GeoJournal 57: 295–304, 2002.

© 2003 Kluwer Academic Publishers. Printed in the Netherlands.

295

Evaluation of water quality pollution indices for heavy metal contamination

monitoring. A study case from Akpabuyo-Odukpani area, Lower Cross River
Basin (southeastern Nigeria)

A.E. Edet1,∗ and O.E. Offiong2

1 Department of Geology and 2 Department of Pure and Applied Chemistry, University of Calabar, Calabar, Nigeria; ∗ Author
for correspondence (E-mail: aniekanedet@yahoo.com)

Received 15 November 2002; accepted 2 June 2003

Key words: contamination, evaluation, heavy metal, nigeria

Abstract
Two documented methods, Contamination index (Cd ) and the Heavy metal potential index (HPI) were evaluated for their
suitability for contamination monitoring of surface water in parts of southeastern Nigeria. Results show that despite the
significant correlation between the data generated from these indices, the final classification gave two extreme results. Thus
a third model (Heavy metal evaluation index, HEI) was developed to accommodate this deficiency. The HEI values show
significant correlation with Cd and HPI but categorised into semi quantitative classes for proper assessment of pollution
level. The HEI values show that 65.5% of the sites are classed as low with values lower than the mean and the remaining
34.5% with values greater than the mean are classed as medium. In contrast, water samples from all the 32 locations were
classified as high and low using the Cd and the HPI respectively. However, a reclassification of the Cd and HPI categories
using the mean values as a criteria show good comparison with the HEI. The differences in the former can be attributed to
the variations in the concentrations of the heavy metals used for the different evaluation schemes.

Introduction
The southern part of Cross River State (southeastern Ni-
geria) is characterised by numerous surface water bodies.
Ground water is not harnessed in the area, since the aquifer
is very deep and will require huge investment for the more
than 50 communities with population generally less than
500 in the eastern part known as Akpabuyo. In the west-
ern part (Odukpani), in addition to the deep aquifer as in
the east, more than 70% of the area is underlain by various
non aquiferous rocks thereby making it impossible to sink
water boreholes. These factors thereby make the inhabitants
to harness the surface water for their drinking and domestic
needs including agricultural activities.
These surface water bodies are prone to impacts from
human activities which may result in the degradation of the
resource in the future. A cost effective way to protect the
quality is to develop a monitoring scheme to assist in the
planning, development and guiding human activities includ-
ing industrial development to minimize adverse impacts on
water quality.
A lot of studies are abound in the literature on heavy
metal pollution of water sources. Such work include Brown-
Adiuku and Ogezi (1991), Edet and Ntekim (1996), Xibao
et al. (1996), Yang et al. (1996), Yiping (1996) and Znongyi
(1996). All these workers concluded that there was the need
to monitor water quality on a regular basis. This is because
the increase in concentration of trace metals in potable water
will increase the threat to man‘s health and life. Also, several
methods exist in literature on the development and applica-
tion of index methods for water quality assessment. Some of
these include the work of Horton (1965), Joung et al. (1979),
Landwehr (1979), Nishidia et al. (1982), Tiwary and Mishra
(1985) and Prasad and Jaiprakas (1999).
This study evaluates the applicability of two documented
pollution indices and compare with a third proposed for
the study area using some heavy element. In addition, the
present level of pollution is assessed using these indices.
General description of area
The study area is situated between latitudes 4◦ 45 –5◦55 N
and longitude 8◦ 00 –8◦30 E covering an area of about
300 km2 . It extends from the Cross River estuary in the
south 70 km into the interior boardering the Oban massif
in the north. Eastwards it extends from the Cross River for
about 70 km to the Akpa Yafe River which shares a bound-
ary with the Cameroun Republic in southern part of Cross
River State, Nigeria (Figure 1). The area has a population
of about 600,000 inhabitants (1991 census) with no major
industry. The main occupation of the people include small
scale farming and fishing.
Meteorological data from the weather station centrally
located in Calabar (Figure 1) for a period of 30 years show
that the annual maximum and minimum temperature are
296
Figure 1. Map of study area including sample locations.
30.1 ◦ C and 22.4 ◦ C, respectively. Annual rainfall is in
excess of 3,000 mm and potential evaporation is 890 mm
(CRBDA, 1982)
The main physiographic features of the area include
coastal plain in the north and east; flood plain and coastal
delta in the south and west. The major river systems draining
the area include the Cross, Calabar, Great Kwa and the Akpa
Yafe Rivers (Figure 1). The discharge of the Cross River
measured at Itu (Figure 1) varies from less than 1,000 m3 /sec
in the dry season to more than 2,500 m3 /sec during the wet
season (CRBDA, 1982). Comparatively, flow measurements
for some of the sampled streams varies between 0.05 m3 /sec
to 0.35 m3 /sec.
The area is underlain by three geologic complexes, the
Precambrian Oban massif (POM), the Cretaceous Calabar
flank (CCF) and the Tertiary to Quarternary Coastal plain
sand (CPS). The basement is made up of metamorphic and
igneous intrusives of various grades and types which is well
documented in literature (Rahman et al., 1981, 1988; Ek-
wueme et al., 1995). The Cretaeous sediments consist of
fluvio-deltaic clastic, carbonate and shale intercalated with
marl, calcareous mudstone and shell beds. Others include
carbonaceous shale with thin beds of marlstone and gypsum.
The Tertiary-Quarternary sediments consist of loose gravel,
sand, silt, clay and lignite.
Experimental work
Surface water samples were obtained from 32 locations (Fig-
ure 1) used by the local people for drinking, domestic and
agricultural purposes. The sampling covered only the Creta-
ceous and Tertiary-Quarternary terrains which concides with
the high density of settlements.
The water samples were collected below the water sur-
face using 200 ml polyethylene bottles. Prior to sampling,
the bottles were rinsed with the water to be sampled and the
samples were preserved by acidifying to pH ∼ 2 with HNO3
and keep at a temperature of 4 ◦ C until analysis.
Water temperature, electrical conductivity (EC), pH and
dissolved oxygen (DO) were determined in the field. The
samples were analysed for heavy metals using atomic ab-
sorption spectrophotometer (AAS), perkin Elmer science
Elan 5000 for As, Cd, Cr, Cu, Ni, and Pb. The ion chroma-
tography (IC), Dionex 2000i was used for the determination
of Fe, Mn, Sr and Zn.
Physicochemical data
The results of the physical and heavy metal concentra-
tions are given in Table 1. The water temperature ranged
from 25.3–30.3 ◦ C with mean ± standard deviation (SD)
 297

Table 1. Surface water chemical data of Akpabuyo-Odukpani area.

Sample noa Stream name Tempb ECb pHb As Cd Cr Cu Feb Mnb Ni Pb Sr Zn Metal load
◦ µS/cm µg/l µg/l µg/l µg/l µg/l µg/l µg/l µg/l µg/l µg/l µg/l µg/l

1 Obot 28.0 27.8 4.5 17.1 76.8 2.47 5.3 140 20 2.52 4 230 2670 3.00
2 Nkong 26.7 27.6 4.36 10.4 69.6 2.21 4.5 150 10 1.72 1.5 320 620 1.03
3 Ekanem Nya 26.9 24.3 5.05 20.1 79.2 4.8 4 930 10 1.22 1.4 410 430 0.95
4 Ikot Ekpo 26.8 14.6 3.47 14.8 33.6 2.71 5.2 160 0 4.96 17 130 90 0.30
5 Etomkpe Yellow Duke 27.7 13.3 4.37 15.6 51.6 3.51 3.1 250 0 0.04 2 210 70 0.36
6 Ikot Ndarake 27.3 16.5 3.41 16.5 74.6 2.98 5.9 180 0 2.49 2.2 140 2680 2.92
7 Abisa 26.5 12.3 5.6 12.9 74.8 3.71 3.2 430 0 1.91 1.6 130 90 0.32
8 Abasi Ukpong 26.6 12.7 3.62 14.8 57 2.8 2.6 210 0 1.29 1.6 120 70 0.27
9 Esuk Mba 27.3 33.2 4.36 12.6 53 3.62 3.4 300 10 1.8 8.9 110 70 0.26
10 Ekpo Eyo 26.7 21.1 3.66 16.4 45 2.71 4.7 140 0 1.57 6.4 100 580 0.76
11 Ikot Okpo Ene 26.9 30 4.5 33.9 83.2 6.88 3.9 620 0 2.55 3.4 110 140 0.38
12 Ayan Mbat 25.7 33.2 4.37 17.6 13 5.01 2.7 280 0 2.19 1.7 40 80 0.16
13 Inwang 26.7 24.4 4.75 16.4 16 9.73 2.8 1030 40 3.72 6.9 40 480 0.58
14 Etakpan 26.6 34 4.92 15.7 16.4 5.15 2.9 570 0 1.23 2.9 40 310 0.39
15 Idundu 25.3 32 5.13 33.2 29 8.44 4.3 2400 40 1.81 4.1 60 330 0.47
16 Ananganse 25.7 27.1 5.01 15.4 15.2 4.93 2.7 630 10 2.39 2.3 40 50 0.13
17 Ebiet Okon Archibong 26.6 29 5.01 15.4 23 4.78 3.4 930 10 2.85 1.4 60 390 0.50
18 Nkwa Itiat 26.1 35.6 5.59 33.7 30.6 7.37 7.2 2420 40 4.01 24 70 1850 2.03
19 Akasoko 25.7 28 5.44 33.2 56 6.49 3.9 840 20 3.89 2.7 80 1190 1.38
20 Akai Efa 25.7 75 3.65 13.7 18 6.86 4.2 1960 130 6.02 1.1 90 1360 1.50
21 Akim Akim 26.7 31.6 6.01 10.3 14.8 4.13 2.9 420 0 2.88 1.8 40 40 0.12
22 Akpako 25.6 34 5.97 15.6 23.5 6.48 3.3 2560 40 3.44 2.5 70 1880 2.00
23 Ikong 26.8 25.5 5.65 12.4 22.6 1.93 3.5 140 10 2.97 1.8 50 500 0.60
24 Obot Akpong 27.2 23.5 5.49 13.6 24.2 2.73 3.1 40 0 2.49 2.1 50 80 0.18
25 Ukem 30.0 25.6 4.47 35.3 10.2 6.19 4.1 820 10 3.01 3.2 10 200 0.29
26 Akim Akim Qua 30.3 45 6.93 28.2 61 7.76 15.1 870 30 5.8 3.5 60 1450 1.63
27 Adukpani 26.5 45 6.85 20.1 14 4.3 4.2 390 0 2.97 3.1 60 210 0.32
28 Odukpani junctic 26.5 42.2 6.97 21.3 9.6 3.52 3.8 200 30 2.01 2.1 40 270 0.35
29 Akpa Ikpong 26.8 48.1 7.47 17.1 13.6 5.04 4.3 970 40 1.46 2.3 80 590 0.71
30 Nki 26.6 41.8 7.15 30.7 17 8.84 5.5 1900 60 4.79 3.5 70 540 0.68
31 Atan 25.5 86 7.47 11.8 16 3.99 3.5 1010 40 2.83 1.4 110 70 0.22
32 Calabar 25.9 47.6 6.78 32.2 25.4 5.99 3.8 1940 170 2.99 3 60 220 0.35
a Figure 1
b Adapted from Offiong and Edet (1998a, b)

Table 2. Descriptive statistics for elements.

Parameter Units Max Min Mean Median Std.Dev. MACa % >MAC

Temp ◦C 30.30 25.30 26.75 26.65 1.10

EC µS/cm 86.00 12.30 32.74 29.50 16.01 1400b
pH 7.47 3.41 5.25 5.03 1.21 6,5-8,5b
As mg/l 35.30 10.30 19.63 16.40 8.04 50.00 0.00
Cd mg/l 83.20 9.60 36.48 24.80 24.38 3.00 100.00
Cr mg/l 9.73 1.93 4.94 4.79 2.08 50.00 0.00
Cu mg/l 15.10 2.60 4.28 3.85 2.23 1000.00 0.00
Fe mg/l 2560.00 40.00 807.81 595.00 750.78 200.00 78.00
Mn mg/l 170.00 0.00 24.06 10.00 37.58 50.00 9.00
Ni mg/l 6.02 0.04 2.74 2.54 1.34 20.00 0.00
Pb mg/l 23.54 1.07 3.96 2.37 4.70 1.50 84.00
Sr mg/l 410.00 10.00 100.94 70.00 84.98
Zn mg/l 2680.00 40.00 613.13 320.00 746.52 5000.00 0.00
a MAC Maximum admissible concentration (Adapted from Siegel, 2002)
b WHO (1993)
298

of 26.75 ± 1.10 ◦ C. The electrical conductivity (EC) var-

ied from 12.3–86.0 µS/cm (mean ± standard deviation,
32.74 ± 16.01 µS/cm). The range, mean and SD of pH
are 3.41–7.47, 5.25 and 1.21. The dissolved oxygen (DO)
varied between 1.3–8.1 mg/l. The mean values indicate that
the water are acidic and fresh. Comparatively high values of
EC (42.2–86.0 µS/cm) and pH (6.78–7.47) were recorded
for locations 26–32 underlain by Cretaceous shale as against
locations (1–25) within the Tertiary-Quarternary sediments.
The results of the major ions are documented in Offiong and
Edet (1998 a, b).

Heavy element concentrations

The descriptive statistics including maximum admissible

concentration (MAC) are given in Table 2. The concentra-
tion of As, Cr, Cu, Ni and Zn are below the the MAC
in drinking water. The concentration of As were found to
be greater than 30 µg/l in 7 out of 32 locations sampled.
The Cd concentration (9.6–83.2 µg/l) in all the locations
are higher than the MAC of 3 µg/l, while 78% of the loc-
ations show Fe in excess of 300 µg/l. The concentration of
Mn in two locations (21, 32) are higher than the MAC of
100 µg/l. Eighty four percent of the 32 locations sampled
had Pb concentration above the MAC of 1.5 µg/l.
The variation of heavy metals between the different loc-
ations by means of ANOVA using the statistical package,
STATISTICA
is insignificant (Table 3). Correlation at 5%
level of significance (P < 0.05) show significant correlation
between the following pairs As and Cr, Cu, Fe ; Cd and Figure 2. Classification of water samples based on the plot of metal load
Sr; Cr and Fe, Mn, Ni, Sr; Cu and Ni, Zn; Fe and Mn and and pH.
Ni and Mn and Ni. Only Cr show significant correlation
with pH (Table 4). The source of these elements are the Table 3. ANOVA test for significance between
sample locations.
Precambrian basement complex. This is supported by the
significant correlation (r = 0.75 P =< 0.0001) between F dF P
the mean elemental concentration of these elements in rocks
and water. Enrichment in some heavy metals is attributed As 0.720 3 0.549
to small scale mining and quarrying activities in the Oban Cd 0.740 3 0.538
Cr 0.706 3 0.557
massif (Edet et al., 2002). Here most of the waste products
Cu 1.256 3 0.311
are washed by surface runoff into the big rivers which feed
Fe 1.489 3 0.242
the smaller ones which were sampled.
Mn 0.983 3 0.416
Ni 1.359 3 0.278
Classification of the sampled water Pb 0.305 3 0.821
Sr 0.715 3 0.552
In order to classify these water, the method of Fick-
Zn 0.441 3 0.726
lin et al. (1992) and modified by Caboi et al. (1999)
was applied. The method uses the water pH and metal
load (mg/l). In this study, the metal load is computed
as As+Cd+Cr+Cu+Ni+Pb+Sr+Zn. From the chart (Fig-
ure 2), samples from 15 locations representing 47% of all Distribution of species and mineral phases
the samples are classied as acid-low metal and 10 locations
(31% of total samples) as near neutral-low metal. Samples The computer program PHREEQC
was used to determine
from 4 and 3 locations are classified as acid-high metal the distribution of major species for the water samples. The
(locations 1, 2, 19, 20) and near neutral-high metal. major species with more than 95% content include H3 AsO3 ,
Cd2+ , Cu+ , Fe2+ , Ni2+ , Pb2+ , Sr2+ and Zn2+ .
The saturation index (SI) indicates whether a particular
water sample is either saturated or not with respect to a
particular mineral. The solution is considered to be in equi-
 299

Table 4. Correlation matrix between elements (bold correlations are significant at P < .05).

Temp EC pH As Cd Cr Cu Fe Mn Ni Pb Sr

Temp
EC −0.253
pH −0.070 0.457
As 0.160 0.094 0.215
Cd 0.266 −0.510 −0.390 0.029
Cr −0.062 0.267 0.266 0.643 −0.248
Cu 0.568 −0.044 0.208 0.356 0.261 0.260
Fe −0.347 0.429 0.315 0.497 −0.285 0.752 0.141
Mn −0.264 0.580 0.301 0.300 −0.273 0.446 0.096 0.667
Ni 0.091 0.316 0.150 0.270 −0.212 0.480 0.523 0.408 0.435
Pb −0.011 −0.136 −0.160 0.241 −0.025 0.144 0.260 0.218 −0.012 0.298
Sr 0.070 −0.235 −0.278 −0.224 0.703 −0.351 0.016 −0.204 −0.154 −0.338 −0.077
Zn 0.144 −0.024 −0.119 0.120 0.326 0.094 0.460 0.252 0.154 0.338 0.168 0.162

Table 5. Saturation inidices for mineral phases.

Sample noa Cu metal Cuprite Cuprous ferrite Goethite Hematite Magnetite

Cu Cu2 O CuFeO2 FeOOH Fe2 O3 Fe3 O4

1 −0.35 −3.77 3.09 −2.22 −2.21 −6.43

2 −0.28 −4.16 2.38 −2.72 −3.30 −7.82
3 0.42 −2.81 5.20 −0.57 1.01 −1.34
4 −1.26 −6.23 −0.48 −4.54 −6.93 −13.22
5 −0.26 −4.44 2.32 −2.65 −3.09 −7.32
6 −1.38 −6.35 −0.55 −4.56 −6.94 −13.28
7 1.02 −1.88 6.29 0.06 2.25 0.65
8 −1.31 −6.39 −0.16 −4.14 −6.15 −12.03
9 −0.20 −4.37 2.39 −2.61 −3.04 −7.23
10 −1.06 −5.80 0.08 −4.19 −6.25 −12.22
11 −0.22 −3.98 3.39 −1.79 −1.44 −5.06
12 −0.65 −4.61 2.59 −2.27 −2.47 −6.75
13 −0.25 −3.75 4.37 −0.93 0.28 −2.64
14 −0.18 −3.37 4.76 −0.73 0.68 −9.84
15 0.54 −2.56 5.88 0.01 2.05 0.19
16 0.32 −3.21 4.65 −0.90 0.26 −2.39
17 0.38 −3.02 4.95 −0.72 0.70 −1.74
18 1.34 −1.20 7.37 0.81 3.71 2.81
19 0.83 −2.02 6.30 0.16 2.37 0.70
20 −1.03 −5.89 1.07 −3.14 −4.22 −9.11
21 1.23 −1.14 7.63 1.03 4.19 3.42
22 1.17 −1.10 8.41 1.81 5.67 5.53
23 1.05 −1.70 6.06 −0.27 1.61 −0.36
24 0.67 −2.14 5.14 −0.97 0.24 −2.57
25 −1.08 −4.25 4.06 −1.04 0.30 −3.12
26 1.82 2.07 12.42 4.16 10.72 12.25
27 1.42 0.86 11.09 3.49 9.10 9.96
28 1.38 1.01 11.28 3.60 9.32 10.17
29 1.42 2.08 13.94 5.72 13.59 16.09
30 1.54 1.68 13.07 5.06 12.25 14.39
31 1.37 1.92 13.84 5.73 13.51 15.97
32 1.34 0.64 11.49 4.01 10.10 11.48
300
Table 6. Percent distribution of mineral phases in relation to geo-
librium regarding a particular mineral if the SI = 0. It is logy.
considered to be undersaturated if the SI < 1 and oversatur-
ated if the SI > 1. The surface water samples in the area Mineral phase Calabar flank Coastal plain sand
tend to be or is in equilibrium with respect to Cu metal 1 2 3 1 2 3
(Cu), Cuprite (Cu2 0), CuprousFerrite (CuFeO2 ), Goeth-
Cu metal - - 100 76 - 24
ite (FeOOH), Hematite (Fe2 O3 ) and Magnetite (Fe3 O4 ),
Cuprite - - 100 100 - -
Table 5. Cuprous
A comparative analysis (Table 6) show that 24% (25 loc- Ferrite - - 100 16 - 84
ations) of the surface water samples within the Coastal plain Goethite - - 100 92 - 8
sands (CPS) are saturated with respect to Cu metal compared Hematite - - 100 68 - 32
to 100% of samples within the shales of Cretaceous Calabar Magnetite - - 100 78 - 12
Flank (CCF), (7 locations). All the water samples from the
CPS are undersaturated with respect to Cuprite but satur- 1 undersaturated; 2 equilibrium; 3 oversaturated
ated for the CCF locations. The samples are saturated with
Table 7. Standard used for the indices computation.
respect to CuprousFerrite for the CCF locations compared
to 84% for the CPS locations. About 92% of the samples W S I MAC RV
from the CPS are undersaturated with respect to Goethite in
contrast to the CCF locations in which all the sample are As 0.02 50 10 50 0.5
saturated. With respect to the mineral phase hematite, 68% Cd 0.3 5 3 3 0.2
Cr 0.02 50 50 50 1
remain undersaturated for the CPS terrain compare to 100%
Cu 0.001 1000 2000 1000 3
saturation for all the CCF locations. Magnetite in the surface
Fe 0.005 300 200 200 50
water samples in all the locations within the CCF are satur-
Mn 0.02 100 500 50 5
ated while only 12% is saturated for the CPS locations. This
Ni 0.05 20 20 20 0.3
shows that all the mineral phases considered are saturated Pb 0.7 100 10 1.5 3
for all the samples from the CCF locations. This is attributed Zn 0.0002 5000 3000 5000 5
to the proximity of these locations to the probable source
of these elements which is the Oban massif and the Calabar W weightage (1/MAC)
S Standard permissible in ppb
flank. I Highest permissible in ppb
MAC Maximum admissible concentration/upper permissible
RV Reference valu in ppb
Evaluation methods
The authors did not consider elements and ionic species
Two documented methods evaluated in this study are the
with analytical values below the upper permissible concen-
Contamination index (Cd) developed by Backman et al.
tration value. Since the concentration of heavy metals below
(1998) and the Heavy metal pollution index (HPI) proposed
this limit does not pose any hazardous problem to the qual-
by Prasad and Bose (2001).
ity of groundwater. The resultant Cd value identify areas of
varying contamination levels which are grouped into three
The contamination index (Cd )
categories as follows: low (Cd < 1), medium (Cd = 1–3)
In this method, the quality of water is evaluated by the cal- and high (Cd > 3).
culation of the degree of contamination the Cd . The Cd is In this study, for uniformity sake all analytical values
computed separately for each sample of water analysed, as were considered irrespective whether above or below upper
a sum of the contamination factors of individual componets permissible concentration value. Secondly, the values were
exceeding the upper permissible value. Hence the Cd sum- not normalised since this is the first ever study in the area.
marises the combined effects of several quality parameters The upper permissible concentration value (CNi ) was taken
considered harmful to household water. The contamination as the maximum admissible concentration (MAC), Table 7.
index is calculated from equation below The components considered include As, Cd, Cr, Cu, Fe, Mn,
Ni, Pb and Zn. The computed Cd values for each location


n
Cd Cfi , is presented in Table 8. These values range from 7.38–39.48
i=1
(mean = 21.09).
where
Heavy metal pollution index (HPI)
CAi
Cfi = −1
CNi The HPI represent the total quality of water with respect
Cfi = contamination factor for the i-th component to heavy metals. The HPI is based on weighted arithmetic
CAi = analytical value for the i-th component quality mean method and developed in two steps. First by
CNi = upper permissible concentration of the i-th compon- establishing a rating scale for each selected parameter giving
ent (N denotes the ‘normative value’) weightage and second by selecting the pollution parameter
on which the index is to be based. The rating system is
 301
Table 8. Evaluation indices. Table 9a. Correlation between index values and concentra-
tion of metal (32 cases P < 0.05).
Sample noa Cd HPI HEI
Parameter Cd HPI HEI
1 31.22 15.59 970.00 r P r P r P
2 27.56 12.78 505.00
3 33.95 17.28 537.00 As 0.170 0.352 0.346 0.052 0.240 0.185
4 26.67 18.75 243.00 Cd 0.919 0.000 0.689 0.000 0.822 0.000
5 22.27 10.84 309.00 Cr 0.036 0.845 0.315 0.079 0.076 0.678
6 29.29 14.00 956.00 Cu 0.458 0.008 0.518 0.002 0.527 0.002
7 30.67 14.43 430.00 Fe 0.073 0.693 0.369 0.038 0.090 0.624
8 23.68 11.11 338.00 Mn 0.047 0.800 0.292 0.105 0.170 0.351
9 27.58 15.86 321.00 Ni 0.010 0.958 0.226 0.213 0.101 0.583
10 23.04 13.50 386.00 Pb 0.259 0.152 0.496 0.004 0.172 0.347
11 34.94 18.56 531.00 Zn 0.731 0.000 0.536 0.002 0.644 0.000
12 9.27 5.63 131.00
13 16.62 12.78 244.00
14 12.77 8.18 188.00 Table 9b. Correlation between different indices
15 25.62 19.52 307.00 values.
16 12.03 7.79 135.00
17 16.46 9.60 244.00 r P
18 39.48 33.36 634.00
HPI vs. Cd 0.876 5.17E-11
19 26.04 15.30 612.00
HPI vs. HEI 0.745 9.88E-07
20 19.60 12.71 448.00
Cd vs. HEI 0.871 9.45E-11
21 10.79 6.27 119.00
22 23.49 17.61 558.00
23 12.26 6.64 254.00
24 13.81 7.09 177.00
25 11.46 9.49 188.00 parameters considered.
26 27.99 16.36 692.00 The sub-index (Qi ) of the parameter is calculated by
27 11.07 7.40 170.00
n
{Mi (−)Ii }
28 7.38 5.25 163.00 Qi = × 100,
29 12.51 9.09 242.00
(Si − Ii )
i=1
30 18.64 15.09 298.00 where Mi is the monitored value of heavy metal of ith para-
31 13.08 9.99 143.00
meter, Ii is the ideal value of the ith parameter and Si is
32 23.59 15.58 291.00
the standard value of the ith parameter. The sign (−) in-
Maximum 39.48 33.36 970.00 dicates numerical difference of the two values, ignoring the
Minimum 7.38 5.5 119.00 algebraic sign. The critical pollution index of HPI value for
Mean 21.09 12.92 367.63 drinking water as given by Prasad and Bose (2001) is 100.
In computing the HPI for the present study, As, Cd, Cr,
Cu, Fe, Mn, Ni, Pb and Zn were used. The weightage (Wi )
was taken as the inverse of MAC, Si the WHO stardard for
an arbitrarily value between zero to one and its selection drinking water and Ii the guide value for the choosen element
depends upon the importance of individual quality consid- (Table 7). The computed HPI values are given in Table 8.
erations in a comparative way or it can be assessed by The values vary between 5.25–33.36 (mean 12.92).
making values inversely proportional to the recommended
standard for the corresponding parameter (Horton, 1965; Heavy metal evaluation index (HEI)
Mohan et al., 1996). In computing the HPI, Prasad and
The HEI method like the HPI gives an overall quality of the
Bose (2001) considered unit weightage (Wi ) as a value in-
water with respect to heavy metals. The HEI is computed as:
versely proportional to the recommended standard (Si ) of the
corresponding parameter as proposed by Reddy (1995).
n
HEI = Hc /Hmac ,
The HPI model (Mohan et al., 1996) is given by
i=1


n
where Hc is the monitored value of the ith parameter and
Wi Qi
Hmac the maximum admissible concentration of the ith para-
i=1
HPI = , meter.

n
Wi The computed HEI values are given in Table 8. The values
i=1
range from 119–970 (mean = 367.63).
where Qi is the sub-index of the ith parameter. Wi is the
unit weightage of the ith parameter and n is the number of
302
Figure 3. Contamination potential index map based on HEI values.
Discussion
The acidic nature of the groundwater is due to the leach-
ing of altered rocks by acidic rainwater (Edet et al., 2002).
The concentration of heavy metals in the area is attributed
to geogenic sources from the adjoining basement complex
(Figure 1), since major industries are non existence and
mining activities are limited to only limestone and granite
quarrying and barite mining. In addition, Offiong and Edet
(1998a, b) attributed the high concentration of Fe and Mn in
surface water of the area to high suspended sediments.
A comparison between the indices and heavy metal con-
centration show significant correlation with Cd, Cu and Zn
(Table 9). This indicate that these metals are the main con-
tributory parameters. The correlation between Cd , HPI and
HEI is significant.
The computed Cd values are in excess of 3, the Cd value
for high contamination. On the contrary, the HPI values for
all the locations are lower than 100 the critical value for
drinking water.
The mean deviation and % deviation for the 3 indices
were computed for each sampling point (Table 10). Analysis
show that 53% of Cd values, 47% of HPI and 53% of HEI
of the index values are lower than the mean value and the
% deviation on the negative side which indicates relatively
better quality as noted by Prasad and Bose (2001).
Since the computed Cd values are too high and the HPI
method cumbersome despite the fact that all the surface
water samples considered are below critical level, the HEI
method is preferable. In this scheme, The values are divided
into 3 classes using a multiple of the mean value to demarc-
ate the different level of contamination as low (HEI<400),
medium (HEI=400–800) and high (HEI>800). The HEI
values are plotted on a map and contamination degree map
produced (Figure 3). The present level show that 66% of the
sampled locations are within the low zone while 28% and
6% fall within the medium and high zones. All the 21 loca-
tions with values less than mean- and percent deviation fall
into the low contamination zone. The remaining 11 location
which fall into medium (9 locations) and high (2 locations)
show high values than the mean-and percent deviation.
In other to apply these two methods in the present study
area, the scales were slightly modified using the multiple of
the mean as a criteria. Thus for the Cd 47% and 53% of the
samples respectively are classed as low and medium. For
the HPI, 63% and 34% are classified as low and medium
(Table 11). This thus makes the three schemes comparable,
but the HEI is preferred due to its simplicity in computation.
Conclusion
The two existing methods, the Contamination index (Cd ) and
the Heavy metal pollution index (HPI) provide two extreme
results although the values show significant correlation using
data from the study area with no major industrial activity.
The differences can be attributed to the variations in the
 303

concentrations of the heavy metals used for the different

evaluation schemes.
Table 10. Mean deviation values.
The Cd (>3) place all the samples as of high con-
Sample Mean deviation % Deviation tamination level. The HPI on the hand consider the level
noa Cd HPI HEI Cd HPI HEI of contamination as not critical (<100) A third method
developed during this study give a better pollution classific-
1 10.13 2.67 602 48.03 20.7 163.6
ation for the water samples which straddle 3 classes viz low,
2 6.47 −0.14 137 30.68 −1.08 37.2
medium and high with more 50% in the low class (<400). A
3 12.87 4.36 169 61.02 33.75 45.9
4 5.58 5.83 −125 26.45 45.1 −33.96
reclassification of the categories using a multiple of the mean
5 1.18 −2.08 −59 5.6 −16.1 −16
show comparable results. Thus the methods are very suitable
6 8.2 1.08 588 38.89 8.36 159.8 for evaluation of heavy metal contamination but due to the
7 9.58 1.51 62 45.42 11.69 16.8 cumbersome nature of computation involved with Cd and
8 2.59 −1.81 −30 12.28 −14 −8.15 the HPI, the HEI is preffered for contamination monitoring.
9 6.49 2.94 −47 30.77 22.75 −12.77
10 1.95 0.58 18 9.25 4.49 4.89
11 13.85 5.6 163 65.78 43.65 42.29 Acknowledgements
12 −11.82 −7.29 −237 −56.05 −56.42 −64.4
13 −4.47 −0.14 −124 −21.19 −1.08 −33.7 The authors are grateful to the German Academic Exchange
14 −8.32 −4.74 −180 −39.45 −36.68 −48.9 Service (DAAD) and the Institute of Geology, University of
15 4.53 6.6 −61 21.48 51.08 −16.57 Tuebingen (Germany) for financial grants and analyses to
16 −9.06 −5.13 −233 −42.96 −39.7 −63.31 the first author.
17 −4.63 −3.3 −124 −21.95 −25.7 −33.7
18 18.39 20.44 266 87.2 15.82 72.28
19 4.95 2.38 244 23.47 18.42 66.3
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