Journal Pre-proof

Compositional and source patterns of potentially toxic elements

(PTEs) in soils in southwestern Ghana using robust compositional
contamination index (RCCI) and k-means cluster analysis

Raymond Webrah Kazapoe , Ebenezer Ebo Yahans Amuah ,

Paul Dankwa , Kwabena Ibrahim , Benatus Mville ,
Sadique Abubakari , Naziru Bawa

PII: S2667-0100(21)00227-4
DOI: https://doi.org/10.1016/j.envc.2021.100248
Reference: ENVC 100248

To appear in: Environmental Challenges

Received date: 1 June 2021

Revised date: 17 August 2021
Accepted date: 17 August 2021

Please cite this article as: Raymond Webrah Kazapoe , Ebenezer Ebo Yahans Amuah ,
Paul Dankwa , Kwabena Ibrahim , Benatus Mville , Sadique Abubakari , Naziru Bawa , Com-
positional and source patterns of potentially toxic elements (PTEs) in soils in southwestern Ghana
using robust compositional contamination index (RCCI) and k-means cluster analysis, Environmental
Challenges (2021), doi: https://doi.org/10.1016/j.envc.2021.100248

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 Compositional and source patterns of potentially toxic elements (PTEs) in soils in southwestern
Ghana using robust compositional contamination index (RCCI) and k-means cluster analysis

Raymond Webrah Kazapoea, Ebenezer Ebo Yahans Amuahb*, Paul Dankwac, Kwabena Ibrahimd,
Benatus Mvillee, Sadique Abubakarif, Naziru Bawag

a
Department of Geological Sciences, University for Development Studies, Tamale, Ghana
b
Department of Environmental Science, Kwame Nkrumah University of Science and Technology,
Kumasi, Ghana
c
Department of Environmental Science, C. K. Tedam University of Technology and Applied
Sciences, Navrongo, Ghana
d
Earth Science Department, University of Ghana, Ghana
e
Department of Physics, College of Natural and Mathematical Sciences, University of Dodoma, P. O.
Box 259, Dodoma, Tanzania
f
Faculty of Engineering, Environment and Computing, Coventry University, United Kingdom
g
Department of Earth Science, C. K. Tedam University of Technology and Applied Sciences,
Navrongo, Ghana

Corresponding author
Ebenezer Ebo Yahans Amuah
+233546339605

1
Graphical Abstract

Abstract
Soils are heavily impacted by geogenic and anthropogenic factors. It forms an integral part in
supporting agriculture, plants, and the natural climate. This study investigated the soil chemistry in
the Wassa and Prestea-Huni Valley areas in southwestern Ghana using the RCCI technique and
multivariate statistics using a total of 300 soil samples. The results showed that 43%, 98%, 50%, and
100% of the samples exceeded the standards respectively for As, Ba, Co, and Cu. Meanwhile, for Cr,
Ni, Mn, Fe, and Zn, 50%, 54%, 5%, 46%, and 71% were above their guideline values. The RCCI
computation showed that 2%, 15%, 48%, 34%, and 1% of the samples were within lower, medium,
moderate, high, and very high ranges respectively. The interpolation of the RCCI results showed
sparse but concentrated hotspots around mid-Wassa Amenfi Central, mid- towards the north of the
Wassa Amenfi West and East Districts. Also, the K-means and ANOVA outputs showed that Cu and
Ni contributed significantly to the chemistry of the soil. The EOF 1 showed a weighted sum of V, Fe,
Cu, Ni, Zn, Ba, Cr, Ag, and Pb. Inferentially, these contained the highest signals of the data and
predominantly influenced the quality and variability of the soils. The variations shown in the levels of
the assessed elements across the areas suggest that processes impacting elemental accumulation and
enrichment were influenced by different processes. These could also impact other environmental
media including surface and groundwater quality, vegetation, and air quality. Residents within hotspot
areas are exposed to several deleterious health impacts through oral, nasal and dermal routes. The

2
areas with elevated concentrations of PTEs could pose a public health challenge down the line as
these elements come into contact with people through crops and groundwater obtained from the area.
Addressing such a challenge calls for interdisciplinary collaboration between environmental
geologist/medical geology researchers, public health practitioners, epidemiologists, environmental
toxicologists, nutritionists, dieticians, and agriculturists.

Keywords: Compositional and Source pattern, Heavy metal, PTEs, RCCI, K-means cluster analysis

1. Introduction
Soils form an integral part in supporting agriculture, plants, and the natural climate since it stores 75%
of the terrestrial organic carbon (Kassa et al., 2017). Understanding the elemental concentration,
sources, patterns, and distribution of soil are essential in solving elemental toxicity issues related to
humans, animals, and plants. The concentrations of these elements are significantly influenced by
geogenic and anthropogenic processes including mining, the geochemistry of parent or underlying
materials, weathering processes, lithology, and geopedological processes (Adriano, 2001; Kazapoe
and Arhin, 2019). Agrochemicals, industrial and domestic activities, municipal and livestock wastes,
and petroleum products have also been studied to contribute largely to soil chemistry and
contamination (Bundschuh et al., 2012). Petrik et al. (2018a) indicate that soil pollution has become
an environmental challenge due to the debilitating impacts it poses to humans and ecosystems in
general. There is a risk of potential toxic elements (PTEs) in soils resulting from the rapid increase in
population, urbanization, industrialization, and agriculture (Wu et al., 2015; Amuah et al., 2021).
Mining is a major environmental factor that impacts soil chemistry resulting in the release of mining
tailings and polluted wastewater into the environment. It also poses deleterious impacts on soil
quality. Studies by Antwi-Agyei et al. (2009), Nude et al. (2011), Bempah et al. (2016) in Obuasi, and
Gyamfi et al. (2019) in Kokoteasua, Ashanti Region of Ghana, Zango et al. (2013), and Arhin et al.
(2019) in the Wassa area, Issahaku et al. (2015) and Ewusi et al. (2017) in the Tarkwa-Nsuaem
Municipality, Mensah et al. (2015) in the Prestea-Huni Valley area, Dorleku et al. (2018) in the Lower
Pra Basin, Mensah et al. (2015) and Petelka et al. (2019) in Damang, and Darko et al. (2019) in
Gbani, northern Ghana have shown elevated elemental concentrations in soils in mining communities
in Ghana which appear to be partly linked to the mining activities. Recently, there has been a
considerable increase in mining companies and small-scale mining (galamsey) in the Wassa and the
Prestea-Huni Valley areas. Also, the influx of people has significantly expanded settlement areas.
This has resulted in the conversion of abandoned mining sites into agricultural lands and settlements
(Owusu-Nimo et al., 2018). This may pose public health implications to the local population due to
direct and indirect exposures to contaminated soils and tailings (Kazapoe et al. (2021).
In addressing these global challenges, geostatistical computations, and mapping tools and procedures
have been employed in the identification and differentiation of the provenance, distributions, and

3
patterns of elements from geological factors and anthropogenic activities for more substantial
assessments (Reyes et al., 2019). Though recognized indices including enrichment factors, the single
pollution index, and the geo-accumulation index have been adopted in the quantification of
contamination and depletion of elements in environmental mediums, studies by Reimann and Garrett
(2005), and Petrik et al. (2018b) showed that these indices are not scale-invariant since modifications
in the units of measurement alter the results of the analysis. Besides, Reimann and de Caritat (2000)
and Reyes et al. (2019) reveal that Enrichment Factors (EFs) and Element Ratio Variations may not
only vary based on the types of parent materials but the reference media and elements. These indices
do not consider the dissimilarities in the biogeochemical processes that influence the elemental
concentration of soils, the naturally-induced elemental fractionations, and the variations in the
solubility of minerals which could affect soil chemistry (Sucharovà et al., 2012).
Petrik et al. (2018a) introduced the Robust Compositional Contamination Index (RCCI) which
involves the compositional structures of obtained datasets, avoiding outlier artefacts. RCCI gives an
understanding of the sources, distributions, and patterns of elements to ascertain if they are influenced
by anthropogenic and/or geogenic factors. However, the studies undertaken in Ghana adopted the use
of the Geo-accumulation index (Igeo), Enrichment Factors (EF), Contamination Factor (CF), Degree
of Contamination (Cd), and Pollution Load Index (PLI) (Zango et al., 2012; Bempah et al., 2016;
Darko et al., 2019). This research presents a spatial abundance of Potentially Toxic Elements (PTEs)
in soils of the Wassa and Prestea-Huni Valley areas by employing the RCCI technique that adopts the
compositional structure of the data, cluster analysis, multi-criteria ranking, and Principal Component
Analysis were used to present the contractional availability and the main controls on the quality of the
soils. Due to the ingestion of chemical elements dermally, evaluating, and monitoring the quality of
soils in the study areas is essential to understanding, protecting, and managing environmental
resources and people's health and wellbeing. The research is essential because no categorical study
using RCCI, K-means and multivariate statistics in the area forms a foundational investigation on the
potential sources, levels, and spatial distributions of PTEs in this area and Ghana. This study seeks to
determine the soil chemistry in the Wassa and Prestea-Huni Valley areas, the possible sources of soil
contamination for remediation processes.

2. Materials and Methods

2.1 Geological features and land use of the study area
A majority of the current mining activities in Ghana are undertaken in the Western and Northwestern
regions of the country (Chamber of Mines, 2014). This study sought to assess the quality of soil
within communities in the Prestea-Huni Valley and the Wassa East, Central, and West districts (Fig.
1). These areas experience an annual rainfall of 1444 mm making them some of the wettest areas of
Ghana. The areas experience bimodal rainfall with temperatures ranging between 24 ºC and 29 ºC in

4
the dry and rainy seasons respectively (GSS, 2014). These climatic conditions make the areas viable
for agricultural activities. Kazapoe and Arhin (2019) indicate that the Tano and Ankobrah Rivers are
the main water systems that drain the areas. The Wassa area is underlain by meta-volcanic, meta-
sedimentary rocks with granitic intrusions (Kesse, 1985). These geological formations are associated
with hydrothermal veins and quartz, which contain high concentrations of sulfide and gold
formations. Findings by Dzigbodi-Adjimah (1993) also reveal that the Birimian rocks in Ghana are
embedded with both essential and toxic elements. The Prestea area falls within western Ghana with
fragmented litho-structural assemblies that are fault-bounded and dipping steeply westward, along the
Ashanti Greenstone Belt (Botwe et al., 2018). The underlying geology is of Birimian and Tarkwaian
gold-bearing types (Kesse, 1985). Studies by Kesse (1985) and Quansah and Amankwah (2011) have
shown that the occurrence of arsenic and sulfur in the Birimian while chlorites, chloritoids, calcites,
sericites, quartz, and limonites can be found in the Tarkwaian.

Fig. 1 Locations of study areas and soil sampling points

2.2 Sampling procedure and analyses

Sampling and handling were done following the recommendations by the USEPA (2004). A total of
three hundred (300) samples of soil at a depth of 0-20 cm were collected from both mining and non-
mining communities in the Wassa and Prestea-Huni Valley areas using a soil auger and were
homogenized into composite samples. The samples were contained in high-density polyethene bags
which were washed using nitric acid (HNO3 4 mol/L), flushed with ultra-pure water, and dried before

5
sampling. The geographical locations of the sampling points were recorded using a Global Positioning
System (GPS). The geochemical composition of both mining and non-mining communities has not
been widely studied interconnectedly. To ensure that the samples representative, were homogenized,
and cross and gross contamination were avoided. The samples were conditioned under air-drying,
sieved through a 2-mm nylon sieve to remove large debris and were sealed in the prepared polythene
bags for analysis (Kazapoe et al., 2019).

2.3 Analytical methods and Quality Assurance and Control Analysis (QA/QC)
Ten soil quality parameters were considered in this study. These include silver (Ag), arsenic (As),
barium (Ba), cobalt (Co), chromium (Cr), copper (Cu), iron (Fe), manganese (Mn), nickel (Ni), lead
(Pb), vanadium (V), strontium (Sr), and zinc (Zn). In this study, the concentrations of Cu, Cr, and Zn
were measured with an Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES)
whereas Pb was determined by an Inductively Coupled Plasma Mass Spectrometer (ICP-MS) and As
was determined using an Atomic Fluorescence Spectrometry (AFS). Ag, Ba, Co, Fe, Mn, Ni, V, and
Sr were measured using the Panalytical Axios-Advanced wavelength dispersive x-ray fluorescence
(WDXRF) spectrometer. The equipment was calibrated following the IAEA-Soil 7 guideline before
use and reagent blanks were used for quality control. All the analytical results were obtained as
averages of three replicates. The precision of the analysis was calculated using three in-house
replicates, and two blind duplicates. The IUPAC standards presented by De Zorzi et al. (2005) were
followed to ensure QA/QC in this study. Accuracy was determined following Reyes et al. (2019) and
presented in Table S1. To enhance the QA/QC analysis for proper analytical quality, nine (9)
reference materials were considered in this study. To ensure the analytical precision of the samples
and analytical quality, one (1) control sample was taken per 19 samples and a duplicate sample per 29
samples. The precision of the obtained data was computed as Relative Percentage Difference (RPD)
using the formula suggested by Reyes et al. (2019) which is presented as:
( )
[ ] (1)

Where SV represents the original sample value, and Ds represents the duplicate sample value.

Information on the lithology of the area, soil types, observed geomorphic and weathering activities
were recorded to establish the impacts of both geogenic and anthropogenic activities impacting the
soil chemistry.

2.4 Geochemical mapping, Robust factor analysis, and K-means clustering

2.4.1 Spatial distribution and baseline values of PTEs

6
The spatial distributions and prediction of possible sources of contamination of elements in the soil
samples were done using ArcGISTM software through interpolation techniques. Though Luz et al.
(2014) indicate that several interpolation techniques have been adopted in the spatial display of
elements and geochemical processes, discrete background values from anomalous values, and reveal
the patterns of the source of elements, Conventional Weighted Average techniques including kriging
and ordinary inverse distance weighted (IDW) usually smoothen the local variabilities of the
geochemical data, whiles the multi-fractal IDW (MIDW) produces geochemical maps that present
details of the local variabilities and high-frequency information (Cheng, 1999; Lima et al., 2003;
Reyes et al., 2019). In the interpolation and mapping of the geochemical parameters, the spatial
associations and scaling were considered. The MIDW method; concentration–area (C–A) model of
the PTEs was done using ArcGIS (ESRI 2012) and GeoDAS whereas the Fourier spectral analysis
was adopted for the spectrum–area (S–A) model, following Reyes et al. (2019). The generated
interpolated maps derived were further transformed into frequency domains whereas the spatial
concentration–area fractal method was used to distinguish the patterns based on the power spectrum
distribution. Log-log plots were adopted in the presentation of the relationship between the area and
the power spectrum values on the Fourier transformed map of the power spectrum. The values
recorded were filtered by fitting straight lines using least squares to model the log-log plots. The
reversed images to spatial domains with the filter applied to indicate areas that represent the baseline
geochemical values of the PTEs.

2.4.2 Robust Compositional Contamination Index (RCCI)

RCCI gives an understanding of the sources, distributions, and patterns of elements to ascertain if they
are influenced by anthropogenic and/or geogenic factors. It is expressed as follows in three
chronological steps:

[ ] (2)

The ratio of the concentration of the metal (Xi), Concentration of the element of concern in the soil
(Ci), and the geochemical background/baseline of the element considered (Bc). In this study, the
geometric mean (GeoM) of baseline values of each of five considered PTEs (As, Cr, Cu, Pb, and Zn)
is considered before the mean value since GeoM considers the central tendency of the data and
remains unaffected by outliers.

( ) (3)

Qi represents the result obtained by computing the geometric mean (GeoM) of each sampling location
constituted of Xi.

7
 [ ] (4)

RCCI represents the Robust Compositional Contamination Index, Zi is the geometric mean of the
sampling point i, and Zmax symbolize the maximum geometric mean. Where GeoMsoil is the geometric
mean of the PTE and Bn is the baseline value of the element considered. The result ranged between 0
and 100% where the highest RCCI contamination grades were near 100%.

2.4.2 K-means clustering analysis

Cluster analysis classifies samples into different groups with samples of similar characteristics (Xu et
al., 2021). Alizadeh et al. (2017) indicate that the K-means clustering algorithm is a partitioning
method that is aimed at partitioning the space into k non-overlapping clusters and classify each
observation to the nearest centre to maximize the between-cluster variance as well as minimize the
within-cluster variance. It is used to measure the similarity between two observations or samples in
the algorithm. In this study, Euclidean distance was selected for the K-means algorithm which was
determined following Xu et al. (2021). The function is presented as:

∑ ∑ ‖ ‖2 (5)
where objective function = Of, ith cluster = Ci, number of samples in ith cluster = fi, distance function
dji = ||Mj - μi||2 represents the calculation of the distance between each sample point Mj and centroid μi
in the ith cluster. The centroid μi is calculated using the function:

∑ (6)
| |

2.5 Statistical data analysis

The R software was used for ―compositions‖ and ―robcompositions‖ geostatistical computations.
Descriptive statistics including minimum, maximum, average, and median values, standard deviation
(SD), coefficient of variation in percentage (CV%), kurtosis, and skewness were computed using the
log-transformed data that were then back-transformed to describe the central tendency and variability
of the concentration of the studied elements. Five (5) PTEs (As, Cr, Cu, Pb, and Zn) were considered
and their relationships with other geochemical elements were determined by Pearson correlation
coefficients (r) and the p values with direct and inverse relationships were considered. The Principal
Component Analysis (PCA) was performed on the data using the correlation matrix. PCA does not
only identify the significant components and factors that aid in the interpretation of large data, but it
also visualizes the correlation between the variables, limits the number of variables, and identifies the
main controls impacting the soil quality (Loh et al., 2019). The variables were transformed using
normal score transformation before the PCA where the North et al. (1982) method was used in

8
selecting the components with the highest signals. Following Bern et al. (2019), the dataset was
subjected to a Centered Log Ratio (CLR) transformation using the formula presented in equation 7.

[ ] (7)
√

CFe = measured concentration of Fe; an immobile element, and C1C2C3…. Cn = measured

concentrations at individual points.

3. Results and Discussion

3.1 Elemental concentration in soils
The quality of soil emphasizes dynamic aspects that examine the sustainability of soil management
practices and should depend on the in-situ factors that are inherent (De la Rosa and Sobral, 2008).
Table 1 presents the statistical summary of the soil quality results. The results for Ag ranged between
4.00 ppm to 17.00 ppm with an average concentration of 4.58 ppm. Jones et al. (1983) indicate that
except for mining areas where Ag may reach 44 ppm, soil Ag is mostly low. The study findings were
dissimilar with a study by Mensah et al. (2015) where Ag ranging between 0.10 ppm to 0.60 ppm was
identified in Damang-Abosso, western Ghana, and Reyes et al. (2019) in Taltal, northern Chile (0.10-
10.90 ppm). Except for certain hotspot areas in the Wassa Amenfi East (central-northwards) and West
(northwards) and the Prestea-Huni Valley (central part), and moderately contaminated areas that are
majorly situated in the Wassa Amenfi East and Prestea-Huni Valley, with a few sites in the Wassa
Amenfi West and Wassa Amenfi Central, the concentration of Ag was generally low (Fig. S1A). This
could be attributed to the deposition of gold-rich soils via mining activities. However, this suggests
that people within the hotspot and moderately contaminated areas may be exposed to the health
implications related to Ag including kidneys and liver dysfunction, argyria and argyrosis, and skin
irritation (Lansdown, 2006).
Arsenic is described as a high-impact toxicant (Drake et al., 2005). The concentration of As fell
within 2.00-246.00 ppm (Avg. 18.37). The study showed that 43% of the As values were above the
baseline value of 15 ppm recommended by Arhin et al. (2016) in the Wassa area. Compared to
Mensah et al. (2015) where As were between 0.90 ppm and 5.40 ppm in Damang-Abosso, the results
of this study were higher. However, the findings of the study were similar to Darko et al. (2019)
where As concentration between 3.50 and 862.50 ppm in a mining community in Gbani, and
dissimilar with Reyes et al. (2019) (5.00-345 ppm). The interpolation map of As (Fig. S1B) shows
that the higher values were situated in the central part of the Wassa Amenfi East and Prestea-Huni
Valley districts and moderately contaminated areas along the boundary between the Wassa Amenfi
Central and West districts. The elevated concentrations could be related to exposure to mining waste
and may pose health implications including renal, hepatic, and immune system disorders, nervous,
cardiovascular, endocrine, respiratory, hematopoietic, integumentary, and reproductive system

9
complications (Abdul et al., 2015) through oral ingestion or dermal interaction. The absorption of As
by plants could also contaminate food produced from the areas.
Both Ba and Co recorded minimum concentrations of 4.00 ppm. However, they respectively had
maximum concentrations of 1005.00 ppm and 65.00 ppm. The deviations and tailedness presented in
Table 1 show that individual results of Ba were wide and dispersed, indicating that some samples
elevated the Ba results. The study showed that 98% and 50% of the sampled points had Ba and Co
respectively exceeding the recommendation by Crommentuijn et al. (2000) (9.00 ppm) and Kazapoe
and Arhin (2019) (6.44 ppm). The kurtosis and CV% of 48% and 69% typify the highly dispersed
concentration of Co across the area. The obtained Co concentration far exceeded the findings of
Mensah et al. (2015) which ranged between 0.10 ppm to 0.70 ppm in Damang-Abosso, and Reyes et
al. (2019) (8-77.10 ppm) in Taltal, northern Chile. This could be attributed to mining activities within
the areas as discussed by the Agency for Toxic Substances and Disease Registry (ATSDR) (2004).
The interpolation of Ba presented in Fig. S1C describes the concentration of Ba as generally
moderate. Low concentrations were sparsely shown for the western and northwestern parts of the
Wassa Amenfi East and Prestea-Huni Valley districts towards the northeastern and western parts of
the Wassa Amenfi West and Central districts. However, hotspot zones were identified in mid-Wassa
Amenfi East towards Wassa Amenfi Central (Fig. S1C). This implies health issues associated with Ba
discussed by Kravchenko et al. (2014) which include cardiovascular, renal, respiratory,
haematological, nervous, endocrine, hepatobiliary, reproductive systems disorders related to high Ba
concentrations may be prone at these areas. Though the concentration of Co was generally low (Fig.
S1D), the central part of the Prestea-Huni Valley district stretching towards the southern part of the
Wassa Amenfi East presents high to moderate concentrations respectively. This shows that inhaling
dust particles from areas with significantly high Co may result in sneezing, asthma, lungs, liver and
kidneys disorders, skin rashes, birth disorders, and death (ATSDR, 2004).
The mean results of Cr and Cu exceeded the respective baseline values of 80.74 ppm and 0.40 ppm
suggested by Kazapoe and Arhin (2019) and Arhin et al. (2016). The results (Table 1) ranged from
17.00-331.00 ppm and 4.00-75.00 ppm for Cr and Cu respectively with 50% and 100% of the samples
exceeding the recommended guidelines of Cr and Cu. These concentrations were similar to Darko et
al. (2019) where Cr and Cu concentrations ranged from 17.8 to 178.3 ppm and 9.70 to 140.10 ppm in
Gbani, a mining locality in the northeastern part of Ghana. Interaction with soils of Cr levels above-
permissible limits and the intake by crops within these areas may cause allergic eczematous and acute
irritative dermatoses, nasal septum reactions through particulate matter, chrome ulcers, systemic
effects in the liver, kidneys, and skin, and carcinogenic and mutagenic effects (WHO, 2000). The
spatial description in Fig. S1E describes the Cr level as moderate with few areas of low
concentrations within the central to the western part of the entire study area, and hotspot zones around
mid-Wassa Amenfi East, and the southern and western of Wassa Amenfi Central. Meanwhile, Cu

10
showed a hotspot in the Wassa Amenfi East with moderate levels sparsely distributed in the entire
area (Fig. S1F).
The European Institute of Copper (2018) reveals that Cu is present in the environment by natural and
anthropogenic processes. Masindi and Muedi (2018) indicate that mineral mining, fertilizer
application, industrial activities, and waste are predominant factors influencing its concentration in
the biosphere. Based on the 100% exceedance of Cu compared to the baseline, long-term
consumption of crops, dermal contact, or inhalation of particulates can cause headache, nose, eye and
mouth irritation, hematemesis, hypotension, kidney and liver damage, coma, melena, cognitive
retardation, and jaundice (Klaassen and Amdur, 2013; New Hampshire Department of Environmental
Services, 2013). Since Cu does not easily biodegrade, the Cu may bio-accumulate in animals, plants,
and the soil medium (Nirel and Pasquini, 2010).
Nickel is a mostly inaccessible element on Earth (Conti et al., 2013). However, 54% of the samples
exceeded the 8.67 ppm recommendation by Kazapoe and Arhin (2019). The results showed a
minimum of 2.00 ppm and a maximum of 71.00 ppm. This exceeded the 0.20-0.68 ppm concentration
of Ni obtained by Mensah et al. (2015) in Damang-Abosso. However, the Ni concentration in Gbani
identified by Darko et al. (2019) exceeded the standards as they ranged from 8.00-118.10 ppm. The
availability of Cu and Ni could be attributed to the unearthing of ore materials that are embedded with
traces of Cu and Ni. The interpolation description of Ni (Fig. S1I) showed a high-level concentration
of Ni around the middle of the Wassa East and Prestea-Huni Valley districts, whereas, in Wassa
Amenfi West and Central, hotspots were located at the northwestern and southeastern parts of the
districts. The deposition of ore materials on the earth's surface could hinder the seepage of these
elements, resulting in elemental accumulation. Since crops naturally contain considerable Ni, it is
expected to increase in larger consumers of crops grown in areas with above-threshold amounts.
Though Ni has been studied to bio-accumulate in biological systems and the food chain, interaction
with these soils could also contribute to respiratory disorders, skin irritation/rashes, and heart
disorders (Brera and Nicolini, 2005; Cadman, 2018).
Soils with high Mn cause toxicity to plants (Rengel, 2000). Mn is one of the most abundant elements
in soil, and it is essential for a wide range of species (Dixon and White, 2002). The Mn concentration
ranged from 80.00-2500.00 ppm (Avg. 212.40 ppm). Though the mean concentration was below the
permissible limit of 500 ppm suggested by McLaughlin et al. (2000), 5% of the samples exceeded the
recommendation and the CV% (95%) and kurtosis (61.04) suggest that the concentrations of the soil
samples were wide and dispersed. The relatively low levels of Mn presented in Table 1 and Fig. S1H
relate to the findings of Weir (1988) who described Mn as a nutrition problem in soils within some
parts of Australia due to waterlogging. Similar to this claim, the Wassa and Prestea areas receive very
high rainfall which is usually logged due to dugouts from mining activities. People within areas with
above-threshold limits (5% samples), especially around mid of the Prestea-Huni Valley District (Fig.

11
S1H) may be prone to these health implications including birth defects, brain, skin, nervous system,
and respiratory tract disorders described by Williams et al. (2012).
Iron as the tenth most abundant element on earth is described as an essential micronutrient and a
major component of haemoglobin. The concentration of Fe and Pb respectively ranged from 0.44 ppm
and 13.00 ppm (Avg. 3.09 ppm) and 5.00 ppm and 71.00 ppm (Avg. 7.85). Fig. S1G shows that the
distribution of Ni was generally sparse and low. All the results for Fe fell below the 35 ppm
recommended by WHO (1996) for soil, whereas 46% of the samples were above the 6.69 ppm
standard by Kazapoe and Arhin (2019). Stoltzfus et al. (2004) indicate that Fe deficiency is prevalent
globally. This results in heart failure, anaemia, limits oxygen circulation in the body, and mortality.
Meanwhile, Pb is naturally occurring and bio-accumulates in the environment (Ogundele et al., 2015).
The obtained results presented in Table 1 exceeded the findings of Antwi-Agyei et al. (2009) where a
Pb concentration between 24-39 ppm was obtained in Obuasi, 2.00-23.00 ppm in the mining areas of
Damang-Abosso, and 3.6-63.20 ppm by Darko et al. (2019) in Gbani, Ghana. People within areas
with above-threshold areas; mid-Prestea-Huni Valley and the southeastern and northwestern parts of
the Wassa Amenfi East and West (Fig. S1J) respectively may be prone to kidney dysfunction, brain
damage, cognitive and behavioural challenges in children, disruption of the biosynthesis of
haemoglobin and anaemia. Pb contamination in soils within the area could be associated with galena
which is a natural mineral related to lead sulfide (PbS) that ensues in gold ores that have high sulfides
(Fashola et al., 2016).
Sr and V obtained had centered results of 99.77 ppm and 92.06 ppm respectively. The concentrations
ranged between 4.00-362 ppm (CV% of 71%) for Sr and 8-519 ppm (CV% of 52%) for V. These
findings were alike with Reyes et al. (2019) in Taltal, northern Chile where Sr and V fell within
19.00-227.00 ppm and 58.00-663 ppm respectively. The study showed that all the results of V
exceeded 1.10 ppm by Crommentuijn et al. (2000). Połedniok and Buhl (2003) reveal that V is
predominant in alkaline and argillaceous-based lithology. The V values were dissimilar with the
findings of Okay et al. (2008) where V values of 19–170 ppm were obtained in Istanbul. The
extremely high V values relate to the findings of Kesse (1985) which described the underlying
geology of the area to compose granitic intrusions which are alkaline-based. The high concentrations
were clustered at the mid-eastern of the Wassa Amenfi Central district and stretched through the
southern part of the Wassa Amenfi East area. The higher values were also sparsely distributed in the
central part of the entire area (Fig. S1L). Meanwhile, from the Sr interpolation (Fig. S1K), hotspots
were identified in the central area of the entire area, stretching towards the northern part of the Wassa
Amenfi East, West, and Central districts. Chadwick et al. (2009) and Amuah et al. (2021) described
Sr as ubiquitous and present in most rocks and soils. This depicts its presence in the soils within the
study areas.
The average (27.86 ppm) Zn content exceeded the 20.00 ppm standard recommended by Arhin et al.
(2016) as 71% of the samples exceeded the guideline. Fig. S1M describes the high distributions of Zn

12
around the southern part of the Wassa Amenfi East district, central to northern parts of the Prestea-
Huni Valley area, the southwestern of Wassa Amenfi Central, and majorly at the Wassa Amenfi West
district. However, some were sparsely distributed at the north of the Wassa Amenfi East, West, and
Central districts. The results of Zn fell between 9.00-123.00 ppm, showing a deviation of 13.30 and
dispersion (CV% of 48%). Singh et al. (2014) mentioned that Zn is usually added to soil as inorganic
fertilizer. However, these Zn-containing fertilizers dissolve relatively slowly in soils for plant
utilization. Therefore, there may be constant availability of Zn in soils within agricultural lands, and
those with high organic matter (Rehman et al., 2012). The study showed that on average, there was an
exceedance of Zn in the non-mining areas than the mining sites following the application of inorganic
fertilizers and the availability of above and below ground litter that contribute to the availability of
organic matter, compared to mining areas that were free of fertilizers and have reduced vegetation
cover, as discussed by Karaca (2004). People within the areas with high Zn contents may be exposed
to health complications including anaemia, skin irritation, nausea, stomach pain, and pancreatic
disorders. It could also hinder microbial activities in soil, therefore limiting soil nutrient availability
for plant uptake (Plum et al., 2010).

13
Table 1
Statistical summary of Results
Variables
Ag As Ba Co Cr Cu Fe Mn Ni Pb Sr V Zn
Min 4.0 2.0 4.00 4.0 17. 4.0 0.4 80.0 2.0 5.0 4.0 8.0 9.0
0 0 0 00 0 4 0 0 0 0 0 0
Max 17. 246 1005 65. 331 75. 13. 2500 71. 71. 362 519 123
00 .00 .00 00 .00 00 00 .00 00 00 .00 .00 .00
Med 4.0 14. 218. 6.0 80. 11. 2.8 156. 9.0 6.0 83. 85. 24.
0 00 00 0 00 00 6 50 0 0 00 00 00
Avg 4.5 18. 213. 7.6 86. 12. 3.0 212. 11. 7.8 99. 92. 27.
8 37 10 0 25 56 9 40 24 5 77 06 86
SD 1.8 20. 113. 5.2 38. 8.5 1.7 202. 9.6 5.5 70. 51. 13.
8 63 68 6 97 3 2 14 5 8 59 83 30
Skew 4.3 6.5 1.26 5.1 2.0 2.9 1.8 6.60 2.9 6.0 1.0 3.6 2.5
5 7 3 2 0 8 7 2 6 8 7
Kurt 20. 60. 7.25 48. 8.6 14. 6.4 61.0 12. 57. 0.9 22. 10.
42 62 26 4 33 2 4 31 52 6 17 93
CV (%) 41. 112 53.3 69. 45. 67. 55. 95.1 85. 71. 70. 56. 47.
09 .34 5 23 18 90 62 7 90 09 75 29 74
Arhin et al. 15. 0.4 20.
(2016) 00 0 00
Kazapoe and 13. 6.4 80. 8.6 6.6
Arhin (2019) 29 4 74 7 9
Zhu et al. (2008) 9.4 9.0 79. 19. 19.
0 0 30 45 50
McLaughlin et 20 100 10 500 15 200
al. (2000) 0 0
Crommentuijn et 4.5 9.0 24 3.8 3.5 2.6 55 1.1 16
al. (2000)
WHO (1996) 35

14
3.2 RCCI Analysis of PTEs
To further determine the level of contamination in the areas studied, RCCI was calculated for five (5)
PTEs including As, Cr, Cu, Pb, and Zn. The study showed that based on the RCCI, 2% of the samples
had RCCI values > 15% which indicated ―lower values‖. This suggests that these areas were not
affected by geogenic and anthropogenic activities that could result in soil contamination. This relates
to the findings of Reyes et al. (2019) where areas with low RCCI values were described to be
composed of lower population densities with limited industrial activities. The medium RCCI values
(> 15% to 25%) comprised 15% of the soil samples. The areas within the lowest and medium RCCIs
were observed to be distant from the mining, residential, and farming areas. The release of the 5 PTEs
was not significant. These areas of the study sites were influenced by very low contamination levels
which could be attributed to limited anthropogenic activities. However, 48% and 34% of the samples
recorded moderate (> 25% to 40%) and high (> 40% to 75%). These are characterized by an
abundance of the studied PTEs since 1% of the soils fell within the highest RCCI range (> 75% to
100%). The interpolation of the RCCI results shows that though the hotspot sites were sparse, they
were concentrated around mid-Wassa Amenfi Central, mid-towards the north of the Wassa Amenfi
West and East Districts (Fig. 2). This could be attributed to mining and agricultural activities which
are predominant in the areas. The areas composed of the ―highest‖ RCCI levels were observed to be
in very close proximity with mining sites, within localities characterized by an influx of people due to
the mining concession and industrial activities, which could significantly contribute to the release and
accumulation of PTEs in the environment.

15
Fig. 2. RCCI Interpolation map of the studied PTEs

3.3 K-means cluster analysis

K-means clustering analysis was performed to determine the hidden spatial patterns in the
geochemistry of the area using the 13 soil elements considered in this study. To detect outliers in the
distribution of the dataset before conducting the K-means cluster analysis, histograms with normal
curves were plotted for the elements that had more than 50% of the samples exceeding their
respective threshold limits. The plots were skewed towards high values in each of the sample
variables otherwise known as outliers (see Fig. 3 and Fig. S2). These Outliers indicate non-normality
in the data distribution. Therefore, the data were transformed using log-transformation which
standardized the data and removed the outliers before conducting K-means cluster analysis (Fig. 3).
Due to the different levels of measurement of the variables used in the K-means cluster analysis, the
data values were standardized using Z scores and a maximum iteration of 10 was employed.
A maximum number of 3 clusters were specified for the test, the initial K-means cluster centres
(Table 2), and an analysis of variance (ANOVA) were also conducted as a part of the cluster analysis
(Table 3). The K-means output for the normal data presented in Fig. 4A showed that cluster 1 was
governed by Co whereas clusters 2 and 3 were respectively characterized by Ba, Co, Cu, Ni and Zn,
and Ba, Cu, Cr, Ni, and Zn. Meanwhile, in the log-transformed data (Fig. 4B) and the ANOVA output
(Table 3), all the elements contributed significantly to the chemistry of the soil. However, the
variables that posed significant influence in both analyses (Fig. 4A and 4B) were Cu and Ni. This is
evident in their high F value in the ANOVA output (Table 3). The deposition of ore materials could
hinder the seepage of these elements, resulting in the accumulation of Ni whereas Masindi and Muedi
(2018) indicate that fertilizer application, mineral mining, industrial activities, and waste are
predominant factors influencing its levels of Cu in the natural environment.
The study further showed that cluster 1 had 136 samples whereas clusters 2 and 3 presented 19 and
145 samples respectively (Fig. 4c). Though these samples were sparsely distributed across the study
area, samples within cluster 1 formed chains in the northern part of the Prestea-Huni Valley District
which is dominantly a non-mining area whereas samples in cluster 2 were dominant in northern-
Wassa Amenfi West District which is a mining-dominated area. These suggest that aside from mining
activities, the chemistry of the soil was impacted by other factors such as agricultural activities and
geological factors. Due to the spatial homogeneity of the geology of the study area (Fig. 4c), there
was less distinction in the spatial orientation of the samples.

16
Fig. 3. (a) Normal and (b) log plot of Cr

Table 2
Initial K-means cluster centres for normal data (ppm) and log-transformed data
Normal data Log-transformed data

1 2 3 1 2 3

Ba -1.45 .76 1.50 Ba 2.19 .60 2.47

Co 1.32 10.92 -.19 Co .68 .95 1.81

Cu -1.00 1.21 2.37 Cu .95 1.66 1.36

Cr -1.76 -1.78 5.50 Cr 1.72 1.95 1.23

Ni -.96 3.88 5.83 Ni .30 1.34 1.69

Zn -.97 3.45 .23 Zn 1.18 1.54 1.87

17
Table 3
ANOVA output of K-means analysis for normal data (ppm) and log-transformed data
Normal data (ppm) Log transformed data

Cluster Error F Sig. Cluster Error F Sig.

Mean df Mean df Mean df Mean df

Square Square Square Square

Ba 29.33 2 .81 297 36.24 .000 Co .40 2 .04 297 8.94 .000

Co 61.62 2 .59 297 104.13 .000 Ba 12.65 2 .04 297 291.81 .000

Cu 72.35 2 .52 297 139.26 .000 Cu 4.57 2 .03 297 138.97 .000

Cr 41.20 2 .73 297 56.49 .000 Cr 1.61 2 .02 297 67.42 .000

Ni 69.42 2 .54 297 128.74 .000 Ni 8.72 2 .04 297 203.74 .000

Zn 53.22 2 .65 297 82.08 .000 Zn 1.28 2 .02 297 62.88 .000

18
Fig. 4. K-means cluster of elements: (a) Normal data (b) Log-transformed data (c) Spatial description
of the K-means output

3.4 Elemental relationships and Source Identification

3.4.1 Covariance-Variance Analysis
Table 4 presents the output of the Pearson correlation analysis (covariance-variance matrix). This was
to determine the relationships between the various elements considered in the study. The covariance-
variance matrix is a measure of the closeness of dissimilar variables (Mugheri et al., 2019). In the
output (Table 4), only positive (direct) and negative (inverse) relationships were highlighted. The
study showed that Ba was directly associated with Cr (r=0.53) and Sr (r=0.54), whereas Cr showed a
direct association with Ni (r=0.56). this association is often found in metamorphic rocks and could
therefore suggest an association with the metavolcanics within the area. Similar to the findings
presented in Table 4, Darko et al. (2019) in a study in Gbani, Upper East Region of Ghana showed
that As did not show any relationship with Cr (r=017), Cu (0.18), Mn (r=0.10), Ni (r=0.24) and Pb
(r=0.41). The computations presented in Table 4 suggest that Ag was influenced by Cu, Fe, V, and Sr
as it established direct relationships with Cu (r=0.54), Fe (r=0.65), and V (r=0.63. Dissimilar with
Darko et al. (2019) where Mn and Zn showed an inverse relationship (r=-0.422), this study presented
a positive relationship (r=0.59). Similarly, Co and Cr showed a positive association of Co and Mn
(r=0.69) and Cu and Fe (r=0.76). Cu, Fe, Pb, V and Zn were directly related with Ni (r=0.72, r=0.60,
r=0.54, r=0.56 and r=0.54) respectively). Mn also presented a negative association with Sr (r=-0.17).
The study further showed that the levels of V and Zn were impacted by Cu and Fe as they established

19
positive correlations of r=0.78 (Cu and V), r=0.56 (Cu and Zn), r=0.80 (Fe and V), and r=0.58 (Fe
and Zn).

Table 4
Variance-Covariance Matrix
Ag As Ba Co Cr Cu Fe Mn Ni Pb Sr V Zn
Ag 1.00
As 0.29 1.00
Ba 0.23 0.08 1.00
Co 0.40 0.48 0.10 1.00
Cr 0.12 0.17 0.53 -0.06 1.00
Cu 0.54 0.18 0.40 0.26 0.43 1.00
Fe 0.65 0.30 0.47 0.23 0.45 0.76 1.00
Mn 0.44 0.10 0.08 0.69 -0.05 0.33 0.32 1.00
Ni 0.45 0.24 0.36 0.30 0.56 0.72 0.60 0.37 1.00
Pb 0.17 0.41 0.19 0.09 0.18 0.32 0.21 0.16 0.54 1.00
Sr -0.02 0.23 0.54 -0.04 0.28 0.61 0.09 -0.17 0.01 0.05 1.00
V 0.63 0.31 0.40 0.20 0.40 0.78 0.80 0.23 0.56 0.18 0.12 1.00
Zn 0.47 0.13 0.24 0.34 0.21 0.56 0.58 0.59 0.54 0.30 -0.19 0.43 1.00

3.4.2 Principal Component Analysis (PCA)

Employing PCA aims at transforming multidimensional datasets to lower dimensions that are
orthonormal and uncorrelated (Machiwal and Jha, 2015). The results provide a small number of
independent groupings which show the basic factors influencing sources and the quality of soils in the
area. The PCA analysis presented 3 components that explained 65.246% of the total variance (Table
5). The first component which explained 42.059% of the total variance was attributed to a weighted
sum of V, Fe, Cu, Ni, Zn, Ba, Cr, Ag, and Pb. Inferentially, these contained the highest signals of the
data and predominantly influenced the quality and variability of the soils. This indicates that the
quality of the soils within the area was highly influenced by both heavy metals and trace elements
which usually emanate from both geogenic processes and anthropogenic activities. The group
suggests one which appears to be controlled by mixed sulphide mineralization, as most of the
elements presented in this factor (with the notable absence of As) are characteristic of the sulphide ore
chemistry which is strongly associated with gold mineralization in that part of the Birimian gold
province of Ghana and may represent the residual contamination of mining activity within the study
area. These findings are corroborated by Wu et al. (2014) in Jiangxi, China where Zn, Pb, and Cu
closely related to that found in PCA 1 were shown to have emanated from mining activities which is

20
one of the predominant sources of heavy metal contamination in soil. Some of the heavy elements
present in PCA 1 such as Pb, Mn, Ni and Cr are commonly enriched in mafic rocks indicating that
some of the elemental associations may partly be from a mafic suite of rocks associated with the
volcanic belt in the area. This is supported by the correlation matrix which shows a significant
positive correlation between Mn and Ni as well as between Pb and Ni. The slight variability in this
group signifies an association of lithological elements driven primarily by the local geology and
anthropogenic effects. Sr and As respectively described PCA 2 and 3 with variances of 57.16% and
65.25%. Kazapoe and Arhin (2020) have previously demonstrated the strong correlation between As
in the soil and the chemistry of sulphide ore in the area. However, the apparent lack of correlation
between As and the other elements point to the As originating from a disparate source and may be the
effect of transported weathered products emanating from neighbouring areas. The variables defined
by the various components suggest that mining, agricultural and other anthropogenic activities
coupled with weathering, geopedological and geomorphic processes can contribute to the unearthing,
deposition, accumulation, and distribution of these elements.

Table 5
Summary of PCA Results of soil quality
Element Component

1 2 3
V .867 .178 -.011
Fe .862 .070 -.157
Cu .861 -.030 -.130
Ni .850 -.082 -.254
Zn .732 -.465 -.162
Ba .649 .421 .109
Cr .625 .460 -.390
Ag .586 -.285 .239
Pb .503 -.139 .194
Sr .263 .691 .305
Mn .439 -.688 .082
As .471 .292 .600
Co .285 -.421 .448

21
4. Conclusion
The study presents the compositional and source pattern of heavy metals using comprehensive
mapping tools and geostatistical analysis in the Wassa and Prestea areas of western Ghana. The RCCI
analysis showed that the majority of the soil samples were within the moderate (48%) and high (34%)
classes. Though the RCCI interpolation presented sparse hotspots, they were concentrated around
mid-Wassa Amenfi Central, mid- towards the north of the Wassa Amenfi West and East Districts. V,
Fe, Cu, Ni, Zn, Ba, Cr, Ag and Pb, and Cu and Ni were the elements governing the soil chemistry of
the area based on the PCA and K-means analyses. This suggests that these elements presented the
highest signals of the data and, therefore, significantly impacted the quality and variability of the soil
samples. The results were attributable to agricultural and mining activities, and anthropogenic factors,
and geogenic processes including weathering, geopedological and geomorphic processes that
influenced the unearthing, deposition, accumulation, and distribution of the elements. The variants in
the elemental concentrations and accumulation within the areas following the RCCIs and K-means
were influenced by varied factors and processes. The areas with elevated concentrations of PTEs
could pose public health challenges down the line as these elements come into contact with
people through crops and groundwater. It is therefore recommended that:
 Areas with high elemental concentrations should be subjected to remediation methods
 Monitoring of mining activities should be enhanced
 Farmers should be educated on how to properly handle agrochemicals
 Regulations aimed at protecting the environment (soil) should be properly enforced to deter
activities that increase soil contamination
 The formulation of these environmental regulations and public health policy must incorporate the
generation of these concentration maps to ensure that the most affected areas are investigated and
adequately addressed.
 It is recommended that periodic environment monitoring exercise be conducted in the
area to assess the concentration levels of As, Cd, Cr and Pb in groundwater, surface water
and from some selected staple crops in the area. in particular, the sampling should
concentrate on the northern western and central most parts of the area. This will permit
effective monitoring, public health education and enhanced management practices in the
area.

Declaration of Competing Interest

The authors declare that they have no competing interests.

Authors contribution

22
R.W.K. and E.E.Y.A. conceived the idea of the paper. E.E.Y.A. conducted the literature review and
did the basic write-up. R.W.K. verified the analytical methods, supervised, edited and reviewed the
entire paper. P.D. handled the analytical and statistical procedures. K.I. assisted in the coordination
and supervision of the paper. B.M. and B.N. assisted in the statistical procedure. S.A. helped in
reviewing and editing the manuscript.

Availability of data and materials

Not applicable

Declarations
Ethical approval
The research meets all applicable standards regarding the ethics of experiments and research. Our
study does not involve human subjects. The paper has been submitted with full responsibility
following the due ethical procedure, and there is no duplicate submission.

Acknowledgement
Special thanks to all who advised us on how to modify this research.

Funding
This research did not receive any grant from any funding agency, commercial or profit sectors.

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Fig S1. Log-transformation of raw data

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