Desalination 278 (2011) 288–294

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Desalination
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / d e s a l

Removal of petroleum hydrocarbons from contaminated groundwater using an

electrocoagulation process: Batch and continuous experiments
Gholamreza Moussavi a,⁎, Rasoul Khosravi a, Mahdi Farzadkia b
a
Department of Environmental Health Engineering, Faculty of Medical Sciences, Tarbiat Modares University, Tehran, Iran
b
Department of Environmental Health Engineering, Faculty of Public Health, Tehran University of Medical Sciences, Tehran, Iran

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

Article history: The efficacy of an electrocoagulation process (ECP) was evaluated for the treatment of petroleum-
Received 16 March 2011 contaminated groundwater and quantified as the total petroleum hydrocarbon (TPH) removed. Various
Received in revised form 15 May 2011 operating variables were examined for their effects on TPH removal; these variables included electrode
Accepted 16 May 2011
materials (aluminum, iron, and steel), water pH (4 to 11), current density (2 to 18 mA/cm 2), reaction time
Available online 6 June 2011
(2 to 60 min), aeration, and the mode of operation (batch and continuous). Batch experiments indicated that
Keywords:
the maximum TPH removal was achieved using steel-iron as the anode–cathode electrode arrangement and a
Groundwater neutral pH level. The increase in current density from 2 to 18 mA/cm 2 at optimum electrode and pH
Petroleum-contamination conditions increased TPH removal from 71.7 to 95.1% during the ECP. The rate of TPH removal followed a
Petroleum hydrocarbon pseudo-second-order reaction. Aeration increased the reaction constant of TPH removal from 0.477 to
Removal technique 0.078 L/g·min. Increasing the hydraulic retention time from 10 to 60 min in the continuous operation mode of
Electrocoagulation process the ECP led to an increase in the TPH removal from 67.2 to 93.4%. Therefore, batch and continuous
experiments showed that the ECP could be efficient in eliminating TPH from water and thus may be a
promising technique for treating petroleum-contaminated groundwater.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction of days. Therefore, considering the extent and volume of contaminated

Crude oil is composed mainly of a mixture of hydrocarbons whose
leakage during extraction, refining, storage, and transportation activities
contaminates surrounding environmental resources [1]. Most petro-
leum hydrocarbons have a low octanol–water partition coefficient;
therefore, they migrate easily through soil columns and reach and
contaminate groundwater sources [2]. Consequently, contamination of
groundwater is one of the increasingly critical environmental challenges
that is presented at petroleum processing and operation sites. Most
petroleum hydrocarbons are toxic to water and thus interfere with
its usage [3]. Therefore, petroleum-contaminated groundwater must
be addressed. One attractive approach for remedying a contaminated
aquifer is an ex situ technique in which water is pumped out of the
aquifer and subsequently treated for target contaminants. Various
techniques have been investigated for the removal of hydrocarbons
from contaminated water, including biodegradation [4], adsorption
onto activated carbon [5], membrane processes [6], and advanced
oxidation processes. These techniques suffer from several technical and
economic disadvantages. Although biodegradation is an environmen-
tally friendly process, the rate of hydrocarbon biodegradation is
considerably slow and thus requires long reaction times in the range
⁎ Corresponding author. Tel.: + 98 21 82883827; fax: + 98 21 82883825.
E-mail address: moussavi@modares.ac.ir (G. Moussavi).
water, employing biodegradation as a removal method of petroleum
hydrocarbons from contaminated aquifers requires extremely large
treatment facilities. Utilizing activated carbon for the removal of
hydrocarbons is a phase change technique that requires the interval
regeneration of saturated activated carbon, which is a costly and
complex operation. Although membranes are efficient for the rejection
of oil and organic compounds, the critical drawback to their utility
in full-scale operations is membrane fouling. Advanced oxidation
processes are very efficient in the degradation of organic contaminants,
but they are very expensive and complex to design and operate. These
disadvantages have motivated researchers to explore the capabilities of
other techniques for the removal of petroleum hydrocarbons from
contaminated waters.
Electrocoagulation process (ECP) is a variant of the conventional
coagulation process in which coagulant agents are generated in situ
through the dissolution of a sacrificial anode by applying current
between the anode–cathode electrodes. The ECP has several advantages
that make it attractive for treating various contaminated streams. It has
been shown that electrocoagulation is an efficient and promising
process in treating various wastewater contaminants, such as reactive
dyes [7], azo dyes [8], oily bilgewater [9], industrial wastewater [10],
petroleum refinery wastewater [11], fluoride [12], pulp and paper mill
wastewater [13], and phosphate and zinc [14]. Based on our literature
review, we could not find any report on the removal of soluble
petroleum hydrocarbons from contaminated groundwater using the

0011-9164/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2011.05.039
 G. Moussavi et al. / Desalination 278 (2011) 288–294
ECP. Therefore, running the ECP at a laboratory scale was required to
determine its optimum experimental conditions for treating petroleum-
contaminated groundwater. Accordingly, the main purpose of this study
was first to investigate the effects of the primary operational factors on
the efficacy of the ECP in treating petroleum-contaminated groundwa-
ter. These factors were examined by performing batch experiments
and included electrode material, water pH, current density, and re-
action time. The second phase of the work was devoted to examining
the performance of a continuous flow ECP in treating petroleum-
contaminated groundwater at the optimum conditions as determined
by the first phase of the study.
2. Materials and methods
2.1. Water sample
Petroleum-contaminated water samples used for electrocoagula-
tion experiments were obtained from a groundwater table located
close to the site of a local petroleum refinery plant. The water samples
were collected in polyethylene containers from a centrifuge pump
installed on a monitoring well at the contaminated site. The sample
containers were preserved in a refrigerator at 4 °C before use. At the
beginning of the study, the collected samples were analyzed for their
main characteristics. The mean values of these water characteristics
are given in Table 1. The water temperature was increased to room
temperature before each electrocoagulation test.
2.2. Electrocoagulation system and method
The ECP experimental setup consisted of a cylindrical glass cell,
which was 30 cm in height and 5 cm in internal diameter, a pair of
electrodes, a direct current power supply with current wires, an
aeration system equipped with a fine bubble diffuser, a magnetic
stirrer, and required accessories. Various materials of aluminum (Al),
iron (Fe), and stainless steel (St) were used as anode and cathode
electrodes within a thin rectangular plate; the plate dimensions were
10 cm × 2 cm × 0.2 cm. The electrodes were installed parallel to each
other in the cell at a fixed distance of 3 cm apart from each other. The
working volume of the electrocoagulation cell was held constant at
200 mL throughout the experiment.
During this study, the ECP was operated in both batch and
continuous modes. For batch experiments, the main operational
variables were investigated in various runs (specified in Table 2) for
their effect on the ECP in treating petroleum-contaminated ground-
water. These variables included the electrode type (Fe, Al, and St) and
arrangement, water pH (ca. 4–11), current density (2–18 mA/cm 2),
aeration (presence or absence), and reaction time (2–60 min). For
each electrocoagulation test, 200 mL of sample water was transferred
into the cell, the electrodes were connected to the DC power supply
with the current density set at a given level, and the reaction was
started while the cell content was gently stirred (200 rpm). At the
end of the test, the suspension was filtered through a Whatman
Table 1
The main characteristics of the petroleum-contaminated groundwater samples.
Parameter Unit
Chloride mg/L
Electrical conductivity ms/cm
Nitrate mg-N/L
Phosphate mg/L
Sulfate mg/L
TDS mg/L
Total Alk. mg/L as CaCO3
Total hardness mg/L as CaCO3
TPH mg/L
289
paper filter (0.45 μm pore size), and the filtrate was analyzed for
its constituents. All tests were carried out at room temperature
(23 ± 3 °C). The water pH was set at the desired level using 0.1 M
NaOH and 0.1 M HCl. At the beginning of each electrocoagulation test,
the electrode surfaces were cleaned to remove impurities by first
using sand-paper, then washing with tap water, and finally rinsing
with distilled water. The cleaned electrodes were dried before
immersing in the electrocoagulation cell in water. All batch tests
were conducted in triplicate, and the average data values are reported
and discussed.
During continuous operation, efficacy of the ECP in treating
petroleum-contaminated groundwater was investigated at a neutral
pH and various hydraulic retention times (HRT) ranging from 10 to
60 min using the best electrode materials and arrangement. At this
phase of the study, the electrocoagulation reactor was operated at
each HRT for a duration of twice as long as the established HRT, after
which the effluent of the reactor was sampled and analyzed for
residual total petroleum hydrocarbons (TPH).
2.3. Analysis
The water samples were analyzed for TPH, EC, pH, and turbidity
both before and after electrocoagulation. The performance of electro-
coagulation in treating petroleum-contaminated groundwater was
evaluated in terms of the TPH elimination percentage. TPH was
analyzed using an InfraCal TPH analyzer (model CVH) with a detection
limit of 2 mg/L. The electrical conductivity and turbidity were
determined using Hack instruments, and the pH was measured using
a pH-meter (GENWAY Co.). The concentration of soluble electrode
materials (of which St was the most efficient anode) leached into the
water was measured from the filtrate of effluent samples. Soluble Fe
concentration in the effluent samples was determined according to the
procedure detailed in standard methods [15].
The amount of sludge generated by performing the ECP at various
current densities with the best performing electrodes (St–Fe) was
measured using the standard procedure of measuring suspended
solids [15]. The electrocoagulation sludge was also analyzed for
elemental composition using an energy dispersive X-ray instrument
(EDX, Philips XL-30).
3. Results and discussion
The results obtained from this study are presented and discussed
below in two separate sections of batch and continuous operation
experiments.
3.1. Batch operation of electrocoagulation process
At this phase of the work, the effects of electrode materials, pH,
current density, aeration, and reaction time on the performance of
electrocoagulation in removing TPH from petroleum-contaminated
groundwater were investigated; the results are presented and discussed
below.
3.1.1. Effect of electrode materials
Fig. 1 presents the effects of anode and cathode electrode materials
and arrangement on the removal of TPH at the experimental
Value conditions given in Table 2. As indicated in Fig. 1, Al–Fe as anode–
419 cathode electrodes produced the lowest TPH removal, with a mean ±
1.61 standard deviation (SD) of 41.1 ± 1.5%, while St–Fe as anode–cathode
9.8
electrodes produced the highest TPH removal of 91.5 ± 0.1% at similar
0.032
60.5 experimental conditions (Table 2). El-Naas et al. (2009) observed a
1178 higher chemical oxygen demand (COD) and sulfate removal from
130 petroleum refinery wastewater with Al electrodes than with Fe or St
900
electrodes in an ECP. However, the literature indicates that the ECP
64
performs better when using St or Fe than it does when using Al for
290 G. Moussavi et al. / Desalination 278 (2011) 288–294

Table 2
The runs and operational conditions of electrocoagulation experiments.

Run Operation mode Experiment Operational conditions

Materials pH Current density Aeration Reaction timea/HRTb

(anode–cathode) (mA/cm2) (presence/absence) (min)

1 Batch Effect of electrodes material Fe, Al, St Natural 18 Presence 30

2 Batch Effect of pH of water St–Fe 4–11 18 Presence 30
3 Batch Effect of current density St–Fe Natural 2–18 Presence 30
4 Batch Effect of aeration and reaction timea St–Fe Natural 18 Presence 2–60
Absence
5 Continuous Effect of HRTb St–Fe Natural 18 presence 10–60
a
In batch operation.
b
In continuous operation.

treating other contaminated streams, including simulated reactive The possible mechanism deduced for TPH removal is described as
dyebath effluent [16,17], sulfide and COD from tannery liming drum follows: in the electrocoagulation cell, the anode is oxidized, which
wastewater [18], and tannery wastewater [19]. Therefore, it can be results in the release of Fe 2+ into the water in the cell, as shown in
concluded that the efficacy of electrode materials for the ECP depends Eq. (1).
on the type of contaminants being removed, as well as the operational
• Oxidation in anode:
conditions.
2+ −
FeðSÞ →FeðaqÞ + 2e ð1Þ
3.1.2. Effects of water pH and the TPH removal mechanism
Solution pH is one of main factors affecting electrochemical The water molecules are concurrently hydrolyzed in the cathode
processes. Therefore, pH (in the range of 4 to 11) was examined as according to Eqs. (2) and (3), generating hydrogen gas and oxygen
one of the main variables affecting electrocoagulation removal of TPH molecules.
from petroleum-contaminated groundwater. The results are shown in
Fig. 2. The average TPH removal sharply increased from 53.6% to 75.1% • Reduction in the cathode:
when the pH was increased from 4 to 6. The TPH removal percentage
þ −
remained almost unchanged at approximately 77% for a pH between 7 H2 O→2H + 1 = 2O2 + 2e ð2Þ
and 9. Further increasing the pH to 11 resulted in a reduction of TPH
þ −
removal efficiency to 62%. This finding support that electrocoagula- 2H + 2e →H2 ð g Þ: ð3Þ
tion efficiency is a function of pH and these results are in accordance
with other researchers who have reported the maximum perfor-
mance for the ECP at pHs between 7 and 8 when using Fe or St as the Due to the presence of oxygen, the soluble Fe 2+ in the water is
sacrificial electrode [10,20,21]. However, those results were for target oxidized to Fe 3+, as given by Eq. (4) [22].
contaminants other than petroleum hydrocarbons. • Reaction in the water:
The trend observed for TPH removal versus water pH in the ECP
can be explained by accounting for the sacrificial electrode material 2+ þ 3+
2FeðaqÞ + 0:5O2 + 2H →2Fe + H2 O: ð4Þ
and its predominant species diagram from which the removal
mechanism can be deduced. Although the mechanism of contaminant
removal in the ECP is complex [22], the following mechanism likely Fe 3+ formed in the water can further react with hydroxide ions;
occurred within the electrocoagulation cell during TPH elimination depending on the water pH, this reaction may also produce gelatinous
from the contaminated water at specified operating conditions hydroxide precipitates or soluble monomeric or polymeric ferric
(Table 2). species [23].

100
100

80
80
TPH removal (%)

TPH removal (%)

60
60

40
40

20
20

0
Al-Fe Fe-Al Fe-Fe Al-Al St-St Al-St St-Al Fe-St St-Fe 0
Electrode material (anode-cathode) 2 4 6 8 10 12
Initial water pH

Fig. 1. The effect of anode and cathode electrode materials on the removal of TPH in the
ECP. Fig. 2. The effect of water pH (4–11) on the removal of TPH in the ECP.
 G. Moussavi et al. / Desalination 278 (2011) 288–294 291

According to the above-mentioned mechanism (Eqs. (1) to (4)) 100

that occurred in the electrocoagulation cell and considering the
solubility of Fe 3+ in water versus pH, the Fe(OH)3 precipitate would 80
be the dominant form of Fe 3+ in the water at pHs between 6 and 9

TPH removal (%)

[24].
Fe(OH)3 is a gelatinous precipitate; therefore, hydrocarbon (HC)
molecules, which are hydrophobic and nonpolar neutral compounds,
have likely been removed from the water through the formation of
surface complexes. The HC molecules complex with the active sites
present on the surfaces of growing ferric hydroxide flocs (coprecipita-
tion) and undergo physical adsorption onto the gelatinous amorphous
Fe(OH)3 flocs by Van der Waals forces [24]. The mechanism involved
in the removal of petroleum HC can be simplified according to the
following equations:
• Formation of ferric hydroxide at 6 b pH b 9:
3+ −
Fe + 3OH →FeðOH Þ3 ðsÞ
• Adsorption of HC:

shows the amount of anode weight loss and sludge formed in the
FeðOHÞ3 ðsÞ + HC→ FeðOH Þ3 −HC floc
(Fe(OH)3 − HC)flocs can be attached to one another and flocculated
by mixing, thus forming a particle that can be separated from the liquid
phase by settling, flotation, or filtration [24].
Decreasing TPH removal percentages at pHs below 6 or above 9
can be attributed to the formation of various monomeric and
polymeric ionic Fe species and thus increased solubility of Fe 3+ at
these pHs. Consequently, this results in a reduction of ferric hydroxide
flocs formation, which in turn leads to a reduction in the number of
hydrocarbon molecules adsorbed. It has been observed that the
maximum TPH removal occurs at the pH of natural waters. This is very
beneficial from both engineering and economic points of view.
Indeed, achieving the maximum TPH removal at a pH close to that
of natural waters overcomes the need to manipulate the water pH via
chemical treatment, which in turn makes the treatment process both
simple and cost effective.
3.1.3. Effect of current density
Another important parameter influencing the performance and
economy of the ECP is the density of current applied at the electrodes
[21]. To understand the effect of current density on the efficacy of
electrocoagulation in removing TPH from petroleum-contaminated
ground water, several current densities in the range of 2 to 18 mA/
cm 2 were applied between the electrodes in the electrocoagulation
cell, and TPH removal was determined at the conditions given in
60
40
20
0
2 5 9 14 18
Current density (mA/cm2)
ð5Þ
Fig. 3. The effect of current densities in the range of 2 to 18 mA/cm2 on the removal of
TPH in the ECP.
ð6Þ
electrocoagulation cell at the conditions given in Table 2 (run 3). As
seen in Fig. 4, the anode dissolution mass and corresponding amount
of sludge formed increased with increasing applied current density.
The greater the amount of sacrificial anode material (Eq. (1)), the
greater the amount of Fe(OH)3 flocs generated (Eq. (5)); accordingly,
a greater number of HCs would be adsorbed (Eq. (6)), and thus, a
higher TPH removal percentage would be achieved. Nevertheless, the
plateau approached by TPH removal as a function of current density
implies that the elimination of TPH at the critical current density is
limited by the rate of HC adsorption on Fe(OH)3 flocs, as shown in
Eq. (6). Similar effects of current density on the ECP has also been
reported for treatment of other organic and inorganic contaminants,
such as baker's yeast wastewater [21], waste metal cutting fluid [27],
dye and color [23,28], mercury (II) [29], and sulfate [11] when using
Fe as the sacrificial anode.
Furthermore, the sludge formed in the electrocoagulation cell was
also analyzed for elemental composition. The EDAX analysis of the
electrocoagulation sludge indicated that the sludge generated was
mainly composed of 98 wt.% of iron. Moreover, analysis of the
electrocoagulation effluent for residual Fe indicated that the concen-
tration of soluble Fe in the effluent was negligible. These findings
confirmed the sacrificial anode material and the precipitation of
scarified Fe.
Anode weight loss and sludge formed (mg)

20
Table 2. Fig. 3 depicts these results, which show a positive effect of
current density on process performance, particularly at lower values
sludge formed
at the given test conditions. The ECP produced a considerable TPH
removal of 71.7% at the low current density of 2 mA/cm 2. Increasing 15 anode weight loss
the applied current density incrementally to 18 mA/cm 2 increased the
TPH removal to an average of 95.1%.
The improvement in TPH removal as a result of current density 10
applied between electrodes in the electrocoagulation cell is related to
the rate increase of the sacrificial anode (St) material [25]. Hence, Fe
(OH)3 flocs generation and growth [24] are enhanced, improving the
5
rate of adsorption of HC based on the mechanisms given in Eqs. (5)
and (6). A closer look at Fig. 3 reveals that the removal of TPH as a
function of current density approaches a plateau, indicating that the
effect of current density is reaching its critical point [26]. Based on 0
Faraday's law, the amount of sacrificial anode material and hence Fe 0 5 10 15 20
(OH)3 flocs generation increases proportional to the increase in Current density (mA/cm2)
current density (as indicated in Eq. (5)) [23]. The increase in Fe(OH)3
flocs generation as a function of current density was confirmed by Fig. 4. The anode weight loss and sludge generated in the ECP as a function of current
measuring the generated sludge as suspended solids (Fig. 4). Fig. 4 densities in the range of 2 to 18 mA/cm2.
292 G. Moussavi et al. / Desalination 278 (2011) 288–294

3.1.4. Effect of aeration on TPH removal percentage and kinetics 4

The removal of TPH with the presence and absence of aeration in a R² = 0.875
the electrocoagulation cell was evaluated as a function of the reaction
time. Fig. 5 illustrates the results as a percentage of TPH removal. As 3
shown in Fig. 5, TPH removal increased with increasing reaction time,
although at a higher rate in the presence of aeration than in the

-Ln Ct
absence of aeration. For electrocoagulation in the presence of aeration, 2
most of the reduction in TPH was achieved within the first 10 min of
the reaction and was approximately 78%. A further increase in
reaction time to 60 min resulted in an improved TPH removal of R² = 0.894
1
approximately 95%. In comparison, the removal of TPH after a 60 min
reaction in the electrocoagulation cell reached a maximum of 73% in
the absence of aeration. This indicates that aeration of the ECP could
enhance TPH removal by 22%. This finding agrees with our ongoing 0
findings on the removal of cyanide from wastewater using an 0 10 20 30 40 50 60 70
electrocoagulation system where a considerable improvement was Reaction time, t (min)
observed with aeration. As given in Eq. (1), sacrificial anode material
leads to a release of iron into bulk solution as Fe 2+, where it is 35
oxidized to Fe 3+ in the presence of oxygen and finally reacts with b
hydroxyl ions to form ferric hydroxide precipitate, as shown in 30 R² = 0.996
Eqs. (4) and (5). Therefore, aeration transfers oxygen into solution,
25
which accelerates oxidation of Fe 2+ ions from anode oxidation into
Fe 3+ ions. This results in the formation of greater Fe(OH)3 flocs and
20
thereby increases TPH adsorption (see Section 3.1.3) and thus
removal, according to the mechanism shown in Eq. (6). 1/Ct
15
To better highlight the role of aeration in enhancing the
performance of the ECP in removing TPH, the kinetics of TPH removal 10 R² = 0.971
were evaluated. To evaluate the kinetics, the experimental data
plotted in Fig. 5 was fit to the pseudo-first- and pseudo-second-order 5
reaction integrated equations given below:
0
ln Ct = ln C0 −k1 t ð7Þ 0 10 20 30 40 50 60 70
Reaction time, t (min)
1 1
= k2 t + ð8Þ
Ct C0
Fig. 6. The plots of pseudo-first- and pseudo-second-order reaction models fitted with
the TPH removal experimental data in ECP.
where C0 and Ct represent the TPH concentration at the beginning and
after time t of the reaction, respectively. k1 and k2 represent the
pseudo-first- and pseudo-second-order reaction constants, respec- data (Fig. 6b), the pseudo-second-order reaction rate constants for
tively. Values of k1 and k2 can be determined from the slope of the TPH removal from the ECP with and without aeration were 0.477 and
plots ln Ct versus t and 1/Ct versus t, respectively. 0.078 L/g·min, respectively. Therefore, it is clear that aeration of the
Fig. 6 presents the plots of pseudo-first- and pseudo-second-order electrocoagulation cell could significantly accelerate TPH removal.
reaction models fitted with the experimental data. According to the Accordingly, the pseudo-second-order reaction rate model predicting
correlation coefficients (R 2) given on the plots, the experimental data the elimination of TPH in the ECP with aeration can be expressed as
fit better to the pseudo-second-order reaction (higher values of R 2). follows:
Based on the linear regression equation fitted to the experimental
2
Electrocoagulation with aeration : rTPH = −0:477 ðCt Þ ð9Þ
100

2
Electrocoagulation without aeration : rTPH = −0:078 Ct ð10Þ
80

The time required (in minutes) to achieve a given level of TPH

TPH removal (%)

60 concentration (with respect to the initial concentration) in the ECP

with and without aeration under the selected operational conditions
can be calculated from the following equations:
40
 
C0 −Ct
with aeration
Electrocoagulation with aeration : t = 2:1 × ð11Þ
C0 Ct
20
without aeration
 
C0 −Ct
Electrocoagulation without aeration : t = 12:8 × : ð12Þ
0 C0 Ct
0 10 20 30 40 50 60 70
Reaction time (min) The results show that aeration of the electrocoagulation cell can
reduce the treatment time of petroleum-contaminated groundwater
Fig. 5. The effect of aeration of the removal of TPH in the ECP as a function of reaction by a factor of one to six compared to that without aeration. Since
time. operating cost of the ECP greatly depend on the required reaction time
 G. Moussavi et al. / Desalination 278 (2011) 288–294
[30], shorter reaction time with aeration lead to a reduction in the
amount of energy consumption and cost of treatment.
3.2. Continuous operation of electrocoagulation process
Thus far, batch experiments showed that the ECP using a St–Fe
anode–cathode electrode arrangement is an efficient process for
eliminating TPH from contaminated groundwater. However, on a
large scale in the field, the treatment process must be run in
continuous mode. Therefore, a set of experiments (run 5 in Table 2)
was designed and conducted to investigate the efficacy of the ECP in
removing TPH from contaminated groundwater. Fig. 6 depicts the
average TPH removal as a function of HRT in the range of 10 to 60 min.
Based on data plotted in Fig. 7, TPH removal increased from 67.2% at
an HRT of 10 min to 93.4% when the HRT was increased to 60 min.
Improvement in TPH removal with an increasing HRT is expected and
can be explained by the increase in anode dissolution and thus
gelatinous flocs formation with increasing electrochemical reaction
time; it can also be explained by the increased opportunity for
reaction/adsorption [14] between petroleum hydrocarbons and flocs
(Eq. 6). This finding agrees with those of other researchers who report
that the performance of a continuously operating ECP is a function of
HRT. These previous studies were performed for the treatment of
various other contaminants and contaminated streams, such as
disperse and reactive dyes [7], fluoride [12], pulp and paper mill
wastewater [13], phosphate and zinc [14], and azo dyes [8].
4. Conclusion
The removal of TPH from petroleum-contaminated groundwater
was examined in an ECP operated in batch and continuous modes.
Several operational variables were investigated for their effects on
process efficacy. The following conclusions were drawn from the
experiments:
a. The electrode arrangement of St–Fe as the anode–cathode
achieved the best efficacy in eliminating TPH during the ECP.
b. The pH had a considerable effect on TPH removal, with the
maximum TPH removal obtained at an approximately neutral pH.
c. Increasing the applied current density at the St–Fe electrode
(at the optimum pH) resulted in improved TPH removal.
d. TPH removal followed a pseudo-second-order rate equation
during electrocoagulation; aerating the electrocoagulation cell
accelerated the rate of TPH removal and reduced the required
treatment time.
100
90
TPH removal (%)
80
70
60
50
0 10 20 30 40 50 60
Hydraulic retention time (min)
Fig. 7. The effect of HRT (10–60 min) on the removal of TPH in the continuously
operated ECP.
293
e. The HRT of contaminated water considerably affected TPH removal
during the ECP; elimination of TPH decreased with decreasing HRT
for given conditions.
f. The ECP, operated both in continuous and batch modes, was
determined to be an efficient and viable process for achieving a
high degree of TPH removal from petroleum-contaminated
groundwater.
Acknowledgment
The authors would like to acknowledge the Tarbiat Modares
University for financial and instrumental supports.
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