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Concentrations of heavy metals and hydrocarbons in groundwater near

petrol stations and mechanic workshops in Calabar metropolis,
Southeastern Nigeria

Article  in  Environmental Geosciences · March 2007

DOI: 10.1306/eg.08230505005

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Concentrations of heavy AUTHORS
T. N. Nganje
Department of Geology,
metals and hydrocarbons in University of Calabar, PMB 1115, Nigeria;
ntonzi@yahoo.com
groundwater near petrol stations Therese Nganje received her B.Sc. degree in
geology, her M.Sc. degree, and her Ph.D. in
and mechanic workshops 2003 from the University of Calabar, Nigeria.
Nganje also holds a certificate in Geochim –
in Calabar metropolis, United Nations Educational, Scientific, and
Cultural Organization postgraduate training
southeastern Nigeria course on ‘‘Geochemical Exploration Methods
and their Environmental Applications’’ from
the Czech Geological Survey. She is currently
T. N. Nganje, A. E. Edet, and S. J. Ekwere a lecturer at the University of Calabar. Nganje is
a recipient of the European Association of Or-
ganic Geochemists Travel Award.

ABSTRACT A. E. Edet
Department of Geology, Univer-

sity of Calabar, PMB 1115, Nigeria
Groundwater and soil samples from 16 locations near petrol sta-
tions (PS) and mechanic workshops (MW) around Calabar, Nigeria, Aniekan Edet received his B.Sc. in geology
from the University of Calabar, Nigeria, his
were analyzed for heavy metals and hydrocarbons to determine
M.Sc. degree and his Ph.D. from the Univer-
their concentrations and assess the impact of the PS and MW on
sities of Ibadan and Calabar. Edet also holds a
groundwater in the area. Results show that mean concentrations
certificate in hydrogeology from the University
of arsenic, cadmium, chromium, copper, iron, mercury, manganese, of Tübingen in Germany. He is currently a
nickel, lead, and zinc in groundwater are higher than the reference professor at the University of Calabar. Edet is a
data (maximum admissible concentration, baseline value, and con- recipient of awards from the Nigerian Mining
trol site value). The mean concentration of total organic content in and Geosciences Society, the German Aca-
soil is low (4.03%), but the mean concentrations of total petroleum demic Exchange Service, the Alexander von
hydrocarbons (46.87 mg kg  1) and naphthalene (340.00 mg g  1) in Humboldt (AvH) and the Commonwealth
the soil are high in comparison to the reference data. The mean Fellowship.
concentrations of parameters in soil and groundwater are higher
S. J. Ekwere
Department of Geology, Uni-
where PS and MW are located near each other (PS/MW). The mean versity of Calabar, PMB 1115, Nigeria
total hydrocarbon content (0.66 mg L  1) and total polycyclic aro-
P S. J. Ekwere received his B.Sc. and his M.Phi.,
matic hydrocarbon ( PAH) (66.64 mg L  1) in groundwater are
degrees and his Ph.D in geology from the
higher than the maximum admissible concentration of 0.1 mg L  1
University of Ibadan. He is currently a
and 0.2 mg L  1, respectively. The concentration of PAH compounds professor of geochemistry and economic
with mean concentrations greater than 1 mg L  1 are of the order geology in the University of Calabar.
phenanthrene > anthracene > fluorene > benzo(b)fluoranthene-
benzo(k)fluoranthene pyrene > naphthalene. The ratios of phenan-
threne/anthracene, fluoranthene/pyrene, and benzo(a)anthracene/ ACKNOWLEDGEMENTS
chrysene and factor analysis indicate several sources for the PAH. The authors thank P. Grathwohl and the staff
The most important sources include anthropogenic (petrogenic, of the Hydrogeology Unit, Institute for Geology,
pyrolytic) and natural. University of Tübingen (Germany) for litera-
ture and analyses. The financial assistance to
T. Nganje by the European Association of Or-
ganic Geochemists is acknowledged. The finan-
cial assistance by Alexander von Humboldt
and field equipment by the German Academic
Copyright #2007. The American Association of Petroleum Geologists/Division of Environmental Exchange Service made literature and field
Geosciences. All rights reserved. measurement possible.
DOI: 10.1306/eg.08230505005

Environmental Geosciences, v. 14, no. 1 (March 2007), pp. 15 – 29 15

INTRODUCTION
The Calabar urban area in southeastern Nigeria (Figure 1)
is underlain by extensive unconfined and semiconfined
aquifers that provide more than 80% of all the water
used in the area. The major soil types include sandy loam,
sandy clayey loam, and loamy sand. The organic carbon
content and the cation-exchange capacity of the soil
range from 0.5 to 1.52% and from 5.0 to 10.2 meq/100 g,
respectively (BICL, 1989). These values are low, indicating
that soils have very poor ability to retain contaminants.
This, coupled with the loose sand and gravel, forms
the major component of the aquifer and makes the
groundwater very vulnerable to surface contaminants.
Waste disposal has been widely recognized as a major
source of groundwater contamination throughout the
Figure 1. Sample location
map of the study area.
16 Heavy Metals and Hydrocarbons in Groundwater in Calabar, Nigeria
world, particularly disposal at sites that are unlined and
have a large component of liquid waste (Appleyard,
1996).
Calabar has witnessed an increase in the volume of
traffic since 1987 by more than 100-fold. This increase
has correspondingly led to an increase in the number of
petrol stations (PS) and mechanic workshops (MW).
Wastes resulting from the day-to-day operations of these
facilities are poorly managed, including illegal dump-
ing and/or burial in shallow pits. Data on groundwater
quality near these facilities (MW, PS) are nonexis-
tent and, hence, need to be documented. This article
presents analytical results showing the concentration of
heavy metals and hydrocarbons in groundwater near
these facilities, outlines their possible sources and im-
pacts on the quality of groundwater in the area, and is
intended as a guide to future vulnerability assessment
of the aquifer.
The effects of metal and petroleum hydrocarbons
(HC) on the environment have been documented by
Forstner and Wittmann (1981), Benner et al. (1989,
1990), Merian (1991), Hillger and Griffiths (1992),
Baedecker et al. (1993), Bennett et al. (1993), Lewe
(1996), Kaplan et al. (1997), Ussenkov (1997), Ricking
and Terytze (1999), Wilcke et al. (1999), Pichtel et al.
(2000), Stigter et al. (2000), Yang (2000), Al-Awadi
et al. (2001), Liu et al. (2001), Tam et al. (2001), Mai
et al. (2002), Maskaoui et al. (2002), and Siegel (2002).
All these studies indicate that the effects of metal and
HC in the environment are highly disastrous.
In the study area, work has not been conducted
to assess the impact of these facilities on the ground-
water. The work of Udom et al. (1998) provided a gen-
eral overview of groundwater quality in Calabar using
physical and chemical parameters, and Ekpo et al.
(2000) characterized leachates and groundwater near
one new and two old waste disposal sites in Calabar.
Recently, Edet et al. (2002) described the baseline con-
centration of 14 major elements and 43 trace elements
in groundwater of the area. The works of Azumatullah
and Ekwere (1985), Ekpo (1985), Ntekim et al. (1993),
and Akpan et al. (2002) described the distribution of
heavy metals in water, sediment, and fish tissues of the
nearby Calabar and Cross Rivers (Figure 1).
STUDY AREA DESCRIPTION
Location and Climate
Calabar area lies between north latitude 4j150 –5j150
and east longitude 8j150 –8j250. The elevation in the
area ranges from less than 10 m (33 ft) above sea level
in the south to more than 100 m (330 ft) in the north.
The area is in the south equatorial climate zone of
Nigeria (Iloeje, 1999), characterized by double rainfall
maxima with mean annual rainfall in the range 1000 –
2000 mm (39–78 in.). The highest mean monthly tem-
perature is about 29jC and occurs between the months
of December and May. The average annual humidity
is in the range of 75 – 90%. During the study period,
the temperature, rainfall, and relative humidity ranged
from 22.7 to 33.4jC, 31.7 to 1113.4 mm (1.25 to
43.83 ft), and 77 to 88%, respectively. The vegetation
of the area, classified as tropical rain forest (Iloeje,
1999), is characterized by luxurious forest growth be-
cause of the combined effect of high temperature and
rainfall. The forest is evergreen, with trees that are
more than 10 m (33 ft) in height. Farming has reduced
30% of the area to secondary forest.
GEOLOGY AND HYDROGEOLOGY
The area is covered by sediments of Tertiary to Qua-
ternary age, referred to as the Benin Formation and
alluvium. The main lithologic units include lacustrine
and fluvial sands, pebble, clay, lignite of varying thick-
ness (coastal-plain sand unit), tidal and lagoonal sedi-
ments, beach sand, and alluvial soil (alluvium unit).
The coastal-plain sand unit forms the major aquifer
in the area. The aquifer is composed of unconsoli-
dated fine-medium-coarse-gravelly sand and gravel.
The groundwater is unconfined, but the occurrence of
clay of various thicknesses in places gives rise to a semi-
confined condition and multiaquifer system (Okereke
et al., 1998). Groundwater recharge is through precip-
itation and the surrounding Calabar and Great Kwa
River. The temperature of groundwater at the study
locations varied between 26.4 and 29.4jC with mean
and standard deviation (SD) of 28.64 and 0.81jC,
respectively. The electrical conductivity (EC) ranged
between 67 and 461 mS cm  1 (mean ± SD: 171 ±
103 mS cm  1), and the pH varied from 5.60 to 6.38
(mean ± SD: 5.91 ± 0.24). This indicates that the water
is fresh (EC < 1400 mS cm  1) and acidic (pH < 7). The
ranges of concentrations of the major cations are 0.11–
0.35 mg L  1 for sodium (mean ± SD: 0.17 ± 0.17), 1.7–
7.65 mg L  1for calcium (mean ± SD: 4.83 ± 1.59),
0.03–0.037 mg L  1 for potassium (mean ± SD: 0.13 ±
0.08), and 0.0–1.02 mg L  1 for magnesium (mean ±
SD: 0.25 ± 0.28). The concentration range of chloride,
sulfate, and bicarbonate are 3.0–25.38 mg L  1 (mean ±
SD: 11.78 ± 6.32 mg L  1), 0.25–5.50 mg L  1 (mean ±
SD: 1.91 ± 1.76 mg L  1), and 0.0 – 0.05 mg L  1
(mean ± SD: 0.02 ± 0.02 mg L  1), respectively. The
main hydrochemical facies is calcium chloride.
POLLUTION SOURCES
The major sources of pollution in the area generated
by the population are from homes and small-scale en-
terprises (e.g., market). Oil- and metal-related pollu-
tion are mainly from PS and MW. The sources of
pollution at a typical PS include leakage from under-
ground storage tanks, spills during unloading, and
other operations and dumping of waste in shallow
Nganje et al. 17
pits. However, the case of MW is complex because a Table 1. Total Organic Content (TOC) (%), Total Petroleum
typical MW consists of various artisans, including me- Hydrocarbon (TPH) (mg kg  1), and Naphthalene (NAPTH) (mg
chanics, auto electricians, panel beaters, spray painters, kg  1) in Soil
welders, vulcanizers, etc., at this facility. The waste from
Facility Location TOC TPH NAPTH
the MW, which is composed of metal scrap, battery,
paint welding product (carbide), spent oil and petrol, PS/MW* 1 6.05 404.80 3618.20
and other chemicals is indiscriminately disposed of. 2 1.85 1.40 221.85
3 2.85 45.60 62.68
4 3.95 23.98 25.83
METHODS 5 5.20 1.88 136.78
6 6.20 7.98 112.56
Groundwater and soil samples were collected from
16 locations within a radius of 50 m (164 ft) of PS and MW 7 3.90 4.39 312.83
MW. Sample locations 1–6 are characterized by both 8 5.60 3.23 104.93
PS and MW located near each other (PS/MW). Loca- 9 2.80 2.94 87.19
tions 7–11 and 12–16 are characterized by MW and PS, 10 4.85 1.80 137.15
respectively. In addition, one location that was free of 11 2.35 2.87 92.10
any such facility was also sampled and designated as the
control site (CNS). The groundwater samples were PS 12 5.30 2.51 111.93
collected from existing wells and boreholes. The soil 13 2.05 18.09 202.84
samples were collected up to a depth of 30 cm (12 in.) 14 3.55 8.94 72.75
below the ground surface using an auger and then mixed 15 5.30 218.35 49.30
to form a composite sample. 16 2.60 1.11 91.08
Groundwater temperature, EC, and dissolved oxy- Statistics Maximum 6.20 404.80 3618.20
gen were measured in the field using standard equipment. Minimum 1.85 1.11 25.83
The bicarbonate was determined by titration with HCl. Mean 4.03 46.87 340.00
Major ions were determined by flame photometer and SD 1.49 109.42 877.13
ion chromatography. The soil total organic content Control 2.58 0.81 6.63
(TOC) was determined following the method of Walkey
*PS = petrol station and MW = mechanic workshop.
and Black (1934). The total petroleum hydrocarbon
(TPH) in the soil was determined by gravimetric method.
The heavy metals in water, total hydrocarbon con-
tent (THC), and polycyclic aromatic hydrocarbon (PAH) The TPH in soils ranged from a low of 1.11 mg kg  1
in water were determined using AAS and GC-MS at location 16 (PS) to a high of 404.80 mg kg  1 at loca-
at the Institute of Geology, University of Tübingen tion 1 (PS/MW), with a mean value of 46.87 mg kg  1.
(Germany). Details of sample preparations for all the This range of values is higher than at the control site
analyses are contained in Nganje (2002). in which a concentration of 0.81 mg kg  1 was obtained
(Table 1). For the different facilities, the mean TPH var-
ied between 3.05 (PS) and 80.94 mg kg  1 (PS/MW).
RESULTS AND DISCUSSION Analysis of PAHs in soil of the area is limited to
naphthalene. The naphthalene concentration in soil
Soil Parameters ranged from 25.83 mg kg  1 at sample location 4 (PS/
MW) to 3618.00 mg kg  1 at location 1 (PS/MW), with
The TOC in soil samples ranged from 1.85% at loca- a mean concentration of 340.00 mg kg  1. The mean
tion 2 (PS/MW) to 6.2% at location 7 (MW), with a concentrations of naphthalene at the three facility types
mean value of 4.03% (Table 1). The low SD value in- were 696.32, 146.84, and 105.58 mg kg  1 for PS/MW,
dicates a uniform distribution. The mean values of TOC MW, and PS, respectively (Table 2). These values are
on facility basis varied from 3.76% for PS to 4.35% higher than that for the control site (6.63 mg kg  1),
P
for PS/MW (Table 2). These values are low, but higher and 20 total PAHs ( 20PAHs) (57–74 mg kg  1) were
than the reported range of TOC for Calabar soils obtained for some forest soils in Ghana (Wilcke et al.,
(0.12 – 2.03%; BICL, 1989). 1999).

18 Heavy Metals and Hydrocarbons in Groundwater in Calabar, Nigeria

 Table 2. Statistics of Parameter Concentration on Facility Basis

PS/MW MW PS

Standard Standard Standard

Maximum Minimum Mean Deviation Maximum Minimum Mean Deviation Maximum Minimum Mean Deviation

TOC 6.200 1.850 4.350 1.772 5.600 2.350 3.900 1.361 5.300 2.050 3.760 1.505
TPH 404.800 1.400 80.940 159.549 4.390 1.800 3.046 0.927 218.350 1.110 49.800 94.461
Naphthalene 3618.20 25.830 696.317 1433.00 312.830 87.190 146.840 94.812 202.840 49.300 105.580 59.066
As 0.039 0.022 0.030 0.006 0.033 0.022 0.027 0.005 0.030 0.028 0.029 0.001
Cd 0.004 0.002 0.004 0.001 0.014 0.002 0.005 0.005 0.004 0.003 0.003 0.001
Cr 0.176 0.130 0.152 0.016 0.174 0.131 0.148 0.016 0.162 0.048 0.119 0.043
Cu 0.689 0.392 0.543 0.102 0.620 0.480 0.553 0.059 0.547 0.400 0.489 0.060
Fe 0.226 0.164 0.197 0.021 0.331 0.179 0.247 0.054 0.276 0.167 0.210 0.043
Hg 0.003 0.001 0.001 0.001 0.002 0.001 0.001 0.001 0.004 0.001 0.003 0.002
Mn 0.383 0.056 0.122 0.128 0.155 0.049 0.111 0.042 0.135 0.018 0.088 0.049
N 0.041 0.032 0.036 0.003 0.0048 0.031 0.038 0.007 0.041 0.036 0.038 0.002
Pb 0.056 0.014 0.044 0.015 0.058 0.043 0.052 0.006 0.055 0.045 0.050 0.006
Zn 1.979 1.347 1.633 0.210 2.057 1.175 1.418 0.367 1.814 1.378 1.562 0.197
THC 1.010 0.290 0.672 0.323 0.870 0.520 0.682 0.130 1.010 0.400 0.602 0.256
Naphthalene NAPTH 0.522 0.005 0.348 0.297 18.987 0.610 9.773 12.959 11.150 0.158 3.848 6.324
Acenaphthylene ACENY 0.253 0.001 0.118 0.127 0.137 0.032 0.085 0.074 0.560 0.006 0.333 0.290
Acenaphthene ACEN 2.520 0.000 1.387 1.279 1.953 0.042 0.998 1.351 1.655 0.038 1.005 0.854
Fluorene FLUO 9.260 2.331 6.372 3.605 10.121 1.875 5.998 5.831 7.453 4.084 5.619 1.704
Phenanthrene PHEN 70.350 1.951 46.444 38.568 42.754 17.089 29.921 18.148 16.523 3.581 9.629 6.513
Anthracene ANTH 30.878 7.012 15.765 13.143 6.289 0.112 3.200 4.368 0.811 0.100 0.523 0.374
Fluoranthene FLUA 11.460 0.117 3.965 6.492 0.354 0.117 0.236 0.167 1.347 0.172 0.697 0.598
Pyrene PYR 11.632 1.309 4.953 5.793 10.807 1.095 5.951 6.868 5.057 4.027 4.624 0.535
Benzo[a]anthracene B(A)A 0.568 0.480 0.529 0.045 0.736 0.469 0.603 0.189 0.834 0.206 0.493 0.318
Chrysene CHRY 11.000 0.503 4.353 5.780 1.606 0.599 1.103 0.712 2.191 0.665 1.673 0.873
Benzo[b]fluoranthene- B(B)F-B(K)F 27.369 0.199 9.298 15.649 9.690 0.186 4.938 6.721 5.928 1.674 3.213 2.359
Nganje et al.

Benzo[k]fluoranthene
Benzo[a]pyrene B(A)P 13.105 0.104 4.453 7.493 0.124 0.009 0.067 0.081 0.186 0.064 0.121 0.061
Indeno[1,2,3-cd]pyrene IND 0.163 0.021 0.082 0.073 0.277 0.030 0.153 0.175 0.212 0.038 0.149 0.096
Dibenzo[ah]anthracene DIBE 0.616 0.003 0.215 0.347 5.180 0.844 3.012 3.066 0.438 0.242 0.312 0.110
Benzo[ghi]perylene B(GHI) 3.899 0.015 1.945 1.942 2.160 0.405 1.283 1.241 1.175 0.593 0.830 0.305
P
PAHs 110.231 90.561 100.042 9.854 68.417 65.384 66.900 2.144 39.682 23.425 33.075 8.545
19

TOC (%), TPH (mg kg  1), heavy metals (mg L  1), PAHs (mg L  1).
 The highest mean concentrations of TOC and
naphthalene in soils for the three facility types are in
the order PS/MW > MW > PS, and for TPH, the
order is PS/MW > PS > MW. The high values char-
acterizing the PS/MW may be attributed to the cu-
mulative effect of waste disposal from PS and MW,
which are located near each other. The high TPH con-
centration at PS relative to MW is caused by the very
high TPH (>100 mg kg  1) at location 15 in comparison
to other PS locations (12, 13, 14, and 16) with con-
centration of TPH < 20 mg kg  1. The sampled site at
location 15 was very close to a dump site. Sporstøl et al.
(1983), Wild and Jones (1995), and Wilcke et al. (1999)
have attributed a high concentration of naphthalene and
other PAHs in soils to spills and leakages of petroleum
product and fuel and specific emitters (e.g., generators).
Correlations between TOC, TPH, and naphtha-
lene with depth show significant negative relation
with correlation coefficient (r) in the range  0.77 to
 0.99. This clearly indicates a reduction in concen-
tration with depth. As the soil and geology have low
TOC, the retardation factor and sorption capacity are
ruled out. Therefore, the major factors responsible
for leaching into groundwater include the depth to wa-
ter table, the waste volume, and the method of waste
disposal.
Heavy Metals in Groundwater
Arsenic
Arsenic (As) ranged from 0.022 to 0.039 mg L  1 (mean
0.029 mg L  1, Table 3). The values are higher than the
control site CNS (0.022 mg L  1) and less than the max-
imum admissible concentration (0.05 mg L  1) and the
baseline of 0.07 mg L  1 values (Table 4). These values are
higher than the mean concentration of As (<1 mg L  1)
in most countries (Edmunds et al., 1989; Welch et al.,
2000). The mean concentration for the different facility
types ranged from 0.027 (MW) to 0.030 mg L  1 (PS/
MW) (Table 2). Major sources of As include auto ra-
diators and lead battery plates (Merian, 1991).
Cadmium
The concentrations of cadmium (Cd) in groundwater
are higher than the maximum acceptable concentra-
tion (MAC) at eight locations. The values ranged from

Table 3. Heavy Metals in Groundwater (mg L  1)

Parameters

Facility Sample Location As Cd Cr Cu Fe Hg Mn Ni Pb Zn

PS/MW 1 0.039 0.004 0.130 0.689 0.209 0.001 0.064 0.039 0.048 1.644
2 0.028 0.002 0.154 0.565 0.185 0.003 0.383 0.033 0.014 1.979
3 0.022 0.003 0.142 0.392 0.226 0.001 0.056 0.041 0.053 1.347
4 0.034 0.004 0.176 0.540 0.195 0.001 0.074 0.036 0.048 1.539
5 0.033 0.004 0.159 0.597 0.164 0.001 0.073 0.032 0.047 1.577
6 0.025 0.004 0.149 0.475 0.200 0.001 0.082 0.035 0.056 1.710
MW 7 0.023 0.014 0.174 0.512 0.331 0.001 0.155 0.044 0.043 2.057
8 0.033 0.002 0.147 0.620 0.242 0.002 0.104 0.031 0.056 1.224
9 0.022 0.002 0.149 0.604 0.179 0.001 0.145 0.034 0.049 1.235
10 0.033 0.004 0.137 0.480 0.244 0.002 0.104 0.034 0.058 1.175
11 0.025 0.003 0.131 0.550 0.239 0.001 0.049 0.048 0.052 1.398
PS 12 0.028 0.003 0.048 0.460 0.215 0.001 0.018 0.036 0.054 1.432
13 0.029 0.004 0.162 0.536 0.214 0.003 0.064 0.038 0.045 1.455
14 0.028 0.003 0.124 0.500 0.167 0.004 0.129 0.037 0.049 1.378
15 0.029 0.004 0.126 0.547 0.177 0.001 0.096 0.041 0.055 1.733
16 0.030 0.003 0.137 0.400 0.276 0.004 0.135 0.037 0.046 1.814
Statistics Maximum 0.039 0.014 0.176 0.689 0.331 0.004 0.383 0.048 0.058 2.057
Minimum 0.022 0.002 0.048 0.392 0.164 0.001 0.018 0.031 0.014 1.175
Mean 0.029 0.004 0.137 0.515 0.214 0.002 0.108 0.037 0.048 1.561
SD 0.005 0.003 0.029 0.095 0.042 0.001 0.077 0.004 0.010 0.273
Control 0.022 0.003 0.095 0.276 0.187 0.001 0.096 0.031 0.042 1.400

20 Heavy Metals and Hydrocarbons in Groundwater in Calabar, Nigeria

Table 4. Reference Quality Data for Groundwater

Leachate from Municipal Groundwater near Municipal

Parameters MAC* (mg L  1) Baseline Value** (mg L  1) Waste Dumpy (mg L  1) Waste Dumpy (mg L  1)

As 0.05 0.07 – –
Cd 0.003 1.25 0.00 – 0.06 0.001 –0.005
Cr 0.05 1.42 0.2– 1 0.01 –0.05
Cu 1.0 16.08 0.03 – 0.21 0.001 – 0.03
Fe 0.2 590 3.32 – 33.72 0.005 –2
Hg 0.001 – – –
Mn 0.05 40 – –
Ni 0.02 1.9 – –
Pb 0.015 5.84 0.1– 0.6 0.01 –0.05
Zn 5.0 0.2 0.48 – 10.5 0.26 –17.6
*MAC = Maximum acceptable concentration (Siegel, 2002).
**Edet et al. (2002).
y
Ekpo et al. (2000).

0.002 mg L  1 (locations 2, 8, and 9) to 0.014 ppm at Iron

sample location 7 (mean ± SD, 0.004 ± 0.003 mg L  1).
The mean concentration exceeds the MAC, base-
line value (BAV), and CNS values of 0.003 mg L  1,
1.25 mg L  1, and 0.003 mg L  1, respectively (Tables 3,
4). In comparison to leachate from a waste dump in the
area (Ekpo et al., 2000), Cd values in the present study
are lower and within the same range for groundwater
(Table 4). The mean values on facility basis ranged from
0.003 (PS) to 0.005 mg L  1 (MW). Cd is mainly asso-
ciated with batteries (Merian, 1991).
Chromium
The major source of chromium (Cr) is anticorrosive
chemicals (Merian, 1991). In this study, more than 90%
of the measured concentrations exceeded the MAC,
BAV, and the CNS values (Tables 3, 4), indicating a
positive influence of these facilities on water quality with
respect to Cr. The mean ± SD is 0.137 ± 0.0029 mg L  1
(Table 3). The mean concentration values on facility
basis ranged from 0.119 (PS) to 0.152 mg L  1 (PS/MW)
(Table 2).
Copper
The concentrations of copper (Cu) in groundwater
varied from 0.392 mg L  1 at location 3 (PS/MW) to
0.689 mg L  1 at location 1 (PS/MW). These values are
below the MAC but higher than the BAV and CNS val-
ues and for groundwater near a waste dump site includ-
ing the leachate (Tables 3, 4). The mean concentrations
are, respectively, 0.543, 0.553, and 0.489 mg L  1 for
PS/MW, MW, and PS, respectively.
Iron (Fe) ranged from 0.164 to 0.331 mg L  1 (mean ±
SD; 0.214 ± 0.042 mg L  1). The concentrations of Fe
are higher than the MAC in nine locations, but below
the BAV and the values for groundwater samples near
a dump site (Table 4). Data from water development
agencies (Cross River Basin Development Agency
[CRBDA]) on the concentration of Fe in groundwater
within the study area ranged from 0.03 to 3.30 mg L  1
(unpublished data). Udom et al. (1998) reported an
average of 1.02 mg L  1 for Fe. The sources of Fe in the
area maybe related to the lateritic nature of the ma-
terials underlying the topsoil and borehole construction
material because the reported historical values of Fe
are higher than those for the present study.
Lead
The concentrations of lead (Pb) ranged from 0.014 to
0.058 mg L  1 (mean ± SD; 0.048 ± 0.010 mg L  1).
The values are generally higher than the MAC, BAV,
and CNS values. The mean value is within the same range
for groundwater samples near the municipal dump site,
but lower than the Pb concentration of leachate from
the dump site. Mean values for the facilities varied from
0.044 (PS/MW) to 0.052 mg L  1 (MW).
Studies have shown that Pb emitted to the environ-
ment is mainly associated with the combustion of Pb-
rich petrol (Fergusson, 1992; Facchinelli et al., 2001).
In the study area, enhanced concentrations of Pb
were attributed to the indiscriminate disposal of car
batteries (Akpan et al., 2002) and anthropogenic in-
fluences (Ntekim et al., 1993).

Nganje et al. 21
Mercury
The concentrations of mercury (Hg) in groundwater
at six locations were higher than the MAC value of
0.001 mg L  1. For the different facility types, Hg
ranged from 0.001 (PS/MW, MW) to 0.003 mg L  1
(PS). Mercury binds strongly to organic components
in soil, so that mobility by leaching is minimized, and
contamination to groundwater is unlikely except at
municipal landfills (USEPA, 1984; Merian, 1991).
Manganese
The results presented in Table 3 show that the concen-
trations of manganese (Mn) ranged from 0.018 mg L  1
at location 12 (PS) to 0.383 mg L  1 at location 2 (PS/
MW), (mean ± SD; 0.108 ± 0.077 mg L  1). The mean
concentration value is higher than the MAC, BAV,
and CNS values. The mean values on a facility basis
range from 0.088 (PS) to 0.122 mg L  1 (PS/MW).
Historical data from water agencies show Mn concen-
trations to be in the range of 0.001–0.220 mg L  1
(CRBDA file report), whereas Udom et al. (1998) re-
ported an average value of 0.04 mg L  1 in groundwater
of the area. Data for the present study are higher, in-
dicating anthropogenic sources for Mn.
Nickel
The concentrations of nickel (Ni) ranged from 0.031 to
0.048 mg L  1 (mean ± SD; 0.037 ± 0.004 mg L  1). The
mean value is higher than all the reference data (MAC,
BAV) (Table 4). The ranges of values for each fa-
cility type are 0.033–0.041 mg L  1 (PS/MW), 0.031–
0.048 mg L  1 (MW), and 0.036–0.041 ppm (PS), re-
spectively. Merian (1991) reported that the toxicity of
Ni is low compared to Cr, Mn, and zinc (Zn).
Zinc
The concentrations of Zn in the groundwater (1.175 –
2.057 mg L  1) are within the range of the MAC and
BAV (Table 4). The mean value (1.561 mg L  1) is
higher than the CNS value, but within the range ob-
tained for groundwater and leachate samples near a
dump site. On a facility basis, the mean values ranged
from 1.418 (MW) to 1.663 mg L  1 (PS/MW).
Trends in Heavy-Metal Concentrations
The highest concentration of Cd, Fe, and Zn were
obtained at location 8 (MW). This represents 30% of
all the metals considered. The highest concentration
of As, Cr, Cu, Hg, Mn, Ni, and Pb were obtained at
locations 1 (PS/MW), 4 (PS/MW), 1 (PS/MW), 14 (PS),
2 (PS/MW), 11 (MW), and 10 (MW), respectively. This
22 Heavy Metals and Hydrocarbons in Groundwater in Calabar, Nigeria
shows no defined pattern for the individual sampled
locations. However, for facilities, the highest concen-
trations of heavy metals are mainly at the PS/MW (As,
Cr, Cu, and Mn) and MW (Cd, Fe, Ni, Pb, and Zn). This
may be attributed to bad yard practices and poor waste
management within these facilities especially at MW.
The effect is greater where PS and MW are located side
by side (PS/MW). In addition, depth to water table at
the sample locations in the southern part of the study
area, where most of the MW are located, is less than
20 m (66 ft), but is greater than 20 m (66 ft) in the
north where most of the PS are located. Thus, pollut-
ants are more likely to migrate faster to the ground-
water system in the south than in the north. This pro-
cess is accelerated by the low organic content of the
topsoil and high permeability of the overburden ma-
terial. In relation to the reference data (Table 4), most
of the heavy metals show higher concentrations than
the mean values.
Hydrocarbons in Groundwater
Total Hydrocarbon Content
The concentrations of the THC in the groundwa-
ter ranged from 0.29 mg L  1 at location 13 (PS) to
1.01 mg L  1 at location 2 (PS/MW) (Table 5). The
mean value (0.66 mg L  1) is higher than the CNS and
the World Health Organization maximum admissible
values of 0.5 and 0.1 mg L  1, respectively (Tables 2
and 4). The ranges of values at the different facility
types are 0.29 – 1.01 mg L  1 (mean 0.62 mg L  1) for
PS/MW, 0.52 – 0.87 mg L  1 (mean 0.682 mg L  1) for
MW, and 0.40 to 1.01 mg L  1 (mean 0.602 mg L  1) for
PS (Table 2), respectively. Elevated concentrations of
THC are related to indiscriminate disposal of spent pet-
rol and oil, especially in shallow pits at MW and leakage
of petrol and diesel from underground storage tanks
at PS.
Polycyclic Aromatic Hydrocarbons
P
The total concentrations of total 15 PAH ( 15 PAH)
ranged from 23.43 mg L  1 at sample location 14 (PS) to
110.23 mg L  1 at location 2 (PS/MW), with a mean
concentration value of 66.64 mg L  1. The concentration
is far in excess of the value at the CNS (0.25 mg L  1),
the USEPA maximum contaminant level of 0.2 mg L  1
in drinking water, and concentrations found in water at
some reference locations near petroleum-handling fa-
cilities (Table 6).
P
The higher PAH concentrations in the study area
are generally from facilities having poor yard practices,
 Table 5. Total Hydrocarbon Content (THC) (mg L  1) and Polycyclic Aromatic Hydrocarbons (PAHs) in Water (mg L  1)

Compound 2 4 5 10 11 13 14 16 Control Maximum Minimum Mean SD

NAPTH 0.0045 0.5176 0.5216 18.9366 0.6100 11.1500 0.1583 0.2363 0.2908 8.9366 0.0045 4.0169 7.1197
ACENY 0.0010 0.090 0.2530 0.0320 0.1370 0.0060 0.5600 0.4330 0.0006 0.5600 0.0010 0.1901 0.2089
ACEN 0.0000 1.6410 2.5200 0.0420 1.9530 0.0380 1.6550 1.3220 0.0000 2.5200 0.0000 1.1464 0.9881
FLUO 2.3312 9.2602 7.5240 1.8747 10.1206 7.4528 4.0837 5.3202 0.0042 10.1206 1.8747 5.9959 3.0858
PHEN 1.9510 70.3495 67.0325 17.0890 42.7538 8.7824 3.5805 16.5233 0.0595 70.3495 1.9510 28.5078 27.8454
ANTH 30.8784 9.4063 7.0115 0.1116 6.2892 0.1003 0.8110 0.6568 0.0138 30.8784 0.1003 6.9081 10.3510
FLUA 11.4599 0.3171 0.1171 0.1174 0.3542 0.1715 1.3472 0.5719 0.0248 11.4599 0.1171 1.8070 3.9212
PYR 11.6320 1.3087 1.9169 10.8074 1.0949 4.0267 4.7894 5.0571 0.0245 11.6320 1.0949 5.0791 4.0889
B(A)A 0.4801 0.5675 0.5387 0.4689 0.7364 0.2058 0.8344 0.4385 0.0193 0.8344 0.2058 0.5338 0.1914
CHRY 11.0000 1.5560 0.5030 0.5990 1.6060 0.6650 2.1910 2.1640 0.0250 11.0000 0.5030 2.5355 3.4869
B(B)F-B(K)F 27.3685 0.1987 0.3274 9.6903 0.1859 5.9284 1.6738 2.0356 0.0059 27.3685 0.1859 5.9261 9.2910
B(A)P 13.1049 0.1041 0.1503 0.0093 0.1240 0.0640 0.1134 0.1858 0.0019 13.1049 0.0093 1.7320 4.5957
IND 0.0211 0.0623 0.1627 0.0295 0.2766 0.0384 0.2118 0.1978 0.0003 0.2766 0.0211 0.1250 0.0990
DIBE 0.0032 0.0272 0.6160 5.1797 0.8440 0.4383 0.2417 0.2546 0.0000 5.1797 0.0032 0.9506 1.7324
B(GHI) 0.0145 3.8990 1.9209 0.4053 2.1604 0.5934 1.1746 0.7222 0.0014 3.8990 0.0145 1.3613 1.2622
P
PAHs 110.23 99.33 90.56 65.38 68.42 39.68 23.43 36.12 0.25 110.23 23.43 66.64 31.78
THC 1.01 0.98 0.89 0.62 0.73 0.40 0.41 0.50 0.05 1.01 0.40 0.70 0.25
Naphthalene (NAPTH), acenapthylene (ACENY), acenaphthene (ACEN), fluorene (FLUO), phenanthrene (PHEN), anthracene (ANTH), fluoranthene (FLUA), pyrene (PYR), benzo[a] anthracene(B[A]A), chrysene (CHRY),
benzo[b]fluoranthene-benzo[k]fluoranthene (B[B]F-B[K]F), benzo[a]pyrene (B[A]P), indeno[1,2,3-cd]pyrene (IND), dibenzo[ah]anthracene (DIBE), and benzo[ghi]perylene (B[GHI]).
Nganje et al.
23

Table 6. Range of PAH (mg L  1) in Water Near Oil-Handling
Facilities
Concentration Reference
0.004 – 0036 Fernandes et al. (1997)
0.001 – 24.83 Law et al. (1997)
1.160 – 13.68 Telli-Karakoc et al. (2002)
6.900 – 26.90 Maskaoui et al. (2002)
P
especially at MW. However, lower PAH concentra-
tions were recorded from locations near the facilities
with better yard practices as in most PS (locations 13–
16). Other possible sources of PAHs include sewage
and traffic; however, these were not documented dur-
ing the present study.
The dominant PAH compounds having mean con-
centrations greater than 1 mg L  1 include naphthalene
(NAPTH), acenaphthalene (ACEN), fluorene (FLUO),
phenanthrene (PHEN), anthracene (ANTH), fluor-
anthene (FLUA), pyrene (PYR), chrysene (CHRY),
benzo[b]fluoranthene-benzo[k]fluoranthene (B[B]F-
B[K]F), benzo[a]pyrene (B[A]P), and benzo[ghi]per-
ylene (B[GHI]). The mean concentration values of
two-, three-, four-, five-, and six-ringed PAHs are 4.02,
8.55, 2.49, 2.87, and 0.74 mg L  1, respectively. The dis-
tribution showed that the three rings dominantly ac-
count for more than 85% of the total. The compositional
pattern also shows that the two-ringed PAH (naphtha-
lene) is abundant in PS; the three-ringed PAHs (ace-
naphthylene, acenaphthalene, fluorene, phenanthrene,
and anthracene) are dominant in PS/MW and MW; and
the four-ringed (fluoranthene, pyrene, benzo[a]anthra-
cene, and chrysene), five-ringed (benzo[b]fluoranthene-
benzo[k]fluoranthene, benzo[a]pyrene, and dibenzo[ah]-
anthracene), and six-ringed (benzo[ghi]perylene) PAHs
are dominant at the PS/MW locations.
Statistical Analysis and Sources of Pollutants
Correlation
The correlation between the soil parameters (TOC,
TPH, NAPTH) is not significant. These parameters
P
also exhibit poor correlation with THC and PAH
in groundwater. However, 50% of the possible correla-
tions pairs between the metals in groundwater are sig-
nificant. Considering the relation between the indi-
vidual PAH compounds and metal, only 11% of the
possible correlation are significant. The generally in-
24 Heavy Metals and Hydrocarbons in Groundwater in Calabar, Nigeria
P
significant correlation between THC, PAHs, and the
metals in groundwater may be attributed to different
P
anthropogenic sources. The THC and PAHs are at-
tributed to crude-oil– related sources and fuel com-
bustion. The metals are caused by rubbish disposal and
incinerations consisting of old tires, paints, batteries,
metal scraps, etc.
Ratios
The sources of PAH in soils and sediments have been
assessed using the ratios between selected PAH com-
pounds (Gschwend and Hites, 1981; Readman et al.,
1987; Sicre et al., 1987; Colombo et al., 1989; Klamar
and Fomsgaard, 1993; Budzinski et al., 1997; Tam et al.,
2001). However, as soils are affected by groundwater
fluctuation (Wilcke et al., 1999) and recharge, the con-
centrations of PAH in groundwater may be explained
by leaching from soil during these processes. The leach-
ing process can be accelerated in a highly vulnerable
terrain such as the study area, which is underlain by
poorly sorted gravel and sand intercalated with silt and
clay.
The ratio values of phenanthrene/anthracene
(PHEN/ANTH) and fluoranthene/pyrene (FLUA/PYR)
have been used to determine the sources of PAH (Sicre
et al., 1987; Budzinski et al., 1997; Soclo et al., 2000).
According to Wise et al. (1988) and Benner et al. (1989,
1990), petroleum commonly contains more phenan-
threne relative to anthracene because PHEN is a thermo-
dynamically more stable tricyclic aromatic isomer than
ANTH; thus, a PHEN/ANTH ratio is observed to be
very high in PAH petrogenic pollution and low in py-
rolytic contamination cases (Gschwend and Hites, 1981;
Soclo et al., 2000; Yang, 2000). The PHEN/ANTH ratios
for crude oil and vehicle exhaust are, respectively, 50
and 4 (Yang et al., 1991). However, Gschwend and Hites
(1981), Colombo et al. (1989), and Budzinski et al.
(1997) suggested that the PHEN/ANTH ratios greater
than 10 and less than 10 represented petrogenic and
pyrolytic contamination.
The ratio of PHEN/ANTH for this study varied
between 0.06 and 170.00 (Table 7), indicating several
sources of PAH contamination. Large PHEN/ANTH
ratios (>10) were found at locations 10, 13, and 16,
indicating petrogenic contamination. At locations 2, 4,
5, 11, and 14, the PHEN/ANTH ratio values are in the
range of 4.45–9.57, indicating pyrolytic-derived PAH.
The different ratios may be attributed to the degree of
photodegradation, chemical degradation, or biodegra-
dation of PAH (Tam et al., 2001) and the volume of
waste generated.
Table 7. Comparison of Ratios of PHEN/ANTH, FLUA/PYR, and B[A]A/CHRY in Samples to Sources of Hydrocarbon

Sample Number/Source Location PHEN/ANTH FLUA/PYR B[A]A/CHRY

1 2 0.06 0.99 0.04

2 4 7.48 0.24 0.36
3 5 9.57 0.06 1.08
4 11 6.79 0.32 0.46
5 12 170.00 0.01 0.78
6 13 87.82 0.04 0.31
7 14 4.45 0.28 0.38
8 16 24.60 0.11 0.20
9 Control 6.00 1.00 0.66
Wood/coal fire* 3.00 1.0– 1.4 1.2– 5.0
Urban air* 8.0 –15.0 0.48 – 7.25
Crude oil* 50.00 0.6– 0.9
Marine activities** 0.84 1.40
Motor exhausty 4.0 –10.0
Crude-oil –contaminated sedimentsyy 0.8– 0.9
*Gschwend and Hites (1981).
**Maher and Aislabie (1992).
y
Yang et al. (1991).
yy
Colombo et al. (1989).

Sicre et al. (1987) also suggested that an FLUA/PYR
ratio of less than 1 was attributed to petrogenic sources,
and values greater than 1 were caused by pyrolytic origin.
For example, the combustion of coal and wood gave
FLUA/PYR ratios of 1.00–1.40 (Gschwend and Hites,
1981). River sediments contaminated by crude oil had
FLUA/PYR ratios of 0.80–0.90 (Colombo et al., 1989).
Therefore, the above ratios of PHEN/ANTH > 10 and
FLUA/PYR < 1 represent petrogenic origin, and PHEN/
ANTH < 10 and FLUA/PYR > 1 represent pyrolytic
origin.
In this study, groundwater samples from locations
10, 13, and 16 having ratio of PHEN/ANTH > 10 and
FLUA/PYR < 1 are considered to be of petrogenic
origin, whereas the samples from locations 2, 4, 5, 11,
and 14, with ratios of PHEN/ANTH and FLUA/PYR
< 10 and > 1, respectively, are of pyrolitic origin. The
samples from locations 2, 4, 5, 10, 11, 13, 14, and 16
represent a mixed pattern of petrogenic and pyrolytic
contamination.
The benzo[a]anthracene/chrysene (B[A]A/CHRY)
ratio has also been used to identify PAH sources. This
ratio tends to increase as petrogenic contribution tends
to decrease (Colombo et al., 1989). The B[A]A/CHRY
ratio in literature for crude and fuel oil ranges from 0.24
to 0.40 (Gschwend and Hites, 1981). In this study, the
B[A] A/CHRY ratio varied from 0.04 to 0.78 except
at location 5 (0.78), suggesting input from petrogenic
sources. Based on the B[A]A/CHRY ratio, the petro-
genic input of the PAHs at the sample locations in-
creases as follows: 5 > 10 > 11 > 4 > 13 > 16 > 2. This
is generally in agreement with the computed PHEN/
ANTH ratios.
The correlation between PHEN/ANTH and
FLUA/PYR is significant (r =  0.95, p = 0.0003).
However, the correlations between PHEN/ANTH and
FLUA/PYR ratios are better indicators of PAH sources
in groundwater of the area compared to the ratio of
B[A]A/CHRY.
Factor Analysis
To get more insight into the origin of the contami-
nants, the R-mode factor analysis was conducted. The
R-mode analysis provides several positive features that
allow the interpretation of the data set. By examining
the factor loadings, commonalties, and eigenvalues, those
variables belonging to a specific process can be identified,
and the importance of the process can be evaluated in
terms of total data set and in terms of each factor (Law-
rence and Upchurch, 1982; Jayakumar and Siraz, 1996).
In this study, five factors (Table 8) are considered, with
eigenvalues in the range 2.302 – 10.784 explaining
87.886% of the total percent variance (Table 8).

Nganje et al. 25
Table 8. Factor Loading for the Different Parameters clude rubbish disposal, bad yard practice, and emission
from cars and generator sets. For this factor, pyrolytic
Factor 1 Factor 2 Factor 3 Factor 4 Factor 5
sources > natural sources > petrogenic sources.
NAP 0.334  0.032  0.642 0.656  0.019 Factor 2 consists of phenanthrene, benzo[ghi]pery-
P
ACENY 0.191  0.559 0.073  0.755 0.200 lene, THC, and PAHs. The PAHs in this factor ac-
P
ACEN 0.364 0.256 0.353  0.763 0.086 count for 31.4% of the PAH. The metals include Cu
P
FLUO 0.487 0.374 0.688  0.103  0.303 and Hg. The high loading of phenanthrene and PAH
PHEN 0.412 0.725 0.329  0.234 0.208 in this factor indicates that phenanthrene is a major
P
ANTH  0.886 0.379 0.150 0.034 0.035 component of PAHs. The presence of phenanthrene
FLUA  0.968 0.044  0.006 0.084 0.011 is 28.9, the highest in comparison to the other PAH
PYR  0.606  0.193  0.657 0.314 0.116 compounds. Phenanthrene represents petrogenic origin
B(A)A 0.017 0.162  0.102  0.867  0.150 (PHEN/ANTH > 10). Benzo[ghi]perylene is generally
CHRY  0.968 0.012 0.037 0.024  0.031 attributed to traffic exhaust (Beak et al., 1991). Again,
B(B)F-B(B)K  0.863 0.019  0.260 0.373 0.013 the metals are related to bad yard practice. The main
B(A)P  0.962 0.100  0.005 0.139 0.008 contributory phenomena for this factor are in the or-
IND 0.271  0.157 0.164  0.786  0.409 der petrogenic > pyrolytic > natural.
DIBE 0.282 0.154  0.892 0.243  0.025 Factor 3 is loaded with fluoranthene, pyrene, and
B(GHI) 0.448 0.567 0.472  0.306 0.094 dibenzo[ah]anthracene. High loading for pyrene indi-
PAHs  0.455 0.821 0.083 0.095 0.187 cates a pyrolytic source. The source of dibenzo[ah]an-
THC  0.430 0.822 0.057  0.059 0.208 thracene has been attributed to the combustion of
As 0.216 0.240 0.386 0.043 0.805 fuel oil and is used as an indicator for oil pollution
Cd 0.759 0.196 0.420 0.210 0.315
(Sporstøl et al., 1983; Ogata and Fujisawa, 1990). The
Cr  0.176 0.108 0.945 0.017 0.147
PAHs in this factor account for 31.5% of the total PAH.
Cu  0.217 0.661 0.374 0.048 0.034
This factor also includes TPH in soil and Cr. This
Fe 0.188  0.337  0.023 0.115  0.535
factor is attributed mostly to petrogenic and pyrolytic
Hg  0.320  0.901 0.177  0.069 0.056
origins.
Mn  0.954  0.128 0.133  0.029 0.093
Factor 4 contains naphthalene, acenaphthylene, an-
Ni 0.318 0.037 0.079  0.161  0.905
thracene, benzo[a]anthracene, and indeno[1,2,3-cd]pyr-
Pb 0.940  0.005  0.171  0.187  0.092
Zn  0.782  0.104 0.153 0.060 0.210 ene, representing 18.1% of the total PAHs. Naphthalene
TOC 0.460 0.370  0.489  0.192 0.575 in soil is also included in this factor. The main source
TPH 0.376 0.099 0.530 0.380 0.190 of the PAHs based on the individual compounds is
NAPTH  0.565  0.119  0.016 0.566  0.079 anthropogenic activities, especially the emission from
Total 10.784 6.136 4.338 2.806 2.302 generator sets and combustion of fuel (Venkatesan and
% variance 35.946 20.454 14.460 9.353 7.674 Kaplan, 1982; Lahmann et al., 1984; Schulz et al., 1991).
Cumulative % 35.946 56.399 70.859 80.212 87.886 Wilcke et al. (1999) suggested a biological origin for
naphthalene in tropical soils. However, data from the
present study do not support a biological source for
naphthalene. This factor is mainly pyrolytic.
Factor 1 includes anthracene, fluoranthene, chry- Factor 5 consists of As, Fe, Ni, and TOC in soil.
sene, benzo[b]fluoranthene-benzo[k]fluoranthene, The major sources for the metals are anthropogenic
and benzo[a]pyrene. The heavy metals included in caused by bad yard practice. Iron is related to borehole
this factor are Cd, Mn, Pb, and Zn. The PAHs here construction materials and natural sources. Thus, anthro-
represent 19.0% of the total PAHs. The high loadings pogenic source is greater than the natural sources for
of anthracene and fluoranthene indicate pyrolitic ori- this factor.
gin (PHEN/ANTH < 10 and FLUA/PYR > 1). The ma- The results of the factor analysis suggest that most
jor source of chrysene is natural and is a result of micro- of the PAHs are derived from the same source, mainly
bial and photochemical degradation (Wakeham et al., pyrolytic and petrogenic, and the heavy metals are
1980; Lee and Ryan, 1983). The high negative load- mainly from anthropogenic sources caused by poor waste
ings for benzo[b]fluoranthene-benzo[k]fluoranthene, management. The relatively high loadings for some pa-
benzo[a]pyrene, and the metals indicate anthropo- rameters in more than one factor suggest several sources
genic more than natural sources. The major sources in- for each parameter.

26 Heavy Metals and Hydrocarbons in Groundwater in Calabar, Nigeria

CONCLUSIONS
The concentrations of heavy metals in the groundwa-
ter are higher than the baseline values and the concen-
trations at the control site. The mean concentrations
are higher for the PS/MW and MW in comparison to
PS. The level of TOC is low, and the concentrations of
TPH and naphthalene in the soil samples are very high.
The concentrations are higher at PS/MW in compari-
son to MW and PS. This is attributed to poor waste
management that results in leachate emanating from
these facilities, especially at MW.
P
The concentrations of THC and PAH in ground-
water are higher than the maximum admissible con-
centration of 0.1 mg L  1 for THC and 0.2 mg L  1 for
P v. 58, p. 85 – 97.
PAHs. The concentrations are also higher than the
values at control points and for some locations affected
by oil activities based on values in literature. The con-
centrations of the PAH compounds having mean con-
centrations greater than 1 mg L  1 are in the order PHEN
> ANTH > FLUO > B[B]F-B[K]F > PYR > NAP, in-
dicating PHEN as the main compound and suggesting
greater pyrolytic than petrogenic or natural input. The
relatively high loadings for some compounds in more
than one factor suggest input from several sources.
The ratios of PHEN/ANTH, FLUA/PYR and B[A]A/
CHRY, and factor analysis indicate various sources for
the PAH. The most important sources include petro-
genic, pyrolytic, and natural. Generally, for the ground-
water near these facilities, the elevated concentrations
of heavy metal and hydrocarbon are associated with
poor yard practice and waste management that result
in leachate emanating from PS and MW.
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