Environment International 28 (2002) 79 – 82

www.elsevier.com/locate/envint

Determination of total petroleum hydrocarbons and heavy metals

in soils within the vicinity of facilities handling refined
petroleum products in Lagos metropolis
A.A. Adeniyi*, J.A. Afolabi
Department of Chemical Sciences, Lagos State University, Ojo, PMB 1087, Apapa, Lagos, Nigeria
Received 1 April 1999; accepted 14 December 2001

Abstract

This article discusses the determination of total petroleum hydrocarbons (TPH) and heavy-metal contamination in soils within areas of
refined petroleum products handling in Lagos metropolis. Soil samples were collected randomly from two petrol stations, two auto-mechanic
workshops, and a National Electric Power Authority (NEPA) station. Control samples were taken from two low-density residential areas.
TPH were estimated gravimetrically following standard methods of TPH analysis, while the heavy metals were determined by atomic
absorption spectrophotometry. Sites studied had higher levels of TPH and heavy metals compared to the control samples. For TPH, the petrol
stations have mean values of 399.83 ± 106.19 and 450.83 ± 90.58 mg/g, respectively; mechanic workshops, 362.60 ± 185.84 and
428.55 ± 119.00 mg/g, respectively; while the NEPA station has 356.20 ± 210.30 mg/g compared to the control mean of 26.63 ± 4.58. It
revealed that the improper handling of refined petroleum products are potential sources of soil contamination in the sampled sites. This is
indicated by the statistically significant levels of TPH and heavy metals observed between the control samples and those collected from
the petroleum products handling sites. Bioremediation using microorganisms and plants is recommended. D 2002 Elsevier Science Ltd.
All rights reserved.

Keywords: Contamination; Soil; Pollution; Total petroleum hydrocarbons (TPH); Heavy metals; Bioremediation

1. Introduction 1998; Massoud et al., 1996; Onianwa, 1995; Hewari et al.,

1995; Hasty and Revesz, 1994; Hayes et al., 1985).
The growth of the petroleum industry in Nigeria and the Petroleum hydrocarbons and heavy metals can impact
marketing of petroleum products have resulted in the soil ecosystems sufficiently to result in significant losses in
pollution of the environment by oil spills involving blow- soil quality (Coyne, 1999; Kelly and Tate, 1998; Amadi
outs, leakages from tanks or tanker trucks, and dumping of et al., 1996). Their negative impact results from their toxicity
waste petroleum products (Ogoke, 1996; Alloway and to biological processes catalyzed by soil microorganisms.
Ayres, 1994; Adekambi, 1989; Osibanjo et al., 1983). The Field studies of contaminated soils have demonstrated that
effects of such oil spills on the environment — human, elevated loadings of these contaminations can result in
livestock, wildlife, aquatic life, crop, and soil have been diminished microbial biomass, reduced viable bacterial
documented (Starr and Taggart, 1998; Martinez-Tabche population densities, inhibition of organic matter minerali-
et al., 1997; Amadi et al., 1996; Kinako and Zuofa, 1991; zation as well as decreased leaf litter decomposition (Testa,
Larsson et al., 1990). 1997; Roane and Kellogg, 1996; Chander and Brooks,
The analytical test procedures used to assess soil con- 1991), and mycorrhizal infection of clover (Trifolium sp.)
tamination by petroleum products are petroleum hydrocar- roots (Koomen et al., 1990).
bons and heavy metals determinations (Kelly and Tate, Remarkable accumulation of petroleum hydrocarbons
and heavy metals have been observed in organisms found
in contaminated soils (Nourteva and Elberg, 1999; Starr and
* Corresponding author. Taggart, 1998; Jinadasa et al., 1997; Adeniyi, 1996; Freed-
E-mail address: [email protected] (A.A. Adeniyi). man, 1996; Abdul-Rida, 1996; Dudka et al., 1996; Sotsky

0160-4120/02/$ – see front matter D 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 1 6 0 - 4 1 2 0 ( 0 2 ) 0 0 0 0 7 - 7
80 A.A. Adeniyi, J.A. Afolabi / Environment International 28 (2002) 79–82

et al., 1994). This have their attendant toxicological and 2.2. Chemicals
health implications as the pollutants find their way into
the complex food chain (Tchernitchin et al., 1998; Starr and Analytical grade reagents, silica gel (Kieselgel 60F254,
Taggart, 1998; Martinez-Tabche et al., 1997; Wu et al., 1997; 70 – 230 mesh) and metal standard stock solutions (1 mg
Albers, 1995; Chapman and Reiss, 1995). dm 3) were purchased from Aldrich, Merck, and Fluka.
Bioremediation techniques using plants and microorgan-
isms have been widely applied in cleaning up petroleum 2.3. Instrumentation
hydrocarbon and heavy-metals-polluted soils as most con-
taminants are usually transformed via natural processes to The determinations of the heavy metals were performed
innocuous compounds (Geller et al., 2000; Marwood et al. with the use of a Philips PY 9100x model atomic absorp-
1998; Kelly and Tate, 1998; Jackson and Pardue, 1997; tion spectrophotometer. The instrument’s setting and opera-
Cosmis, 1996; Ogoke, 1996; Olukoya, 1996). However, the tional conditions were done in accordance with the
degree of soil decontamination using bioremediation tech- manufacturer’s specifications. The instrument was cali-
niques depend largely on the nature and levels of heavy brated with analytical grade metal standard stock solutions
metals and petroleum hydrocarbons present in the soil (1 mg dm 3) in replicate. The mean, correlation coef-
(Marwood et al., 1998; Kelly and Tate, 1998; Amadi et al., ficient, slope, and RSD (%) of the standards and samples
1996; Hewari et al., 1995). were calculated.
The objective of this study was to examine the levels of
total petroleum hydrocarbons (TPH) and heavy metals — 2.4. Physicochemical analysis
cadmium, chromium, copper, lead, and nickel in soils within
the vicinity of facilities handling petroleum products and Soil moisture and pH were determined according to the
control samples from areas far from these locations in the methods enumerated by Adeniyi et al. (1993). The heavy
Lagos metropolis. This is expected to provide baseline data metals were extracted from the soil samples for analysis
that will assist in determining the level of remediation such using 2 N HNO3 following the methods reported earlier
adjoining soils may require over time as well as to alert the (Jinadasa et al., 1997; Adeniyi, 1996). The TPH in the
appropriate agencies on the need to formulate and enforce a samples were determined gravimetrically using 100 g air-
comprehensive environmental action plan for Nigeria’s dried soil samples, 3 g KOH with reflux for 2½ h in 100 cm3
sprawling urban cities. methanol and cleaned up with a short silica gel column
(Kieselgel 60 F254, 70 –230 mesh) following the methods
described in Massoud et al. (1996), Hewari et al. (1995),
2. Materials and methods Onianwa (1995), and IOC (1982).

2.1. Samples
3. Results and discussion
Five sites were used (two petrol filling stations, two auto-
mechanic workshops all located at Ikoyi and one National Mean soil pH values ranged between 3.68 ± 0.82 and
Electric Power Authority (NEPA) Power Station at Ijora). In 6.90 ± 0.18 (Table 1). Except for the NEPA site, the values
addition to the control sites situated in two low-density areas for the other sites fall within the range of 6.00 – 7.00
(Ikoyi and Lagos State University Senior Staff Quarters). expected for most tropical soils (Adeniyi, 1996; Chukwuma,
Composite samples were collected randomly from each site 1996). The mean pH value of 3.68 ± 0.82 found for the
within a depth of 15 cm using a locally fabricated soil auger NEPA station samples may be attributed to the location of a
(screw down and pull). The refined products handled in the demineralization plant, which involves mineral acids in the
five locations are lubricants, gasoline (petrol), kerosene, and immediate vicinity of the NEPA station fuel dump.
diesel. The samplings were done between January and The mean percentage moisture content shown in Table 1
March 1998. reveals values ranging from 1.15 ± 0.95 to 7.69 ± 2.21. These

Table 1
Mean levels of TPH (mg/g) and heavy metals (mg/g) in the sampled soils
Heavy metals (mg/g)
Sample site pH Moisture content (%) TPH (mg/g) Cd Cr Cu Pb Ni
Control 6.90 ± 0.18 0.72 ± 0.04 26.63 ± 4.58 ND ND 0.19 ± 0.06 0.14 ± 0.14 ND
AP petrol station 6.89 ± 0.20 1.15 ± 0.95 399.83 ± 106.19 0.13 ± 0.27 0.31 ± 0.73 2.19 ± 0.69 11.67 ± 2.65 1.96 ± 2.57
Texaco petrol station 6.59 ± 0.25 4.52 ± 0.57 450.83 ± 90.58 0.01 ± 0.02 0.60 ± 0.92 1.30 ± 0.41 31.35 ± 18.65 0.49 ± 1.20
Auto-mechanic workshop (1) 6.90 ± 0.18 5.49 ± 0.41 362.60 ± 185.84 0.03 ± 0.05 1.79 ± 1.13 1.88 ± 0.66 10.73 ± 4.75 2.94 ± 3.35
Auto-mechanic workshop (2) 6.48 ± 0.50 5.37 ± 2.28 428.55 ± 119.00 ND 0.89 ± 0.98 0.89 ± 0.29 1.77 ± 0.38 0.98 ± 1.52
NEPA 3.68 ± 0.82 7.69 ± 2.21 356.20 ± 210.30 0.30 ± 0.22 4.76 ± 2.16 7.23 ± 2.53 19.59 ± 12.23 5.88 ± 3.72
 A.A. Adeniyi, J.A. Afolabi / Environment International 28 (2002) 79–82 81

Table 2
t Test (95% confidence level) of TPH and heavy metals vs. control
Sample site TPH Cd Cr Cu Ni Pb
AP petrol station 8.61 (1.81) 1.18 (1.81) 1.04 (1.81) 7.10 (1.81) 1.87 (1.81) 10.66 (1.81)
Texaco petrol station 11.47 (1.81) 1.22 (1.81) 1.60 (1.81) 6.63 (1.81) 1.00 (1.81) 4.10 (1.81)
Auto-mechanic workshop (1) 4.43 (1.81) 1.47 (1.81) 3.88 (1.81) 6.27 (1.81) 2.15 (1.81) 5.46 (1.81)
Auto-mechanic workshop (2) 8.27 (1.81) 0.00 (1.81) 2.22 (1.81) 5.91 (1.81) 1.58 (1.81) 10.51 (1.81)
NEPA 3.84 (1.81) 3.34 (1.81) 5.40 (1.81) 6.82 (1.81) 3.87 (1.81) 3.90 (1.81)
Figures in parentheses are the t tabulated values.

relatively low values are expected of tropical soils sampled and NEPA samples are (in mg/g): 0.13 ± 0.27, 0.01 ± 0.02,
during the dry season (Adeniyi et al., 1993; Gill, 1991). The 0.03 ± 0.05, ND, 0.30 ± 0.22 for cadmium; 0.31 ± 0.73,
percentage moisture for the control samples is 0.72 ± 0.04. 0.60 ± 0.92, 1.79 ± 1.13, 0.89 ± 0.98, 4.76 ± 2.16, for chro-
This was found to be lower than values obtained from the mium; 2.19 ± 0.69, 1.30 ± 0.41, 1.88 ± 0.66, 0.89 ± 0.29,
sites in the petroleum products handling facilities, an indica- 7.23 ± 2.53 for copper; 11.67 ± 2.65, 31.35 ± 18.65,
tion of the volume of activities in these areas. 10.73 ± 4.75, 1.77 ± 0.38, 19.59 ± 12.23 for lead; and for
The results of the TPH are indicated in Table 1. The nickel 1.96 ± 2.57, 0.49 ± 1.20, 2.94 ± 3.35, 0.98 ± 1.52,
mean control value of 26.63 ± 4.58 mg/g are expectedly 5.88 ± 3.72, respectively. There are generally, statistically
lower than the mean values (mg/g) of 399.83 ± 106.19, significant differences (95% confidence level) among cad-
450.83 ± 90.58, 362.60 ± 185.84, 428.55 ± 119.00, and mium, chromium, copper, lead, and nickel levels in the
356.20 ± 210.30, respectively, for AP, Texaco, auto-mech- products handling samples compared with the control sam-
anic workshop (1), auto-mechanic workshop (2), and NEPA ples (Table 2). This is similar to the observations of Davies
station. A similar trend has been observed before (Chuk- (1997), Adeniyi (1996), and Markus and McBratney (1996)
wuma, 1996; Albers, 1995; Onianwa, 1995), which is an and may be taken as an indication of heavy metals pollution
indication of petroleum hydrocarbon pollution. It should be of the petroleum products handling sites. This is not unlikely
noted however, that the TPH value of 26.63 mg/g obtained as heavy metals are found associated with petroleum (Albers,
for the control sites is higher than the range of 1.00 –10.00 1995). It is worthy to note that the levels of cadmium and lead
mg/g earlier reported for unpolluted soils (Hewari et al., (Table 1) are particular high enough to cause public concerns
1995; Onianwa, 1995; Adekambi, 1989). This may not be since they are not required even in small amounts by living
unconnected with the incessant petroleum products scarcity organisms (Tchernitchin et al., 1998; Martinez-Tabche et al.,
experienced in Nigeria for many years up to the time of 1997; Freedman, 1996; Koomen et al., 1990).
sampling. The erratic petroleum products supply encourages With the indiscriminate location of refined petroleum
illegal storage of these products by city dwellers on an ad products handling facilities in Lagos metropolis and most
hoc basis in surface containers within residential areas. The Nigerian urban cities, without proper regulation and guide-
statistical data (Table 2) for TPH levels of control samples lines it is expected that TPH and heavy-metal contamination
against the petroleum products samples reveal a statistically may become widespread (Onianwa, 1995; Adekambi, 1989;
significant difference at 0 ± 95% confidence level, an indica- Osibanjo et al., 1983). There may be the need therefore to
tion that the sites are contaminated. Texaco filling station evolve a programme of bioremediation using plants and
recorded the highest level of significance. This may be microorganisms (Geller et al., 2000; Kelly and Tate, 1998;
attributed to the fact that the station is located in one of the Amadi et al., 1996; Cosmis, 1996) as a medium- and long-
busiest roads in Ikoyi and the volume of petroleum products term solutions to these potential problems of soil contam-
handled are enormous compared with the AP filling station. ination by refined petroleum products.
The sequence of TPH contamination established (Table 1) is
Texaco > auto-mechanic>control sites. This sequence is
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