Egyptian Journal of Petroleum xxx (2017) xxx–xxx

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Egyptian Journal of Petroleum

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Full Length Article

Kinetics and physicochemical studies of surfactant enhanced

remediation of hydrocarbons contaminated groundwater
W.O. Medjor a,⇑, V.O. Akpoveta b, F. Egharevba c
a
Department of Chemistry, Taraba State University, Jalingo, Nigeria
b
Department of Chemical Sciences, Ondo State University of Science and Technology, Okitipupa, Nigeria
c
Department of Chemistry, Ambrose Alli University, Ekpoma, Nigeria

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

Article history: Kinetics and physicochemical studies of surfactant enhanced remediation of hydrocarbons contaminated
Received 28 December 2016 groundwater were investigated for efficiency and effectiveness. 10% pollution was simulated in the lab-
Revised 1 February 2017 oratory by contaminating groundwater samples with crude oil, automatic gasoline oil (diesel) and
Accepted 20 February 2017
domestic purpose kerosene (DPK) in replicates of five. Physicochemical properties of the hydrocarbons
Available online xxxx
contaminated groundwater samples and a control sample were investigated before and after treatments.
Total petroleum (TPH) hydrocarbon as target contaminant was monitored periodically to assess the
Keywords:
extent of the remediation process. TPH was determined by molecular spectrophotometry technique.
Sodium dodecyl sulphate
Total petroleum hydrocarbon
Other physicochemical parameters such as pH, turbidity, alkalinity, dissolved oygen (DO), biochemical
Safe oxygen demand (BOD), chemical oxygen demand (COD), condutiivity, ammonia, nitrate, phosphate, salin-
W.H.O. ity, total dissolved solids (TDS), total suspended solids (TSS) and total solids (TS) were obtained using
Pollution standard methods while heavy metals levels were determined by atomic absorption spectrophotometry.
Different kinetics models were tested to determine the appropriate kinetics model. The pseudo-first order
kinetics is established with rate constant as 1.80  104; 1.78  104; 1.53  104 mg 1 L h 1 for crude oil,
diesel and kerosene respectively at 30 °C. At the end of the remediation after 6 h there was 89.11%;
93.21%; 87.76% reduction in TPH as crude oil, diesel and kerosene for the treated samples in that order.
The application of surfactant enhanced remediation using sodium dodecyl sulphate is found be very effi-
cient, effective and rapid in reducing total petroleum hydrocarbon as crude oil, kerosene and diesel as
target contaminants. There is the need for post-treatments after remediation for most of the physico-
chemical parameters are impaired and do not meet the Guideline and Standards for Environmental
Pollution Control in Nigeria set by Federal Ministry of Environment and World Health Organization for
drinking water and agricultural uses in order to make them fit for these purposes.
Ó 2017 Egyptian Petroleum Research Institute. Production and hosting by Elsevier B.V. This is an open
access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction poor extraction efficiency. Surfactants may aid in remediation of

Surfactants can be classified according to the nature of the
hydrophilic portion of the molecule: anionic, cationic, nonionic,
zwitterionic. Zwitterionic surfactants have both positive and nega-
tive charge in the head group. Non-ionic surfactants generally have
smaller critical micelle concentration (CMC) values than ionic sur-
factants and are known to be good solubilizers of hydrophobic sub-
stances [1,2]. Cationic surfactants are often toxic in the mg/L range
to a wide variety of aquatic organisms [3]. Skrtic, et al. [4] reported
that cationic surfactants are unsuitable as extracting agents due to
Peer review under responsibility of Egyptian Petroleum Research Institute.
⇑ Corresponding author.
E-mail address: weltime.medjor@yahoo.com (W.O. Medjor).
soil and water contaminated with hydrophobic organic com-
pounds (HOC) [5,6]. These studies showed that aqueous surfac-
tants solutions significantly enhanced the removal of HOC from
soil and water. Extractive efficiencies of surfactant solution for
HOC were seven to ten times greater than those which could be
obtained by flushing with water alone. Surfactants can be used to
vastly increase the solubility of the HOC in water and also lower
the interfacial tension at the water - HOC interface [6,7].
Choosing the best surfactant solution for desorbing and solubil-
ising petro hydrocarbon can be a daunting task since over 700 dif-
ferent types of surfactants are commercially available [8]. Sodium
dodecyl sulphate as a surfactant used in this remediation work is
cheap, non-odorous and soluble in water at room temperature.

http://dx.doi.org/10.1016/j.ejpe.2017.02.005
1110-0621/Ó 2017 Egyptian Petroleum Research Institute. Production and hosting by Elsevier B.V.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Please cite this article in press as: W.O. Medjor et al., Kinetics and physicochemical studies of surfactant enhanced remediation of hydrocarbons contam-
inated groundwater, Egypt. J. Petrol. (2017), http://dx.doi.org/10.1016/j.ejpe.2017.02.005
2 W.O. Medjor et al. / Egyptian Journal of Petroleum xxx (2017) xxx–xxx
Material Safety Data Sheet (MSDS) information on the surfactant
indicated low toxicity and favourable biodegradability.
Although surfactant technology in remediation works are
widely cited in literature yet the application of sodium dodecyl sul-
phate is scantly reported in most literature. The present work is
poised at looking at kinetics and physicochemical studies of surfac-
tant enhanced remediation of hydrocarbons contaminated ground-
water for efficiency and effectiveness with view of contributing to
the existing body of knowledge on chemical remediation
technology.
2. Materials and methods
2.1. Materials
The petroleum contaminants used in the study were (i) Brent
crude oil. It was obtained from Shell Petroleum Development Com-
pany (SPDC) Flow Station, Kokori, Delta State, Nigeria. (ii) Auto-
matic gasoline oil (diesel) and (iii) Domestic purpose kerosene
(DPK). The latter two were obtained from Petroleum Marketers
at Agbor, Delta State, Nigeria. All plastics and glass ware utilized
were pre-washed with detergent water solution, rinsed with tap
water and soaked for 48 h in 50% HNO3, then rinsed thoroughly
with distilled water and air-dried in the laboratory.
2.2. Preparation of samples
Fifteen 30 mL vials were each filled with 14 mL groundwater.
1.4 mL of kerosene, diesel and crude oil were respectively added
to each of the three sets groundwater containing vials and stirred
thoroughly using a magnetic stirrer to obtain 10% contamination
of each contaminant type. These preparations were carried out in
replicates of five for each contaminant.
2.3. Control groundwater samples
Groundwater control samples were investigated for background
contamination with any of the three hydrocarbons.
2.4. Preparation of sodium dodecyl sulphate treatment solution for
surfactant method
Several concentrations of 10,000–90,000 mg/L of sodium dode-
cyl sulphate were prepared by dissolving 1–9 g of sodium dodecyl
sulphate in nine different 100 mL volumetric flasks; thoroughly
shaken and made up to marks using distilled water. The solutions
were left overnight to properly dissolve.
2.5. Optimisation studies
Optimization of concentration and pH of treatment solutions
were investigated to ascertain the optimum conditions for TPH
removal.
2.5.1. Optimization of concentration of sodium dodecyl sulphate on
surfactant method
TPH as crude oil was determined by molecular spectrophotom-
etry following standard procedure adopted by Wang, et al. [9] with
slight novel modification of drying the wet extracts with anhy-
drous sodium sulphate and also to avoid unnecessary interference
of impurities. 4.6 mL of the several prepared sodium dodecyl sul-
phate solutions (10,000–90,000 mg/L) were taken in 30 mL vials
to which 14 mL groundwater and 1.4 mL of crude oil were added.
The vials were properly sealed with Teflon films and shaken for
1 h using a mechanical shaker at 200 revolutions per minute (r.p.
Please cite this article in press as: W.O. Medjor et al., Kinetics and physicochemical studies of surfactant enhanced remediation of hydrocarbons contam-
inated groundwater, Egypt. J. Petrol. (2017), http://dx.doi.org/10.1016/j.ejpe.2017.02.005
m.). The crude oil in the water layers were separated from that
in the sodium dodecyl matrix using separating funnels. Crude oil
in the water layers was extracted using hexane. The wet extracts
were passed through 5 g of anhydrous sodium sulphate on Number
42 Whatmann filter paper in different filtration set ups in order to
obtain clean and dry extracts. TPH as crude oil was read off by UV/
Visible spectrophotometer (made in the United Kingdom, 2007
model) at wavelength of 460 nm. The procedure was repeated
using the other four replicate samples. The experiment was
repeated using diesel and kerosene at wavelength of 350 and
310 nm respectively.
2.5.2. Effect of pH on surfactant method
The effect of pH on surfactant method was investigated by
adjusting the pH of two sets of crude oil contaminated groundwa-
ter samples in 30 mL vials to pH = 3 and pH = 8 using 1 M H2SO4
and 1 M NaOH. The samples were then treated with the optimum
treatment concentration obtained in the same study. The vials
were then properly sealed with Teflon film and shaken with a
mechanical shaker for an hour followed by extraction and analysis.
Crude oil in the water layers were extracted using hexane and TPH
as crude oil were determined by UV/Visible spectrophotometer at
wavelength of 460 nm using standard procedure adopted by Wang,
et al. [9] and also described in the same work. Procedure was
repeated using the other four replicate samples. The experiment
was repeated using diesel and kerosene at wavelength of 350
and 310 nm respectively.
2.6. Kinetics studies
Kinetics experiment was carried out to establish the optimum
time and efficiencies of the remediation method employed in the
study. Several solutions of 4.6 mL of sodium dodecyl sulphate of
concentration of 50,000 mg/L obtained from the same work were
prepared and added to 14 mL groundwater and 1.4 mL of crude
oil in 30 mL vials. The pH of the solutions in the vials were adjusted
to pH = 3, optimum pH obtained in this same study. The vials were
properly sealed with Teflon films and shaken for 1 h using a
mechanical shaker at 200 rpm (r.p.m.). The crude oil in the water
layers were separated from that in the sodium dodecyl matrix
using separating funnels. Crude oil in the water layers were
extracted using hexane and TPH as crude oil were determined by
UV/Visible spectrophotometer at wavelength of 460 nm [9].
The concentrations of TPH as crude oil left were plotted against
time. The kinetics model for the remediation process was tested by
plotting Ln[B]o Ln[B]t against time using the experimental kinet-
ics data. The slope of the graph is the rate constant, k. The actual
rate constant was obtained by multiplying the value of the slope
from the graph with the optimum concentration of the treatment
solution that was used in excess, [A]o in the optimisation experi-
ment in this same work. The kinetics experiment was repeated
using diesel and kerosene at wavelength of 350 and 310 nm
respectively.
2.7. Determination of physicochemical properties of samples
Physicochemical parameters such as pH, turbidity, alkalinity as
CaCO3, dissolved oygen (DO), biochemical oxygen demand (BOD),
chemical oxygen demand (COD), condutiivity, ammonia, nitrate,
phosphate, salinity as chloride, total dissolved solids, total sus-
pended solids and total solids were obtained using standard meth-
ods adopted by APA, [10].
Heavy metal contents were determined using atomic absorp-
tion spectrophotometer (AAS) following procedures adopted by
APA, [10]. Sample was first digested using the standard method
proposed by Nabil and Barbara [11]. 50 mL of the sample was
 W.O. Medjor et al. / Egyptian Journal of Petroleum xxx (2017) xxx–xxx
treated with 5 mL of concentrated HNO3 and heated on a hot plate
with gradual addition of concentrated HNO3 as necessary until the
solution boiled in a fume cupboard. It was then evaporated to
about 20 mL; 5 mL of concentrated HNO3 was finally added, cov-
ered and allowed to cool and then filtered. The filtrate was poured
into a 50 mL standard volumetric flask and made up to the mark
with distilled water. Portion of the solution was used for heavy
metals (Cd, Cr, Ni, Pb, Hg, V, Se and As) determinations.
2.8. Statistical data treatment
SPSS 16.0 Statistical and Microsoft Office Excel 2007 software
were employed for the statistical data treatments. Analysis of vari-
ance (ANOVA) was carried out on the result of TPH obtained from
the kinetics studies. Standard deviations and coefficient of varia-
tions were also calculated to checkmate for indeterminate errors
and ascertain precisions.
3. Results and discussion
The results from the optimisation studies showed that optimum
concentration of 50,000 mg/L sodium dodecyl sulphate solution
was used in the treatment of crude oil contaminated groundwater
samples with an attendant 55.56% removal rate of TPH as crude oil.
The outcome is represented in Fig. 1. Diesel contaminated ground-
water samples treated with 50,000 mg/L of sodium dodecyl sul-
phate solution in surfactant enhanced remediation process gave
an optimum removal rate of 71.56% for TPH as diesel. The result
is displayed in Fig. 2. With a treatment concentration of
50,000 mg/L sodium dodecyl sulphate solution an optimum reme-
diation of 61.79% was obtained for the kerosene contaminated
groundwater samples in the optimisation study. The result is rep-
resented in Fig. 3.
The pH of the sodium dodecyl sulphate treatment solution was
basic (pH = 8.23). It is found that when the pH of the reacting mix-
tures were adjusted, remediation is more favoured at pH = 3 than
at pH = 8 for all the three contaminants used in this study as shown
in Table 1. In similar chemical remediation studies such as the sil-
ica encapsulation and Fenton oxidative methods cited in literature
suggested that remediation is more effective at pH range of 3–6
[12,13] corroborates our findings in this study.
The results from the kinetics studies showed progress profiles
of plots of concentrations of total petroleum hydrocarbons left
against time for each for each of the contaminants in Fig. 4. It is
observe that TPH decreases with time in all cases. This is a strong
indication that there are interactions between total petroleum
Fig. 1. Plot of % remediation of TPH against concentration of sodium dodecyl sulphate solution for the optimization study of crude oil contaminated groundwater in
surfactant enhanced remediation process.
Please cite this article in press as: W.O. Medjor et al., Kinetics and physicochemical studies of surfactant enhanced remediation of hydrocarbons contam-
inated groundwater, Egypt. J. Petrol. (2017), http://dx.doi.org/10.1016/j.ejpe.2017.02.005
3
hydrocarbon molecules and the reacting species of the treatment
solution for the different contaminants used in the study. The
results from correlation statistics at p < 0.05 as shown in Table 2
also indicates that there is substantive negative correlation
between TPH and time. The correlation statistics therefore further
supports the observe decrease in TPH with time.
The results from the kinetics studies are illustrated by the typ-
ical pseudo-first-order rate plots of Ln[B]o Ln[B]t against time
from the experimental kinetics data and represented in Fig. 5.
The plots show good linearity as regression coefficient in each case
with a value >0.9 and the kinetics data adequately fit into the
kinetics model being tested and satisfy the conditions for
pseudo-first order reactions. The actual pseudo-first order rate
constants of the plots obtained from the results of the surfactant
enhanced remediation processes for crude oil, diesel and kerosene
contaminated groundwater samples were calculated as 1.80  104;
1.78  104; 1.53  104 mg 1 L h 1 respectively at 30 °C. The per-
cent reduction in total petroleum hydrocarbon was 89.11% for
the crude oil treated samples, 93.21% for the diesel treated samples
and 87.76% for the kerosene treated samples after 6 h of remedia-
tion. The background TPH as crude oil, kerosene and diesel was
found to be within the range of 22–30 mg/L in the three control
samples used in the study (Table 4); an indication that the ground-
water is not completely free from hydrocarbons. This range is not
within the recommended limit of 10 mg/L allow by W.H.O. [14].
The outcome of the analysis of variance (ANOVA) on the kinetics
result in Table 3 showed that there is significant TPH reduction
for the three contaminants in the surfactant enhanced processes.
This assertion is also supported by the percent statistics. The order
of efficiency and effectiveness of the surfactant enhanced process
for the three contaminants is given as: diesel > crude
oil > kerosene.
The results from the physicochemical properties of the control
groundwater sample, hydrocarbons contaminated groundwater
samples before remediation and after remediation is presented in
Table 4. The pH of the crude oil, diesel and kerosene contaminated
groundwater samples were in the range of 9.40–9.50 while that of
the control groundwater sample was 8.60 ± 0.06. After treatment
there is a slight drop in pH to a range of 8.60–9.50. The pH of the
treated diesel samples is restored at pH of the controlled ground-
water sample i.e. within the limit of 9.2 the pH set by FMENV,
[15]. The pH of the crude oil and kerosene treated samples are
found be higher than that of the control groundwater sample and
the limit set for pH by FMENV, [15]. Although pH usually has no
direct impact on consumers, it is one of the most important oper-
ational water quality parameter [14].
4 W.O. Medjor et al. / Egyptian Journal of Petroleum xxx (2017) xxx–xxx

Fig. 2. Plot of % remediation of TPH against concentration of sodium dodecyl sulphate solution for the optimization study of diesel contaminated groundwater in surfactant
enhanced remediation process.

Fig. 3. Plot of % remediation of TPH against concentration of sodium dodecyl sulphate for the optimization study of kerosene contaminated groundwater in surfactant
enhanced remediation process.

Table 1 The electrical conductivity the control groundwater sample,

Data for optimisation of pH in enhanced surfactant remediation processes.
Treatment % remediation at pH = 3 % remediation at pH = 8
Crude oil + sample 61.88 60.58
Diesel + sample 63.20 63.06
Kerosene + sample 49.67 45.68
The turbidity of the control groundwater sample was
0.2 ± 0.00 NTU while the samples contaminated with crude oil, die-
sel and kerosene had turbidity values that were found to be very
high (1200 ± 4.98 NTU) for crude oil; (856 ± 2.34 NTU) for diesel;
(1124 ± 5.78 NTU). This high level of turbidity likely results from
the particular matter deposited from the sodium dodecyl sulphate
used in the treatment solution. After remediation although there is
sporadic reduction in the turbidity levels only the kerosene con-
taminated samples had turbidity value (4.80 ± 0.08 NTU) that is
within the limit (5.00 NTU) set by FMENV, [15] for turbidity. The
turbidity level for the crude oil treated samples were somewhat
high (205 ± 2.00 NTU) and above the limit (5.00 NTU) set by
FMENV, [15] for turbidity. The diesel contaminated samples had
very low turbidity level (9.94 ± 0.02 NTU) yet above the limit set
by FMENV, [15] (Table 4). The removal of particulate matter by
coagulation, sedimentation and by filtration is important in achiev-
ing safe drinking-water [14].
crude oil and diesel contaminated samples had same value of
100 ± 0.000 lS/cm but that kerosene contaminated sample had a
value of 300 ± 0.000 lS/cm. These values are within the limit
allowed for conductivity by FMENV, [15] (Table 4). These low elec-
trical conductivities values for the hydrocarbon contaminated
groundwater samples are likely due to non-polar environments
provided by the hydrocarbons that help in retarding the move-
ments and immobilizing of ions present in the solutions. The resul-
tant effect is reduce ionic mobility, velocity and electrical
conductivity. After remediation the conductivity of the treated
samples was in the range of 2400–3450 lS/cm and not within
the limit of 1200 lS/cm permissible for conductivity by FMENV,
[15]. The addition of sodium dodecyl sulphate from the treatment
solution introduced polar soluble salts which improve the non-
polar nature of the hydrocarbons with more pronounce ions mobil-
ity that allow the passage of electrical current and responsible for
the high conductivity values observe even after remediation.
The control groundwater sample had an alkalinity concentra-
tion of 148 mg/L while the crude oil, diesel and kerosene contam-
inated groundwater samples had values of 140, 132 and 136 mg/L
respectively as shown in Table 4. The decrease in the alkalinity val-
ues recorded after contamination is likely due to chemical interac-
tion between the acidic components of the contaminants and the
carbonates or hydroxyl ions present in the groundwater sample.

Please cite this article in press as: W.O. Medjor et al., Kinetics and physicochemical studies of surfactant enhanced remediation of hydrocarbons contam-
inated groundwater, Egypt. J. Petrol. (2017), http://dx.doi.org/10.1016/j.ejpe.2017.02.005
 W.O. Medjor et al. / Egyptian Journal of Petroleum xxx (2017) xxx–xxx 5

Fig. 4. Progress profile of TPH as crude oil, diesel and kerosene against time in surfactant enhanced remediation processes.

Table 2
Correlation statistical analysis between Time and TPH of hydrocarbons contaminated
groundwater in surfactant enhanced remediation processes.
TPH & Time N Correlation
Crude oil 7 -0.941
Diesel 7 -0.850
Kerosene 7 -0.879
P < 0.05.
After treatment alkalinity value for the crude oil samples was
164.00 ± 0.001 mg/L; 120.00 ± 0.010 mg/L for the diesel samples
and 124.00 ± 0.060 mg/L for the kerosene samples. These values
are found to be higher than the standard of 100 mg/L allow by
FMENV, [15].
The dissolved oxygen (DO) value of the control groundwater
sample was 7.30 mg/L while those of crude oil, diesel and kerosene
contaminated groundwater samples had value of 3.80, 3.55 and
3.20 mg/L respectively as shown in Table 4. The drop in the dis-
solved oxygen values after the groundwater samples were simu-
lated with the contaminants indicates pollution. Less microbial
activities is depicted by the high value of DO for the crude oil con-
taminated groundwater samples compare with those of diesel and
kerosene. The treated samples had DO value in the range of 4.55–
6.04 mg/L. This indicated significant improvements compare with
the control groundwater sample and within the 15 mg/L limit per-
Sig. missible by FMENV, [15].
0.002 The biochemical oxygen at day – 5 (BOD5) for the control sam-
0.015 ple was 2.8 ± 0.133 mg/L on contamination the value had increased
0.006 to 8.5 ± 0.133 mg/L, 7.39 ± 0.133 mg/L and 4.29 ± 0.133 mg/L for
the crude oil, diesel and kerosene samples in that order. The
BOD5 for the contaminated samples was in the range of 3.25–
3.76 mg/L. The sharp drop in BOD5 value for treated samples com-
pare to those of the polluted samples also corroborates the fact
that remediation has taken at place to a significant varying degrees
[16,17]. All the treated samples have their BOD5 values less than
4 mg/L and within the safe limit of 7.5 mg/L set by FMENV, [15]
(Table 4).
Chemical oxygen demand (COD) value for the control sample
was 524.00 ± 0.01 mg/L and on contamination with crude oil the
value had decreased to 244.00 ± 2.22 mg/L for crude oil samples;
270.00 ± 0.01 for diesel samples and 668.00 ± 0.05 mg/L for kero-
sene samples. The COD being a measure of the total oxidizable
organic matter is expected to increase on addition of the contam-
inants. The observe COD drop for crude oil contaminated ground-
water samples is possibly due to some aromatic hydrocarbons,

Fig. 5. Progress profiles of Pseudo – first order plots for TPH as crude oil, diesel and kerosene against time in surfactant enhanced remediation processes.

Please cite this article in press as: W.O. Medjor et al., Kinetics and physicochemical studies of surfactant enhanced remediation of hydrocarbons contam-
inated groundwater, Egypt. J. Petrol. (2017), http://dx.doi.org/10.1016/j.ejpe.2017.02.005
6 W.O. Medjor et al. / Egyptian Journal of Petroleum xxx (2017) xxx–xxx

Table 3
Analysis of Variance (ANOVA) of the three different contaminants (crude oil, diesel and kerosene) in enhanced surfactant remediation process.

Sum of Squares df Mean Square F Sig.

Between Groups 1835440.651 2 917720.325 4.531 .029
Within Groups 3038170.535 15 202544.702
Total 4873611.186 17

P < 0.05.

Table 4
Results from physicochemical properties of control groundwater sample, contaminated groundwater samples before and after treatments in surfactant enhanced remediation
process.

Parameters Groundwater Crude oil Diesel Kerosene Treated crude Treated diesel Treated FMENV,
Sample (Control) + groundwater + groundwater + groundwater oil sample sample Kerosene Sample (1991)
sample sample Sample
pH 8.60 ± 0.06 9.70 ± 0.010 9.50 ± 0.000 9.40 ± 0.050 9.50 ± 0.04 8.60 ± 0.05 9.50 ± 0.2 9.2
Conductivity 100 ± 0.010 100 ± 0.000 100 ± 0.000 300 ± 0.010 2400 ± 0.00 2400 ± 0.0 3450 ± 80.047 1200
(mS/cm)
Turbidity (NTU) 0.2 ± 0.000 1200 ± 4.98 856 ± 2.340 1124 ± 5.780 205 ± 2.00 9.94 ± 0.02 4.80 ± 0.08 5
Alkalinity (mg/L) 148.00 ± 0.01 140.00 ± 0.01 132.00 ± 0.000 136.00 ± 0.010 164.00 ± 0.01 120.00 ± 0.01 124.00 ± 0.06 100
Dissolved 7.29 ± 0.133 3.80 ± 0.000 3.55 ± 0.058 3.19 ± 0.000 5.02 ± 0.172 4.55 ± 0.000 6.04 ± 0.622 15
Oxygen (mg/
L)
BOD5 (mg/L) 2.80 ± 0.133 8.5 ± 0.066 7.39 ± 0.066 4.29 ± 0.000 3.76 ± 0.000 3.36 ± 0.116 3.25 ± 0.114 7.5
COD (mg/L) 524.00 ± 0.010 244.00 ± 2.22 270.00 ± 0.010 668.00 ± 0.050 6.22 ± 0.0001 37.15 ± 0.01 3.67 ± 0.000 10
COD/BOD5 – 28.71 36.54 155.71 1.65 11.06 1.13 –
Salinity (mg/L) 103.19 ± 0.000 60.29 ± 0.000 103.19 ± 0.000 188.99 ± 0.000 97.45 86.24 99.45 1600
Nitrate (mg/L) 148.00 ± 3.44 17.00 ± 0.01 16.00 ± 0.010 34.00 ± 1.220 1089.00 ± 0.000 1089.00 ± 0.000 1540.34 ± 34.689 50
Phosphate (mg/ 0.28 ± 0.001 0.37 ± 0.003 0.16 ± 0.004 0.34 ± 0.008 29.00 ± 1.13 30.00 ± 1.12 25.00 ± 1.110 0.02
L)
Ammonia (mg/L) 0.53 ± 0.001 0.28 ± 0.006 0.89 ± 0.005 0.42 ± 0.001 0.22 ± 0.0006 0.39 ± 0.0004 0.41 ± 0.0004 0.5
Total Dissolved 115.00 ± 8.086 180.00 ± 0.000 170.00 ± 0.000 160.00 ± 0.000 1080.00 ± 0.000 1245.00 ± 8.086 825.00 ± 8.086 500
Solids (mg/L)
Total Suspended 1.089 ± 0.003 1.387 ± 0.023 1.383 ± 0.024 0.846 ± 0.041 1.921 ± 0.393 1.229 ± 0.00 1.089 ± 0.003 10
Solids (mg/L)
Total Solids (mg/ 116.09 ± 7.76 181.39 ± 4.77 171.38 ± 5.55 160.85 ± 0.01 1081.92 ± 0.01 1246.23 ± 2.09 8226.09 ± 1.11 1500
L)
Cadmium (mg/L) 0.21 ± 0.001 0.20 ± 0.0006 0.45 ± 0.0004 0.33 ± 0.001 0.85 ± 0.01 0.29 ± 0.0001 0.240.0001 0.001
Chromium (mg/ 0.10 ± 0.000 0.70 ± 0.006 0.60 ± 0.006 0.40 ± 0.001 1.03 ± 0.0005 2.70 ± 0.001 5.80 ± 0.01 0.05
L)
Nickel (mg/L) 0.62 ± 0.0003 0.85 ± 0.0006 0.59 ± 0.0006 0.28 ± 0.001 1.18 ± 0.001 1.14 ± 0.001 1.52 ± 0.001 0.02
Lead (mg/L) ND ND ND 0.40 ± 0.001 ND ND ND 0.05
Mercury (mg/L) 0.37 ± 0.0006 0.23 ± 0.0005 0.42 ± 0.0006 0.29 ± 0.0001 0.68 ± 0.0001 0.58 ± 0.0006 0.18 ± 00001 0.02
Vanadium (mg/ ND ND ND ND 0.001 ± 0.0001 0.013 ± 0.00003 0.001 ± 0.0005 0.05
L)
Selenium (mg/L) ND ND ND ND 0.008 ± 0.0001 0.008 ± 0.00003 0.001 ± 0.0001 0.05
Arsenic(mg/L) 0.03 ± 0.0006 0.03 ± 0.0006 0.04 ± 0.0005 0.04 ± 0.0006 0.15 ± 0.0006 0.16 ± 0.0005 0.09 ± 0.0006 0.05
TPH(mg/L) 22.00–30.00 5018.25 ± 2.180 5199.26 ± 3.770 6896.22 ± 3.670 546.76 ± 4.50 353.19 ± 6.31 844.13 ± 14.99 10

straight-chain aliphatic and nitrogeneous compounds present in
crude oil that were not readily oxidizable. After remediation the
value of COD of the treated contaminated samples had drastically
dropped to 6.22 ± 0.000, 37.15 ± 0.01 and 3.67 ± 0.000 for crude
oil, diesel and kerosene samples respectively; an indicator that
remediation has occurred significantly. The low ratio of COD/
BOD5 1.13–11.06 of the polluted samples after remediation com-
pare to those of the polluted samples (28.71–155.71) which shows
low concentration of oxidizable organic matter is indicative that
remediation has occur.
The salinity level for the crude-oil, diesel and kerosene contam-
inated groundwater samples was between 60.29 and 188.99 mg/L
while the control groundwater sample had a value of
103.19 ± 0.000 mg/L. Salinity levels of the treated samples were
in the range of 1089.00–1540.34 mg/L and within the 1600 mg/L
recommended limit by FMENV, [15].
The control groundwater sample had nitrate concentration of
148.00 ± 3.44 mg/L while those of crude oil, diesel and kerosene
contaminated groundwater samples were 17 ± 0.010 mg/L,
16 ± 0.010 mg/L and 34 ± 1.22 mg/L respectively as shown in
Table 4. The high value of nitrate in kerosene contaminated
groundwater samples may be own to less pronounce oxidative
action of the acidic components in the kerosene constituents at
pH < 3 (pH = 3 being the optimum value. After remediation the
treated samples are found to have nitrate level in the range of
25–30 mg/L and within the 50 mg/L limit set by FMENV, [15].
The phosphate concentration in the control water sample was
0.28 mg/L while those of crude oil, diesel and kerosene contami-
nated water samples had concentrations of 0.37 mg/L, 0.16 mg/L
and 0.34 mg/L respectively. There is decrease in the phosphate
level in the crude oil contaminated groundwater samples compare
with that of the control groundwater sample while the values for
contaminated diesel and kerosene groundwater samples are
slightly higher (Table 4). All the contaminated samples have values
for phosphate that are not within the permissible limit set by
FMENV, [15] even after remediation.
The concentration of ammonia in the control groundwater sam-
ple was 0.53 mg/L while those of the crude oil, diesel and kerosene
contaminated groundwater samples were 0.28 mg/L, 0.89 mg/L
and 0.42 mg/L in that order. The low value of ammonia for crude
oil contaminated groundwater samples compare with that of the
control groundwater sample is probably own to chemical interac-

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inated groundwater, Egypt. J. Petrol. (2017), http://dx.doi.org/10.1016/j.ejpe.2017.02.005
 W.O. Medjor et al. / Egyptian Journal of Petroleum xxx (2017) xxx–xxx
tion between the ammonia in the groundwater samples and the
acidic components in crude oil. Up to 3% w/w of crude oil may
be acids of which naphthenic acids are most abundant [18]. The
control groundwater sample had ammonia content of
0.53 ± 0.001 mg/L but on contamination with hydrocarbons, a
range of 0.28–0.89 mg/L was obtained. The treated samples con-
taminated with crude oil and diesel were found to have values
for ammonia levels as 0.28 mg/L and 0.46 mg/L in that order and
within the safe limit of 0.5 mg/L allow by FMENV, [15]. Ammonia
in drinking – water is not of immediate health relevance. However,
ammonia can compromise disinfection efficiency, result in nitrite
formation in distribution systems, causes the failure of filters for
the removal of manganese and cause taste and odour problems
[14].
The total suspended solids (TSS) level for the control groundwa-
ter sample was 1.089 mg/L while the crude – oil, diesel and kero-
sene contaminated water samples had values of 1.39 mg/L,
1.38 mg/L, and 0.85 mg/L respectively as given in Table 4. The
introduction of crude oil and diesel into the groundwater samples
made the mediums to have non-polar hydrophobic environment
and decrease solubility for solutes present thus responsible for
the high values of TSS in comparison with the value of control
groundwater sample. The TSS values for the kerosene contami-
nated groundwater samples are low compared with the value for
the control groundwater sample. A plausible explanation to this
could be that other kinds of molecular interactions as well as lesser
non-polar-hydrophobic medium provided by the kerosene con-
taminant having shorter hydrophobic chain length than crude oil
and diesel. This may certainly have lead to the increase solubiliza-
tion of the solutes in the water-kerosene interface and decrease the
amount of TSS. After remediation there is significant increase in
TSS in the crude oil and kerosene treated samples while a decrease
is observe for the diesel treated samples. All the treated hydrocar-
bons samples have TSS level within the permissible limit of 10 mg/
L set by FMENV, [15] for TSS.
The concentration of the total dissolved solids in the control
groundwater sample was 115 mg/L while those of the contami-
nated groundwater samples ranged from 160–180 mg/L. After
remediation the higher values (825.00–1245 mg/L) of TDS may
have result from the sodium dodecyl sulphate used in the treat-
ment solution. The removal of hydrocarbons from the systems
eradicated the non-polar environment thereby increase the solubi-
lization of the solutes present and then lead to increase in the TDS
values. These values are far higher than the 500 mg/L safe limit set
for TDS by FMENV, [15]. TDS is not of concern at the levels found in
drinking - water. However, the presence of high levels of TDS in
drinking-water may be objectionable to consumers and may affect
acceptability of drinking - water [14].
The total solids ((TS) levels in all the treated samples were
observed to be high (1246.23–8226.09 mg/L) even after remedia-
tion. This is excepted since the TDS value obtained in this same
work was high and total solid is the sum of TSS and TDS. Total
solids values for all the treated samples are within the 1500 mg/L
value for total solids allow by FMENV, [15] for the treated crude
oil and diesel contaminated samples. However, the treated kero-
sene contaminated groundwater samples had very high value
(8226.09 mg/L) that is far the above the limit set by FMENV, [15]
for total solids.
Some heavy metals such as lead (Pb), vanadium (V) and sele-
nium (Se) were found beyond the level of detection in the control
groundwater sample as well as in the crude oil and diesel contam-
inated groundwater samples. The kerosene contaminated samples
had a level of 0.40 ± 0.001 mg/L for Pb, but the levels of V and Se
were also beyond the level of detection. After remediation the
levels of Pb and Se were beyond detectable level in all the treated
samples. Sodium dodecyl sulphate enhanced remediation process
Please cite this article in press as: W.O. Medjor et al., Kinetics and physicochemical studies of surfactant enhanced remediation of hydrocarbons contam-
inated groundwater, Egypt. J. Petrol. (2017), http://dx.doi.org/10.1016/j.ejpe.2017.02.005
7
is found very efficient and effective in the removal of Pb contami-
nant in kerosene contaminated groundwater samples. Vanadium
metal had level of 0.001 ± 0.0001 for the crude oil sample;
0.013 ± 0.000 for diesel treated samples and 0.001 ± 0.000 for ker-
osene treated samples. These values are found to be within the safe
limit of 0.05 mg/L allowed by FMENV, [15] for vanadium. Vana-
dium metal was neither found in the control groundwater sample
nor in the hydrocarbons contaminated samples suggest that the
vanadium metal must have been introduced from the treatment
solution.
Heavy metals levels increase significantly on contamination
with hydrocarbons (Table 4). After remediation 35.5% reduction
(Cd); 350% increment (Cr); 93.2% increment (Ni); increment
38.1% (Hg); 300% increment (As) were observed for treated diesel
contaminated samples. For the crude oil contaminated treated
samples reduction and increment of the metals after remediation
were: 325% increment (Cd); 47.0% increment (Cr); 38.0% increment
(Ni); increment 195.0% (Hg); 400% increment (As). Results for the
kerosene contaminated treated samples after remediation were:
27.3% reduction (Cd); 1350% increment (Cr); 442.9% increment
(Ni); 37.9% reduction (Hg); 125% increment (As). The heavy metals
levels of Cd, Cr, Ni, Hg and As in the hydrocarbons contaminated
groundwater samples are higher than the limits set for these met-
als by FMENV, [15]. Therefore all the treated hydrocarbons con-
taminated samples need post treatments after remediation in
terms of these heavy metals.
4. Conclusion
The application of surfactant enhanced remediation using
sodium dodecyl sulphate is found be very efficient, effective and
rapid in reducing total petroleum hydrocarbon as crude oil, kero-
sene and diesel as target contaminants. There is the need for
post-treatments after remediation for most of the physicochemical
parameters are impaired and do not meet the Guideline and Stan-
dards for Environmental Pollution Control in Nigeria set by Federal
Ministry of Environment and World Health Organization for drink-
ing water and agricultural uses in order to make them fit for these
purposes. In routine analysis the target contaminant, TPH as crude
oil, diesel and kerosene can be determined by molecular spec-
trophotometry via the use of UV/Visible spectrophotometer where
other instrument such as TPH analyzer is not available.
Funding
This research did not receive any specific grant from funding
agencies in the public, commercial, or not-for-profit sectors.
Competing interest
Authors have declared that no competing interests exist.
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Please cite this article in press as: W.O. Medjor et al., Kinetics and physicochemical studies of surfactant enhanced remediation of hydrocarbons contam-
inated groundwater, Egypt. J. Petrol. (2017), http://dx.doi.org/10.1016/j.ejpe.2017.02.005