Austin Paper2

AARJMD VOLUME 1 ISSUE 32 (APRIL 2015) ISSN : 2319 - 2801
A Peer Reviewed International Journal of Asian

Academic Research Associates
AARJMD
ASIAN ACADEMIC RESEARCH
JOURNAL OF MULTIDISCIPLINARY
ASSESSMENT OF SPATIAL VARIABILITY AND CONCENTRATION OF HEAVY

METALS IN SOILS UNDER THE INFLUENCE OF MINING AT ANGLOGOLD
CONCESSION, ADUBIREM, GHANA
OWUSU-PREMPEH, N.1; ASARE, A2
1
Department of Land Reclamation and Restoration, Faculty of Forest Resources Technology,
Kwame Nkrumah University of Science and Technology (KNUST), Kumasi, Ghana
2
Department of Environmental Management, School of Natural Resources, University of Energy
and Natural Resources (UENR), Sunyani, Ghana
Abstract
The assessment of pollution levels of heavy metals soil contamination is crucial to human health
and environmental management. This study seeks to assess the concentration and spatial
variability of heavy metals using Principal component analysis, cluster analysis, geostatistics and
pollution indices in a reclaimed mining area in AngloGold concession at Adubirem, Ghana and
to compare the metal concentrations with the Canadian soil quality guidelines for agriculture,
World ranges in non-polluted soils and Clark geochemical background values. Soil samples were
collected at 0-15cm with soil auger. The metals were digested and analysed for extractable metal
using appropriate atomic absorption spectrometric techniques. From the results Hg was not
detected in study area. All the other metals studied in both the reclaimed mining area and the
control soils (Cu, Zn, Fe, Pb, and Ni) were below the Canadian soil quality guidelines for
agriculture, World ranges in non-polluted soils and Clark geochemical background values except
Arsenic (As). The pollution indices showed that the reclaimed mining area and the control area
not polluted with the metals studied except As. The enrichment of As in both the reclaimed
mining area and the control felled in the extremely high enrichment category. The PCA extracted
two major components: PC-1 explains 55.92 total variance with strong positive loading on As,
Cu, Zn, Fe, and Ni which indicates that these metals are associated with and controlled by
natural process and PC-2 explains 17.48% total variance with strong positive loading on Pb and
moderate loading on Cu and are associated with both anthropogenic and natural process. The
PCA results were similar to the cluster analysis results. All the metals studied showed strong
spatial autocorrelation in the study area suggesting that the mining operation did not influence
the concentration of the metals studied.
Keywords: Geostatistics, Principal component analysis, Cluster analysis, Pollution indices

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www.asianacademicresearch.org
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1.1 Introduction
Mining is considered as one of the most important socio-economic activities which contribute to
the economic growth of Ghana. However, while acknowledging the role of mining to the
economic growth of the country, others are also of the view that the benefits from mining
operation to the socio-economic development of the country are achieved at significant
environmental, health and social cost. Pollution of soils with heavy metals has recently become a
subject of many studies because of the serious risk it represents for the environment and human
health Albanese and Cicchella,( 2012). There have been reports about heavy metal contamination
of soils in vicinity of mining areas Wang et al., (2007). It is also documented that abandoned
mining wastes can leach significant amounts of various elements out to the soil (Liu, et al.,
2005). Mining activity has been reported as a vital source of heavy metals in the agricultural
soils near mining areas Kabata-Pendias and Pendias, (2001). However, the soil type, topography,
geology, and the erosive processes also influence the concentration and distribution of heavy
metals in the environment, including their bioavailability (Costa, 2002). Studies on heavy metal
pollution in various environments within mining communities in Ghana have been undertaken
during the last few decades (Nude et al., 2011). However, information on the impact of mining
operations on contamination of soil environments, which serve as the main sink of pollutants are
very limited (Dorgbetor, 2010). Interest in assessing the impact of mining on the soil quality of
reclaimed mined sites of the AngloGold Concession areas has been stimulated by increasing
awareness that soil is a critically important component of the earth‟s biosphere, functioning not
only in the production of food and fiber but also in the maintenance of local, regional and global
environmental quality. Soils are also critical environments where rock, biology, air, and water
interface. So far, few reports have focused on the pollution of heavy metals of soils in the study
area. The study of the spatial distribution and source identification of heavy metals in soils is
very important in order to identify pollution hot-spots and assess the potential sources of
pollutants (Acosta et al., 2011). Usually, the identification of pollutant sources is conducted with
the aid of multivariate statistical analyses, such as correlation analysis, Principal component
analysis (PCA), and Cluster analysis (CA). Some authors have used multivariate statistical
methods to identify the factors of lithogenic and anthropogenic origin responsible for the heavy
metal pollution of soils (Sollitto et al., 2010). Furthermore, geostatistical analysis has been used
to study spatial distribution patterns and possible hot-spots of elevated concentrations of heavy

401
metal contamination in soil environment (Carr et al., 2008). The use of this approach in
evaluating the quality of mined soils in the study area has received little attention. The objectives
of this study were : (a) to determining and compare the concentrations of heavy metals (As, Pb,
Zn, Fe, Cu, Ni and Hg) in the reclaimed mining area and the control (b) mapping the spatial
distribution of heavy metals through geostatistical analysis for the purpose of identifying their
spatial patterns and possible hot spots of the concentrations of heavy metals, (c) identifying the
potential sources of heavy metals in the soils using correlation analysis, PCA and CA. (d) assess
the study area soil contamination using four approaches, namely Enrichment factor (EF),
Contamination factor (CF), Pollution load index (PLI) and Geo-accumulation index (e) to find
out whether the reclaimed area is safe for agriculture.
2.1 Materials and Methods
2.1.1 Study area description
The study was conducted at the AngloGold concession at Adubirem in the Amansie East
District, Ghana. The study area is located between latitude º6 20‟34.6 “N and longitude º136‟
31‟‟ W within semi-deciduous ecological zone of Ghana. The area is underlain by Birimian
sedimentary rocks and is mainly phyllites, schist, and tuff and greywacke sediments. The
Birimian is overlain by the Tarkwaian rocks made up of sedimentary units and also recent
alluvial deposits. The dominant soil within the study area is Acrisols soil type.

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Figure 1 Geological map of Ghana showing Adubirem in Amansie East District
2.1.2 Sampling design and chemical analysis
One hectare (50m x200m) and 0.5ha (50m x 100m) plot were randomly laid in the reclaimed
mining area and the control area (area not disturbed by mining) respectively. The reclaimed
mining area was subdivided into four 50m x 50m plots and the control plot was subdivided into
two 50m x 50m plots. Each 50m x 50m plot was further divided into 10m x 10m subplots
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making a total of twenty five (25) 10m x 10m subplots. Simple random sampling technique was
used to select five (5) plots from each 50m x 50m plots making a total of twenty 10m x 10m
subplots from the reclaimed mining area and ten plots from the control. GPS coordinates for all
the selected 10mx10m plots were obtained with Garmin GPS 62 Sc version. Composite soil
samples collected with soil auger at a depth of 0-15cm were obtained by mixing subsamples
taken from four corners and the center of each 10m x 10m plot in each sampling site. The bulk
soil samples were air dried and hand crushed to pass through a 2mm nylon sieve and stored in
polyethene plastic bags for laboratory analysis. Metal concentrations for As, Pb, Zn, Cu, Fe, Ni
and Hg were analysed after complete dissolution using a mixture of HNO3-HCLO4 and heated in
a microwave digestion system, using appropriate atomic absorption spectrometric techniques
(Ruiz et al., 1998).
2.2 Assessment of soil contamination
2.2.1 Enrichment Factor
In order to select chemical elements that have been enriched in the soils of the reclaimed mining
area and the control, enrichment factor (EF) for the soil sample was calculated (Li and Feng,
2012). EF was widely employed to identify the anthropogenic sources of metallic elements.
Based on the EF scale, five contamination categories were defined: (a) EF<2 represents deficient
to minimal enrichment; (b) 2 ≤ EF<5 moderate enrichment; (c) 5≤EF<20 significant enrichment
(d) 20≤EF≤ 40 very high enrichment (e) EF > 40 extremely high enrichment (Loska et al.,
2004).. The Clark values (background values) corresponding to mean concentration of heavy
metals in the Upper Continental Crust (UCC) given by Mclennan (2001) were used. In this study
Iron (Fe) was chosen to be the reference value or normalizing element while determining EF-
values, since is one of the widely used reference elements ( Seshan et al., 2010). The enrichment
factor (EF) values were calculated for the heavy metals using the following equation according
to Simex and Helz, (1981).

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2.2.2 Contamination Factor (CF) and Pollution Load Index (PLI)
Another factor, which was employed to classify the quality of the soil samples from the study
area, is contamination factor (CF). For its calculation, a mean concentration of a given element in
at least 5 samples is divided by pre-industrial or Clark background value of the element
(Hakanson, 1980).
Ci – mean content of element in samples taken from at least 5 sampling sites ,Cn – pre-industrial
mean concentration of the element. CF < 1 (low contamination);1≤ CF < 3 (Moderate
contamination); 3 ≤ CF< 6 (Considerable contamination); 6 ≤ CF (Very high contamination). To
effectively determine whether the mining area suffer heavy metal contamination or not, the
pollution load index (PLI ) was used. The PLI is aimed at providing a measure of the degree of
overall contamination of heavy metals in the study area. The PLI was developed by Thomilson et
al., (1980) as follows:
Where n= number of metals studied

2.2.3 Geo-accumulation index (I-geo)
The geo-accumulation index is a quantitative measure of the degree of pollution in water

sediments. This approach was used to quantify the degree of anthropogenic contamination in the
soils. Geo-accumulation indices for the trace elements in each sampling site were calculated
using the equation:

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The factor 1.5 is introduced in this equation to minimise the effect of possible variations in the
background values, which may be attributed to lithogenic variations in soils. Where Cm is the
concentration of the element in soil samples and Cm Background is the geochemical background
concentration of the metal in the world average shale (Clark values). The seven proposed
descriptive classes for I-geo values are given in the Table below (Muller, 1969). Enrichment of
metal concentration above baseline concentrations was calculated using the method proposed by
(Muller, 1969), termed the geo-accumulation index (I-geo). This method assesses the metal
pollution in terms of seven (0 to 6) enrichment classes ranging from background concentration to
very heavily polluted.
2.3 Statistical analysis
In order to study the characteristics of the study area soils, the heavy metals concentrations in the
top soils were subjected to correlation analysis, Principal Component Factor Analysis (PCA) and
Hierarchical Cluster analysis using JMP SAS version 11. Heavy metals concentrations in the
reclaimed mining area and the control soils were also compared using independent sample t-test
using IBM SPSS version 21 and geostatistical analysis by ArcGIS 10.1 software.
3.1 Results and discussion
3.1.1 Assessment of heavy metals contamination
3.1.2 Enrichment Factor
Table 1 shows enrichment factor values which indicate how many times concentration of heavy
metals measured in the reclaimed mining area and the control soils exceed the background
values. The enrichment factor showed that both the soil in the reclaimed mining area and the

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control were in the extremely high enrichment category (EF >40) with As. Copper showed very
high enrichment (20≤EF≤ 40) in the reclaimed area and significant enrichment (5≤EF<20 ) in
the control, both Pb and Ni showed moderately enriched (2 ≤ EF<5 ) in the reclaimed area
and deficient to minimal enrichment in the control (EF <2) and Zn concentration was
significantly enriched (5≤EF<20 ) in the reclaimed area and moderately enriched (2 ≤ EF<5 ) in
the control. The order of enrichment of heavy metals in the reclaimed mining area is As>Cu >
Zn> Pb=Ni and the order in the control was As>Cu > Zn> Pb=Ni. Both the control and the
reclaimed mining area seemed to have the same order of enrichment. This could imply that the
mining operation did not influence the levels of those metals in the soil. This trend is similar to
that reported by Boateng et al., (2012) for the assessment of metals in mine tailing reclamation
on the quality of soils in AngloGold concession at Obuasi.
Table 1 Enrichment Factor (EF)
Sampling EF (As)/ EF (Cu) EF (Pb) EF (Zn) EF (Ni)

Location mg/kg mg/kg mg/kg mg/kg mg/kg
Reclaimed 1272 31 3 9 3
Control 285 10 1 2 1
3.1.3 Contamination Factor (CF) and Pollution Load Index (PLI)
Contamination factors and PLI of the various elements (As, Fe, Cu, Pb, Zn and Ni) in the soil
samples of the reclaimed mining area and the control are presented in Table 2. Using the
contamination factor categories, both the reclaimed mining area and the control (un-mined area)
suffered very high contamination (6 ≤ CF) by As. Both suffered low contamination (CF < 1) by
Fe, Pb, Zn, and Ni and both also displayed moderate contaminations (CF < 1) by Cu. These low
concentrations would not have any adverse effect on humans or animals in the study area. Only
Arsenic concentration was found to be far above the geochemical background level in both areas
(reclaimed mining area and control). Since both areas are contaminated with As, the pollution is
not from the mining operation but could be due to natural process parent materials. The high
level of Arsenic in both areas has rendered the two sites not suitable for agriculture. According to
(Amadi et al., 2010), Arsenic is highly carcinogenic and has no nutritional value for plant and
animal. The PLI results presented in Table 2 also gave a confirmation that the overall degree of
heavy metal contamination in the reclaimed mining area is within the geological background
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level (PLI = 1), whereas the control (un-mined area) denotes perfection (PLI < 1) (i.e. no overall
pollution) Thomilson et al., (1980).
Table 2 Polution Load Index (PLI) and Contamination Factor (CF)
Sampling CF(As) CF (Fe) CF(Cu) CF(Pb) CF(Zn) CF(Ni) PLI

Location
Reclaimed 52.7 0.342857 1.264 0.135294 0.361972 0.115909 1.00
Control 25.8 0.248571 0.94 0.082353 0.183099 0.052273 0.26
3.1.4 Geo-accumulation index (I-geo)
The geo-accumulation index values presented in Table 3 were also consistent with the EF, CF,
and PLI calculations that the heavy metal levels in soils for the two sites did not exceed the
geochemical background values except As. From Table 3 the I-geo value for As in the reclaimed
mining area soil was in class 6 (extremely contaminated) whereas the I-geo value in the control
area soil was in class 5 (strongly to extremely contaminated).
Table 3 Geo-accumulation Index (I-geo)
Sampling IGEO IGEO IGEO IGEO IGEO (Zn) IGEO (Zn)

Location (As)/ (Fe) (Cu) (Pb) mg/kg mg/kg
mg/kg mg/kg mg/kg mg/kg
Reclaimed 5.0607 -2.1372 -0.2595 -3.6469 -2.0727 -3.7353
Control 4.10249 -2.6021 -0.6771 -4.2724 3.0631 -4.8324
Generally, the I-geo values for all the other metals in both the reclaimed mining area and the
control (Fe, Cu, Pb, Zn, and Ni) felled in class zero (0) suggesting that the metals are within the
geochemical background values defined by McLennan (2001) Table 4. The level of these
metals (Cu, Zn, Pb, Fe, Ni) are thus normal in the study area according to literature (Kabata-
Pendias and Pendias, (1992) and thus will not have any adverse health effects.
3.2 Statistical analysis
3.2.1 Independent sample T-test
Independent sample t-test was used to determine whether the mean concentration of heavy
metals levels in the reclaimed mining area and the control (area not mined) are the same. From
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Table 4, heavy metal levels in the reclaimed mining area are significantly higher than the
control (undisturbed area) at p<0.001 for As, Fe, Cu, Zn and Ni and significant at p<0.05 for Pb.
This suggests that the mining operations might have caused some degree of metal pollution. This
confirms Franco-Uria et al., (2009) assertion that Cu, Pb, and Zn concentrations change mainly
through human activities.
Table 4 Independent sample t-test for the comparison of heavy metals (As, Fe, Cu, Pb, Zn,
Hg, and Ni) in the topsoil (0-15cm depth) of reclaimed mining area
Sampling As Fe Cu Pb Zn Hg Ni
Locations
Reclaimed 79.0±27.1 12000±1347.5 31.6±4.4 2.3±1 25.7±4.1 ND 5.1±1.1

mining area
(40 -141) (10500-16000) (26-42) (1-4) (16-32) (3.8-8)
Control 38.7±2.1 8700±1059.3 23.5±1.6 1.4±0.5 13±2.9 ND 2.3±0.4

(36-41) (8000-11000) (22-26) (1-2) (10-18) (2-2.8)
df 28 28 28 28 28 - 28
t-statistic 4.65 6.75 5.58 2.59 8.79 - 7.29
Sig(2-tailed) 0.000 0.000 0.000 0.015 0.000 - 0.000
Canadians soil
quality 12 - 63 70 200 6.6 50
guidelines a
World ranges
in non-polluted 1-15 - 6 - 60 10-70 17- 125 - -
soils b
UCC Clark
Values c 1.5 35000 25 17 71 - 44
All concentrations are expressed in mg/kg

a
Canadian soil quality guidelines (CCME, 2006)
b
Kabata-Pendias and Pendias (1992)
c
Clarke values = mean concentrations of the chemical elements in the upper continental
crust (UCC) given by McLennan (2001)
ND= Not Detected; The values in parenthesis represent range.
The concentration of Arsenic in the topsoil of the reclaimed mining area (79±27.1 mg/kg) and
the control (38.7±2.06 mg/kg) exceeded the soil quality guidelines values adopted by Canada

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and the European community (CCME, 2006; Kabata-Pendias and Pendias, 1992) Table 4. For
agricultural land use, the maximum acceptable concentration of As according to (CCME, 2006)
is 12mg/kg and thus As concentration in both areas far exceed the maximum acceptable limit for
agriculture. Therefore, adverse effect on human health might be expected especially on young
children‟s health that has a higher absorption rate of metals and metalloids because of their
active digestion systems. Past studies have revealed that human exposure to high concentrations
of Arsenic (As) causes severe skin cancer and hyperkeratosis (Chowdhury et al., 2000). The
concentration of Fe range from 10500 mg/kg to 16000 mg/kg in the reclaimed mining area and
the control ranges from 8000 mg/kg to 11000mg/kg. The concentrations of Fe in both areas were
far below the geochemical background values Table 4. Copper concentration in the reclaimed
area ranges from 26mg/kg to 42mg/kg with a mean of 31.6±4.42 mg/kg and the level in the
control ranges from 22mg/kg to 26mg/kg with a mean of 23.5±1.58mg/kg. For agricultural land
use, the maximum acceptable concentration of Cu is 63mg/kg according to the Canadians soil
quality guidelines and 6mg/kg – 60mg/kg according to World ranges in non-polluted soils [4]
(Table 4). Lead was 2.25±0.97 mg/kg with a range of 1mg/kg - 4mg/kg in the reclaimed area
whereas Pb in the control ranges from 1mg/kg to 2mg/kg with a mean of 1.4±0.52mg/kg. Zinc
concentration in the reclaimed mining area range from 16mg/kg to 32mg/kg and the control
range from 10mg/kg to 18mg/kg. Nickel concentration was 5.07±1.15mg/kg with a range of
3.8mg/kg - 8mg/kg whiles the concentration recorded in the control ranges from 2mg/kg to
2.8mg/kg with a mean of 2.34±0.35mg/kg. Mercury was not detected in the topsoil of both the
control and reclaimed area. Lead, Zinc and Nickel were all within the soil quality guidelines
values adopted by Canada and the European community for soils suitable for agriculture
(CCME, 2006; Kabata-Pendias and Pendias, 1992) (Table 4). These guidelines were used in El-
Khalil et al., (2008) research which were undertaken to assess the metal contamination from
mining sites in the southern part of Morrocco.
3.2.2 Pearson correlations Matrix of heavy metals
Heavy metals in soil usually have relationships between them. The inter-elemental association
was evaluated by Pearson‟s correlation matrix and the results presented in Table 5. Zn/Pb (r=
0.314), and Ni/Pb (r=0.330), have positive correlations significant at p<0.05. The following
metals are strongly correlated at p <0.01: Fe/As (r=0.502), Cu/Fe (r= 0.345), Pb/Cu (r=0.333),

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Zn/As (r= 0.548), Zn/Fe (r= 0.638), Zn/Cu (r= 0.438), Ni/As (r= 0.528), Ni/Fe (r= 0.426), Ni/Cu
(r= 0.335), and Ni/Zn (r= 0.718). The high correlations between soil heavy metals may reflect
the fact that these heavy metals have similar pollution sources or metal origin (Armah et al.,
2010).
Table 5 Pearson correlation coefficient matrix of the heavy metals

As Fe Cu Pb Zn Ni
As 1
Fe .502** 1
Cu 0.19 .345** 1
Pb 0.208 0.171 .333** 1
Zn .548** .638** .438** .314* 1
Ni .528** .426** .335** .330* .718** 1
* Correlation is significant at the 0.05 level (2-tailed); ** Correlation is significant at the
0.01 level (2-tailed).
3.2.3 Principal Component Analysis
The data set was subjected to principal component analysis to establish possible factors that
contribute towards the heavy metal concentrations and source apportionment. The number of
significant principal components (PCA) was selected on the basis of Verimax orthogonal rotation
algorithm with Kaiser Normalization with eigenvalues greater than 1. The results are presented
in Table 6 and Figure 2.
Verimax factor loading coefficient (Liu, et al., 2005) with a correlation of: >0.75 are explained
as strong significant factor loading (FL); 0.75-0.50 is considered as moderate FL; and 0.50-0.30
is considered as weak FL. The first two components or factors accounting for 73.392% of the
total cumulative variances were considered. The first principal component, (PC-1) with
55.916% of the total variance is strongly loaded by As, Fe, Zn, Ni and moderately loaded by Cu
which implies that these metals may have originated from similar pollution sources. Close
association of these metals is also supported by their significant correlation (Table 5). The
association of As, Fe, Zn, Ni and Cu on PC-1 could be due to their common occurrence in the

411
bedrock since the concentrations of these elements in this research were lower than the
geochemical background values by Table 4 except the concentration of As, which exceeded the
background values, the elements on PC-1 are thus said to be originated from natural sources but
not from the mining operations.
Figure 2 Loading plots of PCA analysis of heavy metals concentration of soils in the study
area
Mico et al., (2006) reported that the amount of Cu, Fe, Ni, and Zn could be affected by bedrocks
likewise; Jiachun et al. (2004) also asserted that As content could be controlled by bedrock. The
second principal component (PC-2) explains 17.476% of the total variation and exhibited a high
positive factor loading on Pb and moderate factor loading on Cu. Copper had a moderate factor
loading for both PC-1 and PC-2, which could indicate that it might have originated from both
natural and anthropogenic sources. PC-2 is strongly loaded by Pb indicating that its source could
be due to anthropogenic (e.g. Vehicular emissions, transportation and traffic) since the
reclaimed mining area was just by a road. Transportation and traffic were considered as the main
factors contributing to high levels of Pb in soils of Spain Rodriguez-Martin et al.,(2006).

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Table 6 Factor analysis after Verimax rotation with eigenvalue greater than 1
Heavy metals PC-1 PC-2

As 0.861448 -0.165456
Fe 0.856911 0.102076
Cu 0.557060 0.402860
Pb 0.061817 0.951782
Zn 0.812115 0.377680
Ni 0.756253 0.364574
Eigenvalue 3.3550 1.0486
% of total variance 55.916 17.476
Cumulative (%) 55.916 73.392
Extraction Method: Principal Component Analysis; Rotation Method: Varimax with
Kaiser Normalization
Cluster Analysis (CA)
Cluster analysis was used to classify the heavy metals and help identify their anthropogenic or
natural sources (Li and Feng, 2012). Herein, CA was used to check the results of the PCA results
for heavy metals.
Figure 3 Dendrogram derived from hierarchical cluster analysis (Ward method) of heavy
metals content in analysed soils.
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The result of the cluster analysis (CA) is shown in Figure 3. The hierarchical cluster analysis
using Ward method produced two clusters. Cluster 1 contained As, Cu, Zn, Pb and Ni. These
elements were classified as both anthropogenic and natural in origin whereas the second cluster
was classified as natural (Fe). The cluster analysis was similar to the PCA analysis except that
PC-1 discriminated Pb from the group and replaced it with Fe.
3.3 Spatial distribution pattern of metals
Kolmogorov-Smirnov test (Table 8) was performed to check the normal distribution of the data
at 95% confidence level. Only Cu, Zn, and Ni passed the normality test at 0.05 significance
level, thereby providing a basis for geostatistical analysis. Box-Cox transformation was therefore
used to make the variables (As, Fe, and Pb) that did not pass the normality test more normal prior
to the geostatistical analysis. Gaussian model was in reasonable agreement with the data for soil
As, Exponential model was fit for Pb whereas Fe, Cu, Zn, and Ni were best fitted to the
Spherical model. Semivariogram models and parameters of soil heavy metal concentrations are
shown in Table 7. The presence of nugget variance in each soil heavy metal was probably due to
short-range variability and uncertainty caused by sampling errors. The range represents the
average maximum distance over which two samples are related or the distance beyond which
observations were not spatially dependent. The ranges of the studied heavy metals were in the
order of Fe= Zn= Ni >As= Cu > Pb. The zones of influence for Fe, Zn and Ni were the same
(0.003m); and the zone of influence for As and Cu were also the same (0.001m) ; however, for
Pb, the distance was much less(0.0004m). The low ranges for the metals suggested that
anthropogenic activities might have influence the concentration of these metals. The ratio of
nugget variance (C0) to sill variance (C0 +C) indicates the proportion of random components to
system spatial heterogeneity. Spatial dependence index (SDI) for As, Fe, Cu, Pb, Zn, and Ni
were 2.71%, 11.17%, 9.58%, 16.99%, 5.49% and 7.44% respectively. Spatial dependence index
intervals: SDI >75%; 25≤SDI ≤ 75%; SDI <25% proposed by Cambardella et al., (1994) were
used to describe the proportion of the spatial structure that showed low, moderate and strong
spatial autocorrelation respectively. This indicator to some extent reflects predominant factors
which impact the spatial variability of the soil heavy metals between natural factors such as soil
parent materials and anthropogenic factors such as agricultural practices and mining activities.
All the six heavy metals exhibited strong spatial dependencies with ratio of nugget variance to

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sill variance ranging from 2.71% to 16.99%. In general, weak spatial dependence of soil heavy
metals could be attributed to anthropogenic influence and strong spatial dependence can be
ascribed to natural factor Cambardella et al., (1994). All the metals studied in this research
exhibited strong spatial autocorrelation (SDI <25%). This implies that the concentration of heavy
metals in the area were not affected by the mining operation, this is a reconfirmation of the low
PLI and geo-accumulation index analysis of the concentration of the studied metals ( Cu, Fe,
Zn, Pb and Ni). The high concentration of As in the study area could be due to natural process.
The ordinary Kriging interpolation was used to generate smoothed contour maps to show the
spatial variability of these metals in the study area. The smoothed contour maps obtained for the
six variables are presented in Figure 4. Close examination of the smoothed contour maps reveals
that Fe, Zn, Ni, Cu and As have similar spatial distribution pattern except that higher
concentrations of Zn, As, Cu and Ni appear to be slightly widely dispersed than Fe. This
provided reconfirmation of the results in the statistical analysis, in which strong associations
were found among Fe, Zn, As and Ni (Table 5) and with high factor loadings on PC-1 ( Figure
2, Table 6) and belonged to one group in the Hierarchical cluster analysis (Figure 1). However,
Pb did not show a clear spatial structure (Figure 4). The smoothed contour maps showed several
critical concentration „hotspots‟ for As, Fe, Cu, Zn and Ni.
Table 7: Geostatistical parameters for heavy metals
variable Model Nugget Partial Sill Sill Range Nugget/ SDI Predictio
Type (Co) (C) (Co+C) Sill (%) n Errors
RMS
As Gaussian 32.702 1173.19 1205.895 0.0010 2.71 Strong 16.6
Fe Spherical 780250 6205863 6986112.8 0.0030 11.17 Strong 1337.7
Cu Spherical 3.87 36.513 40.383 0.0010 9.58 Strong 3.65
Pb Exponential 0.141 0.689 0.83 0.0004 16.99 Strong 0.935
Zn Spherical 5.36 92.282 97.642 0.0030 5.49 Strong 4.106
Ni Spherical 0.36 4.479 4.839 0.0030 7.44 Strong 1.064

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From (Figure 4) it can be seen that high concentrations of metals (hotspots) are distributed
towards the southwestern and northwestern part of the map which represents the reclaimed
mining area, thus the metal concentrations were closely related to the mining disturbed areas
whereas low metal concentrations were noticed towards the southeastern and northeastern part of
the map represented by areas not disturbed by mining (control). It is clearly evident from Figure
4 that though the concentrations of the metals studied were all below the geochemical
background values except As whose concentration was above the background value, however,
hotspots of metal pollution could be seen in the reclaimed mining area compared to the control.
Therefore, if preventive measures are not put in place there could be pollution of these metals
above the geochemical background values in future. Studies have shown that high concentrations
of heavy metals in soils are mostly due to industrial effluents, and sewage sludge from chemical
and mining industries Jensen, A. and F. Bro-Rasmussen (1992). Plants growing in metal polluted
locations exhibit altered metabolism, growth reduction, lower biomass production, and metal
accumulation which can be transferred to humans through food chain.
Table 8 Kolmogorov-Smirnov tests for Normality
Elements As Fe CF(Cu) Pb Zn Ni
Statistic .166 .187 .126 .219 .142 .133
Sig. .034 .009 .200 .001 .126 .185

416
Figure 4 Smoothed contour maps produced by ordinary Kriging for soil As, Cu, Zn, Ni, Pb
and Fe.
NB: RC = Reclaimed mining area ; CTL = Control

417
Conclusions
In this study, Enrichment factor (EF), Contamination factor (CF), Pollution load index (PLI),
Geo-accumulation index (I-geo), Principal Component analysis (PCA) Cluster analysis (CA) and
geostatistics, were used for determining the environmental quality of soils and spatial variability
of heavy metals in a reclaimed mining area and control (undisturbed mining area) at AngloGold
mining concession, Adubirem. The four pollution indices used (EF, CF, PLI and I-geo) revealed
that the concentration of the metals studied (Fe, Cu, Pb, Zn, and Ni) in the reclaimed mining area
and the control were below the geochemical background level (i.e. the area is not polluted with
the metals studied) except As. This suggests that soil quality in the reclaimed mining area has
been restored except the concentration of As which is naturally high in the study area. The
independent sample t-test showed that the concentration of Fe, Cu, Pb, Zn, Ni and As were
significantly higher in the reclaimed mining area than the control area. However, they were all
within the geochemical background values, the Canadian and the European Community soil
quality guide lines except As. The high level of As in the area has rendered the reclaimed
mining area and the control sites not yet favourable for the production of food crops, but could
be used for the establishment of ornamental plants until the concentration of As reduces to
acceptable limits. The PCA suggested that As, Fe, Zn, Ni and Cu are predominantly derived
from natural sources; Pb originated from vehicular emission, transportation and traffic; and Cu
from both sources (both natural and anthropogenic). The cluster analysis results were similar to
the PCA. The spatial distribution maps of As, Fe, Zn, Ni , Pb and Cu concentrations, which was
generated using Ordinary Kriging interpolation, displayed several hotspots of heavy metal
pollution in the study area. The concentrations seem to be higher in the reclaimed mining area
and decrease father away towards the control site. This seems to imply that the mining operation
has increased the level of those metals in the reclaimed mining area. However, the concentrations
of all the metals studied exhibited strong spatial autocorrelations indicating that spatial
variability of these metals was not affected by the mining operation. Therefore, there is no direct
evidence to confirm that the As pollution in the reclaimed mining area originated from mining
activities, though, the mining activities might have contributed to the rise in the level of As
concentration in the reclaimed mining area to some extent, however, since the As concentration
in the control soils were also above the soil quality guidelines, this implies that the study area
was naturally polluted with Arsenic but not as a results of the mining operation.
418
Acknowledgements
To the Almighty God for the wisdom and to Dr. D.E.K.A Siaw, Dr. Simon Abugre, Mr. I.K.
Abebrese, Dr. Kwame Twum-Ampofo and Mr. Baah Michael, for their support in several phases of the
study.

419
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AARJMD VOLUME 1 ISSUE 32 (APRIL 2015) ISSN : 2319 - 2801

A Peer Reviewed International Journal of Asian

ASSESSMENT OF SPATIAL VARIABILITY AND CONCENTRATION OF HEAVY

Keywords: Geostatistics, Principal component analysis, Cluster analysis, Pollution indices

Asian Academic Research Journal of Multidisciplinary

2.1 Materials and Methods

2.1.1 Study area description

Asian Academic Research Journal of Multidisciplinary

Figure 1 Geological map of Ghana showing Adubirem in Amansie East District

2.1.2 Sampling design and chemical analysis

2.2.1 Enrichment Factor

Asian Academic Research Journal of Multidisciplinary

2.2.2 Contamination Factor (CF) and Pollution Load Index (PLI)

Where n= number of metals studied

The geo-accumulation index is a quantitative measure of the degree of pollution in water

Asian Academic Research Journal of Multidisciplinary

3.1 Results and discussion

3.1.1 Assessment of heavy metals contamination

3.1.2 Enrichment Factor

Asian Academic Research Journal of Multidisciplinary

Table 1 Enrichment Factor (EF)

Sampling EF (As)/ EF (Cu) EF (Pb) EF (Zn) EF (Ni)

3.1.3 Contamination Factor (CF) and Pollution Load Index (PLI)

Table 2 Polution Load Index (PLI) and Contamination Factor (CF)

Sampling CF(As) CF (Fe) CF(Cu) CF(Pb) CF(Zn) CF(Ni) PLI

3.1.4 Geo-accumulation index (I-geo)

Table 3 Geo-accumulation Index (I-geo)

Sampling IGEO IGEO IGEO IGEO IGEO (Zn) IGEO (Zn)

3.2 Statistical analysis

3.2.1 Independent sample T-test

Reclaimed 79.0±27.1 12000±1347.5 31.6±4.4 2.3±1 25.7±4.1 ND 5.1±1.1

Control 38.7±2.1 8700±1059.3 23.5±1.6 1.4±0.5 13±2.9 ND 2.3±0.4

All concentrations are expressed in mg/kg

Asian Academic Research Journal of Multidisciplinary

3.2.2 Pearson correlations Matrix of heavy metals

Asian Academic Research Journal of Multidisciplinary

Table 5 Pearson correlation coefficient matrix of the heavy metals

3.2.3 Principal Component Analysis

Asian Academic Research Journal of Multidisciplinary

Asian Academic Research Journal of Multidisciplinary

Heavy metals PC-1 PC-2

Cluster Analysis (CA)

3.3 Spatial distribution pattern of metals

Asian Academic Research Journal of Multidisciplinary

Table 7: Geostatistical parameters for heavy metals

Asian Academic Research Journal of Multidisciplinary

Table 8 Kolmogorov-Smirnov tests for Normality

Asian Academic Research Journal of Multidisciplinary

NB: RC = Reclaimed mining area ; CTL = Control

Asian Academic Research Journal of Multidisciplinary

Acosta, J.A., A. Faz, , S. Martínez-Martínez, R. Zornoza, D.M. Carmona, S. Kabas, (2011).

Asian Academic Research Journal of Multidisciplinary

Asian Academic Research Journal of Multidisciplinary

Mico C, Recatala L, Peris M, Sanchez J (2006). Assessing heavvy metal sources in

Asian Academic Research Journal of Multidisciplinary

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