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Marine Pollution Bulletin 109 (2016) 14–45

Contents lists available at ScienceDirect

Marine Pollution Bulletin

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

Review

A comprehensive guide of remediation technologies for oil contaminated


soil — Present works and future directions
Mee Wei Lim, Ee Von Lau ⁎, Phaik Eong Poh
School of Engineering, Monash University Malaysia, Jalan Lagoon Selatan, 47500 Bandar Sunway, Selangor Darul Ehsan, Malaysia

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

Article history: Oil spills result in negative impacts on the environment, economy and society. Due to tidal and waves actions, the
Received 20 January 2016 oil spillage affects the shorelines by adhering to the soil, making it difficult for immediate cleaning of the soil. As
Received in revised form 7 April 2016 shoreline clean-up is the most costly component of a response operation, there is a need for effective oil remedi-
Accepted 11 April 2016
ation technologies. This paper provides a review on the remediation technologies for soil contaminated with var-
Available online 4 June 2016
ious types of oil, including diesel, crude oil, petroleum, lubricating oil, bitumen and bunker oil. The methods
Keywords:
discussed include solvent extraction, bioremediation, phytoremediation, chemical oxidation, electrokinetic re-
Oil spills mediation, thermal technologies, ultrasonication, flotation and integrated remediation technologies. Each of
Oil contaminated soil these technologies was discussed, and associated with their advantages, disadvantages, advancements and future
Remediation technologies work in detail. Nonetheless, it is important to note that no single remediation technology is considered the best
Review solution for the remediation of oil contaminated soil.
Advancement Capsule: This review provides a comprehensive literature on the various remediation technologies studied in the
removal of different oil types from soil.
© 2016 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2. Biological remediation technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
2.1. Bioremediation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
2.1.1. Bioaugmentation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
2.1.2. Biostimulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.1.3. Bioventilation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
2.1.4. Advantages and limitations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
2.1.5. Advancements & future work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
2.2. Phytoremediation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
2.2.1. Phytostabilization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
2.2.2. Phytodegradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
2.2.3. Phytovolatization. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
2.2.4. Rhizodegradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
2.2.5. Advantages and limitations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
2.2.6. Advancements and future work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
3. Chemical remediation technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
3.1. Chemical oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
3.1.1. Fenton's reagent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
3.1.2. Ozone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
3.1.3. Other oxidants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
3.1.4. Advantages & limitations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
3.1.5. Advancements and future work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
3.2. Electrokinetic remediation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26

⁎ Corresponding author.
E-mail addresses: lim.mee.wei@monash.edu (M.W. Lim), lau.ee.von@monash.edu (E.V. Lau), poh.phaik.eong@monash.edu (P.E. Poh).

http://dx.doi.org/10.1016/j.marpolbul.2016.04.023
0025-326X/© 2016 Elsevier Ltd. All rights reserved.
M.W. Lim et al. / Marine Pollution Bulletin 109 (2016) 14–45 15

3.2.1. Electrokinetic studies. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26


3.2.2. Advantages & limitations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
3.2.3. Advancements and future work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
4. Thermal remediation technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
4.1. Incineration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
4.2. Thermal desorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
4.3. Microwave frequency heating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
4.4. Advantages & limitations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
4.5. Advancements and future work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
4.5.1. After effects of thermal remediation (soil health and air pollution) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
4.5.2. Numerical modelling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
4.5.3. Advancements in microwave technology as a feasible thermal remediation technology . . . . . . . . . . . . . . . . . . . . . . 29
5. Physical–chemical remediation technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
5.1. Solvent extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
5.1.1. Water/organic solvents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
5.1.2. Surfactant-aided extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
5.1.3. Subcritical fluid extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
5.1.4. Supercritical fluid extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
5.1.5. Advantages & limitations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
5.1.6. Advancements & future work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
5.2. Soil vapour extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
5.2.1. Air sparging/SVE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
5.2.2. Bioventing/SVE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
5.2.3. Thermally enhanced SVE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
5.2.4. Advantages & limitations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
5.2.5. Advancements and future work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
5.3. Flotation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
5.3.1. Flotation studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
5.3.2. Advantages & limitations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
5.3.3. Advancements and future work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
5.4. Ultrasonication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
5.4.1. Ultrasonication studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
5.4.2. Advantages & limitations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
5.4.3. Advancements and future work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
6. Integrated remediation technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
6.1. Integrated physical–chemical remediation technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
6.2. Integrated physical–biological remediation technology. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
6.3. Integrated chemical–biological remediation technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
6.4. Advancements and future work of integrated remediation technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
7. Final recommendations and conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40

1. Introduction 2011). Tang et al. (2011) investigated on the toxic effects of petroleum
soil contamination of up to 10.57% on the earthworm, bacteria and
In the past, marine oil spills have caused devastating impacts on both plant. The death rate of earthworms was at 90% after 7 days at oil con-
shorelines and seas due to the hazardous property of the oil. In 1978, the tent of 2%, while no earthworms survived in the soil contaminated
large oil spill due to the Amoco Cadiz in France released over with oil content of 3% and more. Likewise, inhibition rate of bacteria is
223,000 tonnes of light crude oil and 4000 tonnes of bunker oil, contam- nearly 100% at petroleum content of 1%. In terms of plant germination
inating a total shoreline length of 320 km up to a depth of 20 inches at oil content of 3%, the germination inhibition rate of maize and
(Conan et al., 1982; Haensly et al., 1982). Failure to remove oil from wheat is 51.3% and 48.4% respectively. The root growth also showed
the shoreline resulted in a long term contamination, with layers of oil similar trend whereby higher concentrations of oil inhibit the growth
still remained buried in the beach site up to 8 years after the oil spill in- of roots (Tang et al., 2011). Similarly, increase in oil concentration
cident (Page et al., 1988). Similarly the Exxon Valdez oil spill in 1989 from 31 mg/kg to 1000 mg/kg was found to vastly decrease the survival
which spilled 11 million gallons of crude oil into the sea drifted and dam- rate of earthworms from 80% to 33% after 14 days (Hentati et al., 2013).
aged up to 1300 miles of shoreline (Paine et al., 1996). Despite the efforts In addition, a recent study by Ramadass et al. (2015) also showed that
in clean-up, only 10% of the oil was recovered (Bragg et al., 1994). A used motor oil concentrations of greater than 3.88 g/kg soil caused com-
study by National Oceanic and Atmospheric Administration (NOAA) plete mortality of earth worms. Clearly, it could be seen that the oil spill-
showed that more than 87 m3 of oil still remains in the Alaska's sandy age on soil greatly impacts the surrounding environments, which
soil in the contaminated beaches shoreline as of 2010, breaking down highlights the urgent need for effective removal of oil contaminant
at a rate estimated at 4% per year (Register, 2010). Table 1 summarizes from soil.
the top 10 largest oil spills and the corresponding clean-up costs, ranging At present, most clean-up efforts for oil spill on soil and shoreline re-
from controversial oil spills to accidental oil spills in history. quire mechanical and labour intensive methods as they may be a quick
The toxicity of oil spills on contaminated soil is of a great concern es- and simple solution to remove oil contaminants (Broman et al., 1983).
pecially on the environment, and this issue had been highlighted by sev- However, there are many disadvantages associated to these methods.
eral groups of researchers (El-Sheshtawy et al., 2014; Gao et al., 2015; For instance, the usage of high pressure washing to displace oil may de-
Hentati et al., 2013; Kanarbik et al., 2014; Ma et al., 2014a; Tang et al., stroy the microbial populations, while the chemical sorbents and
16 M.W. Lim et al. / Marine Pollution Bulletin 109 (2016) 14–45

Table 1
Top 10 largest marine oil spills in history (Conan et al., 1982; Haensly et al., 1982; Page et al., 1988).

No Name of oil spill Year Place of oil spill Type of fuel Amount of oil spilled Clean-up cost
(million gallons) estimated
in 2010 (US dollars)

1 Gulf War January 23, 1991 Persian Gulf, Kuwait Crude oil 240–336 $ 540 million
2 Deepwater Horizon April 20, 2010 Mexican Gulf, Mexico Crude oil 210 $ 10 billion
3 Ixtoc 1 oil well June 3, 1979 Mexican Gulf, Bay of Champeche Crude oil 140 $ 283.9 million
4 Atlantic Empress oil spill July 19, 1979 Carribean Sea, off the coast of Trinidad Light crude oil 9 $ 187 million
and Tobago
5 Nowruz oil field February 10, 1983 Persian Gulf, Nowruz Field Platform Oil 80 $161.5 million
6 ABT Summer May 28, 1991 Off coast of Angola, Africa Iranian crude oil 80 $ 163.2 million
7 Castillo de Bellver oil spill August 6, 1983 Table Bay; Saldanha Bay, South Africa Light crude oil 78.5 $ 153 million
8 Amoco Cadiz March 16, 1978 Brittany coast, up to Channel Islands; Light Iranian and Arabian 68.7 $ 136 million
Portsall, France crude oil & bunker fuel
9 M/T Haven Tanker oil spill April 11, 1991 Mediterranean Sea; Genoa, Italy Crude oil 45 $ 85 million
10 Odyssey oil spill November 10, 1988 North Atlantic, off the coast of Nova Scotia North Sea crude oil 43 $ 86.7 million

dispersants may be harsh to the environment. In addition, these me- small-scale study prior to actual on-site bioremediation of contaminat-
chanical methods are tedious, time consuming and are only capable of ed soil.
removing the oil contaminants up to a certain extent, leaving behind a Therefore, it could be seen that the bioremediation demonstrated
large amount of oil adsorbed in the soil. These conventional first re- high potential to successfully remediate oil contaminated soil. The suc-
sponse actions are therefore not able to achieve efficient clean-up of cess of bioremediation could be attributed to the three common mech-
oil spills under a short period of time. anisms, which are bioaugmentation, biostimulation, and bioventilation.
Therefore, there is an urgent need to investigate on other
environmental-friendly remediation methods to remove oil contami- 2.1.1. Bioaugmentation
nants in soil. To date, there is a variety of technologies available for Bioaugmentation is defined as the enhancement of performance of
the remediation of oil contaminated soil, ranging from widely applied microorganism populations through the addition of genetically
technologies such as solvent extraction and bioremediation to the engineered bacteria with specific catabolic activities, isolated bacterial
emerging technologies such as electrokinetic remediation and sonica- strains or enrichment consortia to increase the rate of degradation
tion. The remediation technologies for oil contaminated soil can be clas- (Abdulsalam et al., 2011). In other words, an external source of oil
sified into biological, chemical, thermal and physicochemical methods. degrading bacteria is added to the existing microbial population to
The following sections will discuss about the remediation technologies boost the oil degradation rate. The criteria for choosing microbes are
in detail. the physiology and metabolic ability of the microbes to degrade the oil
contaminated soil (Boopathy, 2000). Since there are no single strain of
bacteria which has the sufficient metabolic capacity to efficiently de-
2. Biological remediation technologies grade all the oil components, many studies have focused on various
types of bacteria and fungi for the remediation of oil contaminated soil.
2.1. Bioremediation The efficiency of crude oil degradation of individual bacterial cul-
tures and designed bacterial consortium was tested by Rahman et al.
Bioremediation is viewed as a method to accelerate the natural bio- (2002). Five bacterial strains (Micrococcus sp. GS2-22, Corynebacterium
degradation process of oil samples, via the supply of nutrients and oxy- sp. GS5-66, Flavobacterium sp. DS5-73, Bacillus sp. DS6-86 and Pseudo-
gen required by the bacteria or through external treatments such as monas sp. DS10-129) were selected for the study out of 130 oil
aeration or temperature control (Hoff, 1993). The bioremediation tech- degrading bacterial cultures, due to their efficiency for crude oil degra-
nology had been developed since the 1940s, but only gained popularity dation. Results showed that a mixed bacterial consortium from these
in the 1980s due to the famed Exxon Valdez oil spill (Bragg et al., 1994; bacterial strains showed up to 78% of oil degradation efficiency after
Hoff, 1993). Table 2 shows a compilation for bioremediation studies to 20 days of sampling period. This was also shown in studies reported
date in the remediation of oil contaminated soil. by Singh et al. (2012) where the use of microbial consortia reduce the
In a field study in 1994, the effectiveness of PES-51 a biosurfactant petroleum contaminant in soil from 30.9% to 0.97% after 360 days of
was investigated for the removal of weathered crude oil from contami- treatment, as compared to only 5% of reduction in the control plot.
nated sand from the Exxon Valdez oil spill at La Touche Island, Prince While the addition of external bacterial consortium could enhance
William Sound. The results from the investigation showed that all the oil degradation, it is noted that the indigenous oil-degrading microor-
diesel range oil was removed below the detection limit of 0.5 mg/kg. ganisms in most environments could accomplish natural attenuation
70% of the semivolatile components was removed as a result from the of the oil contaminant if the environmental conditions are not the lim-
biodegradation as well (Tumeo et al., 1994). Other in situ studies also iting factor (Nikolopoulou et al., 2013a). Hence Ueno et al. (2007) inves-
showed similar enhanced results with the addition of fertilizers (Bragg tigated on the potential use of microorganisms exclusive from the
et al., 1994; Prince et al., 2003) or external microbe for the removal of contaminated soil/sand site, and this concept of bioaugmentation is de-
oil from soil. However, the addition of nutrients/external microbial con- fined as autochthonous bioaugmentation. These microbes are obtained
sortium may not necessarily increase the oil removal efficiency as dem- from the contaminated site, and further enhanced by enriching the bac-
onstrated in works by Venosa et al. (1996). The addition of water teria under similar conditions of the site, and the autochthonous mi-
soluble nutrients with and without the supplement of natural microbial crobe would be better equipped to degrade the oil contaminant from
inoculum for the degradation of crude oil on the shoreline of Delaware soil (Nikolopoulou et al., 2013b; Ueno et al., 2007). A study by Roy
Bay did not provide a significant increase in the remediation rate as et al. (2014) was also conducted on the bioremediation of crude oil con-
compared to natural attenuation of oil. This was attributed to the high taminated soil using four native crude oil degrading bacterial strains
levels of nitrogen already existing in the soil levels, which is sufficient (Pseudomonas aeruginosa AS03, P. aeruginosa N108, P. aeruginosa
to support the oil biodegradation. Thus, tailor-made biological remedia- N002, and Achromobacter xylosoxidans N78). The combination of these
tion plans specific to the contaminated site are usually required in a bacterial strains and fertilizers showed an overall 80% decrease of
M.W. Lim et al. / Marine Pollution Bulletin 109 (2016) 14–45 17

Table 2
Bioremediation of oil contaminated soil.

Type of Additions/supplement specific Oil contaminant Contaminant Process Maximum Reference


addition/supplement name limit duration removal
efficiency (%)

Fertilizer Oleophilic fertilizer Petroleum 2500 mg/kg 38 days 80% (Margesin et al., 2007)
Microorganism and fertilizer Bacterial consortium and nutrient Crude oil 10 w/w% 18 months 99.9% (Singh et al., 2012)
mixture
Soluble and slow-release Prilled ammonium nitrate, super IF-30 fuel grade oil Up to 6% 7 days 89.3% (Prince et al., 2003)
fertilizer phosphate, ferrous sulfate, yeast
extract, Inipol SP1
Microorganism and fertilizer Microbial consortium (Nocardia Heavy crude oil 5.4% 41 days 7.4% (Trindade et al., 2005)
nova & Rhodotorula glutinis var.
dairenesis); inoculum, nutrients
Biopolymer and fertilizer Chitosan and Osmocote (slow Arabian light crude oil 3.5 w/w% 56 days 99.7% (Xu et al., 2005)
release fertilizer) (ALCO)
Biosurfactant PES-51 Weathered crude oil 100 μg/g 3 months 70% (Tumeo et al., 1994)
Fertilizer Bacterial consortium, inorganic Petroleum refinery sludge 5 w/w% 90 days 76% (Vasudevan and Rajaram, 2001)
nutrients (ammonium nitrate &
dipotassium hydrogen
phosphate), compost and bulking
agent (wheat bran)
Commercial product OSEII® (Oil Spill Eater Diesel fuel 10,336 mg/kg 45 days 49.4% (Dias et al., 2012)
International, Corp.)
Metal Cd, Cu, Pb Arabian light crude oil b26 μg/g 15 days 32% (Almeida et al., 2013)
Biosurfactant Guar gum Diesel fuel 4600 mg/kg 12 weeks 82% (Hernández-Espriú et al., 2013)
Air flow Oxygen B20 (80% diesel, 4 w/w% N60 days 85% (Thomé et al., 2014)
20% biodiesel)
Organic solid waste Soycake Diesel 5 w/w% 18 weeks 81% (Dadrasnia and
15 w/w% 42% Agamuthu, 2014)
Microorganism and fertilizer Pseudomonas aeruginosa AS03, Crude oil 2 v/v% 24 weeks 80% (Roy et al., 2014)
Pseudomonas aeruginosa N108,
Pseudomonas aeruginosa N002,
Achromobacter xylosoxidans N78
Fertilizer NH4Cl and NaH2PO4 Arabian oil 55.2 ppm 63 days 9.6%a (Abed et al., 2015)
Biosurfactant Paenibacillus dendritiformis CN5 Motor oil 20 w/w% 24 h 81% (Bezza and Chirwa, 2015)
Organic waste Sugarcane bagasse and oil palm Crude oil 3 v/w% 20 days 100% (Hamzah et al., 2014)
empty fruit bunch, Pseudomonas
aeruginosa UKMP-14T and
Acinetobacter baumannii
UKMP-12T
Microbial inoculates Pseudoallescheria sp., Petroleum 5 g/L 60 days 79.7% (Covino et al., 2015)
lignocellulosic mixture
Microbial inoculates S. saprophyticus UFPEDA 800 and S. Diesel 10 v/v% 7 days 69% (Silva et al., 2015)
marcescens UFPEDA 839 and the
yeasts R. aurantiaca UFPEDA 845
and C. ernobii UFPEDA 862
Microbial consortium Burkholderia cepacia GS3C, Crude oil 5000 mg/kg 40 days 64.4% (Shen et al., 2016)
Sphingomonas GY2B and
Pandoraea pnomenusa GP3B
strains
a
Maximum percentage of oil degraded at 50 °C.

crude oil (2 v/v%) after 24 weeks of testing. Covino et al. (2015) also evaluated the effect of addition of two biostimulating agents, which
assessed the application of autochthonous filamentous fungi from pe- are Bioversal surfactant (commercial surfactant agent) and inorganic
troleum polluted clay soil for the degradation of aliphatic petroleum hy- fertilizer NPK. The maximum degradation efficiency showed the highest
drocarbons from clay soil. Results from this study showed a 79.7% rate of degradation at 50% and 63% in 10 g/kg and 20 g/kg diesel con-
degradation of 5 g/L oil in clay soil augmented with Pseudoallescheria taminated soil respectively, under a blend of surfactant and NPK.
sp. and lignocellulosic mixture as a slow-release fertilizer after 60 days.
Likewise, an ex situ bioaugmentation study by Varjani et al. (2015) 2.1.2. Biostimulation
showed significant crude oil (3 v/v%) degradation of up to 83.7% after Biostimulation involves the adjustment of environmental parame-
75 days. The hydrocarbon utilizing bacterial consortium (HUBC) ters such as limiting nutrients such as slow-release fertilizers,
consisting of six bacterial isolates viz. Ochrobactrum sp. (01), biosurfactants and biopolymers (Prince et al., 2003) that could stimu-
Stenotrophomonas maltophilia (02) and P. aeruginosa (03) was obtained late the growth of oil degrading microorganisms and increase the bio-
from crude oil polluted soil samples in India isolated from crude oil pol- degradation rate of the natural microorganisms affected on site. The
luted sites of ONGC fields of Gujarat, India. This study showed the HUBC influence of nutrient amendments is apparent as demonstrated by
potential for the biodegradation of hydrocarbon contaminants, and fur- Chaineau et al. (2005) whereby the biodegradation of crude oil in soil
ther studies were conducted to evaluate the potential of HUBC for the was investigated over a series of fertilized and unfertilized soil for a pe-
degradation of hydrocarbons in situ (Varjani et al., 2015). Other recent riod of 150 days. The soil added with nitrogen, phosphorus, and potas-
autochthonous studies include investigation of the response of autoch- sium at a ratio of 170:17:48 (low fertilization) showed the highest
thonous microbiota in diesel polluted soils to different biostimulating biodegradation rate at 62% in comparison with unfertilized soil at 47%
agents. Silva-Castro et al. (2015) studied the microbial activity in soils of degradation. Likewise, a recent study by Abed et al. (2015) showed
contaminated with two concentrations of diesel (10 and 20 g/kg) and that the addition of nutrients (NH4Cl and NaH2PO4 as N and P sources)
18 M.W. Lim et al. / Marine Pollution Bulletin 109 (2016) 14–45

for biostimulation of oil polluted desert soil resulted in a 20% increase to scale (Boopathy, 2000; Hoff, 1993; Mearns, 1997; Naseri et al., 2014;
give an oil removal efficiency of 9.6% at 50 °C. The biostimulation effi- Prince, 1993; Swannell et al., 1996; Venosa and Zhu, 2003). In general,
ciency for untreated soil was reported to be at 8.0% under similar condi- bioremediation has demonstrated success in both in situ and ex situ re-
tions. While the addition of nutrients affects the success of mediation of oil contaminated soil. These technologies are capable of
biostimulation, Abed et al. (2015) noted that elevated temperatures degrading the oil contaminants permanently without leaving behind
could further stimulate the activity of thermophilic oil degrading bacte- any adverse long-term toxic effects on the environment. In addition,
ria in desert soils, while a high salinity condition would slow down the this remediation method is low cost, eliminates wastes permanently
growth rate and degradation capacity of bacteria due to the reduced ox- and does not disrupt the environment. Moreover, biological treatments
ygen availability and hydrocarbons solubility. are widely accepted by the society due to their aesthetically pleasing
The type of fertilizers used plays an important role in the oil degra- and low-cost alternative.
dation as demonstrated by Emami et al., 2014. The impact of different However, these technologies require long treatment durations up to
forms of nitrogen fertilizer (NO3-N and NH4-N) was investigated for several years to acquire satisfactory removal efficiency results. It was
the removal of petroleum from contaminated soil. The addition of also observed that high concentrations of oil contaminants render the
NH4-N showed better oil removal efficiency due to its high recovery of activity of the microbial community which resulted in low removal effi-
soil germination capability and better respiration values. Nevertheless, ciencies. Margesin et al. (2007) reported that the total petroleum hydro-
the type of fertilizer used for oil degradation is not limited to nitrogen carbon losses for unfertilized soil samples showed a 60% drop with an
fertilizer only. Present studies showed that various biowastes including increase in initial diesel contamination from 2500 to 20,000 mg/kg
soycake (Dadrasnia and Agamuthu, 2014), poultry droppings (Ezenne soil, attributed to the high toxicity of soil environment, which is not con-
et al., 2014), oil palm empty fruit bunch and sugarcane bagasse ducive for microbial activity. Similar results were obtained using NPK
(Hamzah et al., 2014) have been successfully used as fertilizers to im- fertilized and oleophilic fertilized soil, whereby a drop of 34% and 33%
prove the bioremediation and degradation of oil contaminated soil. In was observed respectively with the increase in initial oil contamination
a separate study, Jung et al. (2014) reported that the presence of red concentration. In addition, the results from biological treatments are in-
clay enhanced the diesel biodegradation by a factor of up to 6.7; consistent, as these treatments are highly dependent on the contami-
which was attributed to the bacterial growth from the presence of red nant, weather and soil parameters such as temperature, pH, salinity,
clay. contaminant composition, contaminant concentration, and weathering
Biosurfactant is another well-studied nutrient as it is non-toxic and effect. For example, high temperatures may affect the concentration of
biodegradable as well. The presence of biosurfactant would accelerate microbial community (Venosa and Zhu, 2003), while extreme pH levels
the biodegradation capability by dispersing the oil. The biosurfactants in soil could be toxic to bacteria and/or fungi. A study by Rahman et al.
are able to increase the substrate bioavailability for the microorganisms, (2002) reported that a pH of 7.5 provides the optimum biodegradation
and are also able to increase the hydrophobicity of cell surface, which al- of crude oil of 78%, while extreme pHs were shown to reduce the ability
lows the hydrophobic substrate to interact freely with the bacterial of microbial populations to degrade the hydrocarbons. The weathering
cells. The effect of cyclodextrin, a form of biosurfactant, on soil bioreme- effect on the oil also affects the efficiency of bioremediation. Trindade
diation and soil toxicity and on soil contaminated with diesel and min- et al. (2005) studied the effect of weathering process on the bioremedi-
eral oil at concentrations of 46,290 and 47,170 mg/kg respectively was ation of 4-year weathered heavy crude oil contaminated soil as com-
investigated by Gruiz et al. (1996) . The addition of randomly methylat- pared to a recently spiked contaminated soil. In both conditions, the
ed β-cyclodextrin (RAMEB) resulted in a slight increase in the removal soil was contaminated with 5.4% of TPH. The maximum bioremediation
efficiency of 2.6% and 4.8% respectively for diesel and mineral oil com- efficiency of the weathered contaminated soil with nutrient supplement
pared to treatment without the use of RAMEB. Besides increasing the was found to be 7.4% after 41 days of biodegradation treatment, which is
biodegradation of hydrocarbons, the RAMEB was found to decrease approximately three times greater compared to biodegradation effi-
soil toxicity and subsequently enhanced further growth of plant roots ciency of recently spiked soil of 2.4%. This was attributed to the adapta-
from 5 to 20 mm. The effects of cyclodextrin concentration in bioreme- tion of native microbial population to the high pollutant concentration
diation of soil contaminated with transformer oil were also reported by in the weathered soil that contributed to the higher biodegradation ef-
Molnar et al. (2005). This study showed that the increase in oil removal ficiency of oil. The authors however noted that while the adaption of mi-
efficiency is attributed to the enhanced availability of aerobic heterotro- crobial concentration is important, the high crude oil concentration in
phic and oil-degrading bacteria, up to 57% due to the presence of sample would inhibit the microorganism growth and limit the biodeg-
RAMEB. As RAMEB is a biodegradable compound, the authors also radation efficiency.
noted that the environmental risk associated with the RAMEB is also
considerably lower. 2.1.5. Advancements & future work

2.1.3. Bioventilation 2.1.5.1. Specific and genetically modified microbial consortium activities.
Bioventilation or bioventing involves the addition of oxygen to the The application of bioremediation had been extensively investigated
soil voids to stimulate the growth of microorganisms. The presence of throughout decades for the remediation of oil contaminated soil.
oxygen is necessary to produce an aerobic condition for the microorgan- While bioremediation has a huge potential for onsite remediation of
isms, as aerobic conditions could enhance the metabolism of organic contaminated soil, this method is not universal for all contaminated
matter and generate more energy. A recent study by Thomé et al. sites due to the different biological activities. Szulc et al. (2014) sug-
(2014) assessed the bioventilation method for the remediation of clay gested that the strategy for the success of bioremediation on site is by
soil contaminated with 4 wt% of B20, a blend of diesel and biodiesel conducting laboratory tests to select the microorganisms for
fuel. A maximum degradation efficiency of 85% was obtained via inoculation. The authors studied on the influence of bioaugmentation
bioventing as opposed to 64% from natural attenuation after 60 days and biosurfactant addition for bioremediation of soil artificially contam-
of remediation, which shows that oxygen air flow enhanced microbial inated with diesel (1 w/w%). The study was conducted for 365 days in
activity and increased degradation of contaminant. both laboratory and field scale using the same type of soil. The laborato-
ry tests were conducted to select the microbial consortium (Aeromonas
2.1.4. Advantages and limitations hydrophila, Alcaligenes xylosoxidans, Gordonia sp., Pseudomonas
The use of bioremediation for oil contaminated soil remediation had fluorescens, Pseudomonas putida, Rhodococcus equi, S. maltophilia,
been extensively researched on, and to date there are many reviews Xanthomonas sp.) that could best degrade the diesel in the contaminat-
available of bioremediation techniques in both laboratory and field ed soil. Following that, the bioremediation was only then conducted on
M.W. Lim et al. / Marine Pollution Bulletin 109 (2016) 14–45 19

field studies, and the results obtained showed that the introduction of The addition of these inorganic nutrients was reported successful in
microbial consortium for bioaugmentation provided the highest diesel aiding the bioremediation, but the leaching of these nutrients into the
oil degradation efficiency of 89% as opposed to 53% without the addition groundwater or any water source could promote algal blooms which
of microbial consortium. The initial laboratory tests to select the micro- would adversely affect the water quality. An alternative to these inor-
organisms for inoculation prior to the in situ work could increase the ganic nutrients is the usage of organic matter derived from plant or an-
chances for success in the field studies as demonstrated in the results. imals. Horel et al. (2015) investigated on the effect of plant (Spartina
Another method to select the microorganisms that could remediate alterniflora) and fish tissue (Chloroscombrus chrysurus) organic matter
the oil contaminated soil is by using the diagnosis method, successfully on the degradation of weathered diesel fuel in sub-tropical sediments.
developed by Kim et al. (2014). The authors had successfully developed The addition of fish tissue was found to significantly increase the degra-
a DNA diagnostic method via an oligonucleotide microarray method dation rates by 104% as compared to inorganic nutrients of nitrogen and
that could select sites that are suitable for bioremediation by detecting phosphorus of 57%, while the addition of plant base organic matter only
microbacterial strains that would lead to hydrocarbon degradation. Re- marginally enhanced the degradation rate by 7% after 42 days. The re-
sults from the DNA diagnosis showed that the remediation of contami- sults showed that the addition of animal based organic material could
nated soil was implemented successfully. This diagnosis would be able enhance the hydrocarbon degradation rate for a successful removal of
to reduce any trial and error, as it could determine the candidate site diesel contaminant from sandy soils.
for bioremediation while assessing the bioremediation progress. Recent works had also been focused on the production of various hy-
While much work had been performed on the effectiveness of sever- drocarbon degrading biosurfactants that are low in toxicity, stable
al bacterial consortiums on the biodegradation of oil, the study on the under heat and alkaline conditions, lower surface tension, while in-
effect of oil on the microbiological matter is currently lacking. Recent creasing oil contaminant solubility. In current literature, the production
work from Smułek et al. (2015) studied on the interaction between of biosurfactant by the following microorganisms: Pseudomonas spp.,
Rahnella sp. strain EK12 cell surface with natural diesel surfactants Acinetobacter spp., Bacillus sp., Streptomyces spp., Rhodococcus spp.,
after long term contact with diesel oil. The study showed significant Achromobacter spp., Brevibacterium spp., and Arthobacter spp. has been
changes in the hydrophobicity, zeta potential and fatty acids profiles, thoroughly reviewed (Petrikov et al., 2013; Xia et al., 2014). Currently,
after interaction with the tested oil surfactants, attributed to genetic research had been focused on finding a novel hydrocarbon degrading
modifications in the genes encoding components of capsules. The re- biosurfactants that would enhance the biodegradation of contaminant.
sults suggest that there is an impact on the genetic material of bacteria Ayed et al. (2015) had successfully produced a biosurfactant from a bac-
after long term interaction with the oil contaminant. Recent works by terial strain Bacillus amyloliquefaciens An6 that has a good stability over
Wu et al. (2015) had also simulated the molecular modelling of the in- a wide range of temperature, pH and salinity while effectively enhances
teractions between the heavy crude oil and soil organic matter to eval- the solubility of diesel by up to 10% as compared to SDS or Tween 80 re-
uate the mobility, diffusivity and partitioning of crude oil fractions such spectively. A significant increase of up to 30% in biodegradation capabil-
as saturates, aromatics, resins and asphaltenes on soil organic matter. ity was observed after the addition of 2 g/L of biosurfactant. Likewise,
The authors concluded that the addition of soil organic matter promotes Bezza et al. (2015) also reported the production of an efficient
the bioavailability of heavy crude oil in an environmental friendly man- biosurfactant from Ochrobactrum intermedium CN3 for degradation of
ner, attributed to the mobilization of oil contaminant by soil organic petroleum. The biosurfactant exhibited tolerance to high temperatures,
matter. extreme salinity and pH, while producing a 70% degradation of petro-
A similar study was conducted by Bastida et al. (2015) to investigate leum sludge in a span of 3 weeks. This shows the potential application
the impact of crude oil contamination on the biomass, composition and of biosurfactant isolated from bacterial strains for the application of bio-
functionalities of the microorganisms, and the corresponding biostimu- remediation of oil contaminated soil.
lation capability with the addition of compost. The results showed that
the decrease of metaproteome of compost-treated soil would increase 2.1.5.3. Better methodologies for bioremediation applications. As men-
the removal of oil by up to 88% as opposed to no significant oil removal tioned earlier, the efficiency of bioremediation is affected by the follow-
through the natural biodegradation of soil without compost. This ing parameters: (i) addition of oil-degrading microorganisms, (ii)
metaproteomic analysis was therefore useful to determine the function- presence of nutrients such as dissolved oxygen, nitrogen and phospho-
al and phylogenetic relationships between petroleum contamination rus, and (iii) environmental factors (Margesin et al., 2007; Mearns,
and microbial community, which would lead to an enhanced under- 1997); and therefore current oil remediation works are focused on
standing of the biodegradation mechanism. Experimental work had obtaining the optimum operating parameters for the best oil removal
also been conducted to investigate on the bacterial resistance on the efficiency. Therefore, optimization of biostimulation process using re-
toxicity effects of oil. Das et al. (2015) investigated on the complete ge- sponse surface methodology was conducted by Álvarez et al. (2015)
nome sequence analysis of bacterial strain P. aeruginosa N002 using Ion for the bioremediation of petroleum contaminated Antarctic soil. Addi-
Torrent method. Results from the genome analysis showed the degrada- tions of nitrogen and phosphorus levels were optimized, and the corre-
tion mechanism of crude oil by N002 strain, and also the different bac- sponding C:N:P ratio would aid the development of pilot scale
terial adaptive responses in the toxic crude oil contaminated soil bioremediation of diesel fuel contaminated soil. The optimized values
environment. The outcome from this work highlights the necessity of were found to be at C:N:P ratio of 100:17.6:1.73 which gave a diesel re-
genome analysis prior to the actual bioremediation, and future work moval efficiency of 54.9% as opposed to 27.8% at unoptimized C:N:P
in this area could be conducted to understand the factors associated ratio of 100:10:1. The results therefore showed the importance of opti-
with crude oil degradation, and the general adaption of the above men- mization that would reduce fertilizer consumption, while proving the
tioned strain on the crude oil contaminated environment. most efficient diesel removal from contaminated shorelines.
Another methodology for bioremediation applications that had
gained popularity from researchers worldwide is anaerobic bioremedi-
2.1.5.2. More environmentally friendly nutrient additions. Recent works ation. Anaerobic bioremediation involves the remediation of oil through
currently had been focused on obtaining novel methods and methodol- the stimulation of microorganism using nitrate, sulfate, iron and carbon
ogy, selection of unique microbial and fertilizer additions, fundamental dioxide as an alternative to oxygen. This is a cost effective method as
studies, and optimization of process parameters that could improve and compared to aerobic bioremediation process, as the delivery of oxygen
accelerate the degradation efficiency. In previous years, research on bio- to the contaminated site could be expensive. This method has been
remediation is mostly focused on aerobic bioremediation, or aerobic oil studied (Franco et al., 2014; Hasinger et al., 2012; Siddique et al.,
degrading bacteria. 2011) as it is considered feasible especially in contaminated sites that
20 M.W. Lim et al. / Marine Pollution Bulletin 109 (2016) 14–45

are already anaerobic in nature. Boopathy (2004) investigated on sever- Likewise, Suja et al. (2014) investigated on the factors that could af-
al anaerobic conditions, namely sulfate reducing, nitrate reducing, me- fect the bioremediation of crude oil contaminated soil from an oil and
thanogenic and mixed electron acceptor conditions for the in situ gas facility in Malaysia. The soil was contaminated in 2002 with an aver-
bioremediation of soil contaminated with No. 2 diesel fuel age of 1% w/w oil concentration to soil. The kinetic tests showed that the
(550 mg/kg). After 310 days of testing, the mixed electron acceptor con- combination of biostimulation and bioaugmentation has the highest
dition showed a high diesel degradation efficiency at 81%, as opposed to degradation rate constant of 0.0339/day in the field test. A high degra-
the sulfate reducing condition which demonstrated a 54.5% diesel deg- dation rate constant was observed, with up to 97% of the crude oil
radation. This could be attributed to the high bacterial counts in the found to be degraded within 1 m depth of soil when bioaugmented
mixed electron acceptor conditions. Similar results were observed by with Acinetobacter sp. and Pseudomonas sp. microbial consortia, nutrient
Sherry et al. (2013) whereby up to 77% of crude oil was degraded addition and air stimulation.
after 302 days using sulphur reducing microorganisms.
Other novel methods that could accelerate the oil degradation rate 2.2. Phytoremediation
include the study of a novel nutrient application strategy for the dissem-
bling of nutrients that could maximize nutrient residence time which Phytoremediation, otherwise known as plant-assisted bioremedia-
could be used for all oil polluted beaches. Li et al. (2007) utilizes the tion is a method of remediating soil removing toxic contaminants using
tidal waves at the beach to help out with the nutrient injection strategy. plants and their roots (Merkl et al., 2005b; Peng et al., 2009). The pres-
The optimal nutrients for flower (nitrogen and phosphorus addition be- ence of the plants aids in the degradation of the contaminant due to
tween 2 and 10 mg/L) were obtained through numerical investigations the presence of root enzymes that could chemically alter and degrade
from tidal wave action, density gradient and saltwater wedge. The au- the contaminants. In addition, the availability of easily degradable organ-
thors concluded that the numerically optimized nutrient injection strat- ic substance such as root exudates and mucilage secretion by root caps
egy is the application of nutrient solution through a perforated pipe at could enhance the degradation of oil contaminant (Dominguez-Rosado
high tide, parallel to the shoreline at high tide and last for a tidal circle et al., 2004; Merkl et al., 2005a). Several recent reported works in
for maximum residence time. On the other hand, the usage of inorganic phytoremediation are summarized in Table 3.
fertilizer such nitrogen and phosphorus as fertilizer to stimulate biore- The successful implementation of phytoremediation is dependent on
mediation had been heavily investigated in the previous years. many factors. One of the factors that could affect is the addition of fertil-
In addition to the above work, other studies that had been conducted izer as an extra source of nutrients between the microorganisms and
include mathematical modelling of biosurfactant effects on petroleum plants. Therefore, the contaminated site must be optimally fertilized
degradation (Montagnolli et al., 2015), simulation of hydrocarbon bio- not only to support plant growth and maximize microbial population,
degradation of an oil spill on a sandy beach via mathematical modelling but also to prevent excessive addition of fertilizer which could be detri-
(Geng et al., 2014), enhanced isolation of bacterial strains at low tem- mental to the environment as well as soil salinity balance. Due to these
peratures (Pham et al., 2014), and the effect of different bioremediation conditions, there is a certain amount of uncertainty about the optimum
methods such as nitrogen addition, Suaeda salsa planting, and amount of fertilizer required for maximum oil degradation. Several stud-
arbuscular mycorrhiza fungi inoculation on the soil physicochemical ies had been conducted on the fertilizer levels on phytoremediation of oil
properties, degradation rate, alterations of crude oil fraction and soil contaminated soils and fertilizer component (Cartmill et al., 2014;
bacterial composition (Gao et al., 2014). Dadrasnia and Agamuthu, 2013; Jagtap et al., 2014; Merkl et al., 2005a;
The understanding of the effect of parameters and additions is im- Ribeiro et al., 2014). Ribeiro et al. (2014) highlighted that the choice of
portant for the success of bioremediation, however there are several nutrient additions may differ among plant species as the type of nutrient
areas which could be further improved on for successful application added (Hoagland nutrient solution) to Phragmites australis shows little to
for in situ bioremediation of oil contaminated soil. Future work could in- no influence on its biomass. On a different note, Jagtap et al. (2014) also
clude studies on novel bioremediation method that could enhance the showed that the diesel degradation rate using Pinus densiflora, Thuja
rate of biodegradation and oil removal efficiency, fundamental studies orientalis, and Populus tomentiglandulosa in 6000 mg/kg diesel contami-
that would understand the biodegradation mechanism, and computa- nated soil increased from 36.9% to 75.2% in the presence of fertilizer
tion studies that could further optimize the operating parameters for treatment, regardless of fertilizer level added.
maximum oil removal. In recent laboratory-scale studies, different types of plants are still
being researched on for the remediation of oil contaminated soil. A re-
2.1.5.4. Recent advancements in bioremediation field studies. Field studies view by Cook and Hesterberg (2013) summarized that the majority of
in the recent years showed highly promising results for removal of oil plants used for phytoremediation were trees and grasses, due to the
from soil (Akbari and Ghoshal, 2014; Beškoski et al., 2011; Ferradji wider root coverage and greater biomass provided for rhizoremediation.
et al., 2014; Meyer et al., 2014; Venosa et al., 2010). In recent studies For example, Moreira et al. (2013) used Avicennia schaueriana, a black
for remediating on site oil contaminated soil, the results show that bio- mangrove plant for the removal of paraffin oil with an initial concentra-
remediation could be a suitable alternative for field treatment. Gomez tion of 32.2 mg/g from contaminated soil. The mangrove system was
and Sartaj (2013) investigated on field scale ex situ bioaugmentation simulated in a lab scale study, where the physical, chemical, microbiolog-
and biostimulation as bioremediation treatment for petroleum contam- ical and biogeochemical parameters were kept under conditions similar
inated soil of 940 μg/g concentration using microbial consortia inoculant to a mangrove site. After 90 days of phytoremediation, it was found that
and mature organic compost at a treatment facility. The usage of indi- the usage of A. schaueriana aids the removal of the oil to achieve a remov-
vidual microbial consortia and mature organic compost showed similar al efficiency of 87%, attributed to the increase in microbial concentration.
removal efficiencies of 55% and 52% respectively, but the combination of On the other hand, the usage of endophyte infected grass (Festuca
microbial consortia and mature compost provided a significant increase arundinacea Schreb. and Festuca pratensis Huds.) showed a removal of
in removal efficiency up to 82% by decreasing the petroleum concentra- petroleum of up to 72% after 7 months of remediation. Endophyte infect-
tion below the allowable limits (166 μg/g) within 40 days of treatment. ed grass was chosen due to its extensive root structure and shoot bio-
Nevertheless, while this treatment is successful ex situ, the use of this mass compared to non-infected endophyte grass (Soleimani et al., 2010).
method still requires further study on its application in situ in cold cli- The field trial of phytoremediation also showed success in the elim-
mate areas. A subsequent study by the same authors investigated on ination for oil contaminant as well. Phytoremediation using willow
the optimization of microbial consortia application rate and amount of stands was carried out on mineral oil contaminated sediment at a
fertilizer added for maximum contaminant removal rates over a period 400 m2 site in Belgium by Vervaeke et al. (2003). The field trial was con-
of 94 days (Gomez and Sartaj, 2014). ducted for 1.5 years. The authors reported that a decrease of 57% in
Table 3
Phytoremediation of oil contaminated soil.

Plant type Plant species Contaminants Initial contaminant Process Maximum removal Reference
concentration duration efficiency (%)

Ornamental plant Mirabilis Jalapa L. Petroleum 5 g/kg 127 days 63.2% (Peng et al., 2009)
Legumes, grasses Calopogonium mucunoides, Centrosema brasilianum, Crude oil 5 w/w% 180 days 57.69% (Eleusine indica) (Merkl et al., 2005b)
Stylosanthes capitala, Brachiaria brizantha, Cyperus
aggregatus, Eleusine indica
Scots pine, poplar, grass mixture, Pinus sylvestris, Populus deltoides × Wettsteinii, red Diesel 0.5 w/w% 180 days 67–74% (Legume mixture) (Palmroth et al., 2002)

M.W. Lim et al. / Marine Pollution Bulletin 109 (2016) 14–45


legume mixture fescue, Festuca rubra, Poa pratensis, Lolium perenne,
white clover, Trifolium repens, Pisum sativum
Ditch reed, alfalfa Phragmites australis, Medicago sativa Bitumen 79.7 g/kg 27 months 82% (Reed) (Muratova et al., 2003b)
Non-edible plant Jatropha curcas Lubricating oil 1 w/w% 180 days 67.3% (Agamuthu et al., 2010)
Crop plant, wild grasses, legume Triticum aestivum L., Secale cereale L., Avena sativa L., Oil sludge 15.6 g/kg 72 days 52% (Rye) (Muratova et al., 2008)
Hordeum vulgare, Sorghum bicolor L. Moench,
Panicum miliaceum L., Zea mays L., Lolium perenne L.,
Bromopsis inermis, Agropyron cristatum L.,
Agropyron tenerum L., Festuca pratensis Huds.,
Medicago sativa L., Trifolium pratense L., Onobrychis
antasiatica Khin.
Non-edible plant Hibiscus cannabinus Lubricating oil 1 w/w% 90 days 91.8% (Abioye et al., 2012)
Willow stand Salix viminalis L. Mineral oil & PAH 245.2 mg/kg 1.5 years 57% (Vervaeke et al., 2003)
Tall rescue plant Festuca arundinacea Petroleum 50 g/kg 120 days 50% (Huang et al., 2005)
Soybean/greenbean, sunflower/Indian Glycine max, Phaseolus vulgaris, Helianthus annuus, Motor oil 1.5 w/w% 150 days 100% (Mixed clover) (Dominguez-Rosado
mustard, mixed grasses/maize, mixed clover Brassica juncea, Zea mays, red clover, Trifolium and Pichtel, 2004)
pratense/ladino clover, Trifolium repens
Alfalfa, reed Medicago sativa, Phragmites australis Bitumen 79.7 g/kg 27 months 82% (Muratova et al., 2003a)
Tropical pasture grass Brachiaria brizantha Crude oil 5 w/w% 22 weeks 18.4% (Merkl et al., 2005a)
Endophyte infected and non-infected grasses Festuca arundinacea Schreb., Festuca pratensis Huds. Petroleum 4700 mg/kg 7 months 72% (Infected endophytic grasses) (Soleimani et al., 2010)
Non-edible plants Dracaena reflexa amended with 5% organic wastes Diesel 1 w/w% 270 days 99% (Dadrasnia and Agamuthu, 2013)
Perennial ryegrass Lolium perenne L. Diesel 50 g/kg 90 days 57.3% (Chuluun et al., 2014)
Salt marsh plants P. australis Arabian light crude oil 5 mL/L 150 days 16% (Ribeiro et al., 2014)
– Pinus densiflora, Thuja orientalis, and Populus Diesel 6000 mg/kg 150 days 86.8% (Jagtap et al., 2014)
tomentiglandulosa amended with microbial
consortium
Black mangrove Avicennia schaueriana Light paraffin oil 32.2 mg/g 90 days 87% (Moreira et al., 2013)
Herbaceous bush Bassia scoparia (L.) A. J. Scott (Chenopodiaceae) Crude oil 40 g/kg 5 months Up to 57.7% (Moubasher et al., 2015)

21
22 M.W. Lim et al. / Marine Pollution Bulletin 109 (2016) 14–45

mineral oil concentration was observed, which shows that the usage of of a large amount of hydrocarbon utilizing microorganism bacteria in
willow stand increases the degradation of mineral oil. the rhizosphere zone at 2.4 × 107 CFU/g soil suggests that the
The success of phytoremediation of soil contaminated with hydro- rhizodegradation mechanism is responsible for the phytoremediation
carbons is conceptualized to occur through four different mechanisms, of the oil contaminated soil using Jatropha curcas. Moubasher et al.
namely phytostabilization, phytodegradation, phytovolatilization and (2015) also demonstrated that a herbaceous bush that easily grows in
rhizodegradation (Germida et al., 2002). different soil types; Bassia scoparia (L.) A. J. Scott (Chenopodiaceae)
could aid the remediation of petroleum contaminated sandy soil. Due
2.2.1. Phytostabilization to its high tolerance of petroleum hydrocarbons up to 2–3 wt%, the av-
In phytostabilization, the root zone acts as a stabilizer to immobilize erage degradation efficiency of petroleum is up to 57.7% for natural soil
the contaminants in soil, thus preventing the hydrocarbon in the con- after 5 months.
taminated soil from mitigating off-site through erosion, leaching or dis-
persion. An extensive root system is required in phytostabilization as 2.2.5. Advantages and limitations
the absorption and accumulation of the hydrocarbons occur within the To date, there are many reviews on the potential application of differ-
root zone, root membrane and root cells (Germida et al., 2002). ent plants, efficiency and challenges on the usage of phytoremediation
Byström and Hirtz (2002) studied the efficiency of Salix viminalis, a for oil contaminated soil (Alkorta and Garbisu, 2001; Bordoloi and
type of willow tree to remediate hydrocarbon-contaminated soils, and Basumatary, 2015; Cook and Hesterberg, 2013; Cunningham et al.,
investigated the effect of phytostabilization in this study for low and 1995; Dhar et al., 2015; Gerhardt et al., 2009; Tripathi et al., 2015).
moderate petroleum contaminated soils. Results showed an increase in There are many advantages of the usage of phytoremediation as a reme-
the petroleum concentrations in soil around the root zone from diation strategy. Phytoremediation is easy to implement for on-site re-
584 mg/kg to 1018 mg/kg after 10 h in the presence of S. viminalis, mediation, with minimal maintenance costs. The implementation of
which leads to the immobilization of contaminants within the root this method is not limited to site size, and can be easily used in any
zone. This indicated that phytostabilization could reduce the fraction of area that supports plant growth. The addition of fertilizer for plant
contaminant in the soil through containment of hydrocarbon in the soil. growth also helps to provide sufficient nutrient and organic materials
which could help to improve the quality of remediated soil in the long
2.2.2. Phytodegradation run. In addition, the plants also help to stabilize the soil due to the exten-
Phytodegradation, on the other hand, involves the breakdown of the sive root structure. In a non-scientific context, the plants are environ-
hydrocarbons through the metabolic processes of the plant. They re- mentally attractive and widely accepted by the community.
lease certain enzymes such as dehalogenase, nitroreductase, and Nevertheless, phytoremediation is a slow remediation process, and
laccase, which act as a catalyst to chemical reactions that are able to ac- could only be considered as a long-term solution. Phytoremediation is
celerate the contaminants degradation process (Germida et al., 2002). a complicated process with many external parameters that could affect
Palmroth et al. (2002) reported the phytoremediation of subartic soil the success, such as type and concentration of contaminant, soil param-
contaminated with diesel fuel using several plant treatments, and ob- eters, water content, nutrient concentration, type of plants, plant charac-
served that low concentrations of diesel-range compound were found teristics, plant resistance to phytotoxic effects and other factors that
in grass roots (up to 10 g/kg of dry plant tissue), while no diesel com- could affect plant growth. The main challenge is the search for plant spe-
pounds were detected in the legume roots extracts. cies which could withstand the toxicity of the oil contaminant, as the tox-
icity of oil causes negative impacts for plant growth, which includes
2.2.3. Phytovolatization inhibition of seed germination, reduction in nutrient uptake, stunts
Phytovolatilization may also occur through the absorption of con- plant roots and harms photosynthesis pigments (Peng et al., 2009). If
taminants through the roots of the plant, metabolization and transpor- the plant species chosen is incapable of growing in oil contaminated
tation through the plant in a different form and finally volatization from site, the plant would not be able to produce sufficient biomass for the mi-
the surfaces of the plant (Germida et al., 2002). However, this method is crobe to facilitate contaminant degradation (Huang et al., 2005). More-
only suitable for volatilizable oil compounds, such as trichloroethylene, over, there is a need to contain the contaminants which may be highly
and napthalene (Germida et al., 2002; Zhu et al., 2010). This mechanism water soluble, as these contaminants may leach outside the root zone
was observed by Wiltse et al. (1998), who reported a leaf burn observa- which defeats the purpose of phytoremediation (Cunningham et al.,
tion in alfalfa plants growing in crude oil contaminated soil, which is at- 1995).
tributed to the translocation of an unknown compound through the
stem and leaves. In this study, it was further observed that this phenom- 2.2.6. Advancements and future work
enon disappeared through the progress of the experiment which indi-
cated that phytovolatilization is responsible for this effect. 2.2.6.1. Field studies of phytoremediation. Recent on-field site studies on
the phytoremediation demonstrated success in the utilization of
2.2.4. Rhizodegradation phytoremediation of remediation of oil contaminated soil. The
Rhizodegradation is defined as the degradation of the soil through phytoremediation field study of four crude oil contaminated drill sites
enhanced microbial activity in the rhizosphere zone of soil, which is ap- in Assam, India was carried out using native plants with the presence of
proximately 1–5 mm from the soil surface (Germida et al., 2002). The hydrocarbon degrading bacterial formulation by Yenn et al. (2014). The
microorganisms benefit the plant by supplying the necessary vitamins, drill sites were contaminated with 15.1 to 32.8% crude oil. Native plants
amino acids, and cytokinins to increase plant growth, while the plant (Azadirachta indica, Michelia champaca, stumps (saplings) of Tectona
roots provide habitat for hydrocarbon degrading microbes grandis and Gmelina arborea) were used for the phytoremediation,
(Dominguez-Rosado and Pichtel, 2004; Qixing et al., 2011). Researchers while bacterial strains P. aeruginosa N3 and P. aeruginosa N4 were isolated
suggest that the key role for phytoremediation is the rhizodegradation for the degradation of crude oil. The initial phytoremediation study using
mechanism, and this area had been highly investigated in the only plants on the crude oil contaminated soil showed that the plants
phytoremediation area. Muratova et al. (2003a, 2003b) demonstrated were not able to grow in the highly contaminated crude oil soil. Subse-
an increase in the amount of degrader microorganisms in the rhizo- quent to that, the added bacterial consortium was shown to enhance
sphere from 2.4 × 106 CFU/g to 1.4 × 107 CFU/g and 4.3 × 106 CFU/g the plant survival rate and growth in the crude oil contaminated soil by
in soil with reed and alfalfa respectively. The reed plant shows a higher up to 40%. This leads to an enhanced removal efficiency ranging between
bitumen degradation of 82% as compared to alfalfa of 74%. Likewise, a 65.23 and 88.5% after 24 months at the remediated field sites, which was
similar research by Agamuthu et al. (2010) showed that the presence attributed to the external application of microbial consortiums. In
M.W. Lim et al. / Marine Pollution Bulletin 109 (2016) 14–45 23

addition, Leewis et al. (2013) studied the effect of long term nutrient ad- contaminated soil (bioaugmented phytoremediation) increased the
dition and phytoremediation on the native plants, microbial communities phytoremediation efficiency to 57.3% as compared to standalone
and oil removal from diesel and crude oil contaminated soils in subarctic phytoremediation (50.0%) and bioaugmentation (52.0%) as reported
Alaska after 15 years without active site management. This study is a con- by Chuluun et al. (2014). The interactions between the plant and bacte-
tinuation from a phytoremediation field study using plants (Festuca rial consortium aided the growth of bacterial population due to the ex-
rubra, Lolium multiflorum) and/or nutrients between 1995 and 1996 by tensive fibrous roots which led to an enhanced diesel degradation.
Reynolds and Koenen (Reynolds et al., 1997a; Reynolds et al., 1997b; Biosurfactants had also been investigated on the potential as biocat-
Reynolds and Koenen, 1997). Within 15 years, the entire area was colo- alyst to enhance the phytoremediation. The presence of biosurfactants
nized by the native plants, which led to a decrease in the oil concentra- could increase the hydrophobicity of the cell surface, which allows the
tion, and the test site achieved successful oil removal rates of up to 95%, direct contact between the cell and hydrocarbon droplets, while de-
which is below the ADEC (Alaska Department of Environmental Conser- creasing surface tension and reducing viscosity of the oil. Almansoory
vation) level required for regulatory clean-up limits (1000 mg/kg). The et al. (2015) investigated on the performance of biosurfactant in com-
authors concluded that the use of phytoremediation may be an effective parison with hydrocarbon degrading bacteria, sodium dodecyl sulfate
remediation method especially for remote sites which in turn could pro- (SDS) and bacterial culture supernatant for phytoremediation of
mote ecological recovery (Leewis et al., 2013), if a long term solution is 2 g/kg of gasoline contaminated soil. Results from the studies showed
required for the remediation of oil contaminated soil. a significant removal of 93.5% using biosurfactant as compared to
85.4%, 70.3% and 86.3% using bacteria, culture supernatant and SDS re-
2.2.6.2. Bioaccumulation in plants and its toxicity. Currently, the main con- spectively after 72 days of testing.
cern of phytoremediation is the bioaccumulation of oil in the plants, Other additions that had garnered much interest from researchers
many recent studies are now focusing on the investigation on the plants' are the addition of plant growth promoting rhizobacteria (PGPR).
resistance to the toxicity of oil. In these studies, the growth of plants and PGPR could help promote plant growth, reduce environmental stress
the impact of oil on plant characteristics such as plant stem density, and enhance the degradation capacity of the existing rhizosphere bacte-
shoot height, and biomass were observed in soils contaminated with ria. In addition, PGPR could also increase the plants' capability to with-
various concentrations of oil fuels as demonstrated in selected publica- stand the toxicity of hydrocarbons compounds. The mechanisms for
tions (Balasubramaniyam and Harvey, 2014; Lin and Mendelssohn, phytoremediation of petroleum contaminated soil using tall fescue (F.
2009; Redondo-Gómez et al., 2014; Shahsavari et al., 2013; Zhang arundinacea L.) enhanced by PGPR were investigated by Hou et al.
et al., 2013). These studies concluded that high concentrations of oil (2015). A total of 67.9% of hydrocarbons were successfully removed
negatively impact the growth of the plants. However, Redondo-Gómez after 4 months of investigation. The authors also noted that petroleum
et al. found that even with the detrimental effects of diesel oil on the degradation highly depends on the presence of specific petroleum de-
plant (Spartina argentinensis), the plants continued growing and did graders and biosurfactant producers, and does not depend on the diver-
not exhibit chlorosis after 250 days of treatment in up to 3 v/w% diesel sity of bacterial community.
contaminated soil. Further works in this field of research may be re-
quired to understand and identify more plants that are capable of grow- 3. Chemical remediation technologies
ing in oil contaminated soils, while investigating on the long term
consequences of oil onto plant growth, as continuous exposure of plants 3.1. Chemical oxidation
to oil may cause acute manner photosynthesis which may affect the nat-
ural mineral balance in the ecosystem. Different types of oxidants have been investigated for the remedia-
In addition to the works mentioned above, the focus of phyto- tion of oil contaminated soil via the chemical oxidation reactions, includ-
remediation on oil contaminated soil had been shifted to the fundamental ing hydrogen peroxide, Fenton's reagent, persulfate, peroxymonosulfate,
studies of phytoremediation, such as the correlation between root mor- permanganate and ozone (Do et al., 2009; Do et al., 2010; Goi et al., 2009;
phology on oil degradation (Merkl et al., 2005c), effect of oil on the plant's Goi et al., 2006; Li et al., 2014; Oh and Shin, 2014; Pardo et al., 2014;
rhizosphere section (Dominguez-Rosado et al., 2004), mechanism of oil Sherwood and Cassidy, 2014; Shin et al., 2005; Tsai and Kao, 2009;
removal (Agamuthu et al., 2010; Palmroth et al., 2002), plant screening Usman et al., 2012; Villa et al., 2010; Yu et al., 2007). Table 4 presents
such as plant resistance to phytotoxic effects and the ability to reduce the recent studies employing chemical oxidation for the remediation of
oil contaminant (Muratova et al., 2008; Redondo-Gómez et al., 2014), oil contaminated soil.
and kinetic model (Dadrasnia and Agamuthu, 2013). The interlink be-
tween these factors has to be further studied to ensure the success of 3.1.1. Fenton's reagent
phytoremediation on site. Chemical oxidation remediation uses hydrogen peroxide (H2O2) as
the reactive oxidant. The H2O2 generates highly reactive free radicals
2.2.6.3. Environmentally friendly enhancements of phytoremediation. (OH•) when coupled together with soluble iron compounds such as
While the enhancement of phytoremediation by the addition of fertil- iron ions, Fe2+ (Eq. 1). The free radicals would then oxidize with either
izers and microbial consortium is commonly investigated on their effi- the unsaturated organic contaminant to form free radical that could
ciencies for oil contaminated soil remediation, there are many other transform into an organic product through electrophilic addition
types of additions that could enhance the phytoremediation efficiency. (Eq. 2) or saturated organic compounds to form free radical and water
Some examples include organic wastes, biosurfactants, and plant via hydrogen subtraction (Eq. 3) (Villa et al., 2010).
growth promoting bacteria. Dadrasnia and Agamuthu (2013) investi-
gated on the use of non-edible plants (Dracaena reflexa and Podocarpus H2 O2 þ Fe2þ →OH− þ OH þ Fe3þ : ð1Þ
polystachyus) enhanced with 5% organic wastes such as tea leaves, soy
cakes and potato skin for the remediation of 2.5% and 1% diesel contam- RH þ OH →ROH þ Hþ : ð2Þ
inated soil. The usage of D. reflexa amended with organic wastes provid-
ed an oil removal efficiency of up to 99%, as compared to 91% using P. RH þ OH →R þ H2 O: ð3Þ
polystachyus and organic wastes. The presence of organic wastes en-
hanced the removal of diesel by up to 50% as the organic waste aided It is interesting to note that there is no need for further addition of
the growth of D. reflexa and increase in bacterial concentration in the soluble iron catalyst for soil rich in natural metal oxide minerals such
soil which enhanced the rhizodegradation mechanism. Likewise, the as hematite α-Fe2O3, goethite α-FeOOH, magnetite Fe3O4, ferrihydrite,
addition of bacterial consortium to phytoremediation of 50 mg/kg diesel MnO and Al2O3. In recent studies, the modified Fenton process was
24 M.W. Lim et al. / Marine Pollution Bulletin 109 (2016) 14–45

Table 4
Chemical oxidation of oil contaminated soils.

Chemical oxidant Catalyst Contaminants Process details Maximum removal Reference


efficiency (%)

H2O2 Fe2+ (FeSO4) Diesel Mechanical stirring with continuous addition of 80% (Villa et al., 2010)
H2O2 of various concentrations using a
peristaltic pump at ambient temperatures
Basic oxygen furnace Fuel oil, diesel oil Mechanical spinning for 30 mins at 10,000 rpm 76% (Fuel oil), 96% (Tsai and Kao, 2009)
(BOF) slag at room temperature (diesel oil)
Fe2+ (FeSO4) Diesel Magnetic stirring at 20 °C in laboratory scale 93% (Goi et al., 2009)
Fe3+-EDTA complex Petroleum (total Mechanical stirring at 25 °C in darkness 85% (Lu et al., 2010a)
dichloromethane-extractable
organics, TEO)
Soil organic matter Diesel No stirring. reaction conducted at 4 °C for 72 h 98% (Sherwood and
Cassidy, 2014)
H2O2, persulfate Magnetite, soluble Fresh crude oil Magnetic stirring at 20–25 °C in darkness N80% (Usman et al., 2012)
Fe (II)
Zero-valent iron, Fe(0) Diesel Mechanical stirring at 180 rpm in shaking water N90% (Oh and Shin, 2014)
bath at 22 °C
Ozone – Diesel Column flushing with 4 inlet and outlet ports ≈95% (Shin et al., 2005)
with flow rate of 11.8 L/min
– Diesel Column flushing with flow rate of 50 mL/min 94% (Yu et al., 2007)
– Diesel Semi-continuous bubble column with gas 48% (Goi et al., 2006)
injection flow rate of 1.0 L/min
– Diesel Ozonation reactor with gas injection rate of 180 92% (Li et al., 2014)
mL/min at 20 °C for 20 h (Fine sands)
Persulfate/Fe (II) Goethite, hematite, Diesel Mechanical stirring at 25 °C 35% (Do et al., 2010)
magnetite, manganese (Manganese oxide)
oxide
Peroxymonosulfate Cobalt Diesel Incubated mechanical shaker at 25 °C 47% (Do et al., 2009)
(PMS)
Persulfate, H2O2, Fe2+ (FeSO4) Diesel, fuel oil Centrifugal spinning for 10 min at 8000 rpm at 60% (Yen et al., 2011)
permanganate 25 °C in darkness

tested on diesel fuel contaminated organic matter rich soil from Canadi- Shin et al. (2005) had investigated the removal efficiency of total pe-
an Arctic in a laboratory scale system. The authors reported that the re- troleum hydrocarbons (TPHs) from sand using ozone while a separate
actors with soil organic matter alone showed a higher diesel fuel study by Yu et al. (2007) also used ozone to remove diesel fuel from un-
oxidation efficiency per hydrogen peroxide compared to reactors with saturated soil. Both studies showed high removal efficiency of 90–95%
EDTA added as chelating agent. The percentage removal of diesel is up and 94% respectively. These results were however contradictory to a
to 98% for all soils studied at reaction temperature and time of 4 °C study by Goi et al. (2006) who compared the efficiency between
and 72 h respectively. This study attributes the success of Fenton oxida- ozone and Fenton reagent on diesel fuel contaminated soil. The authors
tion in the presence of soil organic matter which forms a SOM-FE (III) reported that the Fenton treatment showed higher efficiency of 87.5%,
oxidant which has a lower stability constant of 20 orders than EDTA- compared to oxidation via ozonation at 48%. The low removal using
Fe(III). This therefore increases the native Fe oxides available for Fenton ozone was suggested to be due to the limitation by the rate of diesel de-
reactions (Sherwood and Cassidy, 2014). sorption and high content of organic matter which consumed high
Goi et al. (2009) investigated the effects of H2O2 ratio when amounts of the introduced ozone.
catalysed by Fe2+ in the removal of diesel oil from soil. The uncatalysed Li et al. (2014) investigated on the influence of soil grain size and
degradation of diesel oil with H2O2/diesel ratio (w/w%) of 2:1 showed a water content on the degradation of diesel (25 g/kg) which underwent
degradation efficiency of 95% while the addition of small amounts of ozonation for 20 h for diesel removal from soil. It was found that the re-
Fe2+ as catalyst not only improved the degradation efficiency for diesel moval efficiency of diesel from fine sand particle size was 92%, approx-
removal up to 93%, but also decreased the dosage of H2O2 used by 84%. imately 1.2 factors higher than coarse sand at 77%. This is attributed to
Another study by Villa et al. (2010) showed that multiple additions of the higher surface area available for contact between ozone and sand
H2O2 (0.09–0.18 g/g of diesel contaminated soil) every 20 min resulted particles for fine sand. In addition, it was found that the ozonation effi-
in high remediation efficiencies up to 80%. ciency was not affected by soil water content of less than 18 w/w%
which suggests that the ozonation method would be efficient in both
3.1.2. Ozone wet and dry sand conditions.
The use of ozone (O3) in the chemical oxidation technology for the
remediation of unsaturated hydrocarbon contaminated soil has shown 3.1.3. Other oxidants
promising results. Due to its gaseous nature, ozone is easily delivered Alternative oxidants are being sourced for oxidation due to the neg-
to the contaminated vadose zone for treatment, while the presence of ative impacts of the former two oxidants on the natural attenuation of
natural metal oxides such as goethite, MnO and Al2O3 on the surface soil. Fenton-like oxidation is generally defined as the modification of
of the soil helps to catalyse the decomposition of ozone to hydroxyl rad- Fenton reagent to incorporate different catalysts to increase the efficien-
icals (OH•) (Shin et al., 2005; Yu et al., 2007). The ozone degrades the oil cy of remediation. Tsai and Kao (2009) applied waste basic oxygen fur-
molecules by splitting the C–H bond within the oil molecule through an nace slag (BOF slag) as a catalyst to enhance Fenton oxidation for the
intermediate transient, namely hydrotrioxide (R–O–O–O–H) before remediation of petroleum-hydrocarbon contaminated soil. The major
subsequently converting it into decomposition products as seen in metal oxide compounds found in BOF slag such as α-Fe2O3 (amorphous
Eq. 4 (Yu et al., 2007): iron) and α-FeOOH (soluble iron) act as the iron sink for the Fenton-like
oxidation. Therefore, the use of BOF slag could be a potential catalyst for
Fenton-like oxidation with a reported removal efficiency of 96% for fuel
RH þ O3 →½R–O–O–O–H →R þ OH þ O2 →ROH þ R ¼ O þ ROOH: ð4Þ oil contaminated soil.
M.W. Lim et al. / Marine Pollution Bulletin 109 (2016) 14–45 25

Persulfate anion (PS), S2O28 − which is another strong oxidant and (Lu et al., 2010a). The efficiency of the chemical oxidation is limited by
generally more stable than the hydroxyl radical, has shown to have low soil permeability, highly alkaline soil, and high reactivity of oxidant
less affinity for natural soil organics, and therefore resulting in a higher towards components of soil. It is also difficult to control the heat emitted
remediation efficiency (Usman et al., 2012). Do et al. (2010) evaluated from the oxidation reaction, which could further impact the natural bi-
the pH and PS/Fe(II) molar ratio for diesel degradation on natural soil ological forms in the soil (Goi et al., 2009). Therefore, the soils which
and artificial sand, and found that the highest diesel degradation oc- had been treated by chemical oxidation are not able to sustain vegeta-
curred at pH 3, with an optimum molar ratio of 100:1 [PS/Fe (II)]. tion, or further bioremediation in the future (Usman et al., 2012). In
Usman et al. (2012) also investigated the efficiency of magnetite terms of soil health, the chemical oxidation mobilizes the soil nutrients
mixed with Fe2 + and Fe3 + (catalyst) to activate both persulfate and such as carbon, nitrogen and phosphorus species, which leads to a
H2O2 on crude oil contaminated soil at neutral pH levels. Results from higher treatment cost. In addition, the dissolved organic carbon which
this study showed that the use of magnetite provides high efficiency is released through chemical oxidation is preferentially biodegraded
of oil degradation at 80% for both oxidants, while the use of soluble over hydrocarbon products which delays the bioremediation of hydro-
Fe2 + only showed low degradation efficiencies of 10–15% under the carbons as well (Sutton et al., 2014).
same experimental conditions. The authors suggest that magnetite The adverse effects of chemical oxidation as mentioned above man-
could be used to activate both persulfate and H2O2 oxidants for remedi- ifested during the application of chemical oxidation in field work, as
ation of soil at neutral soil pH which would not affect the natural soil demonstrated through a study by Ferguson et al., (2004) in Antarctica.
properties. Another study by Oh and Shin (2014) also investigated on In this field trial, oxidative treatments using Fenton's reagent, hydrogen
Fenton oxidation using persulfates and zero-valent iron (Fe(0)) for peroxide and sodium hypochlorite were conducted at Old Casey Station,
treatment of diesel-contaminated soil. The reason why zero-valent East Antarctica to remediate diesel contaminated soil aged for over a de-
iron was chosen for this study is due to its low cost and toxicity. The re- cade. They reported a lack of significant reduction in hydrocarbon con-
sults show that the usage of Fe (0) enhanced the removal efficiency centrations using 8.8 mol/L H2O2 solution, which may not be sufficient
compared to Fe2+, attributed to the formation of corrosion which pre- to overcome the strong adsorption of contaminant on soil particles. In
vents the decrease in pH from the formation of SO2− 4 . addition, the strong oxidative conditions, coupled together with the
Another type of oxidant used for oxidation of hydrocarbon contam- heat produced from exothermic reactions and acidic conditions from
inants in soil is the peroxymonosulfate (PMS), HSO− 5 . Similar to persul- the Fenton process caused the decrease in the microbial concentrations
fate anions, PMS has to be activated to form sulfate radicals (SO− 4 ), which would hinder natural attenuation (Ferguson et al., 2004). The au-
which are strong oxidizing species. Do et al. (2009) investigated the thors concluded that the usage of chemical oxidation is not compatible
use of PMS oxidant catalysed by transition metals (Fe2+ and Co2+) for for field use in Antarctica. From the studies, it was observed that the suc-
the remediation of diesel contaminated soil together with the effects cess of in situ applications of chemical oxidation is highly dependent on
of the counter anion (Cl− and SO2− 4 ). It was reported that a maximum the interaction forces between the soil and oil, or in other words the
degradation of diesel was found to be 47% with a single injection of aging time of oil contaminant. The high interaction forces between soil
PMS and CoCl2, while subsequent injections every 2 h showed increased and oil may require high concentrations of oxidant to overcome these
removal efficiencies up to 88%. forces, which may lead to low efficiencies of removal. Hence it could
be concluded that the usage of chemical oxidation remediation may
3.1.4. Advantages & limitations not be compatible for weathered oil contaminated sites.
Chemical oxidation method is a useful remediation method for
remediating oil contaminated soil as it is non-selective and is also not af- 3.1.5. Advancements and future work
fected by the toxicity of the contaminant. This minimizes contaminant
dispersion and helps to contain the oil contaminant. The delivery meth- 3.1.5.1. Soil health upon oxidation. Many researchers had concluded that
od of chemical oxidants is typically via injection of liquid/gaseous chem- the usage of chemical oxidation remediation method reduces the con-
ical to the ground. This is much favoured due to its simplicity in centration of microorganisms due to the type of oxidant used, which in-
operation which could provide fast results with low operational costs. directly means low soil health. Despite the vast study on the effect of
In addition, the chemical oxidation method is also capable of degrading oxidant on organic matters and microbes, the impact of oxidant on the
oil contaminants to more biodegradable compounds without the forma- soil properties, particularly mineralogy and physicochemical soil prop-
tion of toxic by-products. For example, the decomposition of ozone and erties remains a grey area in this research field. The impact of soil fertil-
hydrogen peroxide provides oxygen to the microbial community which ity was studied by da Silva et al. (2012) in the recent years. The authors
promotes aerobic biodegradation (Goi et al., 2009). However, care must showed that the addition of H2O2 during the chemical oxidation treat-
be taken to avoid excessive dosage of ozone and hydrogen peroxide ment resulted in a sharp decrease in organic matter content and swell-
which could cause an adverse impact on the environment. Hence, mod- ing clays in the vertisol soil (predominantly clay with high chemical
erate additions of the oxidant should be applied to protect the environ- fertility). The cation exchange capacity of this soil was also found to di-
ment (Goi et al., 2006). minish, resulting in soil infertility due to reduction in water and nutri-
The toxicity of the soil before and after chemical oxidation using ents retention.
ozone was also studied by Shin et al. (2005) using established methods However, the environmental impact of chemical oxidation on the
to confirm the potential risk of increased toxicity on-site. An ecotoxicity environment, particularly on microbial populations, changes in soil
test using earthworms was conducted, whereby the effect of the ozon- health such as concentrations of nutrient, and soil organic matter con-
ation on the behaviour, survival rate, growth and reproduction system tent, and changes in oil composition after chemical oxidation treatment
of earthworms was carried out in this study. The study was conducted is still lacking, and should be investigated prior to implementation of in
before and after ozonation of diesel-contaminated soil aged for situ chemical oxidation remediation.
2 weeks. They concluded that the mortality of earthworms decreased
significantly at the end of the ozonation which signified that the by- 3.1.5.2. Organic and non-toxic chelating agents. Studies should be carried
products of the chemical oxidation of diesel had no effect on earthworm out to decrease the toxicity of chemical oxidation, by investigating on al-
survival. This indicates that the toxicity of the soil actually decreased ternative oxidants or additives that are less toxic and biodegradable, yet
after the ozonation process. provide a high oil removal efficiency. Some recent works added organic
Despite the high oil removal efficiencies using the Fenton reagent in chelating agents such as cyclodextrins, ethylenediaminete-traacetic
laboratory works, the oxidation process requires low pH (~3) environ- acid (EDTA), and gallic acid to modified Fenton systems to preserve
ments, which results in negative impacts on soil properties and quality the degradation at pH 6.0–9.0. However, the use of chelating agents
26 M.W. Lim et al. / Marine Pollution Bulletin 109 (2016) 14–45

may affect the success of chemical oxidation by decreasing the removal the electric force voltage, electrolyte concentration and the strength of
efficiencies. This is evident in works by Pardo et al. (2014) whom inves- ionic charge of the species (Page and Page, 2002). Typically, pollutants
tigated on the treatment of B20 biodiesel blend (20% biodiesel, 80% die- with an ionic charge such as heavy metals and salts are removed
sel) via modified Fenton process with and without chelating addition through this mechanism (Kim et al., 2011).
(trisodium citrate). The presence of trisodium citrate decreased the re-
moval efficiencies by 15% (approximately 75% without chelating 3.2.1. Electrokinetic studies
agent, 60% with chelating agent) as the chelating agent competes with The effects of electric field voltage, electrode materials, conductivity
the pollutant during the oxidizing reaction. However, it is important of electrolyte and concentration of contaminant which affect the effi-
to note that while the chemical oxidization of oil pollutants without ciency of the electrokinetic remediation of oil contaminated soils have
the usage of chelating agents provides higher removal efficiencies, the been vastly studied (Han et al., 2009a; Jeon et al., 2010; Kim and Lee,
soil condition must be kept in constant acidic condition which may be 1999; Page and Page, 2002; Park et al., 2009; Pazos et al., 2012b; Sri
detrimental in real environment. The presence of the chelating agent Ranjan et al., 2006; Tsai et al., 2010; Virkutyte et al., 2002). Table 5 sum-
helps to maintain the soil pH during oxidizing reactions. Therefore, a marizes the electrokinetic studies for remediation of oil contaminated
balance must be made between oil removal efficiencies and maintaining soil.
soil pH before in situ testing of chemical oxidation method. Pazos et al. (2012b) studied the effect of electric gradient and elec-
While chemical oxidation had shown promising results for the trolyte concentration on the electrokinetic remediation of loamy sand
laboratory-scale oil remediation process, the lack of consistency of the soil samples contaminated with diesel fuel. The maximum efficiency
application of chemical oxidation for in situ field applications highlights of 73% was observed at electrical voltage of 2 V cm−1 and 0.67 M of citric
the necessity for further work to ensure success for remediation on site. acid, mainly due to the high concentration of electrolyte that favours the
The optimization of parameters such as optimum ratio of hydrogen per- electroosmotic flow of contaminants. The effect of electrode materials
oxide to hydrocarbon contaminant, with the corresponding oxidized oil (graphite and iron rods) and electrolyte on the removal of diesel from
percentage for a particular soil type is still required. In addition, the use contaminated soils was also investigated by Tsai et al. (2010). Results
of heat generated on site could also be further investigated. of this study showed that a removal efficiency of 56% was achieved at
the highest concentration of NaCl addition (0.1 M) which provided a
3.2. Electrokinetic remediation high electric current density. The use of iron electrodes was also found
to be more superior than graphite electrodes based on hydrocarbon re-
Electrokinetic remediation is an in situ remediation method which moval efficiency performance due to the higher current density of
employs low levels of direct electric current between appropriately dis- 44 mA/cm2 as compared to graphite electrodes of 29 mA/cm2. Jeon
tributed electrodes (anodes and cathodes) embedded at each side of the et al. (2010), on the other hand, investigated on the feasibility of
oil contaminated soil mass, forming an electric field across the area. This surfactant-enhanced electrokinetic removal of petroleum hydrocarbon
forms a voltage potential gradient which causes the fluid medium to from residual clayey soil after soil washing. The diesel removal efficien-
flow preferentially towards the cathode while dragging the contami- cy was found to be 39% using 0.1 M of NaOH, 1 V/cm voltage across elec-
nant together with the bulk flow (Sri Ranjan et al., 2006). Early studies trodes and 0.5 wt% of Teregitol 15-S-7.
of the electrokinetic remediation are primarily focused on removal of
heavy metals and organic components (Maini et al., 2000), but recently 3.2.2. Advantages & limitations
much attention had been shifted on the usage of electrokinetic remedi- The advantage of this remediation method is that electrokinetic re-
ation for oil contaminated soil. mediation could be performed in situ which provides a faster response
The combination of several mechanisms (electroosmosis, time and lower operating cost in a case of soil remediation. The usage
electromigration, and electrophoresis) contributes to the effectiveness of electrokinetic remediation also provides a more precise control of
of the electrokinetic remediation of oil contaminated soil (Kim et al., movement of the aqueous phase and contaminants through heteroge-
2011). Out of these mechanisms, the main mechanism that determines neous soils. The electric field could provide a uniform flow distribution
the kinetics of electrokinetic remediation is electroosmosis fluid flow. which makes it attractive for the remediation of low permeability soils,
Electroosmosis is the movement of soil moisture and groundwater sands and/or sludges. In addition, the electroosmosis flow rate is not af-
from the positive anode to the negative cathode. Due to the excess of fected by soil pore size and distribution, which means that the electro-
cations in the electrolyte system to neutralize the negatively charged osmotic flow is constant through the entire soil mass (Sri Ranjan et al.,
soil particles, the moving cations impart a viscous drag onto the aqueous 2006). This leads to a successful oil recovery, especially for low perme-
phase (Elektorowicz and Boeva, 1996). The contaminants are subse- ability soils.
quently solubilised and mobilized by the solution of the fluid and are However, the electrolysis process around the electrodes could create
then transported towards the cathode. The efficiency of the electroos- thermal hot spots in the soil and alter the pH of the soil after an extend-
mosis mechanism is thus dependent on the flow rate, whereby the in- ed period of time. This undesirable phenomenon is detrimental to the
crease in flow rate increases the efficiency due to the increased environment. While addition of bicarbonate buffers could maintain
migration of contaminants along with the fluid flow. the pH of the soil, further research should be undertaken on preserving
The mechanism of electrophoresis and electromigration results in soil health while providing maximum oil removal efficiency. In addition,
the movement of charged ions, colloids, and ion complexes towards the electrokinetic process is not effective in low concentrations of con-
the electrodes (Kim et al., 2010). Electrophoresis is defined as the trans- taminant, due to the longer path of migration which could lead to stag-
portation of charged colloids such as surfactant micelles towards the op- nant zones between the electrodes (Mosavat et al., 2012).
posite charged electrode due to the electrical potential gradient. The
contaminants which are absorbed on the surface of the charged colloids 3.2.3. Advancements and future work
would be transported as well (Kim and Lee, 1999; Sri Ranjan et al.,
2006). Electromigration, on the other hand, is the migration of charged 3.2.3.1. Electrokinetic technology to remove selective organic pollutants in-
ions due to the influence of electric force. The application of electric cur- stead of bulk oil. At present, there are limited studies on the use of elec-
rent between electrodes causes the electrolysis of water, forming H+ trokinetic technology as the sole technology for the remediation of oil
and OH− ions in the anode and cathode respectively. The H+ ions that contaminated soil, suggesting the lack of viability of this method in
migrate within the soil create a pH gradient which subsequently causes field scale. While the usage of electrokinetic technology showed some
elution of the contaminant to the cathode for subsequent recovery positive results for remediation of oil contaminated soil, a concern for
(Maini et al., 2000). The electromigration mechanism is affected by electrokinetic remediation is the presence of organic pollutants such
M.W. Lim et al. / Marine Pollution Bulletin 109 (2016) 14–45 27

Table 5
Compilation of electrokinetic studies.

Electric field Electrolyte Contaminants Process details Maximum removal Reference


efficiency

1.0 V cm−1, 2.0 V cm−1 Citric acid Commercial Graphite electrode chambers 4 L using 0.03 73%a (Pazos et al., 2012b)
diesel fuel mol/L citric acid; duration of 15 days
0.5 V cm−1, 1 V cm−1, 2 V cm−1 0.1 mol/L HNO3 (catholyte); Lubricant oil Pt-coated titanium and carbon plate 55.4% (1 V cm−1) (Park et al., 2009)
MgSO4 with 0.5 wt% electrode chambers; duration of 17 days
tergitol (anolyte)
10 mA EDTA & NaCl Diesel oil Soil chamber; duration between 14–25 days 38% (0.01 M EDTA) (Han et al., 2009a)
40 V Tap water, 0.01 M NaCl, Diesel oil Graphite and iron electrodes; duration of 45 56%b (Tsai et al., 2010)
0.1 mol/L NaCl days
1 V cm−1 0.1 M NaOH Diesel oil Electrokinetic reactor using platinum-coated 39% (Jeon et al., 2010)
titanium anode and graphite plate as
cathode; duration of 14 days
a
Electric gradient of 2 V cm−1, 0.67 M citric acid, without any soil amendments.
b
0.1 mol/L NaCl, iron electrode.

as PAH which hinders the efficient removal of cationic contaminants field application of this technology. The installation of electrodes and
(Pazos et al., 2012a). Further work on the removal of such organic pol- probes, gas and fluid volume measurement devices was able to measure
lutants existing in the oil contaminant prior to electrokinetic treatment the two-dimensional distribution of electrical voltage, gas generation
is still required, and therefore recent electrokinetic studies are now and electroosmotic flowrates as a function of time. The simulation ex-
more focused on the removal of organic pollutants rather than bulk oil periments were compared with the bench scale extraction experimen-
(Ammami et al., 2015; Bocos et al., 2015; Boulakradeche et al., 2015; tal for the removal of cadmium on soil. Results from the work showed
Fan et al., 2014; López-Vizcaíno et al., 2014; Xu et al., 2014; Yusni and that the gas generation rate correlates well with the electrical current,
Tanaka, 2015). Hence, it is not surprising that there is a lack of work ob- which was in line with the Faraday's law of electrolysis. The authors
served in many other areas for the overall success of this oil contaminat- concluded that the 2D profiles of the physicochemical parameters
ed soil remediation technology. In particular, understanding the such as voltage distribution and contaminant concentration would be
interactions between the electrokinetic parameters, contaminant and useful to further understand the transport phenomena in the electroki-
microbial community would be crucial in providing a better direction netic remediation. However to the best of our knowledge, there had
in choosing the type of electrolyte to be used. been no papers which investigated on the simulation of electric field
force between electrodes, and further work could be conducted on
3.2.3.2. Environmentally friendly electrolytes. It is therefore important to this area to further understandthe application of electrokinetic technol-
highlight that the efficiency of this process is highly dependent on the ogy for the remediation of oil contaminated soil.
need to modify the properties of the contaminated soil to accommodate
for the process. This process may not be environmentally friendly. For 4. Thermal remediation technologies
example, the changes to the soil condition due to pH, electrolyte and
temperature could affect the soil microbial concentration and activity. Thermal remediation of soil typically applies heat to remove con-
Kim et al. (2010) demonstrated that the usage of EDTA as electrolyte taminants. Currently, there are three different technologies under ther-
could cause a detrimental effect on the microbial community, due to mal remediation, namely incineration, thermal desorption and
the changes in soil pH and electric current. In addition, the simultaneous microwave frequency heating (Rushton et al., 2007). Table 6 summa-
mobilization of soil nutrients such as nitrogen and phosphorus could di- rizes the works of thermal remediation for the removal of oil from soil.
minish the quality and functionality of the soil after electrokinetic treat-
ment (Pazos et al., 2012b). This however contradicts with recent works 4.1. Incineration
by Mena et al. (2014) which show that the direct effect of electric cur-
rent does not significantly affect the microorganisms. In fact, the in- Incineration is the destruction of contaminants through the burning
crease in the DC electric field up to 2.0 V cm− 1 increased the diesel of soil at high temperatures up to 1000 °C and is one of the easiest
degradation rates. The difference in these two works could be attributed methods for removing oil contamination (Rushton et al., 2007). In a
to the choice of electrolyte for the electrokinetic cell, where the former study by Bucala et al. (1994), a laboratory-scale electrically heated foil
used EDTA for their works while the latter used a suspension of diesel- reactor was employed to remove weathered oil from gravel sludge
degrading microorganisms. Further studies could therefore be conduct- under rapid heating conditions of 1000 °C/s. The authors reported that
ed to obtain novel electrolytes which are environmental friendly, non- approximately 100% of contaminant was removed from the soil in a
toxic and biodegradable, yet could withstand the electrical current for mere 0.7 s, quantified through the weight loss of oil-treated soil. In a
in situ electrokinetic applications. In addition, recent works had been fo- pilot-scale investigation, Anthony and Wang (2006) also showed that
cused on a brand new combination of bioremediation and electrokinetic all oil compounds were removed from coal-tar contaminated soil and
remediation to form a new technology called electrobioremediation for oil-contaminated gravel using a pilot-scale combustor under working
oil contaminated soil remediation, with promising results. This would temperatures of up to 800 °C.
be discussed in greater detail in the upcoming Integrated Technology
section. 4.2. Thermal desorption

3.2.3.3. Understanding the electric field flow and its application in the elec- Thermal desorption is the manipulation of temperatures to increase
trokinetic technology. Further studies on the kinetics of soil remediation the vapour pressure of the organic contaminants, leading to their vola-
and its principles of oil contaminant flow under applied electric field tilization and subsequent desorption from contaminated soil (Rushton
(Ghazanfari et al., 2014) would be beneficial to further understand the et al., 2007). Upon thermal desorption, a sweep gas is usually passed
working mechanism of electrokinetic remediation. For this purpose, a through to carry away the volatile contaminants for further treatment
two-dimensional apparatus had been developed by Gu et al. (2015) or disposal. The parameters that determine the efficiency of thermal de-
for an enhanced simulation of the electrokinetic parameters for the sorption include soil composition and temperature, treatment time,
28 M.W. Lim et al. / Marine Pollution Bulletin 109 (2016) 14–45

Table 6
Thermal remediation of oil contaminated soil.

Technology Working temperature Contaminants Process details Maximum removal Reference


(°C) efficiency

Incineration ≈200–300 Coal tar and Saudi Pilot scale fluidized bed combustion technology 100% (Anthony and Wang, 2006)
crude oil
≈850 Oil contaminated Pilot scale fluidized bed combustion technology 100% (Anthony and Wang, 2006)
gravel
300–500 No. 2 fuel oil Heating time of 25 s at 1000 °C/s in a ≈100% (Bucala et al., 1994)
laboratory-scale heating reactor vessel
Thermal desorption 100–300 Diesel Laboratory-scale tubular electric furnace at ≈98% (Falciglia et al., 2011)
maximum power of 1.5 kW
200–900 Diesel fuel oil Heating time of 35 min in an insulated electric 98% (Piña et al., 2002)
oven
200–350 Diesel Fluidized bed desorber in continuous operation ≈100% (Lee et al., 1999)
120–355 Diesel oil Fluidized-bed desorber with a heat pipe 99.9% (Lee et al., 1998)
300–400 Diesel Lab-scale indirectly heated desorber with two N99.5% (Tatàno et al., 2013)
electrical resistor elements
Microwave frequency NA Crude oil Heating time of 15 min in a modified domestic 99% (Li et al., 2009b)
heating microwave oven (power 800 W; frequency 2.45
GHz, absolute pressure 0.08 MPa)
700 Crude oil Heating time of 4 min in a modified domestic 99% (LI et al., 2009a)
microwave oven (power 800 W; frequency 2.45
GHz)
NA Petroleum Heating time of 3.5 h, on-site microwave 75.6–98.4% (Chien, 2012)
heating system (power: 2 kW; frequency: 2450
MHz) using antenna (4 m)
Up to 600 Crude oil Heating time of 10 min in a modified domestic 99% (Li et al., 2008)
microwave oven (power 800 W; frequency 2.45
GHz)
Up to 500 °C Diesel/marine fuel Heating time of 20–150 s in a domestic 92.5% (Chang et al., 2011a)
microwave oven (power: 700 W; frequency 89.5%
2.45 GHz)
Up to 260 °C Diesel fuel Heating time of 5–60 min in a modified 95% (Falciglia et al., 2013)
domestic microwave oven (power: 1000 W;
frequency 2450 MHz)
Up to 275 °C Diesel fuel Heating time of 30 min in a modified domestic N90% (Falciglia and
microwave oven (power: 1000 W, frequency Vagliasindi, 2015)
2.45 GHz)

vapour pressure of contaminant, concentration and composition of con- contaminated soil to aid the conversion of microwave energy to thermal
taminants, bulk density of soil, particle size distribution, and moisture energy. Li et al. (2009b) investigated the effects of granulated activated
content (Falciglia et al., 2011; Troxler et al., 1993). Piña et al. (2002) in- carbon as a microwave absorber to enhance the remediation of soil con-
vestigated the thermal treatment of soils contaminated with gas oil at taminated with crude oil. The authors showed that the addition of 10%
temperatures between 200–900 °C. Results showed that the chemical of granulated activated carbon resulted in the removal of up to 99% of
composition of the soil highly affects the efficiency of the thermal de- oil contaminant. Subsequent studies by the same authors compared
sorption treatment, since this strongly influences the amount and the other types of microwave absorbers including 0.1 wt% of graphite
composition of the flue gases produced. In other works, Falciglia et al. fibre and activated carbon fibre, as well as 10 wt% of activated carbon
(2011) reported that the increase in temperature from 100 °C to powder, granulated activated carbon, MnO2 and Cu2O (Li et al.,
250 °C significantly increased the removal of diesel from sand from 2009a). Results showed that the removal efficiency of oil from soil
47% to 100%. This study also reported that while a removal efficiency using 0.1 wt% of carbon fibre was highest, with nearly 100% oil removal.
of up to 95% of oil from sandy and silty soil was achieved at low temper- The success of these studies was also seen in a latter study by the same
atures below 175 °C, higher temperatures of 250 °Care required to authors which employed the same technology to remove petroleum hy-
achieve similar efficiencies from clayey soils. Likewise, Lee et al. (1998, drocarbon from soil (Li et al., 2008). Other recent studies which investi-
1999) developed a fluidized bed desorber for low temperature desorp- gated the microwave frequency heating to remove oil from soil include
tion for the remediation of diesel-contaminated soils. A fluidized bed studies by Chang et al. (2011a) and Falciglia et al. (2013). The former
which operates at 294 °C was shown to provide a desorption efficiency study showed that a removal efficiency of diesel and marine fuel of up
of more than 95%. In another recent study by Tatàno et al. (2013), more to 92.5% was achieved using a domestic microwave oven at a frequency
than 99.5% of diesel was removed from soil in a laboratory-scale indirect of 2.45 GHz, while the latter study also showed that a maximum of 95%
heated desorber with two electrical resistor elements operating at 300– removal efficiency of diesel fuel was achieved using a modified domes-
400 °C. tic microwave at a frequency of 2450 MHz.

4.3. Microwave frequency heating 4.4. Advantages & limitations

Microwave frequency heating converts microwave energy into ther- Thermal technologies are very effective in destroying oil contami-
mal energy to remove contaminants via heating and volatilization nants when high heat is applied. Out of the three types of thermal tech-
(Rushton et al., 2007). In microwave heating, many organic materials nologies, incineration method is commonly considered in major oil spill
and soil particles are resistant to microwaves, and are not capable of ab- sites due to its capability to treat large volumes of contaminated site,
sorbing the microwave energy directly to heat up the contaminants. quick, reliable, as well as effective removal of hazardous materials up
Therefore, microwave absorbers are usually mixed together with the to 99%. On the other hand, thermal desorption method is preferred as
M.W. Lim et al. / Marine Pollution Bulletin 109 (2016) 14–45 29

compared to incineration in certain cases because it emits little or no pilot-scale low-temperature two-stage fluidized bed (LTTSFB) incinerator
contamination into the atmosphere, and uses less energy comparative- and co-firing of polyethylene blend with co-contaminated soil (PE/CCS)
ly. The recovered contaminants could be collected and recycled for fur- that could control the emission of gaseous pollutants during the thermal
ther use which could help to reduce the overall operational cost. Lastly, treatment. The parameters investigated were operating temperature in
the advantages of microwave heating are similar as compared to incin- the first-stage reactor, ratio of sand bed height/diameter in second-stage
eration, as the oil removal through microwave remediation is rapid, uni- reactor, and gas velocity. Results show that the removal efficiency of
form, and selective and avoids the overheating of soil substrate surface lube oil was N98.3% through incineration, while increase in ratio of sand
which reduces the total energy consumption (Li et al., 2009a). Based on bed height/diameter and gas velocity could reduce the carbon monoxide
all three methods, the advantages of thermal remediation could be sum- concentrations. On the other hand, the presence of PE could subsequently
marized as quick, and easy with high removal efficiencies. reduce the organic gaseous pollutants, as the addition of PE could influ-
However, the challenge for thermal remediation is the destruction of ence the combustion efficiency which results in the reduction of emission
hazardous material while avoiding environmental pollution. For con- concentration of BTEX (benzene, toluene, ethylbenzene and xylenes) and
ventional incineration, the outer layer of the soil must be heated up to PAH. The authors concluded that the usage of LLTSFB incinerator and co-
very high temperatures for sufficient heat transfer to the core of the firing of PE/CCS could be an effective alternative treatment of remediation
test area. This leads to an excessive energy consumption (Li et al., oil contaminated soil.
2009a). Another major setback for incineration is the production of haz-
ardous by-products and unwanted air pollutants. Preventive measures 4.5.2. Numerical modelling
such as scrubbers are required to treat the exhaust air before releasing Recent studies of thermal remediation for contaminated soil had
it into the atmosphere, which subsequently increases the operational been focused on the numerical modelling for the designing and optimi-
cost. In addition, this method is also not suitable for high water content, zation of the remediation process for in situ applications. Hasan et al.
as the presence of moisture in soil would lead to incomplete combustion (2015) present the development and validation of a computational
of oil contaminants, resulting in a lower removal efficiency. Inversely, model that simulates the smouldering combustion of coal tar contami-
while the thermal desorption technology is capable of recovering the nated sand. The authors used an ISSM (In Situ Smouldering Model)
contaminant, this method is only limited to volatile contaminants to en- which uses both the multiphase flow model DNAPL3D with the
sure success of remediation. In microwave remediation instead, great Richards front expansion expressions that could predict the 2D propa-
care should be taken to ensure temperatures do not escalate due to gation of the smouldering front movement through a porous medium.
carbonisation of humus materials in organic-rich soil which could A series of 2D experiments were conducted to observe the time-
pose a safety threat (Kawala and Atamanczuk, 1998). The possible for- dependent vertical and lateral smouldering front. The outcome of this
mation of hot spot areas in the soil also consumes energy and decreases work would therefore be useful for the designing of thermal remedia-
the efficiency of oil removal. In addition, exposure to microwave radia- tion scheme for oil contaminated soil. Likewise, Falciglia and
tion may lead to health concerns in the society. Vagliasindi (2015) also investigated on the diesel oil removal kinetics
from microwave frequency heating. The understanding of the diesel re-
4.5. Advancements and future work moval kinetics would aid the understanding of the parameters (operat-
ing power and type of soil) that could potentially affect the desorption
4.5.1. After effects of thermal remediation (soil health and air pollution) process, and the corresponding response of the decontamination treat-
Many fundamental studies had been carried out to ensure the suc- ment. The contaminant residual concentration data was fitted to a
cess of thermal remediation. For example, the rate of decontamination power low kinetic model equation, as defined in their previous work
per time had been studied as a function of temperature, time, heating (Falciglia et al., 2011), and results showed that the contaminant removal
rate, flow rate of carrier gas, and initial concentration (Falciglia et al., process was dependent on the thermal properties and the specific sur-
2011; Li et al., 2008; LI et al., 2009a; Li et al., 2009b; Piña et al., 2002). face area of soil (Falciglia and Vagliasindi, 2015).
Nevertheless, the drawbacks of thermal remediation highlight many
potential areas for thermal remediation research especially in the ener- 4.5.3. Advancements in microwave technology as a feasible thermal
gy and cost consumption section, modelling of heat and mass transfer of remediation technology
contaminants and soil matrix (Barba et al., 2012), and in situ applica- In the recent work, it was also observed that the direction of thermal
tions of thermal remediation. remediation for oil contaminated soil is in the use of microwave heating.
While the usage of thermal remediation methods could significantly A recent field-scale study performed by Chien (2012) successfully
remove large quantities of oil contaminant from polluted soils, the showed the feasibility of microwave energy for in-site soil remediation
usage of high temperatures may severely impact the chemical and bio- of petroleum contaminated soil in an oil-refinery in Taiwan. A 4-meter
logical quality of soils. This may incur more cost for the restoration of antenna in length was used to radiate microwave energy with power
soil. Pape et al. (2015) investigated on the impact of thermal of 2 kW for 3.5 h, and the removal efficiency was reported to be between
(b1000 °C) and smouldering (N500 °C) remediation of coal tar contam- 75–99% depending on the distance and depth away from the microwave
inated soil (80 g/kg), on the growth of red clover (Trifolium pratense) antenna. The results suggested that microwave energy could be safely
and red fescue (F. rubra). The increase in temperature was observed to used to remediate oil contaminated soils in a short period of time with-
reduce the nutrient availability such as Cu, Zn and P, nitrogen and car- out excavating the soil, and this novel research could provide direction
bon which leads to a declining plant growth; while there is minimal mi- for further research efforts to establish microwave heating in situ in
crobial re-colonization in soils when heated to temperature greater large industrial scales. Nevertheless, the usage of microwave technology
than 500 °C. Therefore, the understanding of the geochemical changes in soil remediation in situ may present a unique set of social impact chal-
after thermal remediation would help and would lead to better rehabil- lenges, as exposure to high levels of microwave radiation could cause an
itation process, and future studies could include the integration of ther- adverse impact on human health. Studies should continue not only in
mal method with biological enhancements to ensure that the the aspect of remediation efficiencies of this technology in situ, but
remediated sites would have the sufficient nutrients for a better also on the social studies for the acceptance of this technology by the
ecosystem. general public.
The study on the simultaneous treatment of by-products after the However, the energy consumption for thermal remediation of soil
combustion of oil is currently lacking in literature as well. A recent has been a subject of concern in industries despite the efficiency of
paper by Samaksaman et al. (2015) reported on the thermal treatment this method in a short time frame. A recent study by Falciglia and
of soil contaminated with both lubricating oil and heavy metals in a Vagliasindi (2014) attempts to bridge this gap by investigating on the
30 M.W. Lim et al. / Marine Pollution Bulletin 109 (2016) 14–45

technical, energy and economical factors on ex situ microwave treat- soil. Other types of solvents investigated include the use of hexane/ace-
ment of diesel contaminated soil. The researchers simulated an ex situ tone (4:1, v/v%) for the removal of crude oil from soil (Li et al., 2012). A
microwave treatment plant using a bench-scale apparatus by modifying recent study by Sui et al. (2014) demonstrated that the usage of petro-
a 2.45 GHz microwave oven to irradiate the diesel contaminated soil leum ether as the solvent for extraction of weathered petroleum from
samples. Up to 94.8% was recorded for the removal of diesel from wet soil showed satisfactory results, removing 76–94% (12,416 mg/kg of
soils at an irradiation power higher than 600 W for 30 min. A first contaminant) of total petroleum hydrocarbons after 20 min in a labora-
order kinetic model was used to model the contaminant removal with tory scale apparatus.
respect to time. The experimental result shows that the operating
power applied to the microwave oven significantly affects the removal 5.1.2. Surfactant-aided extraction
kinetics. In terms of energy and cost consumption, the energy consump- Surfactants are classified into nonionic, cationic or anionic depend-
tion of microwave radiation plant for oil contaminated soil remediation ing on the surface charge of the head group type. Typically, surfactants
decreased by 25% in comparison to an ex situ thermal desorption meth- are amphiphilic molecules (hydrophobic tail, hydrophilic head) that
od using rotary kiln systems. This shows that the microwave remedia- can reduce the surface tension between two liquids or liquid–solid in-
tion method may be a suitable alternative to conventional thermal terfaces. As the concentration of surfactant increases, micelles will be
remediation of oil contaminated soil. Nevertheless, further work is still formed through the aggregation of molecules. The surfactant concentra-
required to investigate on its application for in situ site. Studies on the tion upon formation of micelles is known as the critical micelle concen-
recovery of heat could also be conducted to minimize energy tration, CMC. At this point, the use of the surfactant will exhibit the
consumption. lowest surface tension. This property can be used to access the suitabil-
ity of the surfactant for the efficiency of contaminant removal. For an oil
5. Physical–chemical remediation technologies contaminated soil system, the surfactants used reduce the interfacial
tension between oil/soil and oil/water interfaces. This subsequently re-
5.1. Solvent extraction duces the capillary forces which leads to an enhanced oil removal sys-
tem (Urum and Pekdemir, 2004; Urum et al., 2004).
Solvent extraction is a widely used technology for soil remediation, Nonionic surfactants are also rapidly gaining popularity due to their
in which contaminants are removed from soil using a single or mixture high efficiencies. Han et al. (2009b) investigated the use of non-ionic
of solvents (Gan et al., 2009). Non-aqueous liquid or solvents are used to green surfactants, alkyl polyglucosides (APGs) for the washing of
remove organic contaminants by separation and concentration process. weathered crude oil contaminated soil. APG which is produced from
The effectiveness of the extraction depends on the realization of an inti- fatty alcohols and sugars is characterized based on the length of alkyl
mate contact between the soil and the solvent mixture. Typical solvents chain. The addition of 100 mL of 0.75 wt% of APG to 10 g of contaminat-
which have been studied to remove oil from soil include exhaustive or- ed weather soil at a temperature of 80 °C in an agitator yielded a remov-
ganic solvents, surfactant-aided aqueous solutions, supercritical and al efficiency of 97%. This study shows that green surfactants are
subcritical fluids (Wu et al., 2011). Table 7 summarizes the solvent ex- promising extraction agents for oil from soil due to their environmental
traction studies to date for the remediation of oil contaminated soil. friendly property.

5.1.1. Water/organic solvents 5.1.3. Subcritical fluid extraction


Numerous researches have been conducted on the development of Subcritical fluid extraction uses high temperature and pressure
solvents to achieve high removal efficiencies in oil contaminated soil fluids that are still in the liquid state, maintained below the critical
remediation. Silva et al. (2005) investigated the use of ethyl acetate/ point. Subcritical water extraction (SCWE) is considered a green tech-
acetone/water (5:4:1, v/v/v%) for the removal of petroleum hydrocar- nology that uses superheated water (100 °C b T b 374 °C), at high pres-
bons from contaminated soil. The use of this solvent mixture in a 3- sures above 22.1 MPa to maintain it in its liquid form. At high
stage crosscurrent and counter current batch extraction study showed temperatures, the hydrogen bonding forces between water molecules
a hydrocarbon removal of 85% and more than 97% oil removal from weaken, decreasing the dielectric constant and polarity. Thus, the

Table 7
Solvent extraction/soil washing studies for remediation of oil contaminated soil.

Extraction agent Specific name Contaminant Process details Efficiency Reference

Water/organic solvents Ethyl acetate-acetone-water Petroleum Magnetic agitation at room temperature 85% (Silva et al., 2005)
Hexane/acetone Heavy crude oil 3-stage crosscurrent and countercurrent 97% (Li et al., 2012)
solvent extraction with solvent:soil ratio of
6:1 (v/w%)
Petroleum ether Petroleum Magnetically agitated for 20 min 94% (Sui et al., 2014)
Surfactant-aided Rhamnolipid Crude oil Mechanical shaking with surfactant:soil N80% (Urum et al., 2004)
ratio of 6:1 (v/w%)
Rhodococcus ruber Crude oil Soil column flushing 82% (Kuyukina et al., 2005)
Alkyl polyglucosides (APG) Weathered crude oil Mechanical agitation at 4000 rpm and 70 °C 97% (Han et al., 2009b)
Rhamnolipid Petroleum Mechanical shaking at 50 rpm and 25 °C 63% (Lai et al., 2009)
with surfactant:soil ratio of 2:1 (v/w%)
Sodium dodecyl sulfate (SDS) in Diesel Mechanical stirring at 13,500–22,500 rpm in 96% (Couto et al., 2009)
colloidal gas aphrons (CGA) form a reactor column
(microbubbles)
Bacillus licheniformis MTCC 5514 Crude oil Incubated at 37 °C under shaking for 48 h N85% (Kavitha et al., 2014)
Subcritical fluid extraction Superheated water Lubricating oil Cylindrical extraction cell at temperature of 62% (Islam et al., 2013)
275 °C and pressure of 6 MPa
Supercritical fluid extraction CO2 in presence of acetone Crude oil Extraction cell at temperature of 80 °C and 75% (Morselli et al., 1999)
pressure of 227 atm
CO2 Crude oil Dual-chamber extraction module at 72.4% (Al-Marzouqi et al., 2007)
temperature of 100 °C and pressure of 300
bars
M.W. Lim et al. / Marine Pollution Bulletin 109 (2016) 14–45 31

subcritical water adopts a hydrophobic nature, and behaves as an alter- main disadvantage of solvent extraction technology is the introduction
native organic solvent (Gan et al., 2009). Works by Islam et al. (2013) of a secondary pollution from the solvents used, which may continue to
showed that the increase in temperature of SCWE from 200 to 275 °C persist in the remediated soil and subsequently pose an environmental
at 6 MPa showed a reduction in TPH concentration in soil contaminated risk due to its low biodegradability. There is also a possibility for the ad-
by lubricating oil up to 3.5 times. This is attributed to the decrease in di- sorption of the surfactant/solvent into soil particles, which could de-
electric constant and surface tension of subcritical water, which reduced crease the concentration of the surfactant/solvent which reduces its
the polarity of the water and enhanced the dissolution of the lubricating efficiency. In addition, the solvent extraction technology consumes
oil. Further works in the subsequent year by the same author showed an large amounts of solvent which leads to a high operational cost.
improved removal efficiency of lubricating oil of more than 98% at The current limitations of solvent extraction are the selection of an
275 °C using static dynamic extraction for a 120 min extraction in a effective and environmental friendly solvent, recycling of solvent or sol-
laboratory-scale apparatus, as well as a 150 min extraction in a 30 fold vent regeneration, and development of proper equipment for scale up
scale-up experiment (Islam et al., 2014). The change from static mode process. The selection of environmental friendly solvents showed the
in the earlier works to static-dynamic mode increases the intraparticle use of biosurfactants or non-ionic surfactants instead of chemically pro-
diffusion and mass transfer rate which results in the further increase duced surfactants. While these surfactants show promising result as an
in removal efficiency. environmentally friendly alternative to typical chemical produced sur-
factants, there is still a need to investigate on a universal surfactant
5.1.4. Supercritical fluid extraction that could provide a high oil removal efficiency under any conditions.
Supercritical fluid extraction (SCFE), on the other hand, uses fluid
which is heated and pressurized above the critical point, otherwise 5.1.6. Advancements & future work
known as supercritical fluid (SCF) (Gan et al., 2009). Due to the high
temperatures and pressures, SCF exhibits gaseous–liquid properties 5.1.6.1. Advancements in environmentally friendly solvents/surfactants —
such as liquid-like density, high diffusivity, low viscosity and no surface biosurfactants and ionic liquid. A major concern of solvent extraction is
tension (Anitescu and Tavlarides, 2006; Gan et al., 2009; Morselli et al., the impact of solvents on the environment, as the solvents used are
1999). The efficiency of SCFE depends greatly on the solubility and mass commonly toxic in nature. Recent papers are currently headed towards
transfer of the contaminant into the SCF (Morselli et al., 1999). the direction of green solvents, that would not further impact the envi-
The most commonly used fluid for SCFE is carbon dioxide due to its ronment. One of the green solvents that had garnered much interest
non-polar nature and liquid solubility characteristics. It is also inexpen- from researchers worldwide is biosurfactants, which are formed from
sive, non-toxic, and vastly available and owns a moderate critical pres- biodegradable means. Biosurfactants are amphiphilic compounds, and
sure and temperature. Other SCFs considered include propane and are easily produced from renewable resources with possible reuse by
butane. While the latter SCFs exhibit excellent oil and grease removal regeneration due to their lower toxicity. They are also more stable in
from soil and sludge, these fluids are highly flammable making their harsh and extreme environmental conditions (low/high temperatures,
use potentially hazardous to human health (Low and Duffy, 1995). Al- pH, salinity) (Kuyukina et al., 2005). A study to compare the crude oil re-
Marzouqi et al. (2007) investigated the use of CO2 for the extraction of moval efficiency using synthetic surfactant and biosurfactant was inves-
crude oil from contaminated soil under pressures ranging from 80– tigated by Urum et al. (2006). The surfactants studied were rhamnolipid
120 bars for temperatures between 40–60 °C, and 200–300 bars for (biosurfactant), saponin (biosurfactant) and sodium dodecyl sulfate
temperatures between 100–140 °C. The authors reported that although (SDS) (synthetic surfactant). Weathered oil contaminated soil washing
supercritical CO2 could only remove up to 4% of crude oil in soil at pres- was carried out at 20 °C using 20 mL of surfactant solution at
sures of 80 bars in the temperature range studied, the efficiency of CO2 200 strokes/min for 20 min. Both SDS and rhamnolipid showed equal
was seen to increase with pressure, reaching up to a maximum of 72.4% efficiencies at approximately 45%, followed by saponin at 27%. Results
at 300 bars and 100 °C. showed that both the rhamnolipid and SDS preferentially removes ali-
Other documented works on the use of supercritical CO2 for the re- phatics compared to aromatics, while saponin removed more of the ar-
mediation of petroleum hydrocarbons include the study by Morselli omatic hydrocarbons comparatively to aliphatics. These results are
et al. (1999). This study reported that with an addition of 5 v/v % of ac- consistent with the characteristics of the crude oil contaminant, where-
etone to supercritical CO2 at 80 °C and pressure of 227 atm, the removal by the crude oil used contained more aliphatics compared to aromatics
efficiency of crude oil from soil increased to 75%, as compared to 60% (2:1, v/v%). Therefore, it could be concluded that the selection of surfac-
without the acetone addition. The results suggest that the acetone ex- tant for the removal of contaminant from contaminated soil is crucial for
erts a swelling action on the soil which helps to pry open the inter- the success for soil remediation. Works by Kuyukina et al. (2005)
layers of the soil structure. showed similar observations whereby the efficiency of biosurfactants
Likewise, Geranmayeh et al. (2012) also used carbon dioxide for the depends greatly on the composition of contaminants. They studied the
extraction of oil from contaminated soil from the Pazanan II production use of Rhodococcus ruber for the removal of oil from soil, and reported
unit site in Gachsaran, Iran. In this study, the optimum operating param- that the biosurfactant selected is up to 2.3 times greater than synthetic
eters such as pressure, temperature, flow rate and duration were ob- surfactant, Tween 60 of similar properties. At temperature of 28 °C
tained to optimize the removal of the contaminant. It was found that and concentration of surfactant up to twice the value of its CMC, the
increase in pressure increases the removal efficiency. The optimal oper- maximum oil recovery obtained was 82%. It was also noted that the
ating conditions of this study were shown to be at 328.15 K, 190 bars, crude oil contained up to 95% of biodegradable aromatics and aliphatics,
0.05 cm3/s CO2 flow rate, and extraction time of 75 min to yield removal as opposed to high molecular weight paraffins and asphaltenes, which
efficiencies of 48.7% per 0.03 m3 of consumed CO2. are non-biodegradable compounds. Therefore, the results suggest that
the above mentioned surfactant may not be efficient for contaminants
5.1.5. Advantages & limitations with high compositions of paraffins and asphaltenes. Kavitha et al.
Currently, there are many reviews for solvent extraction remedia- (2014) also investigated the use of Bacillus licheniformis (MTCC 5514)
tion method of contaminated soil in literature (Hall et al., 1990; Mao for the removal of crude oil (10%) from contaminated soil. The authors
et al., 2014; Mulligan et al., 2001; Raghavan et al., 1991). Solvent extrac- reported that the use of MTCC 4413 was able to remove crude oil from
tion is proven effective for oil contaminated soil remediation as it has soil with an efficiency of up to 85%.
shown high efficiencies and quick results. Other advantages include Different forms of biosurfactants such as microfoam for soil washing
low energy consumption and enhancement of heat and mass transfer had been a promising alternative as compared to aqueous
process due to the additional mechanical agitation. Nonetheless, the biosurfactants. Microfoam contains several layers of surfactants and
32 M.W. Lim et al. / Marine Pollution Bulletin 109 (2016) 14–45

liquids surrounding the gas bubble. da Rosa et al. (2015) studied the re- consumption of solvents, methods to reduce the operational cost such
moval of two oil contaminants (5 w/w% petroleum and 5 w/w% diesel re- as recycling, regeneration or recovery of solvents to their original prop-
spectively) from sandy soils using biological and chemical surfactants in erties should be further explored, while cost analysis for the scale up of
both solution and microfoam form. The biosurfactant used was this technology could also be conducted. However, studies on solvent
rhamnolipid, while the chemical surfactants were sodium dodecyl sul- regeneration so far are limited, as it is difficult to recover the solvent.
fate, SDS and cetyltrimethylammonium bromide, CTAB. Microfoams One of the papers published in this area is by Wu et al. (2011), whom
were produced via a homogenizer at 15,000 rpm. Results showed that managed to implement a water washing method for the recycling of
usage of microfoam across all three surfactants provided a significant in- solvent used in the solvent extraction of petroleum hydrocarbons
crease in remediation efficiency by up to 7.3% for the removal of diesel oil, from soil. The recycled solvent could further remove the residual con-
and 13.9% for the removal of petroleum. This was attributed to the small taminant, and this leads to an overall higher removal efficiency. In this
structure and large interfacial area of microfoam which contains several study, water was introduced into a soil column with a solution mixture
layers of surfactants and liquids, that would improve the contact with of hexane/pentane (4:1, v/v%). The solvent floated to the top, which
the contaminated soil, and this allows it to penetrate the soil lattice to then overflowed into a solvent recycling bottle, before being recycled
help degrade the oil contaminant. The usage of microfoam rhamnolipid back into the water wash column. With a high recycling efficiency of
biosurfactant and SDS surfactant provided a petroleum removal efficien- 97%, this study demonstrated a promising method for reducing residual
cy of approximately 42.1% and 44.3% respectively, and diesel removal ef- concentration of solvent in the contaminated soil upon solvent
ficiency of 44.8% and 62.9%. While the usage of microfoam form may be extraction.
an interesting direction for surfactant application, further investigation
should be focused on investigating the type of microfoam biosurfactants 5.1.6.3. Fluid mechanics of solvent extraction. In the previous works of sol-
for bioform which could provide a significant oil removal efficiency for vent extraction, many of the existing works were conducted in laborato-
contaminated soil. The oil removal mechanism involved in the remedia- ry scale with successful removal efficiencies, whereby the operating
tion process using microfoam biosurfactants could be conducted as well. conditions are easily manipulated. While the success rate of laboratory
Other than biosurfactant, recent developments in the solvent extrac- scale solvent extraction is high, few studies had been performed on
tion technology showed that the petroleum industry had been looking the scale up equipment for industrial purposes, or field study for reme-
into the application of ionic liquids for oil recovery applications, due to diation of oil contaminated soil. A recent study by Liu et al. (2014) aims
the surfactant-like properties that are able to dissolve many polar, to bridge that gap by investigating on the use of continuous fluidized
non-polar, organic and inorganic compounds. Ionic liquid is also consid- counter current solvent extraction in a scale-up equipment design as a
ered a green chemical as its characteristics of low vapour pressure and potential application for the removal of oil pollutant from contaminated
high chemical and thermal stability, were reported to not contribute soil. A fundamental fluid mechanic study was conducted to establish a
to air pollution (Benzagouta et al., 2013; Pereira et al., 2014). The advan- counter current extraction system and observe the basic hydro-
tages of ionic liquid over the conventional solvents lead to an increased mechanical performance. The authors successfully obtained an operat-
interest by researchers worldwide on the application of ionic liquid for ing curve for soil remediation by counter-current solvent extraction
oil recovery. The study of ionic liquid based oil recovery process from for solvent (hexane/pentane) and solid (glass beads) flow rates ranging
sands was first conducted by Pereira et al. (2014). Experiments were between 10 to 800 L/h and 8 to 107 kg/h respectively (Liu et al., 2014).
conducted in a crude oil contaminated water-wet sand column, and While the fundamental study by these authors demonstrated a further
the ionic liquid used was 2 wt% aqueous solution of 1-ethyl-3- understanding for the application of counter-current fluid mechanism
methylimidazolium tosylate [C2mim][OTs]. Results showed that the for solvent extraction technology, further work should still be conduct-
flooding process with 4 pore volume of ionic liquid could recover ed for the application of this technology for the solvent extraction of oil
65.7% of oil, which was almost double the amount collected by 2 wt% contaminated soil.
NaCl. The authors suggested that further optimization of the ionic liquid While recent advancements in the solvent extraction technology are
characteristics and concentrations is required to enhance oil recovery in currently looking into fundamental studies for potential scale up, regen-
reservoirs. This was in good agreement with results by Gou et al. (2015), eration of solvents to biodegradable solvents that are not hazardous to
whereby the usage of PAAD/C8mmBr as the ionic liquid was able to re- the environment, nevertheless there are still gaps particularly for
cover up to 63.6% of crude oil from contaminated sand as opposed to scale-up applications. Future work should be conducted on the funda-
40% from the usage of NaCl. The better performance of PAAD/C8mmBr mentals of solvent extraction, particularly in the modelling of mass
as opposed to NaCl was attributed to the superior temperature resis- transfer to understand the contaminant extraction process.
tance of ionic liquid and shear reversible performance that would en-
hance oil recovery. The high potential of ionic liquids for applications in 5.2. Soil vapour extraction
oil recovery from contaminated sand leads to further studies on the oper-
ating parameters such as concentration, salinity and pH that would affect Soil vapour extraction (SVE), also known as soil venting or vacuum
the oil recovery efficiency (Asadabadi and Saien, 2016; Mohsenzadeh extraction is an in situ soil remediation technology that has been studied
et al., 2015), and fundamental work such as the wetting behaviour of to remove organic compound particularly from the soil unsaturated
ionic liquid on an oily surface (Delcheva et al., 2014) and bubble attach- zone using either horizontal or vertical screened wells (Lee et al.,
ment onto oil layer in a ionic liquid medium. However, it should be 2002; Pendersen et al., 1991). The extracted vapour is then drawn to-
noted that the toxicology of ionic liquids is still lacking in literature to wards the extraction wells for further treatment with activated carbon
date (Benzagouta et al., 2013). Therefore, it is crucial to evaluate the before release to prevent atmospheric contamination (Albergaria
ecotoxicity and biodegradability of ionic liquids prior to their application et al., 2008). Factors which affect the efficiency of SVE include opera-
on-site to prevent further environmental problems in the future. tional parameters such as air flow rate and temperature, contaminant
While works on biosurfactants and ionic liquid as an environmental characteristics such as vapour pressure and solubility, and soil charac-
friendly solvent alternative had shown promising results, environmen- teristics such as moisture content and natural organic content
tal analysis such as the impact of the solvents used on the environment (Albergaria et al., 2008, 2012; Lee et al., 2002; Malina et al., 2002).
should also be analysed prior to implementation of solvent extraction The usage of SVE is commonly employed in high porosity and high
for on-site applications. permeability soil, which is contaminated with highly volatile contami-
nant. Nevertheless, SVE exhibits low efficiency for low concentrations
5.1.6.2. Regeneration of used solvents/surfactants. As high operational cost of heavy volatile organic compound (VOC) contamination and contam-
is a disadvantage to solvent extraction technology due to the large inants with low volatility, such as inorganic compounds. Due to the
M.W. Lim et al. / Marine Pollution Bulletin 109 (2016) 14–45 33

limitations of SVE, researchers are currently developing integrated tech- of volatile organic components, but up to a certain extent due to the
nologies to enhance the performance efficiency of SVE, which include lower contact time of air with soil. In the same study, a field pilot scale
the integration of air sparging/SVE, bioventing/SVE and thermally en- study showed that the hot air injection method showed promising re-
hanced SVE. sults with up to 95% removal efficiency compared to the standard SVE
method within 30 days of operation.
5.2.1. Air sparging/SVE
Air sparging (AS) involves the injection of atmospheric air into the 5.2.4. Advantages & limitations
soil, promoting the transfer of aqueous phase contaminants into the va- Similar to solvent extraction, soil vapour extraction aids the removal
pour phase, while the oxygen transferred from the air promotes the bio- of large quantities of volatile contaminants in uniform soils within a
degradation of volatile organic compounds (Al-Maamari et al., 2009). short treatment time. In addition, soil vapour extraction also stimulates
The injected air would form channels through the saturated and vadose the bio growth of microorganisms with oxygen through the flow of air,
zone in soil, volatilize the contaminants, and then be transported back which further enhances the biodegradation rate of organic contaminants.
into the vadose zone where it will be further treated through biological Nevertheless, the efficiency of soil vapour extraction is affected by
methods or SVE (Kirtland and Aelion, 2000). The combination of AS and several factors, namely operational conditions such as soil temperature
SVE is highly suitable for treatment of volatile contaminants in high per- and air flow rate, contaminant properties such as volatility of contami-
meability soils such as sand, whereby a large percentage of the contam- nant, and soil properties such as water and soil organic matter content
inant would be affected by the air flow. Kirtland and Aelion (2000) (Albergaria et al., 2012). SVE is inefficient for heavy volatile organic
studied the effectiveness of AS/SVE system on low permeability sand compounds as well as contaminants with low volatility. In addition, it
in Columbia contaminated with gasoline. The authors reported that is also not suitable for soils with low air permeability, as the air induced
ten pulsed AS/SVE tests were effective in removing TPH in the low per- prefers to flow into paths of lower resistance (high soil permeability).
meability sand up to 17.6 kg/day at low air flow rates (≈25 m3/h) when The low permeability region would not be crossed by air flow, and
compared to the removal efficiency of 14.3 kg/day in continuous opera- could only be remediated by other means which greatly decreases the
tion. This was attributed to the increased mass removal and decreased efficiency of this treatment method. A soil with high water content
energy consumption of pulsed operations. Johnston et al. (2002) also re- also affects the efficiency of SVE, as the water fills up the pores in the
ported that the combination of air sparging to SVE as an in situ technol- soil matrix, which acts as a barrier between contaminant and air flow
ogy improves the volatilization of gasoline petroleum hydrocarbons preventing efficient evaporation of contaminant into the sweep gas. An-
from sandy soils by a factor of 1.9. other main disadvantage for SVE is the treatment of the down-stream
contaminant and sweep gas, which may require a substantial large
5.2.2. Bioventing/SVE amount of cost for subsequent treatment downstream.
The use of both SVE and bioventing (BV) enhances the soil remedia-
tion whereby SVE removes the air phase pollutants through volatiliza- 5.2.5. Advancements and future work
tion, while BV attempts to increase the subsequent bioremediation
rate through an additional aeration of oxygen for microbiological activ- 5.2.5.1. Simulation studies on multi-phase flow of air and contaminants.
ity (Lee et al., 2002; Lee et al., 2001). There are a couple of review papers dedicated for the usage of SVE for
Lee et al. (2001) investigated the feasibility of the integrated BV/SVE remediation purposes in literature (Hutzier et al., 1991; Rathfelder
system to remove toluene, ethylbenzene and xylene compounds from a et al., 1995). A great deal of focus had been placed on the usage of SVE
petroleum-contaminated site. The removal rate via SVE in the field test for in situ remediation. Therefore, the fundamental studies had been ex-
was initially high due to the large amounts of toluene volatized. The tensively conducted, for example on field pneumatic pump test, calcula-
contribution of SVE eventually decreased with the concentration of con- tion of air permeability using transient and stead state pressure data
taminants and the effect of biodegradation on contaminant removal be- (Lee et al., 2002), and understanding the volatilization behaviour and
comes apparent after 30 days. The effect of BV resulted better, with the volatilization rate coefficient of diesel oil under the influence of wind
removal of 130 kg contaminants after 100 days of treatment due to the speed, vessel diameter and mean grain size of porous media from con-
more volatile properties of toluene. A similar study by Malina et al. taminated soil (Ma et al., 2014b). Another fundamental study that was
(2002) also reported that the integrated BV/SVE system showed high conducted in the SVE method includes the simulation study of airflow
removal efficiencies (N 99.5%) of toluene and decane contamination in within the soil system. As the air sparging system is determined by
soil in an intermittent flow regime. the contact between injected air with contaminant and resident time
of air in soil, it is imperative that the air flow distribution is well under-
5.2.3. Thermally enhanced SVE stood before implementing this remediation method for contaminated
Conventional SVE has limited efficiencies in removing semi-volatile soils. Song et al. (2015) simulated the two-dimensional airflow distribu-
contaminants from soil due to their low volatility. Therefore, the in- tion, observed the shape of zone of influence (ZOI) and calculated the
crease in working temperatures would increase the vapour pressures ZOI radius through nine different sizes of transparent fused silica
of the contaminant, making it easier to remove the semi-volatile con- sands that simulate natural soil. Results showed that the airflow distri-
taminants via SVE. There is a variety of methods for increasing the soil bution could be fitted using a unified dimensionless Gaussian function
temperature, such as radio and microwave frequency, hot air injection under different sparging pressures, which would be useful for the de-
and electrical resistance (Park et al., 2005). Poppendieck et al. (1999) in- sign of air sparging for remediation of oil contaminated soil.
vestigated the effect of soil temperatures on the rate of petroleum re- While a large number of modelling studies were conducted to date,
moval from soil in a laboratory-scale study. The increase in soil studies had been previously focused on mass transfer processes using a
temperature from 50 °C to 150 °C increased the removal rate constant one-dimensional (1D) or two-dimensional (2D) model (Carroll et al.,
from 0.0099 h−1 to 0.13 h−1 for C13 (tridecane hydrocarbon) a common 2012; Høier et al., 2009; Kaleris, 2002; Rathfelder et al., 2000). The dis-
component found in petroleum. A similar study by Park et al. (2005) advantage of the usage of 1D/2D models, is that they may not complete-
was also conducted to study the effects of temperature and air flow ly simulate complex fluid flows and transport processes in soils with
rate on thermally enhanced SVE in the remediation of diesel contami- high heterogeneity. Therefore, the recent modelling studies had been
nated soil. Results showed that the increase in working temperatures focused on three-dimensional (3D) models as 3D models could provide
from 30 °C to 100 °C at an air flow rate of 20 mL/min showed a drastic a more realistic prediction than 1D/2D models by utilizing all informa-
increase in the removal rate from 0 to 60% for n-C16. Likewise, a higher tion available to provide a detailed soil mapping process. A 3D multi-
gas flow rate up to 80 mL/min was shown to yield higher removal rates phase flow in a multi-component transport situation had been
34 M.W. Lim et al. / Marine Pollution Bulletin 109 (2016) 14–45

successfully developed by Nguyen et al. (2013) using Comsol increase in process temperature from 35 °C to 50 °C increased the re-
Multiphysics software via a finite element method, that could identify moval efficiency of bitumen from sandy grains by nearly 50%.
the mass transfer value, and is able to predict laboratory findings for re- The efficiency of flotation is also affected by the addition of chemical
moval of NAPL from contaminated soil. products which change the interfacial interactions. High pH is favoured
Other recent studies that had been conducted in the SVE field include due to the formation of OH− groups formed onto the polar surface of the
the kinetic study on the calculation of degradation rate constant of petro- soil particles. The OH− groups would weaken the adsorption energy be-
leum hydrocarbons of up to 4 kg of contaminated soil (loamy sand, silt tween the oil contaminant and soil particles (Hong et al., 2012; Liu et al.,
loam and sandy loam soil) in an intermediate scale experiment to obtain 2005; Long et al., 2007). Moreover, the addition of alkaline additives re-
the degradation model of BV/SVE after a 30 day period (Khan and Zytner, acts with the organic acids in bitumen, forming a natural surfactant
2013). Through numerical modelling of the SVE performance, the clean- which enables the flotation of bitumen from soil (cited by Clark and
up time can be estimated and hence providing a framework on the deci- Pasternack in (Liu et al., 2005)). In contrast to this, however, Al-
sion to continue or terminate soil vapour extraction via numerical Otoom et al. (2009) showed that the amount of base (NaOH) and the
modelling method (Carroll et al., 2012). The estimation of clean-up flotation agent was found to have a negative effect on the release of bi-
time through mathematical/analytical modelling had also been exten- tumen from sand in a fluidized bed flotation. In particular, this was sug-
sively studied (Alvim-Ferraz et al., 2006a; Alvim-Ferraz et al., 2006b; gested to be due to the increase in the hydrophilicity of the bitumen
Kaleris and Croisé, 1997; Zhao and Zytner, 2008). with the increase in NaOH. On a different note, it was shown that the ad-
However, there are certain areas that are currently lacking in litera- dition of surfactants also reduces the surface tension between the solid–
ture which could help and enhance the implementation of SVE on site. liquid (soil-oil) interfaces, therefore enhancing the removal of oil from
While an assessment scheme for the continuation of SVE on site was re- soil through flotation. Typical surfactants that have been studied include
ported successful for understanding the remediation progress over sodium dodecyl sulfate (SDS), sodium dioctyl sulfosuccinate (AOT),
time, the impact of geological factors may cause complexity and the ef- polyoxyethylene lauryl ether (Brij 35), rhamnolipid, and saponins
fect of these factors should be focused on the future researches. Also, the (Urum et al., 2006). The concentration of surfactants added to the flota-
benefit of extra cost to heat soil for thermal enhanced SVE should be in- tion system also affects the flotation efficiency. Zhang et al. (2000) re-
vestigated, as high operating costs are not favoured for industry applica- ported that the increase of SDS from 100 ppm to 300 ppm improved
tions. For that reason, an assessment scheme or cost and energy analysis the paraffin oil removal efficiency from 52% to 57%, attributed to the de-
could be projected from the on-going simulation studies inclusive the crease in surface tension between oil contaminant and soil.
downstream processes (cleaning of sweep gas) prior to SVE field Bubble hydrodynamics such as size, rising velocity and concentra-
application. tion play an important role in the flotation technology. At constant air
flow rates, the decrease in bubble size provides a larger surface area
available for contact, which enhances the adhesion of bubbles to con-
5.3. Flotation
taminants. On the other hand, bubbles which are too small have low ris-
ing velocity and insufficient buoyancy to lift larger contaminants to the
The flotation technology is the combination of chemical, physio-
surface (Tsai et al., 2007). Many other authors have looked into various
chemical and physical methods to separate oil from soil via a gas–liq-
aspects of the flotation technology to remove oil from soil. Zhou et al.
uid–solid system. This technology relies on the difference in surface
(2010) investigated the effect of bubble nucleation in water on bitumen
properties of both contaminant and soil, and thus is capable of separat-
flotation from oil sands. The presence of these bubbles increased the col-
ing very small or light weight particles with low settling velocities. The
lision and adhesion probability of the bitumen to bubbles, contributing
mechanism of flotation lies in the generation of gas bubbles which at-
to a higher oil removal efficiency of 64% compared to 42%. In a different
taches to the hydrophobic contaminants. The gas-contaminant bubble
study, Kim et al. (2012) utilised the collapse energies of microbubbles
which is buoyant then rises to the surface of the liquid, creating a
generated from bubbly water to separate oil contaminants from soil in
layer of separated particles which could be recovered. In short, the flo-
a separation device. By using positively charged bubbles in a dissolved
tation mechanism is dependent on: (a) collision between contaminants
air flotation process, a maximum of 97% of total petroleum hydrocarbon
and bubbles, (b) attachment of contaminants and bubble to form
was removed from soil. In a recent study by Hong et al. (2012), the re-
bubble-contaminant, (c) flotation of bubble-contaminant due to differ-
moval of bitumen from contaminated sand was conducted using
ence in buoyancy and (d) detachment of contaminant from bubble-
microbubbles generated from the compression and decompression cy-
contaminant (Tao, 2005).
cles of air. Under optimum process parameters, bitumen recovery of
92% was achieved after 5 min of treatment time at 4 pressure cycles of
5.3.1. Flotation studies air (6.9 atm) and 105 °C. This process may provide a high bitumen re-
The variables which can affect flotation are broadly classified into moval efficiency, but may incur a high operational cost due to the high
physical, chemical and bubble hydrodynamics. Physical parameters pressure needed for the compression of air.
which affect the efficiency of flotation include agitation rate, tempera-
ture, concentration of oil contaminant, aging time and oil characteris- 5.3.2. Advantages & limitations
tics. The effects of agitation rate were reported by Tsai et al. (2007) The use of flotation and its operating parameters had been exten-
whereby an increase in agitation rate was suggested to increase the in- sively studied especially for Canadian and Utah oil sands in the previous
tensity of turbulence in the cell which promoted bubble-contaminant years (Drelich et al., 1995; Masliyah et al., 2004; Schramm et al., 2003),
collisions and increased the amount of oil removed. However, a further due to its simplicity, low operational cost and high oil removal efficien-
increase in impeller speed was seen to generate a large centrifugal force cies. This technology is capable of separating very small or light weight
which ruptured the bubble-contaminant aggregates, thus reducing the particles with low settling velocities. However, flotation technology re-
flotation recovery efficiency. The increase in temperature also aids the quires large amounts of water to aid the process, which may incur high
removal efficiency of contaminant by reducing the density of oil con- downstream cost for treatment of wastewater. The usage of this tech-
taminants, making it easier for bubble attachment (Zhang et al., 2000). nology may not be efficient for the removal of aged or weathered soil.
This is in agreement with works by Chou et al. (1998) whereby an in- The aging of oil in soil increases the interaction forces between oil and
crease in temperature from 22 °C to 45 °C showed an increase in flota- soil which makes it difficult for efficient flotation. As shown by Wang
tion efficiency from 62% to 78% in the removal of non-volatile paraffin et al. (2009), an increase in the aging time from 7 to 30 days decreased
oil from contaminated soils via a counter-current column flotation. Sim- the flotation efficiency of waxy crude oil from soil by approximately
ilar findings were also shown by Masliyah et al. (2004) whereby an 27%. Research by Urum et al. (2004) also showed that upon evaporation
M.W. Lim et al. / Marine Pollution Bulletin 109 (2016) 14–45 35

of lighter oil components, the remaining higher molecular weight oil in 2009; Mason et al., 2004). In the remediation of soil, ultrasonication
soil acquires stronger interactions which resulted in a low removal effi- also helps desorption of the contaminant, and promotes the formation
ciency for the flotation of weathered soil. of strong oxidant, OH− radicals which would enhance the oil removal
efficiency (Feng and Aldrich, 2000; Shrestha et al., 2009). Table 8 sum-
5.3.3. Advancements and future work marizes the studies to date using ultrasonication for the removal of oil
from soil.
5.3.3.1. Bubble innovations. Currently, new innovations had been intro-
duced to further enhance the flotation efficiency for oil recovery from 5.4.1. Ultrasonication studies
difficult sites such as low grade oil sand ores, while reducing energy Initial ultrasonication studies were conducted by Sadeghi et al. for the
consumption and water use. Harjai et al. (2012) proposed the use of a extraction of bitumen from sand (Chilingarian et al., 1989; Sadeghi et al.,
robust aqueous–nonaqueous hybrid bitumen extraction process at low 1994; SADEGHI et al., 1990a; Sadeghi et al., 1990b). A similar study by
temperatures with reduced intake of feed water for the removal of bitu- van Ellen et al. (1995) concluded that the use of acoustic waves from
men from Athabasca oil sand ores to cater to the environmental and sonication could enhance the removal efficiency by up to 30% of contam-
economic demand. Kerosene and naphtha of 4 to 11 wt% were used as inants from soil. From these studies, the removal of contaminant was at-
the diluent to decrease bitumen viscosity. Zhou et al. (2010) introduced tributed to the breaking of larger contaminant particles to smaller
the usage of carrier flotation for accelerating bitumen extraction from particles due to the alternating pressure applied from the sonication.
Athabasca oil sands by blending coal particles as carrier materials to- The smaller contaminant particles could therefore be easily recovered
gether with bitumen coated glass beads to simulate bitumen droplets. from the system. A similar study was conducted by Mohammadian
The presence of the carrier material aids in the detachment of bitumen et al. (2012) for the removal of kerosene, vaseline and engine oil from
from the particle due to the gravitational effect of the larger and heavier a sand pack using a series of normal and ultrasonic simulated water-
materials. An increase in bitumen removal of up to 30% was observed flooding experiments. The authors reported that the use of ultrasonic
with the addition of the carrier material (coal) (Li et al., 2013). waves triggered a 16% increase in oil recovery as compared to the normal
Other new methods would be the introduction of nanobubbles to aid stimulated water flooding experiment. This was attributed to the in-
the flotation of oil contaminant. Nanobubbles had been applied in min- crease in oil emulsification and bubble cavitation as well as a reduction
eral flotation as nanobubbles with its small bubble size could provide a in oil viscosity which contributed to the improved recovery of oil. Like-
better bubble-particle attachment for enhanced flotation efficiency wise, recent studies had also show that the use of ultrasound increased
(Calgaroto et al., 2014). Therefore, studies on the flotation of oil contam- the removal of super heavy oil from weathered soil in a surfactant en-
inant could gravitate towards the application of nanobubbles to im- hanced solution by a further 13–14%, signifying that the ultrasonication
prove the oil recovery. method is a potentially useful method for the remediation of oil contam-
inated soil (Ji et al., 2011)
5.3.3.2. Fundamental studies on interactions between phases (solid–liquid, Many parameters which influence the efficiency of ultrasonication
liquid–liquid and liquid–gas). Studies on the flotation technology had during the removal of oil from soils have been studied, including type
also gravitated towards the interaction studies between the solid, liquid and density of soil, sonication power (Feng and Aldrich, 2000; Kim
and gaseous phases. For example, the parameters that would affect the and Wang, 2003; Shrestha et al., 2009), sonication period, pH of slurry
oil-sand contact were investigated by Lim et al. (2015) to further under- (Feng and Aldrich, 2000; Shrestha et al., 2009), amount of water used,
stand the detachment process of oil from contaminated sand in a flota- surfactant dosage (Shrestha et al., 2009), and oil content (Feng and
tion process. Flury et al. (2013) on the other hand investigated on the Aldrich, 2000). The effect of sonication power on vegetable oil removal
interaction between oil and bubbles, and the corresponding liquid prop- had been investigated by Kim and Wang (2003). The authors reported
erties that would affect the bubble attachment onto the oil. The authors that there was an increase in oil removal efficiency with the increase
reported that the application of different caustic types (sodium hydrox- in sonication power up to 100 W, followed by a drop in efficiency
ide and ammonium hydroxide) for bitumen flotation would affect the with further increase in power. The drop in efficiency was attributed
induction time between bitumen-bubble attachments. Other funda- to the high occurrence of cavitation which caused the acoustic pressure
mental studies include the understanding of frother like properties of level to decrease as the sonication power was further increased above
process water in bitumen flotation, the natural frother from the bitu- 100 W. Similar results were observed by Shrestha et al. (2009) on the
men process water had been characterized and compared with a well removal of hexachlorobenzene and phenanthrene, both of which are
known frother, DF-250 (Nassif et al., 2014). contaminants commonly found in oil, from soil. A drop in removal effi-
ciency was observed at powers beyond 100 W, which again was sug-
5.4. Ultrasonication gested to be due to the effect of cavitation. Therefore, there is a need
to optimise the level of power input whereby too low a power would
At present, ultrasonication has found many uses in a variety of appli- provide low removal efficiencies, while a high power input will not
cations including medical imaging, synthesis of catalysts, pollution con- only increase the effect of cavitation but also increases the power con-
trol and oil extraction from sand or similar materials. Oil removal from sumption of the sonicator.
soil using ultrasonication is made possible by two important phenome- The same authors also reported that the increase in sonication dura-
na; (i) formation and collapse of cavitation bubbles, and (ii) generation tion in soil increased the temperature up to a certain level, which
of shock waves from the collapse of cavitation bubbles (Abramov et al., remained constant with further increase in sonication time. Hence, the
2009; Mason et al., 2004). The formation and collapse of bubbles at the removal efficiency of organic compound remained relatively constant
nucleation sites create localised hot spots in the liquid, due to the sud- when the sonication time was increased from 1 to 6 h. However, this
den increase in pressure during the implosive collapse of the bubbles. contradicts with results published by Feng and Aldrich (2000), who
High temperatures enhance the breakage of bonds and desorption of noted that the increase in sonication time initially showed a sharp in-
oil contaminant from soil particles (Flores et al., 2007). Moreover, the crease in diesel removal, followed by a gradual decrease after 5 min of
generation of shock waves can induce particle cracking, where the ultra- sonication. This was attributed to the formation of oil droplet emulsions.
sonic vibrations penetrate the interior of soil particles via capillary ac- As the oil emulsion concentration increased with sonication time, the
tion which are typically inaccessible in other separation methods. re-adsorption of oil into the soil was seen to surpass the desorption of
Therefore, detachment of the contaminant occurs when the extraction oil from soil.
reagent penetrates through the formed soil fractures from the effect of Investigations by Feng et al. (2001) reported that larger soil particle
oscillating cavitational bubbles and shock waves (Abramov et al., size had a better contaminant removal due to the weaker bonding force
36 M.W. Lim et al. / Marine Pollution Bulletin 109 (2016) 14–45

Table 8
Ultrasonication in the remediation of oil contaminated soil.

Soil type Oil contaminant Process details Maximum removal Reference


efficiency

Tar sand from Canada High paraffinaceous oil/residual fuel oil Ultrasonication at 22 kHz, sonication power of ≈100% (Abramov et al., 2009)
100–1000 W, temperature of 60 °C ≈90%
White kaolin/clay/natural soil Persistent organic compounds: Ultrasonication at 30 kHz, sonication power of ≈71% (Shrestha et al., 2009)
hexachlorobenzene, phenanthrene, 20–140 W, duration of 1 h ≈55%
hexane, acetone
Chemical grade sea sand Diesel Mechanical stirring prior to ultrasonication at 30 83–87% (Feng and Aldrich, 2000)
kHz, sonication power intensity of 20–100 W/cm2,
temperatures of 60 °C, duration of 5 min
Test soil Ottawa Crisco pure vegetable oil Ultrasonication at 20 kHz, sonication power of 25–45% (Kim and Wang, 2003)
sand & natural soil 0–140 W, temperature of 19–22 °C
Sandy soil Severely biodegraded heavy oil Ultrasonication at 28 kHz, power density of 80 W/L, 75.5% (Ji and Sui, 2010)
temperature of 70 °C, duration of 0–1800 s
NA Crude oil Ultrasonication at 20 kHz, sonication power of 66 ≈65% (Zhang et al., 2012)
W, duration of 10 min
Chemical grade sea sand Diesel Ultrasonication at 30 kHz, sonication power density 63% (Feng et al., 2001)
of 460 W/cm2, temperature of 25 °C
Sand and residual soil Diesel Ultrasonication at 20 kHz, sonication power of 500 ≈70% (Kim et al., 2007)
W, temperature of 30 °C, duration of 30 min
Sandy soil Diesel Ultrasonication at 20 kHz, sonication power density 18% (Wulandari, 2010)
of 462 W, duration of 10 min
Granite soil Naphthalene or diesel-oil Mechanically mixed with ultrasonication at 20 kHz, 85% (Na et al., 2007)
sonication power density of 500 W, temperature of
20 °C
Solids in sludge Crude oil Ultrasonication at 20 kHz, sonication power of 75 N60% (Hu et al., 2014)
W, duration of 6 min, slurry temperature of 25 °C

between the contaminants and the soil surface. In addition, fine soil par- 5.4.3. Advancements and future work
ticles produce high viscosity slurries which may impede the cavitation As ultrasonication is a relatively new technology applied for the re-
of the ultrasound, resulting in a net decrease in the removal of oil mediation of oil contaminated soil, most present studies are still focused
(Feng and Aldrich, 2000). The same study also showed that a higher die- on the effects of ultrasonication parameters. Hu et al. (2014) investigat-
sel content of 5 wt% had a removal efficiency of 99% as compared to die- ed on the oil recovery from crude oil sludge using ultrasonication,
sel content of 0.5% which provided a removal efficiency of 93%. The whereby the effects of sonication power, duration, sludge-to-water
higher removal efficiency in highly contaminated soil was attributed ratio, and slurry temperature were studied. It was found that an optimal
to the initial dissolution of free oil which was not adsorbed to the soil removal efficiency of more than 60% was obtained at ultrasonication
particles. power of 75 W, duration of 6 min, initial slurry temperature of 25 °C,
On a different note, Feng and Aldrich (2000) found that and sludge-to-water ratio of 1:4 in a laboratory scale apparatus.
ultrasonication at extremely low pH (acidic conditions) resulted in Nevertheless, the use of sonication may consume a lot of energy
very low separation of diesel from soil due to the formation of hydrogen which is not cost effective. Therefore prior to industrial applications,
bonds between the two mediums. A high pH environment, on the other the design of acoustic ultrasound generators should be developed for
hand, enhances the hydrophilic behaviour by shifting the hydrophilic- the reduction of energy consumption. The successful design for reduc-
lipophilic balance, decreasing the interfacial tension between bitumen ing energy consumption could decrease the operational cost of
and water surface and improving the negativity of surface of oil and ultrasonication technology. In addition, the understanding of the funda-
soil (Abramov et al., 2009). mentals of ultrasonication for oil removal from contaminated soil is cur-
rently lacking in literature as well. The modelling of pressure wave and
5.4.2. Advantages & limitations cavitation bubble generation that form localised hot spots could provide
The promising potential of using ultrasonication for the removal of an understanding of the sonochemical activity within the reaction reac-
oil from soil had been considered in several review papers (Bordoloi tor and on site. The study on mass and heat transfer should also be con-
and Basumatary, 2015; Mason, 2003, 2007). The ultrasonication tech- ducted as well to further understand the contaminant disposal for
nology has been dubbed as one of the major green science and engi- onsite application.
neering technologies due to its process which uses virtually no
chemicals to eliminate other hazardous chemicals in the system. At
6. Integrated remediation technologies
present, this technology is gaining popularity in the removal of oil
from contaminated soil due to its advantages including its on-site
The remediation technologies discussed in the earlier sections each
heating and intense agitation which enhances heat and mass transfer
has their own characteristics and limitations. Therefore, many present
processes.
studies include integrated remediation technologies for oil contaminat-
However, the downside of the ultrasonication is the costly setup,
ed soil to complement the individual remediation technologies and to
high energy consumption for the generation of acoustic waves and its
further improve the soil remediation efficiency.
difficulty for on site implementation. Son et al. (2012) performed a com-
parison of energy consumption between ultrasonication and a typical
mechanical agitation for diesel removal at various agitation speeds. It 6.1. Integrated physical–chemical remediation technology
was reported that a total of 3.4 W is required for mechanical agitation
to achieve a diesel removal efficiency of 40%. Under the same conditions, The combination of electrokinetic-Fenton (EK-Fenton) technology
the energy requirement for ultrasonication is almost triple the electrical had been studied by Pazos et al. (2011) for the remediation of diesel pol-
power consumed by mechanical agitation at 9.9 W to obtain a diesel re- luted soil. The use of electric field enhances the mobilization of the
moval efficiency of 40% as well. Fenton reagent, which facilitates the Fenton reaction to take place inside
M.W. Lim et al. / Marine Pollution Bulletin 109 (2016) 14–45 37

the soil. The advantage of the integrated EK-Fenton is the use of Fenton reduced the TPH concentration and toxicity in soil, which then provided
oxidants as electrokinetic processing fluids, which renders the need for a more favourable environment for the latter bioremediation treatment.
other processing fluids from the anode and cathode chambers. Results Approximately 90% of contaminants was removed after 15 min of sol-
showed that approximately 78% of diesel fuel was removed after elec- vent extraction. Subsequent bioremediation further reduced the petro-
trokinetic remediation alone, as opposed to 87% using the EK-Fenton leum contamination up to 97% after 132 days. The authors concluded
treatment. A similar study by Tsai et al. (2010) also noted that this inte- that this integrated method showed good performance for remediation
grated technology was suited for soil with high iron content, which pro- of high concentrations of weathered hydrocarbons due its high efficien-
motes the Fenton oxidation. In a later study by Pazos et al. (2012a), the cy and sustainability. An in situ study by Guerin (2015a, 2015b) also
addition of EDTA was shown to remove 90% of TPH in a shorter time pe- showed similar results whereby the combination of biostimulation
riod of 15 days. This addition was suggested to favour the iron and surfactant (Biosolve) could remove the petroleum hydrocarbon
solubilisation and H2O2 stabilization which subsequently enhanced concentration in a sandy rock fill from 20,000 mg/kg to b200 mg/kg
the Fenton treatment process. after 180 weeks of treatment. However, a similar integrated remedia-
A recent ex situ study was conducted for surfactant enhanced soil tion study conducted by Wyrwas et al. (2011) that uses Triton X-100
washing and EK-Fenton technology using a soil column experimental as the extraction solvent prior to bioremediation of diesel contaminated
setup for diesel contaminated soil. Tween 80 surfactant was employed soil demonstrated poor removal efficiency of 25%, which suggested an
at different concentrations greater than CMC value as the washing solu- uneven involvement of the microbial population during the biodegra-
tions. Results showed that initial washing with concentration of 5% of dation process due to the presence of the surfactant.
Tween 80 only removed 1% of the contaminant after 24 h of washing Another study demonstrated the use of bioremediation as the sec-
while further electrochemical treatments after elution showed almost ondary treatment after electrokinetic remediation. Dong et al. (2013)
complete removal of hydrocarbons (N99.5%), within 32 h according to investigated on the integration of electrokinetic remediation with bio-
a linear trend. However, the toxicity test showed that the resulting solu- degradation for remediation of petroleum and heavy metal contaminat-
tion after complete removal has a higher toxicity as compared to the ini- ed soil in a laboratory-scale electrokinetic reactor. The electrolyte used
tial solution, due to the inhibition of up to 95% of Vibrio fischeri bacteria. for the electrokinetic process was a combination of sulfates and nitrates,
This demonstrates that the toxic compounds were not fully removed which coincidently acts as a nutrient supply to the bacterial consortium.
even after complete removal of oil in the soil matrix. The authors con- Replenishment of electrolyte solution was performed every 3 days to re-
cluded that the combination of soil washing with EK-Fenton process plenish the mobile ions in soil. It was found that the addition of Tween
needs to be further improved, and suggested a possible implementation 80 and EDTA as an anolyte and catholyte conditioning agent showed
of thermal treatment on the soil column to increase the efficiency of high efficiency in the removal of both TPH and heavy metals. EDTA
contaminant removal (Huguenot et al., 2015). also helped to remove heavy metals which subsequently decreased
Ji and Zhou (2010) investigated on the effect of ultrasonication time the toxicity in soil, and enhanced the activity of microbial degradation
coupled with non-ionic surfactant (Triton X-1100 micellar) solution on of oil. Tween 80, on the other hand, acts as a second substrate for micro-
the removal of super heavy oil from contaminated soil. Clean soil was bial growth and biodegradation. The TPH removal efficiency through
initially contaminated with super heavy oil at a soil:oil ratio of 9:1 (w/ the combined electrokinetic and biodegradation technology after
w%). The contaminated soil was initially mixed with Triton X-100 solu- 30 days was found to be at 88.3%.
tion and stirred at 180 rpm for 1800 s at a temperature of 70 °C. In the recent years, it was observed that there is an increase in inter-
Ultrasonication was then carried out at a frequency of 28 kHz and est for the integration of biological permeable reactive barrier, or
power density of 80 W/L. The increase in ultrasonication time from biobarriers; and electrokinetic remediation for soil remediation. The
360 to 1800 s was shown to increase the efficiency of solvent extraction combination of these two technologies had been deemed as electro-
from 66.4% to 88.7%. The increase in heavy oil removal efficiency was at- bioremediation, and is efficient for the removal of contaminants and
tributed to the increase in the number of shock waves from the maintains appropriate condition for optimal microorganism growth.
ultrasonication, which helps to overcome the interfacial forces between The working mechanism is that the biobarrier would act as a biodegrader
the soil particles and contaminant. Therefore, the Triton-X surfactant from the attached microbial biofilm which would aid the biodegradation
could easily penetrate into the soil particles' surface, enhancing the de- of the contaminant, while the electrokinetic technology would drive the
tachment of oil from soil. Likewise, the combination of ultrasonication pollutants to the barrier from the mass transport process. Mena et al.
and flotation separation of bitumen from oil sands were also attempted (2015) first investigated on the usage of biobarriers coupled with elec-
by Okawa et al. (2011) in a hydrogen peroxide aqueous solution. The trokinetic soil flushing for the remediation of diesel polluted soil. A diesel
authors investigated on the effect of low (28 kHz) and high (200 kHz) degradation efficiency of 30% was observed after 2 weeks of operation,
frequency sonication on the oil recovery rate, with and without the and the energy consumption was under 70 kWh/m3. Feasibility studies
presence of hydrogen peroxide as the frothing agent. Results showed on the effectiveness of electrobioremediation were also performed by
that the usage of hydrogen peroxide aided in the removal of bitumen, Ramírez et al. (2015a, 2015b). The results showed that for a diesel con-
as the hydrogen peroxide decomposes to water and oxygen bubbles. taminated soil of 10 g/kg, approximately 27% of the diesel was removed
The oxygen bubbles would then attach itself onto the bitumen, which after 336 h, with sodium dodecyl sulfate as the anionic surfactant and
helped the flotation of bitumen during sonication. Therefore, a low fre- constant voltage gradient of 1.0 V/cm. The authors observed that there
quency ultrasonication coupled with H2O2 (concentration N 1000 ppm) was an increase in biomass by 25% after the process, which indicates bi-
could provide an increase in bitumen recovery by up to 10% as opposed ological growth on the biobarrier and leads to biodegradation of the die-
to high frequency sonication without H2O2. sel contaminant. However, it should be noted that the electroosmotic
flow and biodegradation removed a certain amount of water, surfactant
6.2. Integrated physical–biological remediation technology and inorganic nutrients which have to be continuously replaced for a
long-term experiment (Ramírez et al., 2015b).
In a recent study, Wu et al. (2015) evaluated the efficiency and sus- A follow up study by the same authors compared the efficiency of
tainability of the integrated solvent extraction and biodegradation for electrobioremediation with other strategies of combined bioremedia-
the remediation of petroleum contaminated soil. The contaminated tion and electrokinetic soil remediation for the purpose of remediation
soil was initially mixed with organic solvent of hexane and pentane of diesel (10 g/kg) contaminated soil. The four options tested were:
(4:1, v/v%) for 20 min in a mechanical shaker, prior to bioremediation (1) singular control bioremediation test (Bio), (2) direct combination
using microcosms bioaugmented with Bacillus subtilis FQ06 strains of electrokinetic soil flushing and biological technologies (EKSF-Bio),
and rhamnolipid for 132 days. The solvent extraction pretreatment (3) EKSF-Bio with daily polarity reversal of electric field (PR- EKSF-
38 M.W. Lim et al. / Marine Pollution Bulletin 109 (2016) 14–45

Bio), and (4) combination of electrokinetic soil flushing and a perme- remediation of oil contaminated soil. In this system, the electrochemically
able reactive biological barrier (EKSF-BioPRB). Results from the experi- active bacteria (EAB) such as Geobacter spp. (Lovley, 2011; Rabaey and
ments showed a very low diesel removal efficiency for the EKSF-Bio test, Rozendal, 2010), Comamonas testosteroni, P. putida, and Ochrobactrum
due to the high buffer concentration required to control the pH which anthropi (Lu et al., 2014a) are able to catalyse both oxidation and reduc-
affected the microbial growth. The highest diesel removal efficiency tion reactions of hydrocarbon pollutant and extracellularly transfer elec-
was found to be 29% using the EKSF-BioPRB technique as compared to trons respectively, to convert chemical energy into electrical current. A
12% for Bio test and 20% for PR-EKSF-Bio test. This was attributed to prime example of a BES is a microbial fuel cell (MFC) technology.
the presence of biological barrier which protected the biological activity The use of BES has several advantages. BES provides two redox reac-
which therefore improved the degradation of diesel in the contaminat- tions (oxidation and reduction) that results in the integrated microbial-
ed soil (Ramírez et al., 2015a). electro-chemical removal mechanisms, and hence, an improved remov-
al efficiency even for complex contaminants. In addition, BES does not
6.3. Integrated chemical–biological remediation technology require large amounts of energy or external chemical amendments for
operation, due to the presence of electrodes as non-exhaustible electron
Lu et al. (2010b) studied the removal of petroleum from soil via the acceptors and donors for the degradation of oil contaminant. The elim-
Fenton-like treatment followed by biodegradation. The use of chemical ination of energy and chemical costs would then lead to an overall lower
oxidation method as a pre-treatment does not only destroy the targeted operational cost in the long run. The produced electrical current from
compounds, but also reduced the overall toxicity of contaminants to the the reaction could serve as a real-time bioremediation indicator and at
microorganisms in the latter biodegradation process (Gong, 2012; Tekin the same time could power up the wireless sensor for online monitor-
et al., 2006; Yahiat et al., 2011). Results showed that a removal efficiency ing. The easy configuration of BES is also another advantage (Li et al.,
of 67.3% was observed during the Fenton-like treatment using the opti- 2015; Lu et al., 2014b; Wang et al., 2015).
mum ratio of H2O2:Fe3+ of 300:1 (v/v%). A further observation of 50.6% Many studies have reported that the use of BES as a remediation
of contaminant was removed after 10 weeks of microbial treatment, technology could accelerate the remediation process and shorten reme-
resulting in a total oil removal efficiency of approximately 83.5% for diation time as compared to biodegradation alone. Lu et al. (2014b)
this integrated remediation technology. demonstrated that the application of BES in a 50 L pilot scale reactor
This is in good agreement with works performed by Kim and Lee for remediation of diesel contaminated soils could provide a removal ef-
(2012) who also looked into the integrated chemical oxidation and bio- ficiency of up to 89.7%. The observed results are 241% greater than the
remediation method for the remediation of diesel contaminated soil. In conventional biodegradation method. Similar results were also ob-
the chemical oxidation treatment alone using 20% H2O2 solution, the served by Li et al. (2015) who reported that the degradation of petro-
TPH removal efficiency was 63.5%. This removal efficiency was shown leum from soils increased by 268% after 135 days. The increase in the
to increase by 48.6%, resulting in a total removal efficiency of 81.2% degradation rate was attributed to the BES anode electrode influence
upon the latter bioremediation treatment. A pilot scale test on a diesel on microbial activity, which maximizes the reactive surface area for ef-
contaminated site was subsequently performed, whereby 17.5% H2O2 ficient electron collection from the microbial degradation processes. Re-
solution was flushed for 15 days with removal efficiency of 51.5%. sults from these studies suggest that BES could be an innovative and
After the seventh day, the mixed microorganism cultured solution of sustainable alternative for the remediation of oil contaminated soil in
43 L was injected into the contaminated site, which showed a further large field scale. A detailed review of the application of BES for soil reme-
improvement in the TPH removal up to 71.1%. This study showed that diation was compiled by Wang et al. (2015).
the addition of H2O2 did not compromise the biodegradation process, Overall, BES for oil remediation is still in infancy study stage. Due to
and the integrated technologies are efficient in the removal of contam- the complexity and diversity of this application, more process develop-
inants from a contaminated field site. ment needs to be conducted for application of BES for in situ remedia-
Similar works were performed by Gong (2012) whereby the author tion of oil contaminated soil.
performed a bioremediation prior to chemical oxidation process for the
remediation of weathered crude oil contaminated soil. Bioremediation 7. Final recommendations and conclusion
was initially carried out using additional nutrients and peanut hull as
a bulking agent for up to 8 weeks, followed by the modified Fenton ox- The contamination of soil by oil is inevitable in many sectors, ranging
idation which was then conducted with the addition of H2O2 directly from the petroleum industry, transportation and to marine oil spillages
into the soil. The contaminant removal during the bioremediation onto sea water and shorelines. A variety of remediation technologies
stage showed a removal efficiency of 38.6% followed by an increase to have been developed, with some implemented onto field-scale applica-
88.9% with the addition of H2O2. tions. Table 9 provides a brief overview of the advantages and limita-
A pilot scale plant was carried out by Silva-Castro et al. (2013) using tions, average cost, efficiencies and duration for all the remediation
Fenton oxidation and subsequent biostimulation as post treatment for technologies for oil contaminated soil discussed in this review article.
diesel contaminated soil. The modified Fenton remediation technology For a successful oil remediation, the understanding of the site contam-
using H2O2 as oxidant was applied for 14 days, followed by biostimulation inant would lead to a better decision of remediation technology best for
using inorganic NPK fertilizer for a further 28 days for the remediation of the removal of oil contaminant. Therefore, assessment of the soil contam-
soil artificially polluted with 20 g/kg of diesel. Results showed that the ination via integrated field spectroscopy and spatial analysis could be ini-
combination of Fenton oxidation and biostimulation increased the TPH tially conducted to expedite the characterization of onsite concentration
removal efficiency by up to 34% in the non-saturated layer, as opposed and distribution of contaminants. (Horta et al., 2015). Following that,
to natural attenuation of diesel. This was attributed to the latter biostim- the choice of a remediation technology for field application is loosely de-
ulation process which increased the concentration of biodegrading pendent on two factors; (1) site specific conditions such as characteristics
microbe and therefore increased the biological activity within the con- of contaminants, properties of soil, and weather; and (2) operational con-
taminated soil. ditions that would influence the oil removal efficiency.
The site specific conditions play an important role in determining
6.4. Advancements and future work of integrated remediation technologies the success of remediation technology, particularly the characteristics
of contaminants such as volatility, concentration, aging and weathering,
In the previous decade, a new energy saving bioremediation process water content and biodegradability of oil. For example, the use of bio-
called bioelectrochemical systems (BESs), also known as microbial elec- logical remediation method for highly contaminated soil (high concen-
trochemical systems was developed for enhanced and accelerated tration of oil contaminant) would not be recommended as the high
Table 9
Summary of advantages and limitations of oil contaminated soil remediation technology.

Classification Remediation Current Advantages Limitations Maximum Efficiencies Duration References


technology application contaminant (%)
for on-site level
remediation

Biological Bioremediation Yes Low cost, low environmental impact, high Long treatment durations, inconsistent results 2–10% ≈50–90+ Several (Boopathy, 2000; Chang et al., 2011b;
potential for on-site treatments, no waste and highly dependent on the contaminated months/years Chen et al., 2013; Hoff, 1993; Margesin
treatment required site, limited to biodegradable contaminants and Schinner, 1997; Mearns, 1997)
Phytoremediation Yes Aesthetically pleasing, low operational cost, Time-consuming, difficult to implement a 1–8% ≈50–90 Several (Cunningham et al., 1995; Gerhardt
roots of plants helps to stabilize soil which specific plant type for every oil spill, months/years et al., 2009; Muratova et al., 2008; Peng

M.W. Lim et al. / Marine Pollution Bulletin 109 (2016) 14–45


can prevent erosion, capable of remediating dependent on many environmental factors, et al., 2009)
large areas of contamination could only tolerate low concentrations of
toxins
Chemical Chemical No High efficiency, low operational costs, ease Limited by low soil permeability, highly 5–15% N80 Up to 72 h (Goi et al., 2009; Goi et al., 2006)
oxidation of operation, formation of environmental dependent on pH, destroys natural
friendly by-products microorganisms
Electrokinetic Yesa Uniform flow distribution, precise control Dependent on desorption of contaminant, 10–20% ≈40–70 14–45 Days (Ho et al., 1999; Kim and Lee, 1999; Page
remediation of movement, low operating cost, low unenvironmental friendly, time consuming, and Page, 2002; Pazos et al., 2012b;
power consumption may affect microbial activity due to Virkutyte et al., 2002)
mobilization of soil nutrients
Thermal Incineration, Yes High efficiency, quick, reliable, able to treat High costs, formation of greenhouse gases, 2–10% N95 Several (Anthony and Wang, 2006; Chien, 2012;
thermal large volumes of contaminated soil affected by high moisture content seconds–2 h Falciglia et al., 2011; Jones et al., 2002; LI
desorption, et al., 2009a; Smith et al., 2001;
microwave Yakymenko and Kyrjyienko, 2011)
heating
Physical–chemical Solvent No Easily implemented, high efficiency, quick High cost, consumes large amount of solvent, 0.5–30% 60–98 Several (Gan et al., 2009; Wu et al., 2011)
extraction unenvironmental friendly hours–10
months
Soil vapour Yes High efficiency for large quantities of Ineffective for low volatility contaminants and 3–15% 65–95 Several (Agency, 2012; Rathfelder et al., 1995)
extraction volatile content, quick, low cost, enhances soils with low air permeability days–months
growth of microorganisms
Flotation No Easy application, rapid operation time, low Requires large amounts of water, unable to 7.5–35% 65–97 Several hours (Tao, 2005)
technology operational cost, low space requirements treat soil contaminated with non-buoyant
contaminants
Sonication No Environmental friendly, low energy High equipment cost, limited to small area of 1–15% 20–100 Several (Abramov et al., 2009; Feng and Aldrich,
consumption, eliminates the need for treatment per run seconds–45 2000; Mason, 2003)
chemical addition min
a
Mainly when integrated with other types of remediation technology.

39
40 M.W. Lim et al. / Marine Pollution Bulletin 109 (2016) 14–45

concentration would be toxic to the plants and oil degrading microbe. Fundamental Research Grant Scheme (FRGS, Grant No.: FRGS/1/2015/
Likewise, remediation methods such as soil vapour extraction are not TK07/MUSM/03/2) for providing research facilities.
suitable for low volatility oil contaminant. In addition, the use of thermal
remediation for removal of oil contaminant with high water content is
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