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Multivariate studies and heavy metal pollution in soil from gold mining area
January 2023 · Heliyon 9(7):e12661

DOI:10.1016/j.heliyon.2022.e12661
License · CC BY-NC-ND 4.0
Authors:
Osei Akoto Salome Yakubu Linda Aurelia Ofori

Kwame Nkrumah University Of Science and Technology Jiangsu University Kwame Nkrumah University Of Science and Technology
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References (48) Figures (5)
Abstract and Figures
Mining generates large volumes of waste, which if not regulated can release toxic metals,
causing widespread environmental contamination. This study focused on heavy metal Discover the world's
research
contamination in topsoil within a mining area at Nangodi in the Northern Region of Ghana.
A total of 24 soil samples were collected from the study area and control samples were 20+ million
analyzed for Hg, Pb, Cd, As, Cr, and Fe using atomic absorption spectroscopy. Results of members
Pollution Index estimations and Geo-accumulation index (Igeo) classified the soil samples
as moderately contaminated to heavily contaminated. Soil samples were severely enriched 135+ million
with As and moderately enriched with b, and Hg. Multivariate analyses such as factor publication
analysis and cluster analysis were employed to examine the relationship between the pages
metals and also differentiate the influence of the natural background content of metals from 2.3+ billion
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that due to human activities. Factor analysis identified three polluted soil factor citations
associations. Cadmium, Fe, As, and Pb associated with factor 1, were due to
anthropogenic activities. The high intercorrelation revealed by As and Pb shows similarity
in their sources. Factor two dominated by Hg is considered an anthropogenic component.
Factor 3 correlated with Cr and can be considered a natural component. Correlation
analysis and cluster analysis supported each other. Results from the bi-plots showed that
sites S1, S8, S11, and S18, have similar metal composition as the control site. Heavy
metal contents in soils sampled from Zones A and B have been influenced by the mining
activities as seen from the associations of these sites in the bi-plots. The results are useful
for metal source identification, and can contribute to monitoring and regulatory programs.
Biplot of metal Mean ± SD of Mean EF values Mean l geo Cumulative

concentration… physicochemic… for the soil… values of soil… variance of fact…
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Heliyon 9 (2023) e12661
Contents lists available at ScienceDirect
Heliyon
journal homepage: www.cell.com/heliyon
Research article Heliyon 9 (2023) e12661
Multivariate studies and heavy metal pollution in soil from gold

mining area Contents lists available at ScienceDirect
Osei Akoto a, Salome Yakubu b, Linda A. Ofori b, Nesta Bortey-sam c,

Nathaniel O. Boadi a, Jonathan Horgah d
N.A. Sackey d, *
, Lyndonwww.cell.com/heliyon
journal homepage:
a
Departmentof Chemistry, Kwame Nkrumah University of Science and Technology, Kumasi, Ghana
b
Department of Theoretical and Applied Biology, Kwame Nkrumah University of Science and Technology, Kumasi, Ghana
c
Laboratory of Toxicology, Department of Environmental Veterinary Science, Graduate School of Veterinary Medicine, Hokkaido University, Kita
18, Nishi 9, Kita Ku, Sapporo, 060-0818
060-0818,, Japan
d
Department of Environmental Science, Kwame Nkrumah University of Science and Technology, Kumasi, Ghana
Research article
A
a
R T I C L E I N F O A B S T R A C T Heliyon
b
Keywords:
c a b Mining generates large b volumes of waste, which cif not regulated can release toxic metals, causing
,
Environment widespread environmental contamination.d This
Departmentof Chemistry, Kwame aNkrumah University of Science andd Technology, Kumasi, Ghana * study focused on heavy metal contamination in
Heavy metals
d topsoil University
Department of Theoretical and Applied Biology, Kwame Nkrumah within aofmining areaTechnology,
Science and at Nangodi in the
Kumasi, Northern Region of Ghana. A total of 24 soil
Ghana
Pollution
samples Science,
Laboratory of Toxicology, Department of Environmental Veterinary were collected
Graduate from
Schoolthe study area
of Veterinary and control
Medicine, samples
Hokkaido wereKita
University, analyzed for Hg, Pb, Cd, As,
Topsoil
18, Nishi 9, Kita Ku, Sapporo, 060-0818, Japan Cr, and Fe using atomic absorption spectroscopy. Results of Pollution Index estimations and Geo-
Multivariate
Osei studies
Akoto , Salome and, heavy
Yakubu Linda A.metal
Ofori ,pollution
Department of Environmental Science, Kwame Nkrumah University
accumulation
Nesta Bortey-sam in soil, from gold
of Science and Technology,
index Kumasi, the
(Igeo) classied Ghana
soil samples as moderately contaminated to heavily
contaminated. Soil samples were severely enriched with As and moderately enriched with b, and
Nathaniel O.
mining area Boadi , Jonathan Horgah , Lyndon N.A. Sackey
Hg. Multivariate analyses such as factor analysis and cluster analysis were employed to examine
the relationship between the metals and also differentiate the inuence of the natural background
content of metals from that due to human activities. Factor analysis identied three polluted soil
A R T I C L E I N F O A B S associations.
factor T R A C T Cadmium, Fe, As, and Pb associated with factor 1, were due to anthropogenic
Keywords:
Environment activities. The high intercorrelation revealed by As and Pb shows similarity in their sources.
Heavy metals Miningtwo
Factor generates largeby
dominated volumes of waste, which
Hg is considered if not regulated
an anthropogenic can release
component. toxic
Factor metals, causing
3 correlated with
Pollution widespread
Cr and can environmental
be considered acontamination. This study
natural component. focused analysis
Correlation on heavy metal
and contamination
cluster analysis sup-in
Topsoil topsoil each
ported within a mining
other. Resultsarea
from atthe
Nangodi
bi-plotsinshowed
the Northern Region
that sites S1, S8,of S11,
Ghana.
and A total
S18, of similar
have 24 soil
samples
metal were collected
composition from
as the the study
control area and
site. Heavy control
metal samples
contents weresampled
in soils analyzedfrom
for Hg,
ZonesPb,ACd,
andAs,B
Cr, and
have Fe inuenced
been using atomic by absorption
the mining spectroscopy. Results
activities as seen fromofthe
Pollution Indexofestimations
associations and
these sites in Geo-
the bi-
accumulation
plots. index
The results are (Igeo)
useful classied the soil
for metal source samples as moderately
identication, contaminated
and can contribute to heavily
to monitoring and
contaminated.
regulatory Soil samples were severely enriched with As and moderately enriched with b, and
programs.
Hg. Multivariate analyses such as factor analysis and cluster analysis were employed to examine
the relationship between the metals and also differentiate the inuence of the natural background
content of metals from that due to human activities. Factor analysis identied three polluted soil
1. Introduction factor associations. Cadmium, Fe, As, and Pb associated with factor 1, were due to anthropogenic
activities. The high intercorrelation revealed by As and Pb shows similarity in their sources.
Factor two
Artisanal or small-scale gold mining is essential in dominated by Hg is considered
many developing countries an anthropogenic
such as Ghana. component. Factor 3 correlated
Because it provides with
jobs for the
Cr and can
indigenous people, particularly in rural communities be considered
where economicaactivities
natural component. Correlation
are critically analysis
limited and alsoand
makecluster analysiscon-
signicant sup-
tributions to foreign exchange earnings [1]. ported
Ghanaeach other. Results
’s artisanal from the bi-plots
or small-scale miningshowed
sector that sites S1,in
is growing S8,size
S11,and
andsignicance.
S18, have similar
Its
metal composition as the control site. Heavy metal contents in soils sampled from Zones A and B
have been inuenced by the mining activities as seen from the associations of these sites in the bi-
plots. The results are useful for metal source identication, and can contribute to monitoring and
* Corresponding author. regulatory programs.
E-mail address: niiadjiri2004@yahoo.com (L.N.A. Sackey).
https://doi.org/10.1016/j.heliyon.2022.e12661
Received 18 September 2022; Received in revised form 19 December 2022; Accepted 20 December 2022
1. Introduction
Available online 6 January 2023
2405-8440
2405-8440/©/© 2023 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
Artisanal or small-scale gold mining is essential
(http://creativecommons.org/licenses/by-nc-nd/4.0/ ). ’ in many developing countries such as Ghana. Because it provides jobs for the
indigenous people, particularly in rural communities where economic activities are critically limited and also make signicant con-
tributions to foreign exchange earnings [1]. Ghana s artisanal or small-scale mining sector is growing in size and signicance. Its
* Corresponding author.
E-mail address: niiadjiri2004@yahoo.com (L.N.A. Sackey).
https://doi.org/10.1016/j.heliyon.2022.e12661
Received 18 September 2022; Received in revised form 19 December 2022; Accepted 20 December 2022
Available online 6 January 2023
2405-8440/© 2023 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
2
Fig. 1. Map of the study area.
Fig. 1. Map of the study area.

:
O. Akoto et al. Heliyon 9 (2023) e12661
contribution to wealth creation, employment and the economy make it one of the nation’s most important livelihood activities, directly
employing an estimated one million people and supporting approximately 4.5 million more [2].
However, mining activities negatively impact the environment, and the impact’s severity depends on the miners’ methods and
technical skills [3,4,5].
In Ghana, using rudimentary methods by small-scale gold miners has caused signicant environmental damage, especially to
landscape and ecosystem, impact on the quality of ground and surface water, impact on ora and fauna as well as on humans. Mining
Download full-text PDF Download citation Copy link
wastes contain minerals, including silicates, sulphides, oxides, hydroxides, and carbonates. When the sulphides come into contact with
oxygen and water (humidity), they generate aid water which dissolves and mobilize heavy metals and releases them into the envi-
ronment [6,7].
The potential effects of heavy metals on human health and the environment have become a major concern worldwide [6,8–10].
Because of their high toxicity and persistence, heavy metals such as, As, Pb, Cd and Hg ’ are among the priority chemicals of public
health concern. Long-term exposure to these heavy metals can lead to cancers and other diseases like lung and kidney damage,
contribution disorders,
neurological to wealth creation,
DNA damage employment and the[economy
and infertility 11,12,13,make it one oflandscapes
14]. Several the nation s most important
’ worldwide which,livelihood
Ghana is activities, directly
not’ an exception,
employing
have an estimated
been heavily damaged one million people and
due to transient supportinggold
small-scale approximately
mining activity4.5 million
and this more [2].
is occurring because of intensive levels of
However,activity
exploration mining[15 activities
]. negatively impact the environment, and the impact s severity depends on the miners methods and
technical skills [3discovered
Gold deposits ,4,5]. in Nangodi in the Nandam traditional area of the Northern Region of the Republic of Ghana have attracted
a lotInofGhana, using mining
small-scale rudimentaryventuresmethods
to the by small-scale
area. This has goldled tominers
illegal has caused signicant
small-scale gold mining environmental
activities suchdamage, especially
as improper to
tailings
landscapewhich
disposal, and ecosystem,
may contain impact on the quality
sulde-bearing of ground
material such as and surface
pyrite. Whenwater, impact
pyrite on ora
is exposed toand
air infauna as well asofon
the presence humans.
water, Mining
it produces
wastes
acid minecontain minerals,
drainage (AMD), including silicates,
one of the sulphides, environmental
most signicant oxides, hydroxides, issuesand carbonates.
associated withWhen mining theand
sulphides come [into
mine wastes 16,17contact with
]. Without
oxygen andthe
treatment, water (humidity),
harmful effects of they
AMD generate
lead to aid
the water whichofdissolves
destruction surroundingand mobilize
ecosystems, heavy metalsserious
including and releases
health them
impacts intoonthe –envi-
affected
ronment [6,7].
communities [18]. Low pH acid mine drainage enhances the dissolution of heavy metals in water; hence this causes the metals to
The potential
quickly move in the effects of heavy metals
environmental media, onadversely
human health impactingand the
theenvironment
ecosystem’s ora have and
become a major concern worldwide [6,8 10].
fauna.
Because
High of theirofhigh
levels toxictoxicity
metalsand andpersistence,
other contaminantsheavy metals such as, released
are therefore As, Pb, Cd intoand Hgenvironment,
the are among the priority
which can chemicals
pollute surfaceof public
and
health concern.
groundwater. Long-term exposure
Unauthorized to thesecould
mining activities heavyalso metals
resultcan lead to cancershavoc
in environmental and and
otherdestruction.
diseases like lung
Vast landsand kidney
that coulddamage,
be used
neurological
for other economicdisorders, DNA damage
activities, and infertility
such as agriculture, can[11 ,12their
lose ,13,14 ]. Several[19
properties landscapes worldwide
]. The activities havewhich,
causedGhana is not andestruction
the systematic exception,
have
of been heavily
farmlands without damaged
compensation due to totransient small-scale
the affected farmersgold and mining
landowners activity
[20]. and this is occurring because of intensive levels of
exploration activity
Traditionally, [15]. is a farming community where cereals and legumes are mostly grown. Activities of illegal small-scale gold
Nangodi
Goldcan
mining deposits discovered
potentially increase in Nangodi in the Nandam
metal pollution, threaten traditional
the quality area of the Northern
of water, soil and plant Region of the and
growth, Republic
depriveof the
Ghana have attracted
indigenes of their
a lot of small-scale
livelihood. The present miningstudy ventures
seeks totoestimate
the area. theThis
extent hasofled to illegal
heavy metal small-scale
pollution and gold miningtheactivities
identify possible such
sources as improper tailings
of these metals in
disposal,
soil within which may contain
the Nangodi communitysulde-bearing material such
using a multivariate as pyrite.
statistical When pyrite
approach. The is exposedoftothis
outcome air study
in thewill
presence of water,
highlight it produces
potential threats
acid
of mine drainage
mining activities (AMD),
to soil and one human
of the mosthealthsignicant
and determineenvironmental
mitigationissues associated
measures that with
would mining and mine wastes [16,17]. Without
be needed.
treatment, the harmful effects of AMD lead to the destruction of surrounding ecosystems, ’ including serious health impacts on affected
communities
2. Materials[and 18]. method
Low pH acid mine drainage enhances the dissolution of heavy metals in water; hence this causes the metals to
quickly move in the environmental media, adversely impacting the ecosystem s ora and fauna.
2.1.High
Study levels
area of toxic metals and other contaminants are therefore released into the environment, which can pollute surface and
groundwater. Unauthorized mining activities could also result in environmental havoc and destruction. Vast lands that could be used
for Nangodi
other economic
is locatedactivities,
on latitude such10as◦ agriculture,
15′ and 10◦ 60 can′ lose their properties [◦19].′ The activities
north and longitude 0 31 and 1◦ 05′ west have caused the
(Tom-Dery systematic
et al., 2012). Its destruction
total land
of farmlands
area km2 [21
is 244.94without compensation
21] to the affected
] Fig. 1. The topography farmers and
is naturally landowners
undulating [20].with gentle slopes ranging from 1% to 5% gradient
lowlands
withTraditionally,
few hilly terrainsNangodi mainly is a of
farming
quartzitecommunity
and gneiss where cereals [and
formations 22].legumes are mostly
The underline rocks grown. Activities
fall within Ghanaof ’illegal small-scale
s Tarkwaian, gold
Birimian
mining
and can potentially
Voltarian rocks [23increase
]. metal pollution, threaten the quality of water, soil and plant growth, and deprive the indigenes of their
livelihood.
The areaThe present study
experiences seeksrainfall
irregular to estimate the extent
patterns of heavy
with annual metalrainfall
mean pollution and identify
between 800 mm theandpossible
1100 sources
mm. The of rainy
these season
metals inis
soil within
usually from theMay
Nangodi
to Junecommunity using September
and between a multivariate andstatistical
October.approach. The outcome
The dry season, of this study
characterized willdry
by the highlight
northeastpotential
trade threats
winds,
of mining
extends activities
from November to soilto and
April.human
The area health and determine
experiences a maximum mitigation measures
temperature of that would
45 ◦ C and a be needed.of 12 ◦ C in December with a
minimum
relative humidity of 69%.
◦ ′ ◦ ′ ◦ ′ ◦ ′
2. Materials and method
2.2. Sampling
2.1. Study area 2
Nangodi was selected for the study because of the extensive destruction of land by illegal small-scale gold mining activities within
the Nangodi
community. is located
In order onto latitude 10 inuence
study the 15 and 10 60 north
of illegal and longitude
small-scale mining0 on 31the and 1 05ofwest
extent heavy (Tom-Dery et ’al., 2012).
metal pollution Its total
in the soil, the land
area
area divided
was is 244.94 intokmfour[21(4)
] Fig. 1. The
zones; Zonetopography
A represented is naturally
areas whereundulating lowlands
gold-bearing withare
rocks gentle slopes Zone
extracted; ranging from 1% to 5%
B represented areas gradient
where
◦ ◦
with few
mine rocks hilly
areterrains
washed mainly
and Hgofadded quartzite and gneiss
to extract gold; formations [22]. Theanunderline
Zone C represented area where rocks falliswithin
there Ghanaconcerning
no activity s Tarkwaian, goldBirimian
mining
and Voltarian
(control) rocks D[23
and Zone ].
represented an area where mining tailings are dumped. Ten (10) top-soil samples each were collected from
The area
different experiences
locations within irregular
Zone A and rainfall
Zone B. patterns
Two (2)with soil annual
samplesmean rainfall
were also taken between 800 mmlocations
from different and 1100 mm.Zone
within The C,rainy
were season
used asis
usually samples
control from May andtotwoJune (2)andotherbetween
different September
soil samples and October.
were taken The
fromdryZoneseason,
D. Thecharacterized
soil samples were by the dry northeast
collected at a depth trade
of 0–winds,
25 cm
extends
from thefrom November
surface to April. The area
using a stainless-steel experiences
spatula. Samples acollected
maximum temperature
were kept in plastic of 45bags,
C and a minimum
labelled of 12 C intoDecember
and transported with a
the laboratories
relative
of humidityDepartment
the Chemistry of 69%. at Kwame Nkrumah University of Science and Technology (KNUST).
2.2. Sample
2.3. Sampling
treatment
Nangodi
Soil waswere
samples selected for the
air-dried at study
roombecause of thetoextensive
temperature constant destruction
weight. Theof landsamples
dried by illegal
weresmall-scale gold mining
ground using a mortar activities
and pestlewithin
and
the community.
sieved through aIn1 order to study
mm sieve the inuence
to obtain of illegal
a homogenous small-scale
sample. miningsoil
The sieved onsamples
the extent of heavy
were storedmetal pollution
in labelled in the
plastic soil, theuntil
containers area
was divided into four (4) zones; Zone A represented areas where gold-bearing rocks are extracted; Zone B represented areas where
mine rocks are washed and Hg added to extract gold; Zone C represented 3 an area where there is no activity concerning gold mining
(control) and Zone D represented an area where mining tailings are dumped. Ten (10) top-soil samples each were collected – from
different locations within Zone A and Zone B. Two (2) soil samples were also taken from different locations within Zone C, were used as
control samples and two (2) other different soil samples were taken from Zone D. The soil samples were collected at a depth of 0 25 cm
from the surface using a stainless-steel spatula. Samples collected were kept in plastic bags, labelled and transported to the laboratories
of the Chemistry Department at Kwame Nkrumah University of Science and Technology (KNUST).
2.3. Sample treatment
Soil samples were air-dried at room temperature to constant weight. The dried samples were ground using a mortar and pestle and
3
sieved through a 1 mm sieve to obtain a homogenous sample. The sieved soil samples were stored in labelled plastic containers until
:
digestion.
2.4. Digestion of soil samples
Approximately 1 g of each sieved soil sample was weighed and transferred into conical asks. 10 mL of a mixture of HNO3 - HCLO4
(9:4) was added [24]. Each sample was placed on a hot plate and heated until the production of red NO2 fumes ceased. The contents
were further heated until the volume reduced to about 4 mL and became yellowish. Digested samples were allowed to cool and ltered
through Whatman No.1 acid-washed lter paper into 100 mL volumetric ask and lled to the mark with distilled water. The resulting
solution was preserved at 4 ◦ C in pre-cleaned bottles until analysis [24].
Concentrations of Cr, Cd, Fe and Pb were measured using Atomic Absorption Spectrophotometry (AAS 220; PerkinElmer, AAS).
Mercury was analyzed by Cold Vapour Atomic Absorption Spectrophotometry using an Automatic Mercury Analyser model HG-5000
developed at the National Institute for Minamata Disease (NIMD). A Hydride Generator Atomic Absorption Spectrophotometer was
digestion.
used in determining As in all digests [25].
Soil pH and electrical conductivity (EC) were measured in soil/distilled water mixture of ratio 1:10 (w/v). The solution was 3
allowed 4
2.4.
to Digestion
settle for 30of soil Electrical
min. samples conductivity and pH were measured using a calibrated conductivity meter and a pH meter (HANNA HI
2
98150) with the ion-selectivity hydrogen electrode respectively. Soil organic matter content was determined using the Loss on Ignition
◦
Approximately
method whiles soil 1texture
g of each
wassieved soil sample
determined was
by the weighed
pipette and transferred
method into
described by conical [asks.
Kroetsch 23]. 10 mL of a mixture of HNO - HCLO
(9:4) was added [24]. Each sample was placed on a hot plate and heated until the production of red NO fumes ceased. The contents
were Enrichment
2.5. further heated until the volume reduced to about 4 mL and became yellowish. Digested samples were allowed to cool and ltered
factor
through Whatman No.1 acid-washed lter paper into 100 mL volumetric ask and lled to the mark with distilled water. The resulting
solution was preserved
Enrichment factor (EF) at 4is C in pre-cleaned
used to determinebottles until analysis
the presence [24]. of heavy metals pollution by anthropogenic deposition in
and intensity
soilConcentrations
compared to their of Cr, Cd, Fe
natural and Pb were
abundance. Themeasured using described
EF calculation Atomic Absorption Spectrophotometry
by Ref. [25 (AAS 220;
] as dened in equation PerkinElmer,
(1) was adopted for AAS).
this
Mercury was analyzed by Cold Vapour Atomic Absorption Spectrophotometry using an Automatic Mercury Analyser model HG-5000
study.
developed at the National Institute for Minamata Disease (NIMD). A Hydride Generator Atomic Absorption Spectrophotometer was
used inEF determining (X/AsFe)in
soil
all digests [25].
= (1)
Soil pH and (electrical
X/Fe)background
conductivity (EC) were measured in soil/distilled water mixture of ratio 1:10 (w/v). The solution was allowed
to settle for 30 min. Electrical conductivity and pH were measured using a calibrated conductivity meter and a pH meter (HANNA HI
where (X/Fe) soil is the ratio of heavy metal (X) to Fe in the soil from the mining site.
98150) with the ion-selectivity hydrogen electrode respectively. Soil organic matter content was determined using the Loss on Ignition
(X/Fe)background is the natural background value of the metal to Fe ratio.
method whiles soil texture was determined by the pipette method described by Kroetsch [23].
Iron (Fe) was used as a reference element because Fe is naturally present in soils and its concentration is not altered anthropo-
genically [26].
2.5. Enrichment factor
The higher the EF value of a metal the more severe its contribution from anthropogenic sources.
Enrichment factor (EF) is used to determine the presence and intensity of heavy metals pollution by anthropogenic deposition in
2.6. Geoaccumulation Index ((IIgeo )
soil compared to theirX Fenatural
soil abundance. The EF calculation described by Ref. [25] as dened in equation (1) was adopted for this
EF
study. X Fe background
Another factor( used/ )to determine the intensity of metal pollution in the soil is the geoaccumulation index (Igeo) introduced by
=
Ref. [27]. Thesoilgeoaccumulation
( / ) index (Igeo) was calculated using equation (2)
(1)
background
Cm
Igeo = log2 (2)
where (X/Fe) 1.is 5Bthe
n
ratio of heavy metal (X) to Fe in the soil from the mining site.
(X/Fe)
C is the natural
m = measured concentration geo background value of the metal to Fe ratio.
of metal in soil.
Iron
B n =(Fe) was used as abackground
geoaccumulation reference element because
values of metalsFe is naturally present in soils and its concentration is not altered anthropo-
genically
1.5the[background
26]. matrix correction factor due to the lithogenic effects
I
The Ihigher theconsists
geo scale EF valueof of a metal
seven the(0
grades more severe its
–6) ranging contribution
from from anthropogenic
uncontaminated sources.
to extremely contaminated.
m
geo
2.6. Pollution
2.7. Geoaccumulation
index
2
n Index ( )
Another factor
Pollution indexCused toused
(PI) is determine the intensity
to evaluate of metal
the pollution pollution
status in metals
of heavy the soilinissoil.
the The
geoaccumulation indexfrom
PI was calculated (Igeo) introduced
equation (3). by
Ref. [27I ]. The
loggeoaccumulation index (Igeo) was calculated using equation (2)
Pi = Ci /Si 1 5B (3)
m
=
n .
(2)
where P i the pollution index of heavy metal (i).
=
Ci (mg/kg) is the concentration of heavy metal in the soil.
C = measured concentration of metal in soil.
S i (mg/kg)
geo is the concentration of standard heavy metal value for soil quality.
B geoaccumulation background values – of metals
1.5the background matrix correction factor due to the lithogenic effects
2.8. Statistical analysis
The Ii scalei i consists of seven grades (0 6) ranging from uncontaminated to extremely contaminated.
The mean and standard deviation of the studied physicochemical parameters and heavy metals were calculated with Microsoft
2.7. Pollution index
Ofce Excel (2013) spreadsheet. All statistical analyses were done using JMP 10 Statistical Software (SAS Institute). Pearson’s cor-
relationP wasC performed
S to identify the important parameters affecting soil chemistry (at a signicant level p less than 0.05). Factor
Pollution index (PI) is used to evaluate the pollution status of heavy metals in soil. The PI was calculated from equation (3).
analysis and
i= Cluster
/ analysis were carried out to describe the degree of association and identify possible sources of metals in the soil
samples.
i The principal components were extracted with eigenvalues >1 through a varimax rotation. Cluster analysis was also (3)
i
where P the pollution index of heavy metal (i). 4
C (mg/kg) is the concentration of heavy metal in the soil.
S (mg/kg) is the concentration of standard heavy metal value for soil quality.
2.8. Statistical analysis

’
The mean and standard deviation of the studied physicochemical parameters and heavy metals were calculated with Microsoft
Ofce Excel (2013) spreadsheet. All statistical analyses were done using JMP 10 Statistical Software (SAS Institute). Pearson s cor-
relation was performed to identify the important parameters affecting soil chemistry (at a signicant level p less than 0.05). Factor
analysis and Cluster analysis were carried out to describe the degree of association
> and identify possible sources of metals in the soil
4
samples. The principal components were extracted with eigenvalues 1 through a varimax rotation. Cluster analysis was also
:
performed based on Euclidean distance using Ward’s clustering method.
3. Results and discussion
3.1. Physicochemical parameters of the soil samples
The results of the mean values of physicochemical parameters (pH, EC, TOM and Texture) measured in the soil samples collected
from different sampling sites from the Nangodi illegal gold mining area are represented in Table 1.
The pH of soil samples from the sampling zones at Nangodi are represented in Table 1. The pH varied from 5.6 ± 1.2 at Zone A,
where the gold-bearing rocks were extracted to 7.7 ± 0.6 at Zone D where the mine tailings are kept, indicating that the soil is slightly
acidic to near neutral. pH is considered a parameter ’that controls the bioavailability of metals in soil [27]. For most heavy metals, the
acidity of the soil results in a higher solubility than adsorption. Thus, the mobility of metals is promoted by an acidic pH. The mean soil
performed
pH based on from
values recorded Euclidean
the study distance
areausing
may Ward s clusteringinuence
not signicantly method. the solubility and mobility of the heavy metals in the soil
because the acidic pH is high and near neutral [28]. Soil EC is dened as the ability of soil water to carry electrical current [29]. In
3. Results
general, the and
greaterdiscussion
the concentration of the ions in the soil, the higher the conductivity. EC of soil samples from the study area varied
from 142.5 ± 7.6 μ S/cm in Zone A to 206.7 ± 2.3 μS/cm in Zone C. Soil samples from the control site (Zone C) recorded the highest EC
3.1. Physicochemical
values. This may be because parameters of the soil
the mining sampleshave compromised the soil compatibility in the mining areas and the soil has become
activities
loose and more porous.
The results
Total organic of matter
the mean (OM) values of physicochemical
recorded in the soil samples parameters
ranged(pH, from EC,
0.9TOM
± 0.4%and Texture)
at Zone Ameasured
to 1.8 ± in 1.2the
at soil
Zonesamples
B. The collected
extreme
from different
removal of humus sampling
horizon sites from the
(topsoil) from Nangodi illegal
the activity goldand
zones mining area vegetation
the poor are represented
cover in Table with
coupled 1. annual bushres ± have resulted
Thelevels
in low pH ofofsoil OMsamples
within the from the sampling
study area. Thiszoneslow OM ±at Nangodi
content ofare therepresented
soil samplesinwill Table
not1inuence
. The pH the varied from 5.6 capacity
cation-holding 1.2 at Zone A,
of the
where
soil, the gold-bearing
resulting in low levels rocks ofwere
EC inextracted to 7.7 0.6 at Zone D where the mine tailings are kept, indicating that the soil is slightly
the soil samples.
acidic to near neutral. pH is considered a parameter that controls the bioavailability of metals in soil [27]. For most heavy metals, the
acidity
3.2. of the
Levels of soil
heavy results
metalsin ainhigher
soil solubility than adsorption. Thus, the mobility of metals is promoted by an acidic pH. The mean soil
pH values recorded from the study area may not signicantly inuence the solubility and mobility of the heavy metals in the soil
because the acidic
The results of thepHmeanis high and near neutral
concentrations [28].metals
of heavy Soil EC is dened
(Hg, Cr, Cd, as As,the
Pb,ability
Fe) in of
thesoil
soilwater
samples to carry
from electrical current Zones
the four selected [29]. Inof
μ μ
general,
illegal the±greater
mining around theNangodi
concentrationcommunity of the± ions
are in the soil, in
represented theTable
higher 2. the conductivity. EC of soil samples from the study area varied
from 142.5
Mean 7.6 S/cm
Hg levels in theinsoilZone A to 206.7
samples ranged2.3 fromS/cm2.20in±Zone0.14 C. toSoil
7.46samples
± 2.96from the Zone
mg/kg. control C site
and (Zone
Zone BC)recorded
recordedthe thelowest
highestandEC
values. This
highest meanmay Hgbe because the mining
concentrations, activities
respectively, ashave compromised
presented in Tablethe 2. soil
Thecompatibility in the mining
illegal gold mining activityareas
has and the soil
increased thehas become
mean Hg
loose and
levels more
in the soil porous.
samples from Zone B above the control samples. This is a result ±of the Hg added to amalgamate ± the gold after washing.
TheTotal organic
observed levelmatter
of Hg (OM)at Zone recorded
C (controlin the
site)soil
maysamples
be because rangedHg is from 0.9 and
volatile 0.4%
canat ZonebeAtransferred
easily to 1.8 1.2 at Zone
through theB.atmosphere
The extreme to
removalareas.
remote of humus horizonstudy
In a similar (topsoil) from
in the the activity
Amansie zones and
West District of the poor
Ashanti vegetation
Region of cover
Ghanacoupled
[17], with annual
recorded Hgbushres
levels as have
high as resulted
11.20
in low levels
mg/kg, whichofwas OM within
equivalent the study
to an area. Thisoflow
increase 300%OM of content
Hg over of the soil samples
control sample,will not inuence
suggesting a higher the cation-holding
use of Hg for gold capacity
miningof the
by
soil, resulting
small-scale gold in miners
low levels of EC in
in Ghana. the soilinsamples.
Mercury soil is an indicator of an industrial activity such as mining and has a unique property of
propagation over long distances [30].
3.2.Mean
Levels Pbofconcentration
heavy metals in the soil soil samples was highest in Zone D (21.65 ± 0.21 mg/kg) and lowest in Zone C (1.45 ± 0.21 mg/kg).
The highest mean Pb concentration was observed at the site where the tailings are dumped after the gold-bearing rocks are crushed and
goldThe results of
extracted. the mean
It was, however, concentrations
lower thanofthe heavy
1200metals
ppm [(Hg, Cr, Cd, As, Pb,for
31] recommended Fe)non-residential
in the soil samples areas.from the four
Leopold [30selected
] observed Zones
19.02of
illegal mining
mg/kg Pb in a around
traditionalNangodi community
gold mining site inare represented
Kombo-laka, in Table 2.Bempah
±Cameroun. ± and Ewusi [32] recorded 35 mg/kg Pb around Obuasi
goldMean
mineHg levels inThe
in Ghana. thepresent
soil samplesstudy ranged
tends tofromsupport2.20the observation
0.14 to 7.46made 2.96by mg/kg.
Ref. [33Zone
] thatCanthropogenic
and Zone B recorded
activitiesthe lowest and
contribute to
highest
Pb mean Hg concentrations,
concentrations in soil. The highrespectively,
concentration asofpresented
Pb in the in Table
active 2. The
mining illegal
areas gold mining
compared to Zone activity
C couldhas beincreased
due to thethe mean
nature Hg
of the
levels in the soil
gold-bearing rockssamples
in thefromstudyZone area,B which
above themaycontrol
contain samples.
high levels Thisof is Pb,
a result of the Hgatadded
as observed Zone to amalgamate
D where the gold
the tailing wasafter
dumped washing.
after
The observed
gold extraction. level of Hg at Zone C (control site) may be because Hg is volatile and can easily be transferred through the atmosphere to
remote
Averageareas.CdInconcentrations
a similar studyrecorded in the Amansie
from the West District
different zonesof the Ashanti
during the Region of Ghana
study ranged from[172.0], recorded
± 0.28 mg/kg Hg levels as high
at Zone C to as 11.20
14.60 ±
mg/kg,
0.28 mg/kgwhich was equivalent
at Zone D. differences to an in increase of 300% ofbetween
Cd concentrations Hg over control
Zones A, Bsample,
and D weresuggesting a higher
signicant, use of possible
indicating Hg for gold mining by
anthropogenic
small-scaleexcept
inuence gold miners
that of in Zone Ghana. Mercury to
C. According inWHO,
soil is the
an indicator
standardof an industrial
requirement foractivity
Cd in thesuchsoilasismining
1.4 mg/kgand [has
34],a suggesting
unique property that theof
propagation
Cd recorded over from longZones distances
A, B and[30 D,].as presented in Table 2, were extremely ± high. This indicates Cd pollution in the soils ± within the
Mean
study area.PbHowever
concentration in the soil0.5
[35], recorded samples
–3.8 mg/kgwas highest
Cd in thein Zone D (21.65
artisanal mining site0.21inmg/kg) and lowest
Dakoto-Shega in Zone
in the UpperCEast
(1.45 Region0.21ofmg/kg).
Ghana.
TheLevels
highest ofmean
arsenic PbAsconcentration
in the soil samples was observed
from Zone at the site where
D were extremelythe tailings are dumped
high (21.7 after thecompared
± 0.57 mg/kg) gold-bearing rocksrecorded
to values are crushed and
in soils
gold extracted.
from the other Zones.It was, Soil
however,samples lower than
from theC1200
Zone ppm [the
recorded 31]least
recommended for non-residential
As the concentration of 0.35 areas.
± 0.07Leopold
mg/kg[(30 ] observed
Table 2). Mean 19.02
As
mg/kg Pb in a traditional gold mining site in Kombo-laka, Cameroun. Bempah and Ewusi [32] recorded 35 mg/kg Pb around Obuasi
gold mine
Table 1 in Ghana. The present study tends to support the observation made by Ref. [33] that anthropogenic activities contribute to
Pb concentrations
Mean in soil. Theparameters
± SD of physicochemical high concentration of Pbfrom
of soil samples in thetheactive
zones mining areas compared to Zone C could be due to the nature of the
in Nangodi.
gold-bearing rocks in the study area, which may contain high levels of Pb, as observed at Zone D where the tailing was dumped after
Parameters Zone A Zone B Zone C Zone D
gold extraction. ± ±
pH Range
Average Cd concentrations recorded from4.8the –6.4
different zones during 5.1–8.0
the study ranged from 2.0 6.5–6.6
0.28 mg/kg at Zone 7.5 –8.1
C to 14.60
Mean 5.6 ± 1.2 6.8 ± 1.6 6.5 ± 0.1 7.7 ± 0.6
0.28
EC( μmg/kg
S/cm) at Zone D. differences Range in Cd concentrations
133.8–158.1 between Zones 162.9 A, B–and
204.2D were signicant, 205.1indicating
–208.4 possible anthropogenic
165.6–167.4
inuence except that of Zone MeanC. According – to142.5 WHO, the standard requirement
± 7.6 for Cd in the soil 206.7
179.2 ± 13.8 is 1.4±mg/kg
2.3 [34], suggesting 166.5that
± 1.3the
Cd recorded
TOM (%) from Zones Range A, B and D, as presented 0.2–1.2 in Table 2, were extremely 0.1–3.5 high. This indicates 0.1–Cd2.2 pollution in the soils 0.3–within
1.7 the
study area. However [35],Mean recorded 0.5 3.8 mg/kg 0.9 ± 0.4Cd in the artisanal mining 1.8 ± 1.2site in
± Dakoto-Shega 1.7 ±in0.3
the Upper East Region 1.1 of
± 0.9
Ghana.
Texture Sandy/Loamy Clay Sandy/Loamy Clay
Levels of arsenic As in the soil samples from Zone D were extremely high (21.7 0.57 mg/kg) compared ± to values recorded in soils
from the other Zones. Soil samples from Zone C recorded the least As the concentration of 0.35 0.07 mg/kg (Table 2). Mean As
5
Table ±
1 – A – B – C – D
Parameters
Mean Zone
SD of physicochemical parameters of soil samples from the zones inZone
Nangodi. Zone Zone
pH Range 4.8 6.4

±– 5.1 8.0
±– 6.5 6.6
±– 7.5 8.1
±–
μ Mean 5.6 1.2 6.8 1.6 6.5 0.1 7.7 0.6
EC( S/cm) Range 133.8
– ±158.1 162.9
– ±204.2 205.1
– ±208.4 165.6
– ±167.4
Mean 142.5 7.6 179.2 13.8 206.7 2.3 166.5 1.3
TOM (%) Range 0.2 1.2
± 0.1 3.5
± 0.1 2.2
± 0.3 1.7
±
Mean 0.9 0.4 1.8 1.2 1.7 0.3 1.1 0.9
Texture Sandy/Loamy Clay Sandy/Loamy Clay
5
:
Table 2
Range and mean concentrations of heavy metals (mg/kg) in soil samples from the selected zones in Nangodi.
Heavy Metals Zone A Zone B Zone C Zone D
Hg Range 3.9–7.5 3.4–12.4 2.1–2.3 3.3–3.4

Mean 5.97 ± 0.94 7.46 ± 2.96 2.2 ± 0.14 3.35 ± 0.07
Pb Range 7.43–12.60 1.93–11.43 1.30–1.68 21.51–21.82
Mean 11.71 ± 3.86 7.31 ± 2.52 1.45 ± 0.21 21.65 ± 0.21
Cd Range 1.92–11.44 4.76–11.31 1.80–2.25 14.44–14.81
O. Akoto et al. Mean 8.78 ± 4.55 8.45 ± 2.03 2.0 ± 0.28 14.60
Heliyon ± 0.28
9 (2023) e12661
As Range 0.82–11.14 0.53–9.25 0.34–0.48 21.38–22.16
Mean 5.30 ± 3.63 4.67 ± 2.94 0.35 ± 0.07 21.70 ± 0.57
Cr Range 2.87–13.35 5.438–10.61 2.77–2.99 8.55–9.34
Mean 7.87 ± 3.53 7.75 ± 14.97 2.80 ± 0.14 8.90 ± 0.57
Table 2 – A–634.76 – B–585.13 – C–296.21 – D–843.28
Fe
Heavyand
Range Metals Range of heavy metals
mean concentrations 463.61
Zone 412.92
Zone
(mg/kg) in soil samples from 248.73
Zone
the selected zones in Nangodi. 824.60
Zone
Mean 571.40 ± 69.80 484.53 ± 70.10 272.35 ± 33.50 833.80 ± 13.10
Hg Range 3.9 –7.5
± 3.4 12.4
–± 2.1 2.3
–± 3.3 3.4
±
–
Mean 5.97 0.94 7.46 2.96 2.2 0.14 3.35 0.07
Pb Range 7.43 –12.60
± 1.93 11.43
–± 1.30 1.68
± 21.51 –±21.82
concentrations in soil from Zone D exceeded11.71
Mean
the recommended
3.86
level 7.31
by WHO 2.52
which is 12 mg/kg1.45
[–34]. In other studies, Gyasi
0.21
et al. [36]
21.65 0.21
recorded
Cd relatively lowerRange
mean As concentration ± (0.16 mg/kg) in soil
1.92 –11.44 from
4.76 ± Buruli Ulcer endemic
– 11.31 1.80± communities
–2.25 in the Ashanti Region of
14.44 –14.81
±
Ghana, where activities ofMean small-scale gold8.78
mining 4.55are high. The extremely
8.45 2.03 high levels of As2.0
recorded
0.28 in soils from Zone 14.60D is0.28
mainly
As arsenopyrite gold-bearing
from Range rocks tailings
0.82–dumped
11.14
± haphazardly0.53 9.25
at that
–± site. Thus As levels 0.34in 0.48
–± 21.38
the soil have been enriched– 22.16
± by the
Mean 5.30 3.63 4.67 2.94 0.35 0.07 21.70 0.57
activities of the mining operations and the mine tailings dumped at that site.
Cr Range 2.87 13.35
±– 5.438 ±10.61
– 2.77 2.99
±– 8.55 9.34
±–
Chromium in the soil is predominantly
Mean affected
7.87 3.53 by rock weathering and
7.75 14.97erosion and only slightly
2.80 by
0.14 anthropogenic activities
8.90 0.57 [37].
Chromium
Fe concentrations in the soil samples
Range varied
463.61 ± from 2.8 ± 0.14412.92
634.76 mg/kg585.13
±at Zone C to 8.9 ±248.73
0.57 mg/kg
296.21
± at Zone D. Another ±study by
824.60 843.28
Ref. [38] recorded muchMean higher Cr concentrations
571.40 69.80 in the range 104.3
484.53–938.7
70.10mg/kg in Dakoto-Shega
272.35 33.50another illegal gold mining
833.80 13.10
community Upper East Region of Ghana. The miners’ activities have not signicantly impacted the levels of Cr in the soils from the
study area.
Iron is one of the most abundant metals in soil [39]. It was the most predominant of all the metals considered in this study because it
recorded a relatively higher concentration than the other metals with concentrations varying from 272.35 ± 33.45 mg/kg to 833.8 ±
concentrations
13.01 in soil3from
mg/kg ((Table
Table ). TheZone D exceeded
presence the recommended
of iron-rich levelwhich
laterite sub-soils by WHO FAO which is 12as
classies mg/kg [34].and
ferrasols In other studies,
oxisols Gyasifor
accounted et al.
high[36Fe]
recorded relatively
concentrations lowerin
observed meanthis As concentration
study [40]. made(0.16 mg/kg)
a similar in soil from
observation in Buruli Ulcer
his study in endemic
Tarkwa gold communities in the Ashanti
mining community Region of
in Ghana.
Ghana, where activities of small-scale gold mining are high. The extremely high levels of As recorded in soils from Zone D is mainly
from Enrichment
3.3. arsenopyrite gold-bearing
factor (EF) rocks tailings dumped haphazardly at that site. Thus As levels in the soil have been enriched by the
activities of the mining operations and the mine tailings dumped at that site.
Chromium infactor
Enrichment the soil is predominantly
values are presented affected
in Table by3 rock
3.. All weathering
the metals
± hadand–EF erosion and only
values equal ±slightly by
or exceeding anthropogenic
1.0, except for Cdactivities
(0.99) in [Zone
37].
Chromium
C and Hg (0.50)concentrations
in Zone D.inThe the highest
soil samples varied
EF value from
20.26,’ was2.8 recorded
0.14 mg/kg for Asat Zone C toD.8.9 0.57 mg/kg at Zone D. Another study by
in Zone
Ref.Enrichment
[38] recorded factor much
(EF)higher Cr concentrations
estimations for heavy metal in concentrations
the range 104.3 in 938.7
soils aremg/kg in Dakoto-Shega
necessary for geochemical another
studiesillegal gold mining
in differentiating
community
heavy metalUpper
sources East
thatRegion of Ghana.
originated from The
humanminers activities
activities have not signicantly
and lithogenic processes. EFimpacted
can be usedthe levels of Cr in the
to determine the source
soils from
and the
in-
study area.
tensity of metal contamination from human activities in soil [41,42]. EF values calculated for Cd and Hg in the soil samples from Zones
Iron
C and D is one less
were of the most
than 1, abundant
indicatingmetals in soil
that their [39sources
main ]. It wasare
the mainly
most predominant of allprocesses.
from lithogenic the metalsEF considered
± theinstudied
for all this study because
metals in the
±it
recorded
soil sampleda relatively
from Zone higher concentration
A showed minor tothan the other
moderate metals with
enrichment concentrations
except for As, whichvarying
showedfrom 272.35 severe
moderately 33.45enrichment
mg/kg to 833.8(7.55).
13.01
EF mg/kg
values (Tablefor
recorded 3).all
The thepresence
studied of iron-rich
metals (Hg,laterite
Pb, Cd,sub-soils
As and Cr) which
showedFAOmoderate
classies as ferrasols and
enrichment oxisols
in Zone accounted
B, with for highthe
Hg recording Fe
concentrations
highest value. Thisobserved
can beinattributed
this studyto [40 ]. made
the a similar that
amalgamation observation
occurredinathis Zonestudy
B asinthe
Tarkwa
main gold
source mining
of Hg.community
Soils in Zone in Ghana.
D showed
moderate to minor enrichment for Pb, Cd and Cr (Table 3). Arsenic in Zone D showed the highest EF value of 20.26. This can be
3.3. Enrichment
attributed to the factor
fact that(EF)
associated minerals in the gold-bearing rocks are principally arsenopyrite and the soil around where the mine
tailings are dumped recorded high concentrations of As. This As could leach into surface and groundwater and increase their As
Enrichment From
concentrations. factorthevalues areAs
study, presented
and Pb in inthe
Table
soil,3.from
All the metals
Zones A, Bhad
andEF values equal
D showed high orEFexceeding 1.0,metals
values. These exceptarefor highly
Cd (0.99) in have
toxic, Zone
C and
no Hg (0.50)
known in Zone
biological D. The highest
importance, and can EFpotentially
value 20.26, wasthe
enter recorded
food chainfor As
andincause
Zoneadverse
D. health impacts to humans [43,44]. The
Enrichment
enrichment factor
of the metals(EF) estimations
(As, Pb, Cd, Crfor andheavy metal
Hg) in concentrations
the soil samples wasininuenced
soils are necessary
by miningfor geochemical
which studies
is the main human in differentiating
activity in the
heavy area.
study metal sources that originated from human activities and lithogenic processes. EF can be used to determine the source and in-
tensity of metal contamination from human activities in soil [41,42]. EF values calculated for Cd and Hg in the soil samples from Zones
C and D were less than 1, indicating that their main sources are mainly from lithogenic processes. EF for all the studied metals in the
soil sampled from Zone A showed minor to moderate enrichment except for As, which showed moderately severe enrichment (7.55).
EF values recorded for all the studied metals (Hg, Pb, Cd, As and Cr) showed moderate enrichment in Zone B, with Hg recording the
highest value. This can be attributed to the amalgamation that occurred at Zone B as the main source of Hg. Soils in Zone D showed
Table 3 to minor enrichment for Pb, Cd and Cr (Table 3). Arsenic in Zone D showed the highest EF value of 20.26. This can be
moderate
Mean EF to
attributed values for the
the fact thatsoil samples collected
associated mineralsfrom selected
in the zones inrocks
gold-bearing the study area.
are principally arsenopyrite and the soil around where the mine
tailings
Metalsare dumped recorded high Zoneconcentrations
A of As. ThisZoneAs Bcould leach into surface Zone and Cgroundwater and increase their
Zone D As
concentrations.
Hg
From the study, As and Pb in the soil, from Zones1.91
1.30
A, B and D showed high EF values. 1.01
These metals are highly toxic,0.50
have
no known
Pb biological importance,3.94 and can potentially enter the2.95 food chain and cause adverse1.02 health impacts to humans [43 ,44]. The
4.88
enrichment
Cd of the metals (As, Pb,2.06 Cd, Cr and Hg) in the soil samples 2.44 was inuenced by mining0.99 which is the main human activity 2.39 in the
As area.
study 7.55 4.46 1.02 20.26
Cr 1.32 1.61 1.01 1.04
Table 3
MetalsEF values for the soil samples
Mean Zone A
collected from selected zones Zone
in theB study area. Zone C Zone D
Hg 1.30 1.91 1.01 0.50

Pb 3.94 2.95 1.02 4.88
Cd 2.06 2.44 0.99 2.39
As 7.55 4.46 1.02 20.26
Cr 1.32 1.61 1.01 1.04
6
:
3.4. Geoaccumulation Index (I geo)
In this study, Igeo was used to determine and describe the extent of heavy metal contamination in the soils by comparing recent
concentrations with background levels. Igeo class includes seven grades (0–6) varying from uncontaminated to highly contaminated.
Calculated means Igeo for heavy metal concentrations in all the zones varied from 0 to 5.37 (Table 4), which suggests contamination in
some Zones. The I geo values obtained for the metals in Zone A indicate that Hg and Cr were uncontaminated to moderately
contaminated; however, As and Pb were moderately to heavily contaminated in the soil, as presented in Table 4. In Zone B, all metals
except Cr were in class 2, representing moderate contamination for the metals in the soil. Chromium and Fe were in Class 1 with Igeo
values of 0.86. However, Zone D was uncontaminated for Hg (0.02), Cr was moderately contaminated with Igeo values between 1 and 2.
Cadmium (2.28) was put in Class geo
3. Pb was heavily contaminated in Zone D. Results revealed that Igeo value for As was >5, which puts
As in class 6, implying that the soil is extremely contaminated with As. The average I geovalue of the studied metals calculated for all the
zones was in the order geo
Hg < Cr < Cd < Pb < As. This shows that Hg and Cr were the least polluted metals in the study, while Pb and As
3.4. Geoaccumulation
showed Index (Iin all
signicant pollution ) the activity areas within the study area. The result of I geo suggests that gold mining, the major
geo
anthropogenic activity geo
in the area, has signicantly affected concentrations – of As, Pb and Cd in the soils.
In this study, I was used to determine and describe the extent of heavy metal contamination in the soils by comparing recent
geo
concentrations
3.5. with (PI)
Pollution index background levels. I class includes seven grades (0 6) varying from uncontaminated to highly contaminated.
Calculated means I for heavy metal concentrations in all the zones varied from 0 to 5.37 (Table 4), which suggests contamination in
geo
some Zones.
PI was The I tovalues
calculated evaluateobtained for the
the pollution metals
status in Zone
of heavy A indicate
metals in the soilthat
fromHg theand
studyCrarea.
werePIuncontaminated
of the to moderately
geometal in soil from Zone A
contaminated; however, As and Pb were moderately to heavily contaminated in the
revealed that Hg, Cd and Cr were moderately polluted. Lead and As recorded PI values of 8.08 and geo soil, as presented in Table 4. In Zone B, all metals
15.14, respectively, indicating that
except
the Cr were
pollution in class
levels 2, representing
of these metals are moderate contamination
high. PI values for Hg and forCd
theinmetals
Zone Binwere
the soil. Chromium and Fe were in Class 1 with I
geo>3 but Pb and As once again recorded high PI
values of
values of 5.04
0.86.andHowever, Zone D was uncontaminated
7.63, respectively, at Zone D. Hg had for Hgleast
the (0.02), Cr was
PI value atmoderately contaminated
Zone D, indicating with
moderate I values
pollution between
(Table 1 and 2.
> 5). However,
Cadmium
all (2.28)inwas
other metals soilsput in Classfrom
sampled 3. Pbzone
was Dheavily contaminated
recorded in Zonehigh
PI > 3, indicating D. Results revealed
pollution, that
with geo
As I value
showing thefor As was
highest 5, which
PI value puts
of 62, Pb
As in class
(14.93), Cr6,(3.18).
implying that<the soil < is extremely
< < contaminated with As. The average I value of the studied metals calculated for all the
zones
Thewas in theillegal
intense ordergold
Hg mining
Cr Cd Pb characterized
activities As. This showsby that
theHg and Cr were
arsenopyrite the least
nature polluted
of the metals rocks,
gold-bearing in the haphazard
study, while Pb and As
dumping of
showed
mine signicant
residues pollution
and tailings, in all
which arethe activitysources
potential areas within thePb
of As and study area. The result
and by-products of I which
of mining suggests that other
releases gold mining, the major
contaminants into
anthropogenic
the activity in to
soil have contributed thethe
area, has signicantly
buildup of the heavyaffected
metals inconcentrations of As,
soils within the Pb and
study area.Cd in the soils.
3.5. Correlation
3.6. Pollution index (PI)
analysis
PI was calculated
Pearson
Pearson’ to evaluate
’s correlation the pollution
coefcients of heavystatus
metalsofin
heavy metals inand
soil samples thephysicochemical
soil from the study area. PI ofof
parameters the metal
the soil in
aresoil from Zonein
summarised A
revealed
Table 6 that
6.. A Hg, Cd and
signicant Cr were
positive moderately
correlation waspolluted.
observedLead and AsPb
between recorded PI values
–As (0.81) >
and Cdof–8.08 and 15.14,
Cr (0.72), respectively,
indicating that theindicating that
same anthro-
the pollution
pogenic levels
activity of these
might metals are high.
have inuenced these PI values
metals at afor99%
Hg condence
and Cd in Zone
level.BAgain,
were Fe3 has
but aPb and As once
signicant again recorded
correlation with Pb high PI
(0.68),
values
Cd of 5.04
(0.64) and and 7.63, at
As (0.64) respectively, at Zone
95% condence D. Hg
level, had the
which > least that
suggests PI value atmetals
these Zone D, indicating
may have themoderate pollution
same source (Table
or sink 5). locations.
in some However,
all other
There was metals in soils sampled
no signicant from zone
correlation D recorded
between Hg andPI 3, indicating
the other metals,high pollution,
signifying with As
a degree ofshowing the highest
uniqueness, PI value
indicating of 62, Pb
that different
(14.93), Cr (3.18).
anthropogenic activities inuence Hg. Cd and Pb also exhibited a positive correlation at p (0.05). There was also a negative but
The intense
signicant illegal gold
correlation mining
between ECactivities
and Pb and characterized
EC and Fe. by the arsenopyrite nature of the gold-bearing rocks, haphazard dumping of
mine residues and tailings, which are potential sources of As and Pb and by-products of mining which releases other contaminants into
the soil have contributed to the buildup of the heavy metals in soils within the study area.
3.7. Factor analysis
3.6.ToCorrelation
’ to analysis
be able properly identify the possible sources (lithogenic or anthropogenic) and better understand the relationship among the
metals in the soil, factor analysis was applied using Varimax rotation to– the experimental –data [40,45]. The results in Table 7 show that
onlyPearson s correlation
three eigenvalues arecoefcients
>1.00 andofexplain
heavy 87.6%
metalsof inthe
soiltotal
samples and physicochemical
variance of the system. parameters of the soil are summarised in
Table
The6.rst
A signicant
factor (F1)positive correlation
accounted for 49.5% was observed
of the betweenand
total variation Pb was
As (0.81) and Cd
dominated by Cr
Pb,(0.72), indicating
Cd, As and that8).the
Fe ((Table
Table same
Lead andanthro-
As are
pogenic activity
strongly might
associated, have
while Cdinuenced
and Fe arethese
highlymetals at a with
afliated 99% these
condence
metals. level.
ThisAgain, Fe has
association a signicant
could correlation
be tentatively namedwith Pbspecic
as ore (0.68),
Cd (0.64)
since theseand As (0.64)
metals at 95%
’ common condence
source level, which
of occurrence suggests
is the that and
basic rock thesethe
metals may haverock,
gold-bearing the same
which source or sink
contain in some
As and Pb [locations.
46]. This
There was the
represents no signicant correlation
effect of pollution between
caused by goldHg and the
mining other The
activity. metals, signifying
second a degree
factor (F2) of uniqueness,
accounted for 20.4% indicating
of the totalthat different
variance and
anthropogenic activities inuence Hg. Cd and Pb also exhibited a positive correlation at p (0.05). There was
was highly dominated by Hg, indicating the main metal contribution from the inuence of the amalgamation process, which involves also a negative but
signicant
the correlation
use of Hg. Factor 3between
accountedEC for
and17.62%
Pb and ofECthe
andtotal
Fe. variance and was dominated by Cr. The mean concentration of Cr in the
topsoil samples from the control area was not signicantly different from the active mining areas. Again EF, Igeo, and PI values
3.7. Factorfor
calculated analysis
Cr, showed that Cr was not signicantly affected in the active mining areas. Therefore, Cr levels in the soil are controlled
mainly by natural factors of the lithogenic process during the weathering process of parent rocks.
To be able to properly identify the possible sources (lithogenic or anthropogenic) and better understand the relationship among the
metals
Tablein4 the soil, factor analysis
> was applied using Varimax rotation to the experimental data [40,45]. The results in Table 7 show that
only three
Mean l geoeigenvalues
values of soilare 1.00collected
samples and explain 87.6% of
from selected the in
zones total
the variance
study area.of the system.
The rst factor’(F1) accounted for 49.5% of the total variation and was dominated by Pb, Cd, As and Fe (Table 8). Lead and As are
Metals Zone A Zone B Zone C Zone D
strongly associated, while Cd and Fe are highly afliated with these metals. This association could be tentatively named as ore specic
Hg 0.84
since these metals common source of occurrence is the basic 1.07 0
rock and the gold-bearing rock, which contain As and Pb 0.02[46]. This
Pb 2.37 1.63 0 3.32
represents
Cd the effect of pollution 1.29
caused by gold mining activity. The second factor (F2) accounted
1.45 0 for 20.4% of the total variance
2.28 and
wasAshighly dominated by Hg, indicating2.91 the main metal contribution
1.60 from the inuence of the
0 amalgamation process, which involves
5.37
the Cr
use of Hg. Factor 3 accounted 0.70for 17.62% of the total variance
0.86 and was dominated by Cr. 0 The mean concentration of1.08 Cr in the
topsoil samples from the control area was not signicantly different from the active mining areas. Again EF, Igeo, and PI values
calculated geofor Cr, showed that Cr was not signicantly affected in the active mining areas. Therefore, Cr levels in the soil are controlled
7
mainly by natural factors of the lithogenic process during the weathering process of parent rocks.
Table 4
Metalsl
Mean Zone A from selected zones in the
values of soil samples collected Zone B
study area. Zone C Zone D
Hg 0.84 1.07 0 0.02

Pb 2.37 1.63 0 3.32
Cd 1.29 1.45 0 2.28
As 2.91 1.60 0 5.37
Cr 0.70 0.86 0 1.08
7
:
Table 5
Pollution Index values of soil from in the study area.
Metals Zone A Zone B Zone C Zone D
Hg 2.71 3.39 1.00 1.52

Pb 8.08 5.04 1.00 14.93
Cd 4.39 4.18 1.00 7.30
As 15.14 7.63 1.00 62.00
Cr 2.81 2.86 1.00 3.18
Table 6
Correlation matrix for heavy metal concentrations and Physico-chemical Parameters.
Table 5
Metals Index values of soil fromZone
Pollution A Zone B Zone C Zone D
Variables Hg Pb in the study Cd
area. As Cr Fe pH EC TOM
Hg 2.71 3.39 1.00 1.52
Hg 1
Pb 8.08 5.04 1.00 14.93
Pb − 0.25 1
Cd 4.39 4.18 1.00 7.30
Cd 0.10 0.66
0.66** 1
As 15.14 7.63 1.00 62.00
As − 0.35 0.81
0.81**
** 0.45 1
Cr 2.81 2.86 1.00 3.18
Cr 0.25 0.37 0.72
0.72**
** 0.26 1
Fe 0.09 0.68
0.68** 0.64
0.64** 0.64
0.64** 0.45 1
pH 0.00 0.017 0.15 0.17 0.00 − 0.03 1
EC − 0.17 ¡0.51 − 0.32 − 0.19 − 0.26 ¡0.50 0.52 1
TOM 0.54 − 0.27 − 0.03 − 0.23 0.09 − 0.06 0.20 0.19 1
Table 6
**Correlation is signicant at 0.01Pb
level.
Variables matrix
Correlation Hg
for heavy metal¡ concentrationsCd As
and Physico-chemical Cr
Parameters. Fe
¡ pH EC TOM
*Correlation is signicant at 0.05 level.
Hg −1
Pb 0.25 1
Cd 0.10
− 0.66* 1
Table
As 7 0.35 0.81** 0.45 1
Cumulative
Cr variance
0.25of factor Coefcients.
0.37 0.72** 0.26 1
Fe 0.09 F1 0.68* 0.64F2
* 0.64* F3 0.45 1
−
F4 F5 F6
pH −0.00 0.017 0.15
− −0.17 0.00
− 0.03 1
Eigenvalue
EC 0.17 2.97
− 0.51 1.22
− 0.32 − 0.19 1.05 0.26 0.34
− 0.50 0.52 0.25 1 0.14
Variability
TOM (%) 0.54 49.590.27 20.44
0.03 0.23 17.62 0.09 5.73
0.06 0.20 4.24 0.19 2.38
1
Cumulative (%) 49.59 70.03 87.65 93.38 97.62 100.00
**Correlation is signicant at 0.01 level.

*Correlation
Table 8 is signicant at 0.05 level.
Varimax-rotated factor loadings of metals in the soil samples.
F1 F2 F3 F4 F5 F6
Table 7
Hg
Cumulative variance of0.04 F1
factor Coefcients. 0.73 F2 0.17 F3 F4
0.01 F5
0.05 F60.00
Pb 0.86 0.014 0.00 0.00 0.04 0.07
Eigenvalue 2.97 1.22 1.05 0.34 0.25 0.14
Cd 0.61 0.18 0.01 0.17 0.00 0.02
Variability (%) 49.59 20.44 17.62 5.73 4.24 2.38
As 0.75 0.11 0.00 0.04 0.04 0.05
Cumulative (%) 49.59 70.03 87.65 93.38 97.62 100.00
Cr 0.01 0.14 0.81 0.04 0.00 0.00
Fe 0.71 0.05 0.05 0.08 0.11 0.00
*high positive factor loading is shown in bold

bold..
TableFor8 further assessment of the extent of heavy metal contamination in the study, source identication and metal distribution Figs (2)
Varimax-rotated factor F1
loadings of metals F2soil samples. F3 F4 F5 F6
1a, 1b and 1c were used. A loading plotin1athe
is used to identify the sources of metals in the samples. Three (3) components similar to that
ofHgTable 4 were extracted.
0.04 These three components
0.73 constitute 0.17
the metals and their 0.01association with samples.
0.05 These 3 components0.00
Pb
signicantly explain 0.86
metal contamination 0.014 in the study area, which 0.00 0.00
constitutes the metals 0.04
and their associations 0.07
with the soil samples,
Cd 0.61 0.18 0.01 0.17 0.00 0.02
asAsseen in plot1b. For0.75 instance, mercury is highly
0.11
associated with samples
0.00
from sites S12,
0.04
S13, S15, S16, S17, S19
0.04
and S20, all in Zone
0.05
B
(Fig.
Cr 3
3).
). Chromium is highly
0.01 associated with samples
0.14 obtained from
0.81 S4, S5, S6, S10 and S14.
0.04 Arsenic and Pb are
0.00 highly associated with
0.00
sites
Fe R1 and R2, where 0.71mining waste (tailings)
0.05 are dumped. 0.05 0.08 0.11 0.00
No association was observed between metals and the control samples (C1 and C2) as the concentration of all metals within the
control zones was low. Similarly, low metal concentrations were detected in S1, S3, S8, and S18 in the back box as they had no as-
*high positive
sociations factor
with theloading
metalsis ((Fig.
shown in which
Fig. 2), bold. suggests these areas had low metal concentrations or the presence of the metal in the samples
were from natural sources.
For further assessment of the extent of heavy metal contamination in the study, source identication and metal distribution Figs (2)
3.8.
1a, 1bCluster
and 1canalysis (CA)A loading plot 1a is used to identify the sources of metals in the samples. Three (3) components similar to that
were used.
of Table 4 were extracted. These three components constitute the metals and their association with samples. These 3 components
CA organizes
signicantly variables
explain metalinto homogenous
contamination in groups where
the study area,variables within thethe
which constitutes same cluster
metals andexhibit associationswith
their associations and the
are soil
dissimilar to
samples,
variables
as seen in in other For
plot1b. clusters. Clusters
instance, are formed
mercury based
is highly on existing
associated similarities,
with samples fromwhich become
sites S12, S13,useful for data
S15, S16, S17,interpretation and
S19 and S20, all in pattern
Zone B
(Fig. 3). Chromium is highly associated with samples obtained from S4, S5, S6, S10 and S14. Arsenic and Pb are highly associated with
sites R1 and R2, where mining waste (tailings) are dumped. 8
No association was observed between metals and the control samples (C1 and C2) as the concentration of all metals within the
control zones was low. Similarly, low metal concentrations were detected in S1, S3, S8, and S18 in the back box as they had no as-
sociations with the metals (Fig. 2), which suggests these areas had low metal concentrations or the presence of the metal in the samples
were from natural sources.
3.8. Cluster analysis (CA)
CA organizes variables into homogenous groups where variables within the same cluster exhibit associations and are dissimilar to
8
variables in other clusters. Clusters are formed based on existing similarities, which become useful for data interpretation and pattern
:
Fig. 2. Biplot of metal concentration (1a) sampling sites (1b) and a combination of the plots A (loading plot) and B (score plot) (1c).
recognition. This study grouped sampling locations into clusters based on Euclidean distance using Ward’s method. The results of the
CA are presented in a dendrogram as shown in Fig. 3. In this dendrogram, all sampling sites were grouped into four statistically
signicant clusters.
Cluster 1 is composed of S2, S3, S4, S5, S6, S9, S10, S12, S13, S14, S15, S16 and S17. The sampling sites grouped in this cluster are
either in Zones A or B, indicating similarities in heavy metal content in topsoil samples. Thus, the metal content in the top soil from
these sites has been inuenced by similar anthropogenic factors. The associations of these sites can also be seen in loading plots in plot
1b. Cluster 2 is represented by site 20. Cluster 3 includes S1, S8, S11, S18, C1 and C2, indicating their heavy metal content similarity to
that of the control samples. Thus, the heavy metal content of soil from these sites is not affected by the mining activity and could be
attributed to lithogenic sources. This result is consistent with that of the score plot, plot 1b. The fourth cluster is made up of S7 R1and
R2 andFig.are Biplot of metal
2. associated withconcentration
As and Pb as (1a) samplinginsites
observed the (1b)
Factorandanalysis
a combination
Tablesof7 the
andplots A (loading
8 loading plotsplot) and1bB and
(plot (score plot)
1c). (1c).
Correlation
analysis, FA and CA highlight the sources of heavy metals in the top soil of the study site. The combination’ of these three (3) statistical
analyses showed a strong correlation between Pb, As, Cd and Fe represented in PC1 (Table 8) indicating signicant associations.
recognition. This
Furthermore, study
these grouped
metals sampling
had high locations
positive loads ofinto clusters
0.86, based
0.75, 0.61 on 0.71,
and Euclidean distancewhich
respectively, usingexplains
Ward s method.
that the The
levelresults of the
of pollution
CAthese
of are presented
metals wasinnot a dendrogram as shown
affected by their in characteristics
natural Fig. 3. In this in dendrogram,
the soil, butall sampling
precisely by sites were grouped
anthropogenic into four
activities withinstatistically
the study
signicant
area, whichclusters.
was mining. All the clusters formed were based on existing relationships between soil samples and metals.
Cluster 1 is composed of S2, S3, S4, S5, S6, S9, S10, S12, S13, S14, S15, S16 and S17. The sampling sites grouped in this cluster are
either
5. in Zones A or B, indicating similarities in heavy metal content in topsoil samples. Thus, the metal content in the top soil from
Conclusion
these sites has been inuenced by similar anthropogenic factors. The associations of these sites can also be seen in loading plots in plot
1b. Findings
Cluster 2of is represented by site 20.
the study indicated Cluster
that heavy3metal
includes
(Hg,S1,Pb,S8,
As,S11,
Cd,S18, C1 and
Cr and C2, indicating
Fe) levels their
in top soils heavy
from themetal
miningcontent similarity
areas were to
higher
that of
than theofcontrol
that samples.
the control Thus,
site. EF, the
Igeo heavy
and metalestimated
PI values content of forsoil
As,from these
Pb, Cd, Hg sites is not
showed affected by
widespread the mining
pollution withactivity
varying and couldThe
degrees. be
attributed
soil samples to’ lithogenic
sources of sources. This result
heavy metals were is consistent
examined withmultivariate
using that of the score plot, plot
statistical 1b. The The
techniques. fourth cluster
results is made up ofFA
of correlation, S7and
R1and
CA
R2 and areeach
supported associated with
other. The As and Pb
examined as observed
metals in the Factor
were classied into threeanalysis
main Tables
groups.7Concentrations
and 8 loading Fe,plotsCd,(plot 1b As
Pb and andin1c). Correlation
the soil samples
analysis, FA and CA highlight the sources of heavy metals in the top soil of the study site. The combination of these three (3) statistical
analyses showed a strong correlation between Pb, As, Cd and Fe represented in PC1 (Table 8) indicating signicant associations.
Furthermore, these metals had high positive loads of 0.86, 0.75, 0.61 9 and 0.71, respectively, which explains that the level of pollution
of these metals was not affected by their natural characteristics in the soil, but precisely by anthropogenic activities within the study
area, which was mining. All the clusters formed were based on existing relationships between soil samples and metals.
5. Conclusion
Findings ’of the study indicated that heavy metal (Hg, Pb, As, Cd, Cr and Fe) levels in top soils from the mining areas were higher
than that of the control site. EF, Igeo and PI values estimated for As, Pb, Cd, Hg showed widespread pollution with varying degrees. The
soil samples sources of heavy metals were examined using multivariate statistical techniques. The results of correlation, FA and CA
supported each other. The examined metals were classied into three 9
main groups. Concentrations Fe, Cd, Pb and As in the soil samples
:
Fig. 3. Dendrogram of sampling sites.
signicantly contribute signicantly to the mining activity. The amalgamation process-controlled Hg distribution in the soil and can be
considered an anthropogenic component since Hg levels in soil samples from Zone B were extremely high. Cr distribution in the soil is
not affected much by the mining activities since the geoaccumulation and EF values showed that Cr has background concentration at
most of the sampling sites. Results from CA and the loading plots showed that sites S1, S8, S11, S18, have a similar metal composition
as the control, indicating that soils from these sites are not affected by the mining activity. The high intercorrelation revealed by As and
Pb in this study shows similarity in their sources. The study showed preliminary yet relevant information concerning the pollution
status of artisanal gold mining on soils. The results also provide useful information that can contribute to monitoring and regulatory
programs at regional and national levels.
Funding Fig. 3. Dendrogram of sampling sites.
The Ghana Government supported this work through the Postgraduate’s Scholarship Programme.
signicantly contribute signicantly to the mining activity. The amalgamation process-controlled Hg distribution in the soil and can be
considered anofanthropogenic
Declaration component since Hg levels in soil samples from Zone B were extremely high. Cr distribution in the soil is
competing interest
not affected much by the mining activities since the geoaccumulation and EF values showed that Cr has background concentration at
most of authors
The the sampling sites.
declare thatResults fromno
they have CAknown
and the loading plots
competing showed
nancial that sites
interests S1, S8, S11,
or personal S18, havethat
relationships a similar
couldmetal
have composition
appeared to
as the control,
inuence indicating
the work thatinsoils
reported thisfrom these sites are not affected by the mining activity. The high intercorrelation revealed by As and
paper.
Pb in this study shows similarity in their sources. The study showed preliminary yet relevant information concerning the pollution
status of artisanal gold mining on soils. The results also provide useful information that can contribute to monitoring and regulatory
Acknowledgement
programs at regional and national levels.
The authors would like to thank the Technicians at the Department of Chemical Engineering in KNUST for the analysis.
Funding ’
References
The Ghana Government supported this work through the Postgraduate s Scholarship Programme.
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Citations (0) References (48) 11

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Abstract and Figures

Biplot of metal Mean ± SD of Mean EF values Mean l geo Cumulative

Figures - available via license: Creative Commons Attribution-NonCommercial-

Available via license: CC BY-NC-ND 4.0

Heliyon 9 (2023) e12661

Contents lists available at ScienceDirect

Research article Heliyon 9 (2023) e12661

Multivariate studies and heavy metal pollution in soil from gold

Osei Akoto a, Salome Yakubu b, Linda A. Ofori b, Nesta Bortey-sam c,

Fig. 1. Map of the study area.

Fig. 1. Map of the study area.

2.3. Sample treatment

2.4. Digestion of soil samples

2.8. Statistical analysis

performed based on Euclidean distance using Ward’s clustering method.

3. Results and discussion

3.1. Physicochemical parameters of the soil samples

pH Range 4.8 6.4

Hg Range 3.9–7.5 3.4–12.4 2.1–2.3 3.3–3.4

Hg 1.30 1.91 1.01 0.50

3.4. Geoaccumulation Index (I geo)

Hg 0.84 1.07 0 0.02

Hg 2.71 3.39 1.00 1.52

**Correlation is signicant at 0.01 level.

*high positive factor loading is shown in bold

3.8. Cluster analysis (CA)

O. Akoto et al. Heliyon 9 (2023) e12661

O. Akoto et al. Heliyon 9 (2023) e12661

Fig. 3. Dendrogram of sampling sites.

Funding Fig. 3. Dendrogram of sampling sites.

Citations (0) References (48) 11

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Lyndon Nii Adjiri Sackey · Linda Aurelia Ofori · Abdul-Aziz Adam

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Osei Akoto · Lilian Sarpong · Nathaniel Boadi

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