Refinery Sludge Disposal
Refinery Sludge Disposal
Refinery Sludge Disposal
Review
Oil sludge is a thick viscous mixture of sediments, water, oil and hydrocarbons, encountered during
crude oil refining, cleaning of oil storage vessels and waste treatment. Polycyclic aromatic
hydrocarbons (PAHs), which are components of crude oil sludge, constitute serious environmental
concerns, as many of them are cytotoxic, mutagenic and potentially carcinogenic. Improper
management and disposal of oil sludge causes environmental pollution. The adverse effects of oil
sludge on soil ecology and fertility have been of growing interest among environmental scientist and an
important consideration in the development of efficient technologies for remediation of contaminated
land, with a view to making such land available for further use. Oil sludge can be treated by several
methods such as physical, chemical and biological processes. The biological processes are mostly
cost effective and environmentally friendly, as they are easy to design and implement, as such they are
more acceptable to the public. Compost, the product of biological breakdown of organic matter is a rich
source of hydrocarbon-degrading microorganisms such as bacteria and fungi. These microorganisms
can degrade the oil sludge to less toxic compounds such as carbon dioxide, water and salts. Compost
bioremediation, the application of composting in remediation of contaminated environment, is
beginning to gain popularity among remediation scientists. The success or failure of compost
bioremediation depends on a number of factors such as nutrients, pH, moisture, aeration and
temperature within the compost pile. The bioavailability and biodegradability of the substrate to the
degrading microorganisms also contributes to the success of the bioremediation process. This is a
review on the biological remediation technologies employed in the treatment oil sludge. It further
assesses the feasibility of using compost technology for the treatment of oil sludge, as a better, faster
and more cost effective option.
Key words: Biodegradation, bioremediation, composting, oil sludge, polycyclic aromatic hydrocarbons (PAHs).
INTRODUCTION
Oil sludge is a thick, viscous mixture of sediments, water,
oil and high hydrocarbon concentration, encountered
during crude oil refining, cleaning of oil storage vessels
and refinery-wastewater treatment. The chemical
*Corresponding author. E-mail: onyedika.ubani@gmail.com. Tel: +27 78 419 2899. Fax: 086 2245 824.
Abbreviations: PAHs, Polycyclic aromatic hydrocarbons; VOCs, volatile organic carbons; SVOCs, semivolatile organic carbons;
CNS, central nervous system; PCBs, polychlorinated biphenyls; TPHs, total petroleum hydrocarbons.
Ubani et al.
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Afr. J. Biotechnol.
1
2
(1)
3
6
4
OH
A1
H
OH
H
(2)
A2
OH
OH
(3)
A3
COOH
(4)
OH
A4
OH
(5)
COOH
A5
O
OH
(6)
CHO
A6
OH
(7)
A11
OH
COOH
COOH
A7
OH
A15
(13)
(8)
A12
HO
COOH
A16
COOH
COOH
OH
(19)
COOH
(14)
A8
OH
(20)
COOH
OH
A19
A17
COCOOH
COOH
COOH
COOH
(9)
COOH
(15)
HO
COOH
COOH
(22)
A18
A9
COCOOH
A20
COOH
COOH
A21
O
COSCoA
CH3
(11)
COOH
A14
A10
COOH
CH3
(17)
CH3
CH3
O
A22
CH3
+
CHO
COSCoA
COOH
COOH
(23)
(16)
HO
OH
A13
COSCoA
(10)
(21)
(18)
COOH
COSCoA
(24)
COOH
(12)
Figure 1. Proposed catabolic pathways of naphthalene by aerobic bacteria. The compounds are 1, Naphthalene; 2, cis-1,2dihydroxy-1,2-dihydronaphthalene (cis-naphthalene dihydrodiol); 3, 1,2-dihydroxynaphthalene; 4, 2-hydroxy-2H-chromene-2carboxylic acid; 5, trans-o-hydroxybenzylidenepyruvic acid; 6, salicylaldehyde; 7, salicylic acid; 8, gentisic acid; 9, maleylpyruvic
acid; 10, fumarylpyruvic acid; 11, pyruvic acid; 12, fumaric acid; 13, catechol; 14, cis,cis-muconic acid; 15, -ketoadipic acid; 16,
-ketoadipyl-CoA; 17, succiny-CoA; 18, acetyl-CoA; 19, 2-hydroxymuconic-semialdehyde; 20, 2- hydroxymuconic acid; 21, 4oxalocrotonic acid; 22, 2-oxo-4-pentenoic acid; 23, 4-hydroxy-2-oxovaleric acid; 24, acetaldehyde. The enzymes involved in
each reaction step are naphthalene dioxygenase (NahAaAbAcAd) (step A1), cis-naphthalene dihydrodiol dehydrogenase
(NahB) (A2), 1,2-dihydronaphthalene dioxygenase (NahC) (A3), 2-hydroxy-2H-chromene-2-carboxylate isomerise (NahD) (A4),
trans-o-hydroxybenzylidenepyruvic hydratase-aldolase (NahE) (A5), salicylaldehyde dehydrogenase (NahF) (A6), salicylate 5hydroxylase (NagGHAaAb) (A7), gentisate 1,2-dioxygenase (Nahl) (A8), maleylpyruvate isomerise (NagL) (A9), fumarylpyruvate
hydrolase (NagK) (A10), salicylylate hydroxylase (NahG) (A11), catechol1,2-dioxygenase (A12), -ketoadipate:succinyl-CoA
transferase (A13), -ketoadipyl-CoA thiolase (A14), catechol 2,3-dioxygenase (NahH) (A15), hydroxymuconic-semialdehyde
dehydrogenase (Nahl) (A16), 4-oxalocrotonate isermerase (NahJ) (A17), 4-oxalocrotonate decarboxylase (NahK) (A18),
hydroxymuconic-semialdehyde hydrolase (NahN) (A19), 2-oxo-4-pentenoate hydratase (NahL) (A20), 2-oxo-4hydroxypentennoate aldolase (NahM) (A21) and acetaldehyde hydrogenase (NahO) (22) (Ri-He et al., 2008).
Ubani et al.
6547
(1)
6
H
(2)
(24)
10
OH
2
OH
H
OH
HO
(9)
(3)
(6)
OH
HO
OH
COOH
OH
OH
(25)
HO
(10)
COOH
COOH
(5)
(12)
COCOOH
OH
HO
(4)
O
COOH
COCOOH
(11)
HOOC
COOH
(14)
(7)
COOH
OH
(8)
COOH
(13)
COOH
COOH
OH
(15)
OH
COOH
OH
COOH
(20)
O
(16)
COOH
COOH
OH
(21)
CHO
OH
COOH
(17)
COOH
(22)
COOH
OH
(18)
CHO
HO
COOH
(23)
HO
OH
(19)
COOH
Figure 2. Proposed catabolic pathways of phenanthrene by aerobic bacteria. The compounds are 1, Phenanthrene; 2, cis -1,2-dihydroxy1,2-dihydrophenanthrene; 3, 1,2-dihydroxyphenanthrene; 4, 2-[(E)-2-carboxyvinyl]-1-naphthoic acid; 5, trans-4-(2-hydroxynaph-1-yl)-2oxobut-3-enoic acid; 6, 5,6-benzocoumarin; 7, 2-hydroxy-1-naphthoic acid; 8, naphthalene-1,2-dicarboxylic acid; 9, cis-3,4-dihydroxy-3,4dihydrophenanthrene; 10, 3,4-dihydroxyphenanthrene; 11, 1-[(E)-2-carboxyvinyl]-2-naphthoic acid; 12, trans-4-(1-hydroxynaph-2-yl)-2oxobut-3-enoic acid; 13, 1-hydroxy-2-naphthoic acid; 14, 7,8-benzocoumarin; 15, 1,2-dihydroxynaphthalene; 16, 2-hydroxy-2H-chromene2-carboxylic acid; 17; trans-o-hydroxybenzalpyruvic acid; 18, salicylaldehyde; 19, salyclic acid; 20, trans-2-carboxybenzalpyruvic acid;
21, 2-carboxybenzaldehyde; 22, o-phthalic acid; 23, protocatechuic acid; 24, cis-9,10-dihydroxy-1,2-dihydrophenanthrene; 25, 2,2/diphenic acid (Ri-He et al., 2008).
6548
Afr. J. Biotechnol.
10
(1)
7
H
4
5
OH
(2)
(17)
OH
OH
HO
(6)
H
H
OH
COOH
(18)
OH
OH
OH
OH
(7)
(3)
HO
COOH
OH
CH3
OH
CH3
HO
COOH
(5)
(19)
(8)
O
O
COOH
COOH
(9)
(4)
OH
COOH
(10)
OH
OH
HOOC
(11)
OH
OH
O
COOH
OH
COOH
COOH
COOH
OH
OH
(12)
(16)
COOH
(13)
COOH
(14)
(15)
Figure 3. Proposed catabolic pathways of pyrene by aerobic bacteria. The compounds are 1, Pyrene; 2, cis-1,2-dihydroxy-1,2dihydropyrene; 3, 1,2-dihydroxypyrene; 4, 4-hydroxyperinaphthenone; 5, 1,2-dimethoxypyrene; 6, cis-4,5-dihydroxy-4,5dihydropyrene; 7, P2,4,5-dihydroxypyrene; 8, phenanthrene-4,5-dicarboxylate; 9, phenanthrene-4-dicarboxylate; 10, cis-3,4dihydroxyphenanthrene-4-carboxylate;
11,
3,4-dihydroxyphenanthrene;
12,
1-hydroxy-2-naphthoate;
13,
trans-2/carboxybenzalpyruvate; 14, phthalate; 15, 1,2-dihydroxynaphtharene; 16, cinnamic acid; 17, trans-4,5-dihydroxy-4,5-dihydropyrene;
18, 6,6/-dihydroxy-2,2/-biphenyl dicarboxylic acid; 19, pyrene-4,5-dione (Ri-He et al., 2008).
Fluorene
Fluorene is a polycyclic aromatic hydrocarbon and has
Ubani et al.
(1)
4
3
(2)
2
8
OH
(12)
H
OH
OH
H
(6)
OH
6549
H
HO
(3)
(13)
OH
OH
(7)
(19)
OH
O
OH
HOOC
(14)
O H OH
OH
OH
COOH
H
OH
OH
H
OH
(15)
(20)
COOH
O
OH
(8)
(4)
HO
OH
O
O
O
O
O
O
(9)
HOOC
OH
(5)
(16)
COOH
OH
(10)
COOH
COOH
(17)
COOH
OH
COOH
HO
(11)
OH
COOH
COOH
(18)
HO
OH
Figure 4. Proposed catabolic pathways of fluorene by aerobic bacteria. The compounds are 1, Fluorine; 2, cis-1,2-dihydroxy-1,2dihydrofluorene; 3, 1,2-dihydroxy fluorine; 4, 2-indanone; 5, 3-isochromanone; 6, cis-3,4-dihydroxy-3,4-dihydrofluorene; 7, 3,4dihydroxyfluorene; 8, 1-indanone; 9, 3,4-dihydrocoumarin; 10, 3-(2-hydroxyphenyl) propionic acid; 11, salicylic acid; 12, 9-fluorenol; 13,
9-fluorenone; 14, 1,1a-dihydroxy-1-hydro-9-fluorenone; 15, 2/-carboxy-2,3-dihydroxybiphenyl; 16, phthalic acid; 17, 4,5dihydroxyphthalate; 18, protocatechuic acid; 19, 1,2-dihydro-1,2dihydroxy-9-fluorenone; 20, 8-hydrixy-3,4-benzocoumarin (Ri-He et al.,
2008).
genase to yield 9-fluorenol and 1, 1a-dihydroxy-1-hydro9-fluorenone. The catabolic pathway for fluorene degradation has been proposed as shown in Figure 4 (Kasuga
et al., 2001; Wattiau et al., 2001; Habe et al., 2004; Ri-He
et al., 2008).
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Afr. J. Biotechnol.
(1)
2
1
10
4
(2)
OH
7
OH
HO
OH
(14)
OH
HO
(15)
(23)
OH
(3)
OH
(16)
HO
O
HOOC
O
COOH
COOH
CH3
HOOC
HOOC
(4)
(11)
HO
O
HOOC
HOHC2
(5)
COOH
COOH
HO
(17)
HOOC
(18)
HOOC
(12)
OHC
(8)
(6)
OH
HOOC
HO
(13)
(19)
(20)
HO
(9)
(7)
HO
HO
COOH
O
HOOC
HO
COOH
(21)
HOOC
COOH
COOH
(10)
(22)
COOH
Figure 5. Proposed catabolic pathways of fluoranthene by aerobic bacteria. The compounds are 1, Fluoranthene; 2,
7,8-dihydroxy fluoranthene; 3, 7-methoxy-8-hydroxy-fluoranthene; 4, (2Z,4Z)-2-hydroxy-4-(2-oxoacenaphthylen-1(2H)ylidene) but-2-enoic acid; 5, 1-acenaphthenone-2-carboxylic acid; 6, acenaphthylene-1(2H)- one; 7,1H,3H-benzo[de]
isochromen-1-one; 8, acenaphthylen-1-ol; 9, acenaphthylen-1,2-diol; 10, naphthalene-1,8-dicarboxylic acid; 11, 2(hydroxymethy)-acenaphthylene-1-carboxylic acid; 12, 2-formylacenaphthylene-1-carboxylic acid; 13, 1,2dihydroacenaphthylene-1,2-diol; 14, 2,3-dihydroxy fluoranthene; 15, 1,2-dihydroxy fluoranthene; 16,
(9E)-9(carboxymethylene)-9H-fluorene-1-carboxylic acid; 17, 9-fluorenone-1-carboxylic acid; 18, 9-hydroxy-9H-fluorene-1carboxylic acid; 19, 9-fluorenone; 20, 9-hydroxyfluorene; 21, 1,2,3-benzene-tricarboxylic acid; 22,
monohydroxyfluoranthene; 23, phthalic acid (Ri-He et al., 2008).
Fluoranthene
This is a polycyclic aromatic hydrocarbon consisting of
naphthalene and it is a four fused benzene ring. Many
microorganisms showed the capability of utilising
Ubani et al.
(1)
12
11
6551
10
3
9
4
8
O
HO
HO
HO
HO
HO
(2)
(4)
(18)
(13)
OH
HO
HO
OH
OH
(8)
HO
OH
HO
HO
HO
(3)
OH
OH
(5)
(9)
(19)
(14)
HO
OMe
HO
HO
O
HOOC
CHO
COOH
(6)
HOOC
O
HO
(20)
(15)
(10)
OHC
OMe
HO
MeO
HO
COOH
COOH
OHC
(21)
(16)
(11)
(7)
HOOC
HO
COOH
HO
HOOC
(22)
(17)
(12)
Figure 6. Proposed catabolic pathway of benzo[a]pyrene by aerobic bacteria. the compounds are 1, Benzo[a]pyrene; 2,
benzo[a]pyrene-11,12-epoxide; 3, trans-benzo[a]pyrene-11,12-dihydrodiol; 4, cis-benzo[a]pyrene-11,12-dihydrodiol; 5,
11,12-dihydroxy-benzo[a]pyrene; 6, hydroxymethoxybenzo[a]pyrene; 7, dimethoxybenzo[a]pyrene; 8, cisbenzo[a]pyrene-4,5-dihydrodiol; 9, 4,.5-dihydroxy-benzo[a]pyrene; 10, 4-formylchrysene-5-carboxylic acid; 11, 4,5chrysene-dicarboxylic acid; 12, chrysene-4(5)-carboxylic acid; 13, cis-benzo[a]pyrene-9,10-dihydrodiol; 14, 9,10dihydroxy-benzo[a]pyrene; 15, cis-4-(8-hydroxypyrene-7-yl)-2oxobut-3-enoic acid; 16, pyrene-8-hydroxy-7-aldehyde; 17,
pyrene-8-hydroxy-7-carboxylic acid; 18, cis-benzo[a]pyrene-7,8-dihydrodiol; 19, 7,8-dihydroxy-benzo[a]pyrene; 20, cis-4(7-hydroxypyrene-8-yl)-2-oxobut-3-enoic acid; 21, pyrene-7-hydroxy-8-aldehyde; 22, pyrene-7-hydroxy-8-carboxylic acid
(Ri-He et al., 2008).
Benzo[a]pyrene
This is a five ring polycyclic aromatic hydrocarbon
(C20H12) whose metabolites are mutagenic and highly
carcinogenic (Le Marchand et al., 2002). Benzo[a]pyrene
can be oxidised by different microorganisms to various
6552
Afr. J. Biotechnol.
10
(1)
3
7
6
H
OH
OH
OH
H
(5)
(2)
CH3
OH
OH
(12)
OH
OH
OH
(6)
(3)
(13)
COOH
COOH
OH
OH
(7)
COOH
O
O
OH
(4)
(8)
COOH
O
(9)
COOH
(10)
COOH
HO
(11)
HO
COOH
Figure 7. Proposed catabolic pathways of anthracene by aerobic bacteria. the compounds are 1, Anthracene; 2,
anthracene-9,10-dihydrodiol; 3, 9,10-dihydroxyanthracene; 4, 9,10-anthraquinone; 5,
cis-1,2-dihydroxy-1,2dihydroanthracene; 6, 1,2-dihydroxyanthracene; 7, cis-4-(2-hydroxynaphth-3-yl)-2-oxobut-3-enoic acid; 8, 2-hydroxy3-naphthoic acid; 9, 6,7-benzocoumarin; 10, o-phthalic acid; 11, protocatechuic acid; 12, 1-methoxy-2hydroxyanthracene; 13, and 3-(-2carboxyvinyl)-napthalene-2-carboxylic acid (Ri-He et al., 2008).
2008).
Anthracene
This is a polycyclic aromatic hydrocarbon consisting of
three fused benzene rings. It is also component of coal
tar (Iglesias et al., 2010). The initial reactions in the
bacterial degradation of anthracene involve the formation
of trans-1, 2-dihydroxyanthracene prior to ring fission
(Gibson and Subramanian, 1984).
Additional studies showed that Pseudomonas putida
strain 199 and Beijerinckia sp. strain B-836 oxidised
Ubani et al.
Other PAHs
The other PAHs are classified as acute/chronic toxic
hazardous organic compounds. They include compounds
such as benzo[a]anthracene, benzo[k]fluoranthene with
five fused benzene rings and indenol (1, 2, 3-cd) pyrene
with six fused benzene rings. They are present in
substantial quantities in oil sludge and can also be
susceptible to microbial degradation (Gibson and
Subramanian, 1984; Mueller et al., 1991; Field et al.,
1992; Sutherland et al., 1995).
6553
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Afr. J. Biotechnol.
compost will enhance metabolism of organic contaminants because they provide extra nutrients, additional
carbon source and assist in retaining moisture contents
of the pile (Namkoog et al., 2002).
Effect of pH
Biosurfactants
Nutrients
Ubani et al.
Salinity
Studies have shown that there are generally positive
correlations between salinity and rates of mineralization
of PAHs such as phenanthrene and naphthalene (Leahy
and Colwell, 1990). However, it has been noted that
hypersalinity will result in the decrease in microbial
metabolic rates (Micky, 2006).
Oxygen
Aerobic biodegradation is the most effective pathway for
bioremediation. This means that, the presence and
concentration of oxygen is important in such process.
Also, lack of aeration, in the system may be a ratelimiting parameter in the biodegradation and catabolism
of hydrocarbons by bacteria and fungi (van Hamme et al.,
2003).
The breakdown of oil sludge components may possibly
involve the utilization of oxygenase, in which molecular
oxygen is required. Great efficiency of natural microbial
hydrocarbon degradation occurs mostly when oxygen is
available (Ward et al., 2003). Although anaerobic
degradation of PAHs by microorganisms has been shown
to occur, the rates are somewhat negligible and limited to
halogenated aromatics compounds such as the
halobenzoates, chlorophenols and alkyl-substituted
aromatic (Suflita et al., 1982; Boyd and Shelton, 1984;
Angelidaki et al., 2000).
Temperature
Temperature is another important variable that has effect
on oil sludge biodegradation. Microorganisms can grow
at temperatures below 0 to above 100C with good water
supply (Atlas and Barther, 1987). Optimum temperature
dictates the rate of oil sludge metabolism by microorganisms and also the pattern of the microbial community. Temperature has direct effect on the physical
nature and chemical composition of the PAHs constituents (Atlas, 1981). Increases in temperature have
been reported to be proportional to the solubility of
contaminants and induces higher metabolic activity in a
compost system (Gibb et al., 2001). When temperatures
are low, PAHs tend to be more viscous and their water
solubility is greatly reduced (Leahy and Colwell, 1990).
Low temperature also affects microbial growth, propagation and subsequently results in decrease in the rate
of degradation (Gibb et al., 2001). Low temperature also
results in a decrease in enzymatic activities, which is
essential for degradation of the oil components. The
optimum temperature for hydrocarbon degradation has
reported to be in the range of 30 to 40C. At temperatures above this range, enzymatic activities are
inhibited as proteins denature at higher temperature
6555
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Afr. J. Biotechnol.
Incineration
Incineration is a technology commonly used in large
refineries. The common types are rotary kiln and fluidized
bed incinerators. In rotary kiln incinerator, the combustion
temperature is from 980 to 1200C and the residence
time is about 30 min. While in fluidized bed incinerators,
the combustion temperature is from 732 to 760C, and
the residence time may be in order of days. The
incineration process requires sophisticated equipments
and experienced operators to achieve adequate
combustion of oil sludge. Usually the incineration of oil
sludge using fluidized bed technique produces ash
scrubber sludge, with low contents of heavy metals.
These products are usually disposed of in a landfill (Liu et
al., 2010). Incineration is an expensive technique and oil
sludge contains high concentration of hazardous compounds including those that are resistant to incineration.
Incineration is not only expensive but generates toxic
residues such as ash, scrubber water, scrubber sludges,
sulphur dioxide, nitrogen monoxide, carbon monoxide
and some organic compounds (Srinivasarao et al., 2011).
Some of these residues such as ash containing metals
need to be treated before being disposed of. During the
incineration process, waste feed rates, oxygen: air ratio,
residence time, combustion temperature and gas
emission are critical parameters that needs to be
controlled (Mahmoud, 2004).
Lime stabilization
Stabilization involves mixing a solid additive material to
the oil sludge in order to produce a matrix within which the
oil and metal are fixed and will not leach out. The use of
lime for this purpose has being established in the
literature, the addition of lime produces physical and
chemical changes in the oil sludge which facilitates
hydrocarbon adsorption and immobilization of metals as
insoluble salts (Wright and Noordhius, 1991; Mahmoud,
2004).
The high pH provided by adding the lime is essential in
this process, some additives can be added to produce
hydrophobic matrix to prevent contaminants from
becoming acidic due to rainfall percolation in the landfill
(Mahmoud, 2004).
This technique may also generate residual products
that may need to be treated by using other methods
before disposal in a landfill which will make the techniques expensive.
Solvent extraction
In this method, the oil sludge is extracted with a solvent
to remove oil and other organics, the solvent is recovered
and recycled. Many refineries believe that recycling is the
most desirable environmental option for handling oil
sludge, due to the possibility of recovering valuable oil for
reprocessing, reformulating and energy recovery
(Bonnier et al., 1980; Taiwo and Otolorin, 2009). During
recycling, the condensed solvent and water are continuously separated in a trap. The condensed liquid
contains water and hydrocarbon.
The hydrocarbons in condensed liquid may amount to
73.24% of the sludge, and they are both volatile and nonvolatile hydrocarbons. The solvent extraction technique
has a tendency to greatly reduce sludge contaminants
from 100 to 30% water and solid wastes. The method
may possibly reduce the pollution effects of oil sludge on
the environment with the recovery of recyclable
hydrocarbons. If the optimum conditions are carefully
selected, solvent extraction approach can significantly
mitigate the non-compliance to standard limit of industrial
discharge into the environ-ments and the permissible
allowances for oil sludge.
Evaluation of the extent of sludge treatment before
disposal can be done and can make significant impact on
refinery and petrochemical industries. The advantage of
solvent extraction techniques is that the recovery
approach to oil sludge treatment explored can serve as a
precursor to in-situ treatment and cleaning of oil storage
facilities (Taiwo and Otolorin, 2009). It will also reduce
economic losses and out of operation period, since there
will be a reduction in time requirements for treatments,
also the oil, water and mud can be effectively used and
extraction solvents can be recycled. The limitation is the
adaptation of selected solvent to the sludge treatment.
Solvent extraction may not remove heavy metals such as
arsenic, lead and selenium; these residues must be
treated using other methods before disposal (Mahmoud,
2004; Taiwo and Otolorin, 2009).
Ubani et al.
Pyrolysis treatment
It is a technique for recovering oil and organic liquid gas
by breaking down large molecules into smaller ones. The
6557
BIOREMEDIATION
Bioremediation is defined as the use of living organisms
to reduce or eliminate environmental hazards resulting
from accumulations of toxic chemicals or other hazardous
waste (Gibson and Sayler, 1992). Bacteria are generally
used for bioremediation, but fungi, algae and plants could
also be used. Bioremediation is not a new technology
however; perspectives on the use of bioremedial
technologies to treat contaminants vary. There are three
classifications of bioremediation. The first defines biotransformation as the alteration of contaminant molecules
into less or non-hazardous molecules; the second defines
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Afr. J. Biotechnol.
Biostimulation
This involves the management of the natural environment
Bioaugmentation
This technique refers to the introduction of specialized or
genetically engineered microorganisms that target
specific chemical compounds. These organisms have
been developed to biodegrade most common organic
contaminants ranging from polychlorinated biphenyls
(PCBs), organic solvents and petroleum hydrocarbons
(Mehrashi et al., 2003; Atlas and Philip, 2005). The identi-
Ubani et al.
Landfilling
Landfilling is a deliberate dumping of oil sludge into land
(pit) without formal treatment. It has been the most
common form of sludge disposal. This process has
limitations as it requires a large land area and volatile
6559
Landfarming
Landfarming involves the controlled application of the oil
sludge on the land surface. This method requires tilling of
the topsoil (for easy mixture with oil sludge), addition of
water and addition of desired nutrient such as organic
fertilizers and manures. Tilling in this process is important
as it aids aeration, proper mixture of sludge and nutrient,
thereby making the sludge bio-available for microbial
degradation. Proper landfarming practice has minimal
impact on the environment (good site appearance,
absence of odour, relatively low-cost compliance with
sound industrial practices and government regulation,
minimal residue disposal problems and compatibility of
the method with the climate, location and type of sludge
treated).
Landfarming gained popularity over incineration and
landfilling following its advantages such as low energy
consumption, low risk of pollution of the surface and
groundwater due to the immobility of hydrocarbons and
metals through the soil (Hejazi et al., 2003; Besalatpour
et al., 2011). Landfarming technique only lost its popularity when the USA Environmental Protection Agency
(USEPA), issued the land disposal restriction conservation and recovery act (RCRA), establishing treatment
standards under the land disposal restriction program
(USEPA, 1997). The restriction prohibited the land
disposal of untreated oil sludge. This led to treating the oil
sludge to meet EPA treatment standards and making
sure that there was no migration of hazardous
constituents from the injection zone (Hejazi et al., 2003).
However, landfarming was an acceptable disposal
method as long as it is within EPA guideline that aims to
minimize the possibility of wash out and groundwater
contamination. Simplicity and cost-effectiveness are
some of the major advantages of the technology (Hejazi
et al., 2003). It is simple in that, typical equipments which
are used for landfarming is used widely in the farming
community and is therefore readily available.
Although, landfilling is reported as the most cost
effective oil sludge treatment method, landfarming gained
popularity among refineries following restrictions on
landfilling oil sludge (Mahmoud, 2004). The challenges of
landfarming include the release of hydrocarbon
compounds (VOCs) during the application and
degradation of oil sludge (greenhouse structure can help
minimise emission), and its requirement of a large land
area for treatment (just as in landfilling). There is also risk
6560
Afr. J. Biotechnol.
Bioreactors
This is the use of a bioreactor process as a fermentation
technology to degrade oil sludge into non-hazardous
effluents with very low level of hydrocarbon (Daubaras
and Chakrabarty, 1992; Oolman et al., 1996; Singh et al.,
2001; Soriano and Pereira, 2002). These methods uses a
naturally selected and acclimated indigenous bacterial
culture supplemented with a carefully designed blend of
nutrients such as nitrogen, phosphate, essential minerals
and a surfactant for degradation. The design and process
operating conditions of the technique promoted the
growth of highly active microbial population, which rapidly
converted the oil sludge components to carbon dioxide
and water (Soriano and Pereira, 2002).
It was further reported that the bacteria involved are
known oil-degrading bacteria such as Pseudomonas,
Acinetobacter, Rhodococcus and Alcaligenes (Singh et
al., 2001). In Singh et al. (2001) study, more than 90% of
the total petroleum hydrocarbons contained in the oil
sludge were degraded. After a successful treatment, 80%
of the processed materials were disposed of and the
reactor were reloaded with another batch of oil sludge
using the remaining 20% left in the reactor to serve as
inoculums for the next run (Singh et al., 2001; Soriano
and Pereira, 2002). The analysis of the total petroleum
hydrocarbons obtained from the treatment process
indicated that oil sludge was treatable to non-hazardous
levels (Daubaras and Chakrabarty, 1992; Oolman et al.,
1996; Singh et al., 2001; Soriano and Pereira, 2002).
However, the effects of the oxygen supply on the
biodegradation of PAHs was more important as increase
in PAHs degradation was observed in one of the
experiment by Soriano and Pereira (2002), from 1.7 to
10.2% per day with high oxygen availability and the result
obtained after 21 days was very promising (Field, 1991;
Salameh and Kabrick, 1992; Hahn and Loehr, 1992;
Huesemann et al., 1993).
The aqueous low total
petroleum hydrocarbons (TPHs) can be sent to the
wastewater system, solid residues can be disposed of in
a landfarm, to a non-hazardous landfill, dewatered and
reused in other industrial purposes (Singh et al., 2001).
This technique can be used in the process recovery of
recyclable oil, biodegradation of oil sludge and disposal
of treated oil sludge. It also eliminates the need to spray
high concentration oil sludge on large areas of land.
Bioreactor processes has high rates and extent of
degradation than landfarming process due the minimization of mass-transfer limitation, high organic matter
biodegradation and progressive reduction in the total
Composting
Despite decades of research, successful biological
remediation of oil sludge in the environment remains a
challenge. It is noticed that, there are physical, chemical
and biological aspects of landfilling, landfarming and
bioreactor treatments that can hamper the degradation
processes of oil sludge, making them partially effective
and sometimes prohibitively expensive. It is necessary to
search for cheaper and environmentally friendly options
that can enhance bioremediation of oil sludge. Such
options should be able to take care of the limitations of
the previous methods while improving oil sludge
bioremediation. Therefore, composting process which
involves the careful control and addition of nutrients,
watering, tilling, addition of suitable microbial flora and
bulking agents (wood-chips or hay) were considered an
alternative option to improve the bioremediation of oil
sludge (De-qing et al., 2007). The process leads to the
production of carbon dioxide, water, minerals and
stabilized organic matter (Pereira-Neta, 1987).
Composting is a controlled biological process of a
mixture of substrates carried out by successive microbial
populations combining both mesophilic and thermophilic
activities. It is applied to solid and semi-solid organic
waste such as nightsoil, sludge, animal manures,
agricultural residues and municipal refuse, whose solid
content are usually higher than five percent. The process
can be classified into mechanical and non-mechanical
processes (aerobic and anaerobic composting system);
using technology as the key (the classification is divided
into static pile or windrow, and mechanical or enclosed
composting). Compost systems can be on three general
bases: oxygen usage, technological approach and
temperature. Oxygen usage is divided into aerobic and
anaerobic. Aerobic composting involves the activity of
aerobic microbes, and hence the provision of oxygen
Ubani et al.
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Afr. J. Biotechnol.
from one environmental medium to another. The biological reactions occurring during composting will convert
organic wastes into stable, mainly inorganic forms. These
stable inorganic forms may cause little pollution effects if
discharged onto land or into a water course. As already
stated, composting could be ex situ or in situ process
depending on whether the oil sludge is taken out from its
source or not. It is often less expensive and disruption is
minimal. It eliminates waste permanently, eliminates long
term liability, and has greater public acceptance, with
regulatory encouragement, it can also be coupled with
other physical or chemical methods. As far as the effectiveness of the by-products is concerned, the treated
sludge is found enriched in organic matter along with
sufficient amount of nutrients (nitrogen, phosphorus and
potassium). This technique does not only reduce the
PAHs concentrations, but tends to improve soil quality
through the addition of organic matters. Also, if compared
to landfill or landfarming and destructive treatment
methods, such as incineration, the use of composted
material and co-composting as bioremediation technique
may possibly promote soil sustainability and re-use.
It is reported in the literature that animal manure cocomposted with oil sludge can enhance the degradation
of oil sludge. Also composting and the use of compost for
the bioremediation of oil sludge have been reported to be
cost-effective and environmental friendly. Hence, this
technique has some physical, chemical and biological
limitations. Such limitations can be addressed by applying the current findings as the way forward on biodegradation and bioavailability of oil sludge constituents to
the degrading bacteria.
It also addresses the partitioning of oil sludge between
environmental media, genetic transfer of the
biodegradation knowledge to indigenous microbial
communities and impact of oil sludge constituents on soil
microbial diversity. These findings and knowledge on
biodegradation and bioavailability of oil sludge add on the
advantages that have been reported about composting
techniques. Stimulated biological process and cometabolism of recalcitrant (heavy molecular weight
PAHs) will be an added advantage of the composting
technique. Therefore, it is important to implement the
technique in such a way that takes care of all the
limitations.
Amidst limitations that may hamper the composting
processes, co-composting techniques for bioremediation
of oil sludge have its advantages. The technique has not
only reduced the PAHs concentrations, but tends to
improve soil quality through the addition of organic
matters. However, if compared to landfill or landfarming
and destructive treatment methods, such as incineration,
the use of composted material and co-composting as
bioremediation technique may possibly promote soil
sustainability and re-use. The reports described in this
study, have shown that co-composting of oil sludge with
compost materials can promote degradation of oil sludge.
Ubani et al.
6563
CONCLUSION
In conclusion, it is evident that researchers and most
refineries have tried to treat oil sludge using conventional
methods which includes physical treatment (storage,
landfilling, combustion and incineration in a rotary kiln,
lime stabilization, stabilization and solidification) chemical
treatment (oxidative thermal treatment, treatment with flyash, pyrolysis treatment and solvent extraction) and
biological treatment (landfarming, bio-reactor treatment
and composting).
However, safe disposal and treatment of huge quantity
of oil sludge generated during the processing of crude oil
have been the major challenges faced by oil refineries
and petrochemical industries. This is because these
methods may require expensive equipments and high
energy to treat the oil sludge. Although, some of these
methods convert oil sludge into lighter products and
reduce the quantity before disposal but some of the
methods may generate by-products that may need to be
treated using other methods before disposal to a landfill,
making their cost significantly higher. Nevertheless, this
paper has reviewed the current position in the
composting of oil sludge, the extent of development in
methodology, the successes and the challenges
encountered.
The pathways of aerobic transformation have been
reported and it is established that microorganisms
capable of degrading oil sludge could be found in the
contaminated environments. This have been of growing
interest to the potential use of microbes to degrade oil
sludge and more recent work has established that it is
possible to use microbial-based processes to remediate
contaminated environments. It is clearly evident from the
review that substantial progress has been made in the
development and application of biological techniques in
the degradation of oil and oil sludge in the environment.
However, application of these technologies to the
degradation of relatively complex organic substrates has
continued to be a challenge. In all, bioremediation of oil
sludge is feasible given the depth of our current
knowledge. Although the inherent limitations of
bioremediation of oil sludge are known, further research
is required to test these limitations and to exploit the
potential of the in-situ microbial communities to
metabolise the oil sludge.
The findings will also help to deeply understand the
microbial ecology and their activities in the degradation of
oil sludge. It was necessary for further improvement of
compost bioremediation process.
ACKNOWLEDGEMENT
The authors wish to acknowledge the financial support
given by the South African National Research Foundation
for this project.
6564
Afr. J. Biotechnol.
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