Water-Energy Nexus 1 (2018) 134–141

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Water-Energy Nexus
CHINESE ROOTS
GLOBAL IMPACT
journal homepage: www.keaipublishing.com/en/journals/water-energy-nexus/

Remediation of hydrocarbons contaminated groundwater by silica

encapsulation technique
W.O. Medjor a,⇑, V.O. Akpoveta b, Medjor Eunice Adebowale c
a
Department of Chemistry, Taraba State University, Jalingo, Nigeria
b
Department of Chemical Sciences, Ondo State University of Science & Technology, Okitipupa, Nigeria
c
Department of Civil Engineering, Taraba State University, Jalingo, Nigeria

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

Article history: Silica encapsulation technique was investigated for effectiveness as a green remediation technology for
Received 21 September 2018 the cleanup and restoration of hydrocarbons contaminated groundwater. Optimum conditions of pH,
Revised 21 December 2018 contact time, and the concentration of the treatment solution for each of the contaminants were known.
Accepted 23 December 2018
After testing different kinetics models, the pseudo-first-order kinetics gave the best result in each case
Available online 24 December 2018
with the regression coefficient in the range of 0.9964–0.9988. Rate constants of 2.56
102, 2.70
102
and 1.23
102 mg1 L h1 were obtained from the kinetics plots for crude oil, diesel and domestic pur-
Keywords:
pose kerosene in that order. The 82.34%, 86.24% and 97.58% reduction in chemical oxygen demand (COD)
Post-treatment
Pollution
for crude oil, diesel and domestic purpose kerosene contaminated samples respectively at the end of the
Optimum residence time of 144 h depicts that remediation occurs significantly. Percentage reduction in total pet-
Rate constant roleum hydrocarbon was in the range of 51.97–90.68%. The material data sheet of the reagents used indi-
Pseudo-first-order kinetics cates low toxicity. The encapsulated hydrocarbon in the silica coating is stable even in extreme acidic and
basic states. At the end of the remediation only dissolved oxygen, biochemical oxygen demand, nitrates
and ammonia as physicochemical parameters were within the safe permissible levels set by the Federal
Minstry of Environment, Guideline and Standards for Environmental Pollution Control in Nigeria while
others were not and therefore the need for post-treatment in order to make the treated contaminated
groundwater safe for drinking and agricultural use.
Ó 2019 The Authors. Production and hosting by Elsevier B.V. on behalf of KeAi Communications Co., Ltd.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-
nd/4.0/).

1. Introduction devastating effects of oil pollution as a result of oil spillage have

Our planet, the earth is sufficiently rich in water, which
accounts for 75% of its surface. Water is indispensable for the sur-
vival of both plants and animals lives. 97.2% of water available is
located in the oceans, highly salty and can only be used by human
beings after desalination. Polluted water particularly with hydro-
carbons is unsafe for human consumption and accounts for most
of the water-borne diseases (Sunita, 2012). The world today is
heavily industrialised. Crude oil and its derivatives serve as fuel
for industrial machinery, cars, trucks, trains, airplanes and as start-
ing raw material for most petrochemical industries (Obire and
Putheti, 2009). This huge demand for crude oil is responsible for
the extensive exploration, exploitation, refining, production and
transportation which in turn resulted in gross pollution of the envi-
ronment (soil, surface and groundwater). This is no doubt that the
⇑ Corresponding author.
E-mail address: weltime.medjor@tsuniversity.edu.ng (W.O. Medjor).
environmental negative impact and ecological consequences on
humans, aquatic and plants lives as documented in the recent
ranking of environmental issues in the Niger Delta region of Nige-
ria by the World Wildlife Fund (World wildlife Fund, 2006). The
survey indicated that human interference with the geological
endowments of the region led to environmental problems. This
assertion was buttressed by Gbadagesin (1997) who also reported
that apart from loss of fishing ponds and farmlands, oil spills have
led to extensive deforestation with the aftermath effect of shorten
fallow periods, land degradation, destruction of lives and proper-
ties coupled with incessant crises in the Niger Delta region, where
the bulk of exploitation, exploration and oil production takes place.
Many technologies are available for the remediation of contami-
nated or polluted water. These remedial measures include: floating
barriers and skimmers, dispersants, solvents and/or detergent
chemicals, and burning (Sharma and Reddy, 2004). Chemical reme-
diation through the use of liquid, oil dispersant agents is the most
frequently employed clean-up method because such liquids can be

https://doi.org/10.1016/j.wen.2018.12.001
2588-9125/Ó 2019 The Authors. Production and hosting by Elsevier B.V. on behalf of KeAi Communications Co., Ltd.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
 W.O. Medjor et al. / Water-Energy Nexus 1 (2018) 134–141
readily applied to large oil spills and because this method is gener-
ally more cost-effective than physical remediation methods. Most
of the more effective methods of chemically remediating oil spills
involve the use of various surfactant compositions.
In the bid of finding adequate, efficient and effective cleanup
methods for hydrocarbons contaminated groundwater many green
technological remedies have been used in recent years (Arocha
et al., 1996). Although the silica encapsulation technique is not a
new method in the treatment of groundwater contaminated with
hydrocarbons, in most cases often optimum conditions are omitted
in literature. The aim of the present study is to establish the effec-
tiveness of silica encapsulation as a green technology in the reme-
diation of hydrocarbons contaminated groundwater with specific
optimum operational conditions properly documented as a contri-
bution to the existing knowledge base.
This aim is achieved by the following objectives:
(a) To apply silica encapsulation as a green technology to reme-
diate groundwater samples contaminated with crude oil,
diesel (automotive gas oil) and domestic purpose kerosene
(DPK).
(b) To utilise the optimization process to find the optimum con-
ditions of pH and concentrations for the study of kinetics of
the remediation process.
(c) To determine the physicochemical characteristics of treated
and untreated contaminated groundwater.
(d) To compare the effectiveness of the silica encapsulation
technique on the groundwater contaminated with crude
oil, automotive gas oil and domestic purpose kerosene.
(e) To establish the practicability and environmental friendli-
ness of the silica encapsulation technique.
2. Silica encapsulation
The silica encapsulation process involves four unique chemical
reactions that are initiated by sodium silicate. These reactions have
been defined as:
2.1. Hydration/dehydration
Sodium silicate reacts with water to give silicic acid as depicted
in the reaction below:
Na2 SiO3 + H2 O + HCl ! Si(OH)4 + 2NaCl ð1Þ
2.2. Precipitation
Gelatinous precipitate which readily loses water form partially
hydrated silica by the addition of strong acid to the starting mate-
rial of sodium silicate as represented in Eq. (1). This precipitate is
dried to about 5% of its water content to obtain a porous silica
gel material.
n[Si(OH)4 + (OH)4 Si] ! n[(OH)3 Si—O—Si(OH)3 ] + H2 O ð2Þ
2.3. Gelation
The silica gel has large absorption capacity for water, benzene,
sulphur(IV)oxide, and also to encapsulate hydrocarbons in water.
n[(OH)3 Si—O—Si(OH)3 ] dried ! Silica gel
These reactions allow silicate to act as a: film binder, matrix
binder, chemical binder and surface charge modification. The addi-
tion of sodium dodecyl to the sodium silicate solution as a surfac-
tant was to reduce the surface tension and facilitate wetting and to
135
furnish an acidic medium for silica precipitation from the sodium
silicate solution. Silicate acts as a chemical binder by reacting
instantaneously with polyvalent metal cations such as Mg2+, Ca2+
Zn2+, Cu2+, Fe3+,Cd2+ Ni2+ etc. to form the corresponding insoluble
metal silicate (Mbhele, 2007; Mitchell and Pedersen, 2000).
3. Mechanisms of silica encapsulation
For hydrous silica, the pH dependent negative charge arises
from ionisation of the weakly acidic surface silanol groups (Si–
OH = Si–O– + H). Silica accepts a hydrogen ion to become a SiOH+2
site having a positive charge, or they release a hydrogen ion to
become SiO– site having a negative charge.
The chemical reactions are written as:
SiOH + Hþ (aq) ! SiOH2 þ
SiOH ! SiO + Hþ (aq)
The concentration of the SiOH+2 and SiO species depends on the
pH of the aqueous phase. The SiOH+2 species increases at pH < 7,
while the SiO species increases at pH > 7. It has been found that
silica encapsulation reaction begins with pH adjustment that initi-
ates the precipitation of hydrocarbons/ heavy metals from water
(including pore water in solid media) and conditions metal-
bearing surfaces in solid phases.
The precise mechanism of how hydrocarbons encapsulation
takes place is not fully understood. It seems the surfactant (sodium
dodecyl) orients itself with the hydrophobic portion towards the
hydrocarbon and the hydrophilic end towards the polar sites of
the hydrophilic silica (Fig. 1). Microencapsulation is observed
within a few minutes with the formation of precipitated agglomer-
ates of wet silica containing the contaminant (hydrocarbon/metal)
species in the micelle trapped inside the silica matrix in an approx-
imately neutral medium (Mbhele, 2007).
4. Materials and methods
The hydrocarbons used in this work as contaminants are Brent
crude oil, automotive gas oil (diesel) and domestic purpose kero-
sene (DPK).
4.1. Preparation of samples
Five plastic containers containing 90 mL of groundwater
each was simulated with ten mL of domestic purpose kero-
sene and adequately mixed using a magnetic stirrer to obtain
Fig. 1. Micelle and silica matrix formation during silica encapsulation process.
(Adapted from www.tepco.com.)
136 W.O. Medjor et al. / Water-Energy Nexus 1 (2018) 134–141
10% contamination. The process was repeated with crude oil
and diesel contaminants.
4.2. Control experiments
Groundwater samples containing none of the three hydrocar-
bons served as part of the control in this work. Nine plastic con-
tainers were each filled with 90 mL groundwater sample of
known hydrocarbon level for each of the contaminant in replicates
of three. Ten mL of DPK, diesel and crude oil was added to each of
the setup to produce 10% contamination. The simulated control
samples without the silica encapsulation treatments were left to
undergo remediation in the laboratory for an optimum time of
144 h. The total petroleum hydrocarbon in the contaminated sam-
ples were analysed following the method described by Wang et al.
(2011) with slight modifications of passing the filtrates through 5 g
of anhydrous sodium sulphate to remove water, impurities to
obtain clean and dried extracts as adopted by Medjor et al.
(2018a, 2018b). The TPH values were determined by Uv/visible
spectrophotometer (2007 Model, made in United Kingdom). The
instrument was first calibrated employing prepared standards
(10, 20, 40, 60, 80 and 100 mg/L) of TPH as domestic purpose ker-
osene at a wavelength of 310 nm. The procedure was repeated
using crude oil and diesel samples at wavelengths of 460 and
350 nm respectively.
4.3. Preparation of treatment solution
A mix of sodium silicate and sodium dodecyl sulphate in a ratio
of 1:2 dissolved in distilled water served as the treatment solution
in the study. Several concentrations of 10,000–90,000 mg/L were
prepared and left overnight to ensure proper dissolution.
5. Optimization study
5.1. Effect of concentration
Domestic purpose kerosene infected groundwater samples
were treated in the ratio of 1:1 with several concentrations of
sodium silicate and sodium dodecyl sulphate solutions and left
for 144 h to undergo remediation until extraction and analysis.
The samples were then poured into five different 250 mL separa-
tory funnels and allowed to settle for 30 min. After this period,
the DPK solution had separated into two layers: the aqueous and
the organic in the silica-dodecyl matrix. 50 mL of each of the
extract (aqueous portion) was decanted into a 150 mL separating
funnel. 10 mL of n-hexane was then added, shaken manually for
2 min and allowed to settle for 20 min with the stopper removed,
followed by extraction and determination of TPH as described in
Section 4.2. The entire procedure was repeated using crude oil
and diesel samples in turns.
5.2. Effect of pH
The pH of two sets of domestic purpose kerosene contaminated
groundwater samples were adjusted to pH = 3 and pH = 8 using
1 M H2SO4 and 1 M NaOH and treated with the optimum concen-
tration obtained in Section 5.1 this was followed by extraction
and analysis. The process was carried out again using diesel and
crude samples.
6. Kinetics study
The pH of domestic purpose kerosene contaminated groundwa-
ter samples were set to pH = 3 and treated with the optimum
concentrations of 30,000 mg/L of sodium silicate, and 60,000 mg/
L sodium dodecyl sulphate obtained earlier in Section 5.1. Several
extractions and analyses were carried out at different times until
optimum remediation was attained. The experiment was repeated
using diesel and crude oil samples. Optimum concentrations of
60,000 mg/L of sodium silicate; 120,000 mg/L of sodium dodecyl
sulphate and 20,000 mg/L of sodium silicate; 40,000 mg/L sodium
dodecyl sulphate were used for diesel and crude oil respectively.
We obtained the appropriate kinetics model that fits our kinetics
data by plotting Ln[A]o  Ln[A]t against time for the different
kinetics models.
Where: [A]o = Concentration of hydrocarbon before
remediation.
[A]t = Concentration of hydrocarbon after cleanup.
The gradients of the graphs represented the rate constants, k.
The actual pseudo-first-order rate constants for the three contam-
inants were calculated multiplying the values of the slopes from
the graphs with the optimum concentrations of the treatment
solutions in excess, [A]o in the optimization study for each of the
hydrocarbon contaminants.
7. Determination of physicochemical parameters
The physicochemical properties of the samples such as pH, con-
ductivity, turbidity, alkalinity, salinity, dissolved oxygen (DO), bio-
chemical oxygen demand (BOD), chemical oxygen demand (COD),
nitrate, phosphate, ammonia, total dissolved solids (TDS), total sus-
pended solids (TSS) and total solids (TS) were determined by stan-
dard methods as described by APA (American Public Health
Association, 1999) while heavy metal levels were obtained follow-
ing procedures adopted by Caroline et al. (2007).
8. Statistical analysis
Statistical analyses were carried out with the aid of Microsoft
Office Excel 2007 and IBM SPSS Statistic Version 23. Standard devi-
ations accounted for indeterminate errors. The analysis of variance
at P  0.05 was carried out using the means of the total petroleum
hydrocarbons reductions from the kinetics study for the three con-
taminants to ascertain if there exists any significant difference in
total petroleum hydrocarbon reduction at the course of the reme-
diation period. The hypotheses tested were:
Null (Ho): The means of the total petroleum hydrocarbons in the
course of the remediation for crude oil, diesel and domestic pur-
pose kerosene contaminated samples are equal.
Alternative (H1): The means of the total petroleum hydrocarbons
in the course of the remediation for crude oil, diesel and domes-
tic purpose kerosene contaminated samples are not equal.
9. Results and discussion
Crude oil polluted groundwater samples treated by silica encap-
sulation method using a concentration of 20,000 mg/L of sodium
silicate, and 40,000 mg/L of sodium dodecyl sulphate solutions
had an optimum remediation of 64.37%, and the outcome is dis-
played in Fig. 2.
In the case of diesel contaminated groundwater samples, there
was an optimum cleanup of 42.61% with an optimum concentra-
tion of 60,000 mg/L for sodium silicate and 120,000 mg/L sodium
dodecyl sulphate solutions (Fig. 3).
The silica encapsulation of domestic purpose kerosene infected
groundwater samples had an optimum remediation of 24.02%
when treated with 30,000 mg/L sodium silicate and 60,000 mg/L
sodium dodecyl sulphate solutions as depicted in Fig. 4.
 W.O. Medjor et al. / Water-Energy Nexus 1 (2018) 134–141 137

Phelelani, (Mbhele, 2007). Other workers have also established

Fig. 2. Plot of % remediation of TPH against concentration of (sodium silicate and
sodium dodecyl sulphate) solutions for the optimization study of crude oil
simulated water using silica encapsulation method.
Fig. 3. Plot of % remediation of TPH against concentration of (sodium silicate and
sodium dodecyl sulphate) solutions for the optimization study of diesel simulated
water using silica encapsulation method.
that in extremely high acidic conditions, the high concentration
of the H+ ions tends to compete with the contaminant for encapsu-
lation and hence decrease the rate of removal of the contaminants.
Fig. 5 shows the progress profiles of the plots of total petroleum
hydrocarbon against time. The total petroleum hydrocarbon
decreases with time for all the three contaminants, an indication
that there is an interaction between hydrocarbon molecules and
the species of the treatment solution. Correlation statistic also
shows a high negative correlation between TPH and time, giving
credence to the earlier assertion.
The linear equations for the pseudo-first order plots for TPH as
crude oil, diesel and domestic purpose kerosene in the profile of
the silica encapsulation method are given in Fig. 6. The kinetics
data in Table 2 adequately fit into the pseudo-first-order kinetics
models and satisfy the conditions that best describes the models
with the regression coefficient in the range of 0.9964–0.9988 (Fig. 6).
Rate constants of 2.56
102, 2.70
102 and 1.23
102 mg1 L h1
were obtained from the plots for crude oil, diesel and domestic
purpose kerosene in that order. These findings are consistent with
works of Phelelani (Mbhele, 2007) and Obielumani et al. (2017)
who also reported first-order-kinetics in their studies.
The analysis of variance result at P  0.05 shows that there was
a significant difference in the total petroleum hydrocarbon reduc-
tion for the three target contaminants in the course of the remedi-
ation period (Table 3).
The least significant difference (LSD) also indicates a substantial
difference in total petroleum hydrocarbons reduction between the
domestic purpose kerosene samples and those of crude oil and die-
sel samples while there was no appreciable difference in the total
petroleum reduction between the crude oil samples and those of
diesel. The order of TPH reduction is crude oil samples > diesel
samples > domestic purpose kerosene samples and suggests that

Fig. 4. Plot of % remediation of TPH against concentration of (sodium silicate and

sodium dodecyl sulphate) solutions for the optimization study of domestic purpose
kerosene simulated water using silica encapsulation method. Fig. 5. Progress profile of TPH as crude oil, diesel and domestic purpose kerosene
against time in silica encapsulation method.

The results of the pH of the treatment solutions showed that the

pH of the mixture of the sodium silicate and sodium dodecyl
sulphate solutions was basic (pH = 11.3). Remediation was more
slightly favourable at pH = 3 than pH = 8 (Table 1). These results
are in agreement with the work of a previous investigator

Table 1
Effect of pH in silica encapsulation method

Treatment % Remediation at % Remediation at

pH = 3 pH = 8
Crude oil + sample 24.02 23.38
Diesel + sample 42.61 37.00
Domestic purpose kerosene 64.37 61.72
Fig. 6. Kinetics profile of pseudo-first order plots for TPH as crude oil, diesel and
+ sample
domestic purpose kerosene in silica encapsulation method.
138 W.O. Medjor et al. / Water-Energy Nexus 1 (2018) 134–141

Table 2
Data for pseudo-first order plots for crude oil, diesel and kerosene in silica encapsulation method

Time/h TPH left as crude oil Ln [A]o/[B]t TPH left as diesel Ln[A]o/[B]t TPH left as domestic purpose kerosene Ln[A]o/[A]t
(mg/L) [A]t (mg/L) [A]t (mg/L) [A]t
0 5018.25 ± 7.75 – 5199.26 ± 10.70 – 6896.22 ± 35.98 –
3 2845.23 ± 2.95 0.5676 2133.83 ± 4.08 0.8906 5864.07 ± 3.89 0.1624
9 2620.71 ± 2.48 0.6498 2070.20 ± 3.88 0.9206 5711.29 ± 4.25 0.1888
18 2316.7 ± 2.38 0.7731 1979.11 ± 3.96 0.9656 5489.54 ± 5.96 0.2284
36 1810.39 ± 4.31 1.020 1808.77 ± 4.47 1.056 5071.54 ± 6.46 0.3076
72 1105.45 ± 2.19 1.513 1510.81 ± 4.35 1.236 4328.60 ± 8.64 0.4660
144 467.78 ± 2.18 2.373 1136.83 ± 3.77 1.520 3312.31 ± 3.67 0.7336

Table 3
Analysis of variance for the three contaminants used in the study

Sum of squares DF Mean square F Sig.

Between Groups 39605860.181 2 19802930.090 30.336 0.000
Within Groups 9791883.155 15 652792.210
Total 49397743.336 17

the treatment method is more effective and efficient in reducing
total petroleum hydrocarbon as crude oil and diesel samples and
least for the domestic purpose kerosene samples.
One plausible reason for the higher remediation as TPH
observed in the crude oil contaminated samples could be as result
of crude oil better interaction with the sodium dodecyl solution
and reduction in the oil–water interfacial tension and with the
facilitation of the formation of smaller oil droplets (NRC, 2005) in
comparison with those formed by diesel and domestic purpose
kerosene. This increases its solubility; efficiently mobilise the con-
taminant and subsequently a more effective encapsulation. The
main function of the sodium dodecyl as a surfactant is to reduce
the surface tension and facilitate wetting and to furnish an acidic
medium for silica precipitation from the sodium silicate solution.
Another tenable explanation could be as result of the presence of
acidic components in the crude oil. 3% w/w of crude oil consists
of acids of which naphthenic acids are most abundant. These acidic
components enhance precipitation of silica. Such acidic compo-
nents due their volatility are usually lost in the process of distilla-
tion and refining that produce other crude oil derivatives
(domestic purpose kerosene and diesel) therefore a more efficient
and effective encapsulation in the crude oil contaminated ground-
water samples.
A comparison of the percentage remediation of hydrocarbon
contaminated groundwater by silica encapsulation method with
the results obtained by other workers is summarised in Table 4
below:
These results especially for the crude and diesel contaminated
groundwater samples are favourably comparable with those
obtained in our studies.
The results of the physicochemical properties of the uncontam-
inated groundwater, contaminated groundwater, treated contami-
nated groundwater samples are represented in Table 5.
The pH values of the crude oil, diesel and DPK infected ground-
water samples were 9.7 ± 0.01, 9.50 ± 0.00 and 9.40 ± 0.05 in that
order while that of the uncontaminated groundwater sample was
8.60 ± 0.06. After remediation, there is a slight drop in the pH value
to 9.3 ± 0.01 for the crude oil contaminated samples and sharp
increase in those of the DPK and diesel contaminated samples
(Table 5). The readings are not within the limit allowed for pH
by FMEnv (1991). The pH does not have any direct impact on con-
sumers, but it is an indispensable operational water quality param-
eter (World Health Organization, 2011).
The groundwater sample had turbidity level of 0.2 ± 0.00 NTU
while those of the samples contaminated with crude oil, diesel
and domestic purpose kerosene had turbidity levels that were very
high relative to that of the unpolluted groundwater sample,
(1200 ± 4.98 NTU) for crude oil contaminated samples;
(856 ± 2.34 NTU) for contaminated diesel samples;
(1124 ± 5.78 NTU) for DPK polluted samples. These extremely high
values depict that the prepared groundwater samples are highly
contaminated compared to 100–275 NTU turbidity values for
highly polluted water reported by Rump (1999). The result after
remediation shows a drastic reduction in the turbidity value
although no reading is within the recommended limit of 5.00
NTU allowed by FMEnv (1991) (Table 5). Hence the need for
post-treatment to free the groundwater treated samples from par-
ticulate matter via sedimentation aided coagulation and filtration
in obtaining safe drinking water (World Health Organization,
2011).
The electrical conductivity of the unpolluted groundwater sam-
ple and the crude oil and diesel contaminated samples had the
same value of 100 ± 0.000 lS/cm while that of DPK contaminated
samples had an amount of 300 ± 0.000 lS/cm. The values are
within the allowable limit set for conductivity by FMEnv (1991)
(Table 5). The astronomically high range of electrical conductivity
between 4150 and 10,050 lS/cm after remediation may be due
to polar-environments provided by the ions in the treatment solu-
tions. The net effect is high ionic mobility, velocity and electrical
conductivity. These conductivities values of the treated samples
are quite more elevated than the 1200 lS/cm permissible limit
for conductivity allowed by FMEnv (1991).

Table 4
A comparison of the percentage remediation of hydrocarbons in water by silica encapsulation method with the results obtained by other workers

S/N Workers Title of work % Remediation of

hydrocarbon as TPH
1. Mbhele (2007) Remediation of soil and water contaminated by heavy metals and hydrocarbons using silica encapsulation >70%
2. Obielumani et al. (2017) Kinetics study of remediation of crude oil contaminated surface water by silica encapsulation 92.78%
3. Present work Remediation of hydrocarbons contaminated groundwater by silica encapsulation technique 51.97–90.68%
Table 5
Results of the physicochemical characterization of uncontaminated groundwater sample, contaminated samples and treated samples used in the study

Parameter Uncontaminated Crude oil Diesel Domestic purpose Treated crude oil Treated diesel Treated Domestic purpose FMEnv
groundwater sample + groundwater + groundwater kerosene + groundwater samples by silica samples by silica kerosene samples by standards
sample sample sample encapsulation encapsulation silica encapsulation
pH 8.60 ± 0.06 9.70 ± 0.01 9.50 ± 0.00 9.40 ± 0.05 12.60 ± 0.10 12.50 ± 0.01 12.40 ± 0.00 9.20

W.O. Medjor et al. / Water-Energy Nexus 1 (2018) 134–141

Conductivity (mS/cm) 100.00 ± 0.01 100.00 ± 0.00 100.00 ± 0.00 300.00 ± 0.01 4150.00 ± 8.05 10050.00 ± 10.03 5550.00 ± 7.95 1200
Turbidity (NTU) 0.2 ± 0.00 1200.00 ± 4.98 856 ± 2.340 1124 ± 5.78 25.27 ± 0.00 107.00 ± 0.01 68.03 ± 0.000 5.00
Alkalinity as CaCO3 (mg/L) 148.00 ± 0.01 140.00 ± 0.01 132.00 ± 0.00 136.00 ± 0.01 260.00 ± 0.01 500.00 ± 5.27 280.00 ± 3.39 100
Dissolved Oxygen (mg/L) 7.29 ± 0.13 3.80 ± 0.00 3.55 ± 0.058 3.19 ± 0.00 5.74 ± 0.07 6.46 ± 0.07 6.90 ± 0.18 15
BOD5 (mg/L) 2.80 ± 0.13 8.5 ± 0.07 7.39 ± 0.07 4.29 ± 0.00 5.63 ± 0.11 6.18 ± 0.00 3.95 ± 0.07 7.5
COD (mg/L) 524.00 ± 0.010 244.00 ± 2.22 270.00 ± 0.010 668.00 ± 0.050 43.1 ± 2.17 37.15 ± 1.43 16.12 ± 0.01 10
COD/ BOD5 – 28.71 36.54 155.71 7.66 6.01 4.08 –
Reduction in COD – – – 82.34 86.24 97.58 –
Salinity as chloride (mg/L) 103.19 ± 0.00 60.29 ± 0.00 103.19 ± 0.00 188.99 ± 0.00 1840.63 ± 34.71 4371.74 ± 34.69 2439.74 ± 37.11 1600
Nitrate (mg/L) 148.00 ± 3.44 17.00 ± 0.01 16.00 ± 0.01 34.00 ± 1.22 12.00 ± 0.01 16.00 ± 0.01 38.00 ± 0.00 50.00
Phosphate (mg/L) 0.28 ± 0.00 0.37 ± 0.00 0.16 ± 0.00 0.34 ± 0.01 0.58 ± 0.00 0.21 ± 0.00 0.16 ± 0.00 0.02
Ammonia (mg/L) 0.53 ± 0.00 0.28 ± 0.01 0.89 ± 0.01 0.42 ± 0.00 0.19 ± 0.00 0.25 ± 0.00 0.22 ± 0.00 0.5
Total Dissolved Solids (mg/L) 115.00 ± 8.086 180.00 ± 0.00 170.00 ± 0.00 160.00 ± 0.00 2120.00 ± 0.00 2000.00 ± 0.00 2100.000.00 500
Total Suspended Solids (mg/L) 1.09 ± 0.00 1.39 ± 0.02 1.38 ± 0.02 0.85 ± 0.04 1.46 ± 0.39 7.14 ± 0.00 2.62 ± 0.02 10.00
Total Solids (mg/L) 116.09 ± 7.76 181.39 ± 4.77 171.38 ± 5.55 160.85 ± 0.01 2121.46 ± 1.11 2007.14 ± 0.01 2102.62 ± 1.61 1500
Cadmium (mg/L) 0.21 ± 0.00 0.20 ± 0.00 0.45 ± 0.00 0.33 ± 0.00 0.29 ± 0.00 0.20 ± 0.00 0.14 ± 0.00 0.001
Chromium (mg/L) 0.10 ± 0.00 0.70 ± 0.01 0.60 ± 0.01 0.40 ± 0.00 0.20 ± 0.00 0.74 ± 0.00 0.83 ± 0.00 0.05
Nickel (mg/L) 0.62 ± 0.00 0.85 ± 0.00 0.59 ± 0.00 0.28 ± 0.00 0.87 ± 0.00 1.41 ± 0.01 0.20 ± 0.00 0.02
Lead (mg/L) ND ND ND 0.40 ± 0.00 ND 0.10 ± 0.00 ND 0.05
Mercury (mg/L) 0.37 ± 0.00 0.23 ± 0.00 0.42 ± 0.00 0.29 ± 0.00 0.39 ± 0.00 0.20 ± 0.00 0.09 ± 0.00 0.02
Vanadium (mg/L) ND ND ND ND 0.001 ± 0.00 0.001 ± 0.00 ND 0.05
Selenium (mg/L) ND ND ND ND ND ND ND 0.05
Arsenic (mg/L) 0.03 ± 0.00 0.03 ± 0.00 0.04 ± 0.00 0.04 ± 0.00 0.51 ± 0.00 0.48 ± 0.00 0.12 ± 0.00 0.05
TPH (mg/L) 22.00–30.00 5018.25 ± 2.18 5199.26 ± 3.77 6896.22 ± 3.67 467.78 ± 2.18 1136.83 ± 3.77 3312.31 ± 3.67 10.00

139
140 W.O. Medjor et al. / Water-Energy Nexus 1 (2018) 134–141
The unpolluted groundwater sample had an alkalinity level of
148 mg/L and those of crude oil; diesel and DPK contaminated
groundwater samples had values of 140 ± 0.001 mg/L,
132 ± 0.000 mg/L and 136 ± 0.01 mg/L respectively as shown in
Table 5. The interaction between the acidic components of the con-
taminants and the carbonates or hydroxyl ions present in the
groundwater samples resulted in the decrease in alkalinity. At
the end of remediation the values have increased significantly for
all treated samples (Table 5) and likely due to the alkaline nature
of the treatment solutions with a pH of 11.3. Therefore the need
for post-treatment in terms of alkalinity as the values are not
within the standard limit of 100 mg/L allowed by FMEnv (1991).
The dissolved oxygen level of the unpolluted groundwater sam-
ple was 7.30 mg/L. The contaminated samples had dissolved oxygen
values in the range of 3.20–3.80 mg/L (Table 5). The treated samples
had dissolved oxygen values in the level of 5.74–6.90 mg/L and this
shows close restoration back to its initial state before contamination
and within the 15 mg/L limit set by FMEnv (1991).
The biochemical oxygen at day-5 (BOD5) for the unpolluted
groundwater sample was 2.8 ± 0.133 mg/L, and on simulation with
the hydrocarbons, the values had increased to 8.50 ± 0.066 mg/L,
7.39 ± 0.066 mg/L and 4.29 ± 0.000 mg/L for crude oil, diesel and
DPK samples in that order. The BOD5 for the contaminated samples
after remediation was in the range of 3.95–6.18 mg/L. The
observed reduction in BOD5 values for treated samples compared
to those of the contaminated samples supports the fact that reme-
diation has occurred to some significant extent (Yavuz and Koparal,
2006; Saien and Nejat, 2007). The values are within the limit of
7.5 mg/L set by FMEnv (1991).
Chemical oxygen demand (COD) value for the unpolluted
groundwater sample was 524.00 ± 0.01 mg/L, and on contamina-
tion, with the hydrocarbons, the reading had decreased to
244.00 ± 2.22 mg/L and 270.00 ± 0.01 mg/L for crude oil and diesel
samples and elevated to 668.00 ± 0.05 mg/L for the domestic pur-
pose kerosene samples. The observed COD reduction is due to
not readily oxidizable aromatic hydrocarbons, straight-chain ali-
phatic and nitrogenous compounds that may be present in diesel
and crude oil. After treatment the value of COD for contaminated
samples had sporadically reduced to 43.1 ± 2.17 mg/L,
37.15 ± 1.43 mg/L and 16.12 ± 3.34 mg/L for the crude oil, diesel
and DPK samples respectively; a chemo-indicator that remediation
has occurred appreciably although the values are far higher than
the 10 mg/L limit set by FMEnv (1991). The ratio of COD/BOD5
for crude oil, diesel and DPK contaminated samples were 7.66,
6.01 and 4.08 in that order after remediation. These values are
low in comparison with those of the polluted samples (36.54–
155.71). This reading has a correlation with the significant reduc-
tion in chemical oxygen demand for the contaminants: 82.34%,
86.24% and 97.58% for the crude oil, diesel and domestic purpose
kerosene treated samples in that order and depicts significant
restoration to its initial state before contamination.
The salinity concentrations for the crude oil, diesel and domestic
purpose kerosene contaminated groundwater samples were in the
range 60.29–188.99 mg/L and the unpolluted groundwater sample
had a value of 103.19 ± 0.00 mg/L. Salinity level of the treated sam-
ples was exceptionally very high in the range of 1840.63–
4371.74 mg/L, probably as a result of contributions from the salts
used in the preparation of the treatment solution and are not within
the 1600 mg/L recommended limit by FMEnv (1991) for salinity.
The unpolluted groundwater sample had nitrate level of
148.00 ± 3.44 mg/L and those of crude oil, diesel and DPK contam-
inated groundwater samples had values of 17.00 ± 0.01 mg/L,
16.00 ± 0.01 mg/L and 34 ± 1.22 mg/L in that order (Table 5). The
high level of nitrate in DPK contaminated groundwater samples
is because of the less pronounced oxidative action of the acidic
components in the DPK constituents (Jones et al., 2001). The nitrate
levels were in the range of 12–38 mg/L and within the 50 mg/L
allowed by FMEnv (1991) for nitrate at the end of the remediation
period.
The phosphate level in the unpolluted groundwater sample was
0.28 mg/L while those of the contaminated groundwater samples
had a range of 0.16–0.37 ± mg/L. There is an appreciable drop in
the phosphate levels in the DPK infected groundwater samples after
remediation, but we observed an increase in the crude oil and diesel
samples (Table 5). All the treated samples have values for phos-
phate that were not within the allowable level by FMEnv (1991).
The unpolluted groundwater sample had an ammonia concen-
tration of 0.53 ± 0.001 mg/L, but on contamination with the
hydrocarbons, a range of 0.28–0.89 mg/L was obtained. After reme-
diation, there was an enhanced reduction in the ammonia content
in the hydrocarbons contaminated samples (Table 5) and within
the safe level of 0.5 mg/L set by FMEnv (1991). The failure of filters
needed for the removal of manganese in treatment plants is due to
the presence of ammonia, and it does not in any way pose any seri-
ous health challenge, but causes taste and odour problems (World
Health Organization, 2011).
The total suspended solids concentration for the groundwater
sample was 1.089 ± 0.00 mg/L and those of the crude oil, diesel
and domestic purpose kerosene contaminated groundwater sam-
ples had values of 1.387 ± 0.02 mg/L, 1.383 ± 0.02 mg/L and
0.85 ± 0.041 mg/L in that order (Table 5). The introduction of crude
oil and diesel into the groundwater samples in their respective
mediums helps to provide non-polar hydrophobic environments
and reduced solubility for the solutes present and is responsible
for the high value of TSS in comparison with the amount of the
unpolluted groundwater sample. The low total suspended solids
level for the DPK contaminated groundwater in contrast with the
value for the uncontaminated groundwater sample. A possible rea-
son could be that some other kinds of molecular interactions occur.
The lesser non-polar-hydrophobic medium offered by the DPK con-
taminant with shorter hydrophobic chain length than those of the
diesel and crude oil contaminants, led to the increased solubilisa-
tion of the solutes in the groundwater-DPK interface and reduced
concentration of TSS as also reported by earlier investigators
(Medjor et al., 2018a, 2018b). There is an increase in total sus-
pended solids in the hydrocarbons treated samples at the end of
remediation. All the processed hydrocarbons contaminated sam-
ples with TSS range of 1.46–7.14 mg/L is within the permissible
limit of 10 mg/L allowed by FMEnv (1991).
The level of the total dissolved solids (TDS) in the unpolluted
groundwater sample was 115.00 ± 8.09 mg/L, and those of the con-
taminated groundwater samples ranged from 160 to 180 mg/L.
After remediation, the treated samples had a TDS range of 2000–
2120 mg/L. These high values observed for TDS is due to the high
level of dissolved salts in the treatment solution and much higher
than the safe concentration of 500 mg/L set by FMEnv (1991). The
presence of high level of TDS in drinking-water makes it unattrac-
tive to the consumers and therefore affects its acceptability as
drinking water (World Health Organization, 2011).
The total solid (TS) of the unpolluted groundwater sample was
116.09 ± 7.76 mg/L. After contamination with the hydrocarbons,
the total solid was in the range of 160.85–181.39 mg/L. After reme-
diation, the samples had TS range of 2007.14–2121.46 mg/L. These
values are much higher than the 1500 mg/L safe limit set by FMEnv
(1991).
The levels of lead (Pb), vanadium (V) and selenium (Se) were
undetectable in the unpolluted groundwater sample except for
the DPK contaminated sample (Table 5). The levels of V and Se
were beyond detectable levels in all the treated samples. Similarly,
the concentrations of Pb and Se were also negligible in the crude
oil, and domestic purpose kerosene treated samples. The diesel
treated samples had values of 0.1 ± 0.00 mg/L. Vanadium metal
 W.O. Medjor et al. / Water-Energy Nexus 1 (2018) 134–141
was beyond the level of detection in all treated samples and within
the safe concentration of 0.05 mg/L allowed by the FMEnv (1991).
Vanadium metal was beyond the level of detection in the unpol-
luted groundwater samples, and the hydrocarbon contaminated
groundwater samples suggest that the vanadium metal was pre-
sent in the treatment solution. The heavy metals concentrations
of Ni, Cd, and Hg in all the treated samples were not within the safe
limits set by FMEnv (1991).
Although some metals showed significant remediation with the
silica encapsulation method, generally hydrocarbons have negative
effects on the encapsulation of heavy metals. This may be as a
result of the formation of metal complexes through complexation
and chelation in the presence of hydrocarbons (Mbhele, 2007).
10. Conclusion
The controlled experiments ensure high internal validity for the
study; hence relationships between time, pH, concentrations and
reductions in TPH were of interest. The study establishes optimum
conditions of pH, contact time and levels of silicate-dodecyl sul-
phate treatment solutions for each of the target contaminants.
The application of the silica encapsulation technique is quite effi-
cient and effective in reducing total petroleum hydrocarbon as
crude oil, DPK and diesel as target contaminants. The reagents used
have a low level of toxicity and are biodegradable thus pose no
serious threat to the environment. The material data sheet of the
reagents used indicates low toxicity. The encapsulated hydrocar-
bon in the silica coating is stable even in extreme acidic and basic
states. Only dissolved oxygen, biochemical oxygen demand,
nitrates, ammonia as physicochemical parameters are within the
safe permissible levels set by the Federal Minstry of Environment,
Guideline and Standards for Environmental Pollution Control in
Nigeria while others are not and thus the need for post-
treatment after remediation in order to make the treated ground-
water safe for drinking and agricultural use.
Silica encapsulation method seems to be better remediation
technologies than other chemical methods such as the Fenton
Oxidative since it does not emit green house gases. Other impor-
tant observations related to the performance of silica encapsula-
tion technology are:
 Encapsulation is by silica, an economic and environmentally
safe material whose physical and chemical characteristics
resemble soil, provides a metal and hydrocarbon impermeable
coating of the soil-sorbent mixture therefore exposure to the
environment poses no threat to the environment.
 Remediation is accomplished within a short period of time and
with minimal environmental disturbance.
 It is effective in the acidic environment.
 It can be used to remediate the environment contaminated by
both hydrocarbons and metals.
 The silica coating is stable over a broad pH range; contaminants
cannot be released even when the environment is subjected to
harsh acidic and basic conditions.
141
Conflict of interest
Authors declare that no conflict of interest exists among them.
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