel – crude oil, silica aerogel – crude oil, EG – different grades of heavy oil, NW –
various types of oils, ambient pressure dried silica aerogel – diesel oil, TEGO (thermally exfoliated graphite oxides) – not known, cotton towel – not known).
Source: Reproduced from Mahajan (2011) with permission

Table 2
Selected current and possible nanotechnology-related routes for oil spill cleanup.

Method and its type Description References

Nanodispersants/reactive and adsorptive; in situ
Hydrophobic organoclays/absorptive; in situ
Nanowire membranes/absorptive; in situ
Micro- and nano-TiO2/reactive; in situ
Cotton absorbent pads and filter papers/
absorptive; in situ
DAG–PEG lipids/absorptive and reactive; in situ
Exfoliated graphite oxide, CF3 functionalized
aerogels and CNTs sponges/absorptive; in situ
Recams/absorptive and reactive; in situ
Magnetic polymer composite/absorptive and
reactive; in situ
Superhydrophobic and superoleophilic hybrid
foam of graphene and CNTs/absorptive; in situ
Multifunctional device on the basis of
superhydrophobic and superoleophilic nickel
foam/absorptive; in situ
Use of surfactants molecules reducing interfacial tension “oil–water”. Tiny oil Fingas (2008)
droplets get dispersed into the water and become a good source of food for the
naturally occurring bacteria. The dispersants catalyze the biodegradation process.
Modification of hydrophilic natural clays (bentonites) with quaternary amines Adebajo et al. (2003) and
converting them to hydrophobic. These organoclays can very efficiently and Carmody et al. (2007)
selectively adsorb the oil from water.
Absorbents on the basis of superhydrophobic nanowire membranes with Yuan et al. (2008) and http://
inorganic nanowires capable of absorbing oil up to 20 times their weight. Low web.mit.edu/press/2010/
energy consume, duration for weeks and high capacity to clean. seaswarm.html
Photocatalytic decomposition of the oil-contaminated water using nanoscale or Ziolli and Jardim (2002), Kwon
microscale TiO2 particles. et al. (2008) and Narayan (2010)
Value-added cotton absorbent pads using non-woven materials. Oil absorbing http://www.firstlinetech.com
capabilities to soak the oil are up to 70 times its weight.
Diacylglycerol–polyethyleneglycol (DAG–PEG) lipids entrap both water and oil Keller (2008)
and disperse the contents and vesicles into a suspension. The formed vesicles are
stable until disrupted by high energy mechanical shear, by enzyme activity or by
heat.
Lightest, free-standing MWCNTs aerogel having a density of 4 mg/cm3 (compared Gui et al. (2010) and Zou et al.
to 5.8–25.5 mg/cm3 for CNT sponge) and a surface area of 580 m3/g (surface area (2010)
for pristine MWCNT is 241 m2/g). Works better being comparing with graphite
oxide and CNTs.
Recams is based on carbon containing graphene cell and CNTs. Capacity to absorb Aglietto (2010a, 2010b)
the oil: 90 g of oil per 1 g. Being coupled with TiO2 nanoparticles, contributes to
oil removal from contaminated water through photocatalytic degradation process.
A magnetic polymer composite, wherein superparamagnetic nanoparticles of De Souza et al. (2010)
maghemite (γ-Fe2O3) are incorporated within the matrix of an alkyl resin polymer.
One part of the polymer product could be used to remove more than eight parts of
oil from water.
A monolithic 3D hybrid of graphene and CNTs can selectively remove oils and Dong et al. (2012)
organic solvents from water with high absorption capacity and good recyclability.
This device has a lower density than that of water and it can take up oil that is Cheng et al. (2011)
3.5 times its own weight, with the water–oil separating yield of the as-prepared
device being up to 92%.

and desorption studies of organic liquids. The hydrophobic aerogel keeping the liquid absorbed aerogel granules at various tempera-
granules showed (Fig. 2) a very high uptake capacity and high rate tures and weighing them at regular time intervals until all the
of uptake. The desorption of solvents and oils was studied by absorbed liquid got totally desorbed. Additionally, it was shown
708 B.I. Kharisov et al. / Journal of Petroleum Science and Engineering 122 (2014) 705–718

Fig. 2. (a) Engine oil and water in the beaker, (b) only oil present in water is absorbed by the aerogel granules and (c) separated water and oil absorbed aerogels in beakers.
Source: Reproduced from http://www.nanoparticles-microspheres.com/water-treatment-nanoparticles.html with permission.

that the aerogel structure was not much affected by the solvent
absorption, while the oil absorption led to the shrinkage, resulting
in a dense structure after desorption.
4. Carbon nanotubes and sponges
One of the most known and studied materials in nanotechnol-
ogy, having numerous applications, carbon-containing nanoparti-
cles, in particular those functionalized, have been widely used to
eliminate a series of various contaminants from water. Among
them, we note different (MWCNTs, SWCNTs) carbon nanotubes
(1,2-DCB, phenantrene, pyrene, naphthalene elimination), fuller-
ene C60 (naphthalene), β-cyclodextrin grafted MWCNTs (PCBs),
OH-functionalized MWCNTs (phenantrene, lindane, chloroben-
zene), SWCNTs (benzene, toluene, ethylbenzene, p-xylene), etc.
CNTs in their distinct forms alone and nanocomposites, have been
successfully applied to resolve also oil spilling problems. Thus, two
kinds of CNTs, vertically aligned CNTs (VACNTs), prepared using
ferrocene as the catalyst precursor, and agglomerated CNTs were
used for oil adsorption (Fan et al., 2010). It was established that oil
sorption by CNTs does not depend on the surface area of the
carbon materials. The high sorbtion of VACNTs was caused by the
intertube space with large-sized macropores. VACNTs were found
to have a high oil sorption capacity. Additionally, CNTs and
nanofibers on the surface of expanded vermiculite {(Mg2 þ , Fe þ 2,
Fe3 þ )3 [(AlSi)4O10]  (OH)2  4H2O, a hydrous, silicate mineral that is
classified as a phyllosilicate and that expands greatly when
heated} were fabricated through CVD process and applied for
removal of oil spilled in water (Moura and Lago, 2009).
Carbon nanotube (CNT) sponges were used to cleanup oil slicks
on sea waters (Zhu et al., 2013). This method was compared with
two traditional representative sorbents, including polypropylene
fiber fabric and woolen felt. The CNT sponges had a larger oil
sorption capacity than the other two sorbents (Fig. 3). The
maximum oil sorption capacity (Qm) of the CNT sponge was
92.30 g/g, which was 12–13.5 times larger than the Qm of the
other two sorbents (the Qm of the polypropylene fiber fabric and
woolen felt were 7.45 and 6.74 g/g, respectively). In addition,
unlike the other two sorbents, the CNT sponge was superhydro-
phobic and did not adsorb any water during oil spill cleanup.
5. Nano zero-valent iron (nZVI) and iron nanocomposites
Nanoscale ( o1 μm) ZVI particles have larger specific surface
area than microscale ZVI, which results in a higher reactivity. nZVI
have been demonstrated to treat more than 70 environmental
contaminants like polychlorinated hydrocarbons (aliphatic and
aromatic), highly toxic substances such as As(III), As(V), Cu(II),
Co(II), Cr(VI), nitrite, and a wide range of toxic industrial dyes.
Therefore, nano zero-valent iron (nZVI) has the potential
 B.I. Kharisov et al. / Journal of Petroleum Science and Engineering 122 (2014) 705–718 709

Fig. 3. Photographs showing the sorption effects of the three sorbents after 15 min: (a) sea water; (b) oil spill on the sea water; after cleanup by (c) the CNT sponge, (d) the
polypropylene fiber fabric, and (e) the woolen felt.
Source: Reproduced from http://abstracts.gulfofmexicoconference.org/2012/magnetite-nanoparticles-stabilized-by-pamino-benzoic-acid-terminated-carbon-black-particles-
for-oil-spill-remediation/ with permission.

to become an important material for the treatment of soil, water

and ground water polluted by a large spectrum of contaminants.
During the process, the particles are usually transformed to iron
compounds. However, the main factors which impede the use of
nZVI for commercial use are as follows (http://blog.soilutions.co.
uk/2013/11/12/nanoscale-remediation-zero-valent-iron/):

(1) Cost uncertainties: despite the encouraging results coming

from research, nZVI is still a new technology and only little
examples of field approach are known, therefore the real cost
of application in the field are still uncertain.
(2) Nanoparticle performance: nZVI are extremely reactive and
oxidize fairly rapidly at air contact, which affects particle
storage, safe transport and reactivity.
(3) Nanoparticles fate in large scale application: nZVI particles tend
to aggregate and adhere to solid surfaces resulting in a limited
migration in groundwater.
Conventional production methods of Fe micro- and nanoparti-
cles via top-down routes (grinding metallic iron) have the following
disadvantages: energy intensive, expensive, difficult to achieve
nanoscale diameters, reactive with air – spontaneous combustion,
hazardous process. In case of bottom up routes {chemically reducing
Fe(II) or Fe(III)}, the disadvantages are: harsh reductants (NaBH4) –
toxic, corrosive, hazardous, aggressive reaction with borohydride
with gas production, excess borohydride needed and is present in
products; rinsed off and waste listed as hazardous, extremely
reactive with air & water, capping and/or special handling required.
In this respect, “greener” methods, using biorenewable sources,
could be offered (Kharissova et al., 2013), applying plant extracts,
Fig. 4. A schematic diagram of experimental setup for preparation of nZVI. .
Source: Reproduced from Ahn et al. (2013) with permission.
wine, tea, readily available fruits, vegetables, herbs, grain contain
high concentration of polyphenols (polyphenols are antioxidants,
reducing agents and capping agents).
nZVI (Watlington, 2005; Taghizadeh et al., 2013) and its
nanocomposites are currently applied for water cleanup also from
oil. Thus, the synthesized (reaction (1) and Fig. 4) Fe nanoparticles
(with particle size ranging between 40 nm and 80 nm and BET
surface area is 35.8 m2/g) were utilized as a Fenton-like catalyst for
degradation of oil (hydrocarbon contamination in soil), using
ultrasound method (Fig. 5) (Roozbeh Jameia et al., 2013). Influences
of ultrasound power, temperature effects, nZVI and H2O2 concen-
trations on oil elimination were studied. From the studies, it has
been observed that degradation does not indefinitely with an
increase in ultrasound power, but instead, it reaches an optimum
value and decreases with a further increase in the ultrasound
power. The degradation of contaminant increased with increasing
temperature, nZVI and H2O2 concentration. The result indicated
710 B.I. Kharisov et al. / Journal of Petroleum Science and Engineering 122 (2014) 705–718
that the efficiency of hydrocarbon removal by Fenton oxidation
and NZVI is from 80.12% to 98.57%. The optimum conditions of
degradation are (pH 3.5, ultrasonic power: 500 W, nZVI concen-
tration 0.4 g/L, temperature 40 1C and H2O2 concentration 30 mM).
Fe2 þ ðaqÞ þ BH4  ðaqÞ þ 7NH4 OH-4FeðsÞ↓ þH3 BO3 ðaqÞ
þ 7NH4 þ ðaqÞ þ 4H2 O
A method of separating oil from water using Fe nanoparticles and
magnets has been developed (http://carboninspired.com/blog/?
p ¼610&lang ¼en; (http://laradiodelsur.com/?p ¼135740;
http://web.mit.edu/newsoffice/2012/how-to-clean-up-oil-spills-
0912.html). This technique would allow the oil to be reused, so as
to offset the costs of cleaning. The proposed method involves
adding to the mixture nanoparticles with iron and them, separate
the oil using a magnet. The researchers suggested that this is a
Fig. 5. A schematic diagram of experimental setup for degradation experiments.
Source: Reproduced from Ahn et al. (2013) with permission.
Fig. 6. SEM images of (a) Fe/C-1, (b) Fe/C-2, (c) Fe/C-3, and (d) Fe/C-4 samples; inset images are the water contact angles of the corresponding macroporous nanocomposites.
Source: Reproduced from Narayan (2010) with permission.
very simple maneuver but should, however, be performed in one
vessel so that the nanoparticles do not pollute the ocean. In other
works similar methods have been proposed but have the dis-
advantage that it was necessary to know the concentration of oil
and water in the mixture. The proposed technique by placing the
magnets into the stream, and not outside it, as in the above
ð1Þ methods can be applied always with good results, regardless of the
concentration of each component in the mixture. Magnetic
carbon-iron nanocomposites, applied for separating a liquid
hydrocarbon material from a body of water, are also patented
(Viswanathan, 2011).
In addition to “free” Fe nanoparticles, 3D macroporous Fe/C
nanocomposites {Fe–C–1/4 (Fig. 6), depending on the diameter of
PS microsphere (0.67/4.2) and pore size (0.35/3.0)} were investi-
gated as highly selective absorption materials for removing oils
from water surface. The macroporous nanocomposites were
synthesized by sintering a mixture of closely packed polystyrene
microspheres and ferric nitrate precursor (Fig. 7). Pure metallic
phase of α-Fe and iron carbide (Fe3C) phase were detected in the
XRD pattern, indicating the formation of Fe/C nanocomposites.
These nanocomposites exhibited superhydrophobic and super-
oleophilic properties without the modification of low-surface-
energy chemicals. The macroporous nanocomposites fast and
selectively absorbed a wide range of oils and hydrophobic organic
solvents on water surface, and the removal of the absorbed oils
from the water surface was readily achieved under a magnetic
field (Fig. 8). The oil absorption capacity of these nanocomposites
was found to be much higher than that of reported Fe2O3@C
nanoparticles. Moreover, the nanocomposites still kept highly
hydrophobic and oleophilic characteristics after repeatedly remov-
ing oils from water surface for many cycles (Chu and Pan, 2012).
Other iron-carbon composites, magnetic carbon nanotube
sponges (M-CNT sponge), porous structures consisting of inter-
connected CNTs with rich Fe encapsulation, were fabricated by
 B.I. Kharisov et al. / Journal of Petroleum Science and Engineering 122 (2014) 705–718 711

Fig. 7. Illustration for the synthesis of three-dimensionally macroporous Fe/C nanocomposites.

Source: Reproduced from Narayan (2010) with permission.

Fig. 8. Removal of lubricating oil from water surface by Fe/C-2 sample under magnetic field. The oil was dyed with oil red 24 for clear observation.
Source: Reproduced from Narayan (2010) with permission.

CVD using ferrocene and dichlorobenzene as the precursors. They
showed (Gui et al., 2013) (Fig. 9) high mass sorption capacity for
diesel oil reached 56 g/g, corresponding to a volume sorption
capacity of 99%. The sponges are mechanically strong and oil can
be squeezed out by compression (Fig. 10). They can be recycled
using through reclamation by magnetic force and desorption by
simple heat treatment. The M-CNT sponges maintain original
structure, high capacity, and selectivity after 1000 sorption and
reclamation cycles. The authors also compared sorption capacities
(as well as mechanical strength and reusability) of different
sorbents. In particular, the following sorbents were analyzed {g/g
approximately; the sorption capacity was normalized by the
density of solvent (gasoline or hexane)}: polydimethylsiloxane
(PDMS) sponges (8) {see also an important work (Choi et al., 2011)
on PDMS}; MTMS-DMDMS gels (9); graphene aerogels (38); CNT
solids (43); carbonaceous nanofibers aerogels (62); CNTs sponges
(135); 3D graphene framework (380); carbon aerogels (326). The
desorption methods applied are generally heat treatment, squeez-
ing and burning.
6. Iron oxides – carbon nanocomposites
A composite material based on commercially available polyur-
ethane foams (PU) functionalized with colloidal superparamag-
netic iron oxide nanoparticles (SPIONs) and submicrometer
polytetrafluoroethylene (PTFE) particles can efficiently separate
oil from water (Fig. 11) (Calcagnile et al., 2012; http://www.
nanoparticles-microspheres.com/water-treatment-nanoparticles.
html). It was found that combined functionalization of the PTFE-
treated foam surfaces with colloidal iron oxide nanoparticles
significantly increases the speed of oil absorption. In addition to
the water-repellent and oil-absorbing capabilities, the functiona-
lized foams exhibit also magnetic responsivity. Finally, due to their
light weight, they float easily on water. This low-cost process can
easily be scaled up to clean large-area oil spills in water. In a
related report (Chen and Pan, 2013), ultralight magnetic Fe2O3/C,
Co/C, and Ni/C foams (with a density o5 mg.cm3) were fabricated
(Fig. 12) on the centimeter scale by pyrolyzing commercial poly-
urethane sponge grafted with polyelectrolyte layers based on the
712 B.I. Kharisov et al. / Journal of Petroleum Science and Engineering 122 (2014) 705–718
Fig. 9. Removal of spilled oil from water surface by M-CNT sponges under magnetic field: (a) Optical image of a box of sponges with volume of approximately 5 L; (b) SEM
image of the porous CNT; (c) TEM image of a CNT filled with magnetic Fe nanowires; (d) Oil (dyed blue) spreading on water; four M-CNT sponge blocks have been placed
onto the oil; (e) Clean water surface after complete oil absorption by the sponges; (f) Collecting the sponges using a magnet. (For interpretation of the references to color in
this figure legend, the reader is referred to the web version of this article.)
Source: Reproduced from Liu et al. (2010) with permission.
Fig. 10. Schematic of the recycling of M-CNT sponges used for spilled oil sorption.
(I) sprinkled on the oil; (II) adsorb spilled oil; (III) collected by magnet; (IV)
regeneration; (V) reuse.
Source: Reproduced from Liu et al. (2010) with permission.
corresponding metal acrylate at 400 1C (see also the section above
on Fe/C nanocomposites). After modification with low-surface-
energy polysiloxane, the ultralight foams showed superhydropho-
bicity and superoleophilicity, which quickly and selectively
absorbed a variety of oils from a polluted water surface under
magnetic field. The oil absorption capacity reached 100 times of
the foams' own weight, exhibiting one of the highest values
among existing absorptive counterparts. In addition, a stable
magnetic nanocomposite of collagen and SPIONs was prepared
(Thanikaivelan et al., 2012) by a simple process utilizing protein
wastes from leather industry. This nanocomposite exhibited selec-
tive oil absorption and magnetic tracking ability, allowing it to be
used in oil removal applications. The environmental sustainability
of the oil adsorbed nanobiocomposite was also demonstrated
through its conversion into a bifunctional graphitic nanocarbon
material via heat treatment.
p-Amino benzoic acid (PABA) functionalized carbon black (CB)
particles are interfacially active and can stabilize oil-in-water
emulsions at high dilutions. In addition to their ability to absorb
environmentally toxic polycyclic aromatics, the interfacial proper-
ties of these particles can be tuned by varying environmental
factors such as ionic strength and pH. On their basis, an innovative
cost-effective, environmentally benign technology was proposed
(http://abstracts.gulfofmexicoconference.org/2012/magnetite-
nanoparticles-stabilized-by-pamino-benzoic-acid-terminated-
carbon-black-particles-for-oil-spill-remediation/) for oil spill
remediation using magnetite nanoparticles stabilized by PABA
functionalized CB particles. It was hypothesized that the carboxyl
groups of the PABA attached to CB particles can conjugate with
iron salts and can be reduced to synthesize magnetite nanoparti-
cles. The authors proposed that the magnetic properties imparted
by magnetite and tunable surface properties due to PABA functio-
nalized CB particles make these composite particles attractive
agents for oil emulsification and enhanced surface oil removal.
7. Other oxides, peroxides, nitrides, salts, and zeolites
Recently, a material using nanosized oxides and peroxides
(mostly calcium (Karn et al., 2009; Mueller and Nowack, 2010))
was used in situ to clean up heating oil spills from underground oil
tanks. Preliminary results from this redox-based technology suggest
faster, cheaper methods and, ultimately, lower overall contaminant
levels compared with previous remediation methods. Most of these
sites have been in New Jersey, with cleanup conducted in consulta-
tion with the New Jersey Department of Environmental Protection
(http://www.continentalremediation.com/HomeHtgOIl.htm). In
case of calcium peroxide use (50–200 nm particles of CaO2 with a
metal catalyst), advantages and peculiarities of using this nano
peroxide for soil and groundwater contaminated with any petro-
leum hydrocarbon are as follows: (1) injection is performed through
1 to 114 in. holes in soil or paving. Soil and paving resealed at end of
day with almost no disruption of lawns; (2) the number of points
installed is 5–20 injection points per day depending on soil
conditions, access, and depth of treatment needed. There is no
limit to the depth that is treatable as long as a well or injection
 B.I. Kharisov et al. / Journal of Petroleum Science and Engineering 122 (2014) 705–718
point can be installed to the depth; (3) process will continue
bioremediation for up to 6 months if necessary; (4) petroleum
odors eliminated within minutes of injection or application. The
contaminants, proven to be treatable, are gasoline, heating oil, #6
oil, MTBE (methyl tertiary butyl ether), ethylene glicol, solvents, and
coal tar, in such geological conditions as sand, silt, fractured rock,
landfills, fill materials, and sediments. The oxygen produced in the
reaction of calcium peroxide with water leads to an aerobic
environment that supports natural bioremediation by aerobic
organisms present in the soil.
Discussing the “peroxide” topic, we emphasize a certain atten-
tion of researchers to the use of persulfate anion (PS, S2 O8 2  ) in
combination with the nZVI (for PS activation, alone or together
with Pd(0) (Al-Shamsi and Thomson, 1780)) for efficient destruc-
tion of several organic molecules, for instance naphthalene or
trichloroethylene, or for water disinfection (Ahn et al., 2013). Thus,
Fe0 was used as a source for ferrous ion activated PS oxidation of
trichloroethylene (TCE) (Liang and Lai, 2008). It was indicated that
in the TCE/Fe0/PS system, the rapid TCE degradation was
accompanied by the rapid persulfate decomposition and chloride
ion formation as evidence of TCE mineralization. The similar
results with use of naphthalene showed (Al-Shamsi and Thomson,
2013) that its degradation using nZVI-activated persulfate is more
effective than nZVI alone. For example, the degradation of
naphthalene by nZVI-activated persulfate was 499% compared
to o 10% by nZVI alone. However, despite the higher effectiveness,
the nZVI particles were passivated quickly following exposure to
persulfate, causing the reaction rate to reduce to a magnitude
representative of an unactivated persulfate system. An iron sulfate
layer was formed on the nZVI particle surfaces following exposure
to persulfate compared to the FeOOH layer that was present on the
713
fresh nZVI surfaces (Fig. 13). Fe2 þ ions, appearing as a result of the
direct reaction pathway (reaction (2)), can activate persulfate to
generate sulfate free radicals (reaction (3)). Also, Fe2 þ can be
recycled by reaction with Fe3 þ that is present with the ZVI surface
(reaction (4)). Although the nZVI particle surfaces are passivated,
nZVI appears to be a promising persulfate activator compared to
the conventional persulfate activators such as Fe2 þ and granular
ZVI. Additional studies using Fe2 þ ion (instead of nZVI) and PS
indicated that SO4 d  was potentially effective in selectively
degrading toluene (reactions 5) in surfactant flushing effluents.
We believe that the further development of this approach could
lead to creation of persulfate-based methods for oil elimination.
Fe0 þ S2 O8 2  -Fe2 þ þ 2SO4 2  ð2Þ
Fe2 þ þ S2 O8 2  -Fe3 þ þ SO4 2  þ SO4 d  ð3Þ
2Fe3 þ þ Fe0 -3Fe2 þ ð4Þ
Oxide-based photo-assisted oxidation of organic pollutants (crude
oil in salt water) and their decomposition to eco-friendly consti-
tuents, through the use of oxide photocatalysts (CuO/WO3 nano-
grids) that absorb in the visible range of solar radiation, for the fast
and effective cleaning of the oil spill, was offered (Lee and Gouma,
2011). Its targeted use to decompose oil spills simulants (such as
benzene in sea water). These 3D CuO nanogrids were synthesized
by the combined use of electrospinning and thermal oxidation of a
composite metal mesh/polymer mat architecture. The obtained
nanogrids result from three steps encompassing: (1) Cu atom
clusters diffusing into the nanofibers producing polymer-metal
714 B.I. Kharisov et al. / Journal of Petroleum Science and Engineering 122 (2014) 705–718

Fig. 11. (a) Prolonged water squirt on the PU/NPs/PTFE sample. (b1,2,3,4) Mixed oil (colored with blue dye) and water drop are phase separated, and the oil is immediately
absorbed while water remains on the surface. The arrows in (b2) represent the absorption of the oil. Time interval between frames b2 and b3 is less than 1 s. (c) Experimental
setup used to determine the foams' oil-absorption capacity. The sample is kept in horizontal position by two needles, and the excess of oil lost through the foam is collected.
(For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
Source: Reproduced from Salem (2003) with permission.

exhibit reduced catalytic activity. Another difficulty in the use of

Fig. 12. Illustration of the fabrication of ultralight magnetic foams from a
polyacrylic acid (PAA)-grafted polyurethane sponge. The foams were constructed
from 3D interconnected microtubes having nanoscale wall thickness.
Source: Reproduced from Anpo and Takeuchi (2003) with permission.
“core-shell”-type fibers; (2) decomposition of the polymeric shell;
(3) oxidation of the metallic core of the nanofibers to form self-
supported, open nanogrids consisting of continuous nanofibers of
CuO nanoparticles with an average diameter of 20 nm. In general,
nanogrids – i.e. miniaturized “fishing nets” – like self-supported
mats that float on water – of these nanocatalysts rapidly decom-
pose crude oil and other contaminants using solar irradiation, and
fast and at low cost turn them into water, carbon dioxide, and
biodegradable organics (http://www.nsf.gov/awardsearch/show-
Award?AWD_ID ¼1156513). While current photocatalysts are acti-
vated by only about 2% of the solar irradiance, the nanogrids
respond to radiation from the full solar spectrum. In addition, solar
power is free. Apart from water remediation, immediate uses of
the nanogrids technology are envisioned in filtration, as well as in
biomedical and pharmaceutical industries.
The anatase phase of crystalline titania is considered to be an
excellent material for oil spill remediation, exhibiting high photo-
catalytic efficiency, resistance to deactivation, absorption in the
near ultraviolet range, stability in acidic and basic aqueous media,
activity under ambient temperatures, and an absence of biological
toxicity in bulk form (Hoffmann et al., 1995; Beydoun et al., 1999;
Salem, 2003; Anpo and Takeuchi, 2003; Na et al., 2009; Neatu et
al., 2009; (Narayan, 2010; Liu et al., 2010). Despite these impress-
ive photocatalytic and material properties, titania has not to this
point been incorporated within commercial oil spill remediation
products due to a series of complications (O’Regan et al., 1990;
Shanbhag et al., 1994; Xuzhuang et al., 2009). Titania in powder
form has a strong tendency to cluster; these agglomerations
titania for oil spill remediation has involved separation and
recovery of suspensions containing nanoparticles and/or micro-
particles after use. Unrecovered titania nanoparticles may enter
human or animal cells and demonstrate toxic effects. For example,
titania microparticles and nanoparticles were shown to inhibit 3H-
thymidine incorporation by human monocyte-macrophage cells.
However, for future uses, it is anticipated that titania-containing
materials, particularly titania incorporated within environmentally
acceptable bulk materials, will be used commercially in oil spill
remediation.
Nanoparticles of titanium dioxide when subjected to solar
irradiation can generate reactive oxygen species (ROS); coupled
with their high aspect ratio and their catalytic effect can degrade
(despite the problems above) crude oil components in water
pollutants into less harmful CO2 and H2O compounds. Fig. 14
represents a schematic diagram of the photo catalytic generation
of reactive oxygen species on TiO2 nanoparticles. These free
radicals have one or more unpaired electrons in their outer-most
shell and are hence capable of initiating and sustaining more chain
reactions. Once ROS generation is confirmed, the stock solutions of
the pollutants (crude oil spill) containing the desired concentra-
tion of the substrate could be prepared in double well photo-
chemical reactor equipped with a magnetic stirring bar, water
circulating jacket and an opening for supply of molecular oxygen
as shown in Fig. 15 (Ziolli and Jardim, 2001; Seery 2011; Agbe and
Ducati).
A type of water–oil separation material has been fabricated by
depositing mesoporous silica microspheres (MS) on filter paper
(Tao and Wang, 2014). MS (200–800 nm in diameter) had been
prepared via surfactant-template method and modified by octyl-
triethoxysilane (OTS). Uniform mesopores in the microspheres
were detected, and the surface area of the microspheres was more
than 1000 m2 g  1. The thin film, showing both hydrophobicity
and lipophilicity, presented excellent separating efficiency
between water and oil, which could reach 98.8%. In addition, the
ability of the modified zeolites to remove petroleum hydrocarbons
such as BTEX from oilfield wastewater was evaluated (Bowman,
2003). In particular, it was established that zeolites can be used
 B.I. Kharisov et al. / Journal of Petroleum Science and Engineering 122 (2014) 705–718 715

Fig. 13. Conceptual model that illustrates the formation of an iron sulfate complex on the surface of a nZVI particle.
Source: Reproduced from Tao and Wang (2014) with permission.

Fig. 14. Photo catalytic generation of ROS.

Source: Reproduced from Ziolli and Jardim (2002) with permission.
along with other techniques (chemical reduction by ZVI, biological
degradation by microorganisms) to provide combined contami-
nant retention and destruction. Also, the developments of nano-
wires made of potassium manganese oxide can clean up oil and
other organic pollutants while making oil recovery possible
(http://dujs.dartmouth.edu/winter-2009/turning-to-
nanotechnology-for-pollution-control-applications-of-
nanoparticles#.UuKqEtK3Xs0; Yuan et al. (2008). These nanowires
form a mesh that absorbs up to twenty times its weight in
hydrophobic liquids while rejecting water with its water repelling
coating. Since the potassium manganese oxide is very stable even
Fig. 15. The photocatalytic reactor for degrading oil spill.
Source: Reproduced from http://web.mit.edu/press/2010/seaswarm.html with
permission.
at high temperatures, the oil can be boiled off the nanowires and
both the oil and the nanowires can then be reused. On their basis,
an oil remediation and recovery application, which used the water
repelling nanowires to clean up the oil spilled by the damaged oil
platforms and refineries, was launched (Lamba). Finally, porous
boron nitride nanosheets with very high specific surface area
exhibited excellent sorption performances for a wide range of oils,
solvents and dyes (Lei et al., 2013). The nanostructured material
716 B.I. Kharisov et al. / Journal of Petroleum Science and Engineering 122 (2014) 705–718
absorbed up to 33 times its own weight in oils and organic
solvents while repelling water. The saturated nanosheets still float
on the cleaned water surface and are therefore easy to be
removed. The saturated boron nitride nanosheets can be readily
cleaned for reuse by burning or heating in air because of their
strong resistance to oxidation.
8. Toxicity of nanomaterials
As it is seen above, the nascent area of the treatment of oil
spills with nanomaterials possesses a series of successful attempts
and has advantages. However, at the same time, there are certain
risks associated with their use. The nanomaterials may have
negative impact on human health when these nanoparticles are
inhaled, absorbed through skin, or ingested. There is also some
scientific evidence, showing that the nanoparticles can travel
through the food chain from smaller to larger organisms. In
addition, they could damage important microbes in the environ-
ment. A number of studies exist concerning the toxicity of
nanoparticles (Uo et al., 2011; De Stefano et al., 2012; Khan and
Arif, 2012; Sharifi et al., 2012). Generally these studies suggest that
smaller particles are more toxic than larger ones, although large
differences among different particle types exist. It is thus impos-
sible to simply extrapolate toxicity data from bulk material to
nanoparticles. For instance, it is well-known fact that SiO2 in the
form of macroparticles (i.e., sand) is non-harmful and the nano-
silica is toxic. For carbon nanotubes (pristine CNTs are toxic), the
toxicity depends on their functionalization. The nanotoxicity is
currently not a well-developed area of knowledge, so certain
precautions are needed before extensive application of nanoma-
terials in the environment.
9. The best nanomaterial for water cleanup and oil
remediation: does it exist?
Despite on an apparent variety of nanomaterials, nanocompo-
sites, absorbents, and oxidative reagents, it seems difficult to
conclude definitely, what is the most appropriate method and
material/substance for oil remediation. Many factor influence on
such a decision: simplicity of nanomaterial fabrication, stability in
air and water, possible decrease of its activity, final products of its
use and their toxicity, and costs of production, storage, and
application. For example, in case of the nZVI, cost uncertainties,
nanoparticle performance (nZVI particles are extremely reactive
and oxidize fairly rapidly at air contact), tendency to agglomerate
and adhere to solid surfaces, result their limited usage, while their
final dissolution and low toxicity are in favor of their use. The
fabrication of carbon nanotubes is still expensive, although high
absorption capacity and possibility to form magnetic composites
with iron and its oxides is a considerable advantage. Using
magnets, it would allow the oil being then reused, so as to offset
the costs of cleaning. CNT sponge was superhydrophobic and did
not adsorb any water during oil spill cleanup. The hydrophobic
aerogel granules showed a very high uptake capacity and high rate
of uptake. In case of TiO2, despite impressive photocatalytic and
material properties, titania has not to this point been incorporated
within commercial oil spill remediation products due to a series of
complications (tendency to cluster; involvement of separation and
recovery of suspensions containing nanoparticles and/or micro-
particles after use; unrecovered titania nanoparticles may enter
human or animal cells and demonstrate toxic effects).
All these and other obstacles, together with advantages of each
method, cause the need to expand the number of possible
nanomaterials for water cleanup and oil remediation, allowing a
selection of their usage depending on conditions of application
{close of far from clean water sources, cities and villages, current
temperature, type of water (percentage of salts), geological struc-
ture of oil wells, work in situ or ex situ, etc.}. From the point of view
of toxicity, absence of wastes, the nZVI or its combinations with
persulfates use seems most appropriate in some cases; in others,
use of absorbents or treatment with magnetic nanoparticles could
be more attractive. So, possible application each time depends on
concrete conditions and scale. In case of costs, a useful discussion
on the commercial viability of the nanotechnologies is given in an
excellent review (Mahajan, 2011). Thus, the author notes that the
aerogel is one of the prime candidates for the mitigation of oil
spills; however, its high cost is a major inhibiting factor for its
widespread adoption. Currently, the typical cost of aerogel pro-
duced by supercritical drying is about $2870 per kg while the
aerogel made from discarded rice husks is reported to cost only
$276 per kg, thereby making the latter a commercially viable
proposition. CNTs, CNT sponges and other carbon nanostructured
materials, as well their magnetic nanocomposites, also have great
potential for oil spill cleanup due to their outstanding properties.
MWCNTs are priced at $100–150/kg and expected to reduce to
$10–20/kg in the near future. The present price of graphene
nanoplatelets is $385–525/kg and it is predicted that nanoplatelets
could be produced at $11/kg. Therefore, it is likely that these
technologies could become commercially viable solutions for oil
spill cleanup in the future. Other performance factors such as
sorption capacity, rate of sorption of crude oil, regeneration factor,
recyclability, cost of disposal of the material, nanosorbents based
on naturally occurring materials like cotton, jute, wood, as well as
nanoengineered mineral products such as sand, perliteor scoria,
are also discussed.
10. Conclusions and further outlook
Oil spill remediation using engineered nanomaterials seems to
be a more effective option than conventional techniques as it leads
to improved response and the effects, which are distinct in
comparison with those caused by using conventional chemicals.
The superior performance of nanomaterials can be attributed to
their increased surface area and, in turn, higher reactivity as well
as the possibility of in situ treatment. Capture of oil impurities
with magnetic nanoparticles and its further elimination by mag-
nets, in our point of view, need to be optimized. Despite their
possible toxicity, nanomaterials are proven to have enormous
potential to provide innovative solutions for oil spill cleanup by
virtue of their unique structure, superior properties and outstand-
ing performance. As a future work in this direction, the methods
based on triple systems {nanosorbent/nZVI/strong oxidant (for
example organic or inorganic peroxides); aerogel/oxidant/mag-
netic nanoparticles (for magnetic recovery)} seem to be very
promising, as well as a search of nanoengineered materials on
the basis of low-cost natural minerals or naturally occurring
materials.
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