Science of the Total Environment 718 (2020) 137235

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Science of the Total Environment

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Contamination, sources and risk assessments of metals in media from

Anka artisanal gold mining area, Northwest Nigeria
A.J. Adewumi a,⁎, T.A. Laniyan Dr., PhD b
a
Department of Geological Sciences, Achievers University, Owo, Ondo State, Nigeria
b
Department of Environmental Health, University of Ibadan, Ibadan, Oyo State, Nigeria

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Mining of minerals play significant roles

in environmental degradation.
• Environmental media around mining
area are contaminated by mining
activities.
• Geogenic sources also play important
roles in the release of toxic metals.
• Polluted media pose very high
ecological risks.
• Ingestion, inhalation and contact with
polluted media aids health risks in
humans.

a r t i c l e i n f o a b s t r a c t

Article history: Mining is a major human activity that has contributed significantly to high degree of environmental and human
Received 3 January 2020 health degradation. This study was done to uncover the degree of contamination and risks associated with metals
Received in revised form 4 February 2020 in environmental media collected from Anka area, Northwest Nigeria. A total of eighty-two (82) samples which
Accepted 8 February 2020
include 42 soils, 22 stream sediments, 13 tailings and 5 plants were collected. Media were air-dried, pulverized
Available online 13 February 2020
and sieved to collect fine particles. They were digested and analyzed for toxic metal contents using High
Editor: Diego Hernan Fridman Performance Liquid Chromatography-Inductively Coupled Plasma Mass Spectrometer (HPLC-ICPMS). Metals
analyzed include As, Cd, Co, Cr, Cu, Hg, Ni, Pb, Sb, Zn and Fe. From the results, degree of contamination in samples
Keywords: were obtained using pollution indices, while ecological and health risks were calculated using acceptable risk
Anka indices. Average concentrations of metals in the soils were: As: 0.64 μg/g; Cr: 42.55 μg/g; Pb: 131.76 μg/g; Hg:
Contamination 0.85 μg/g while in sediments, the average concentration were As: 15.46 μg/g; Cr: 111.82 μg/g; Pb: 2234.02 μg/
Heavy metals g; Hg: 2.12 μg/g. In tailings, the mean concentration were As: 4.79 μg/g; Cr: 96.95 μg/g; Pb: 2802.56 μg/g; Hg:
Ecological risk 1.25 μg/g. Metals in plants are above acceptable limits. Metals in the media are both from geogenic and mining
Health risk
activities, and they pose high ecological risks. High carcinogenic (N10−4) and non-carcinogenic (N1) health
risks are associated with metals in media from this area. Further epidemiological studies should be carried to
know the extent of occurrence of diseases associated with mining in the area.
© 2020 Elsevier B.V. All rights reserved.

⁎ Corresponding author.
E-mail addresses: adewumiadeniyi27@yahoo.com, adewumiadeniyi@achievers.edu.ng (A.J. Adewumi), ttlaniyan@gmail.com (T.A. Laniyan).

https://doi.org/10.1016/j.scitotenv.2020.137235
0048-9697/© 2020 Elsevier B.V. All rights reserved.
2 A.J. Adewumi, T.A. Laniyan / Dr.Science of the Total Environment 718 (2020) 137235
1. Introduction
The presence of heavy metals in soils and sediments has become a
major threat to the environment due to their persistence, non-
biodegradable and toxic nature (Islam et al., 2019; Wuana and
Okeimen, 2011; Liu et al., 2005). Toxic metals such as Cr, Cu, Cd, Pb
and As are considered the most dangerous elements in the environment
(Lei et al., 2010). Human activities such as mining and dumping of mine
wastes have played significant roles in increasing the concentrations of
these metals in the environment (Fashola et al., 2016; Lottermoser,
2007). They can also be introduced from geogenic sources, especially
weathering of rocks (Finkelman et al., 2018; Ayuso and Foley, 2018).
Although some of these metals are essential to the continual existence
of human beings and their well-beings, only small are required and at
higher concentrations may be toxic (Kumar and Trivedi, 2016). Some
metals such as arsenic, lead and mercury, which are extremely
dangerous at very low level are less valuable to human physiology
(Jaishankar et al., 2014; Tchounwou et al., 2012). Once they find their
way into the human body, they accumulate in important organs such
as brain, kidneys, bones and liver for years, which may eventually lead
to death (Lanocha-Arendarczyk et al., 2016; Zioła-Frankowska et al.,
2015). Under natural conditions, only a small portion of the metals in
soils can be available for plants (Chibuike and Obiora, 2014;
Viehweger, 2014; Tangahu et al., 2011) thus providing little information
about toxicological impacts (Chibuike and Obiora, 2014).
Bioaccumulation of heavy metals in plants depend on the soil type,
plant species, growth conditions, the surrounding environment, and
the presence of other ions which are usually measured using soil-
plant transfer factors (Usman et al., 2019; Oves et al., 2016). Due to its
importance to human health and their ability uptake metals, elemental
concentration assessment in plants are an integral part of risk
assessment studies (Adewoyin et al., 2019). It had been shown that
consumption of metal-laden plants in high quantities can cause clinical
harms to both animals and humans (Chibuike and Obiora, 2014).
Ingestion of contaminated plants may pose high risk to human health
(Du et al., 2013; Han et al., 2006). One of the most commonly adopted
technique for evaluating human health risk is the target hazard
quotients (THQs) which is based on the concentration of a metal in
edible parts in comparison with a reference dose of the metal and
intake/body weight of consumers while its carcinogenic health risk is
assessed by calculating the targeted cancer risk (TCR) (Onyedikachi
et al., 2018; Zhou et al., 2016).
Anka area is one of the prominent areas in Nigeria, where gold is
being mined and processed using crude techniques (Uriah et al.,
2013). Studies showed that soils (Salisu et al., 2016; Uriah et al., 2013)
and sediments (Nuhu et al., 2014) have elevated metal loading. In this
area, both men, women and children are involved in mining and
mineral processing. In the year 2010 there was a reported Pb poisoning
outbreak in the area which led to the death of N400 children (Laing,
2010). Therefore, there is a need to continuously monitor the extent
of heavy metals concentrations in environmental media from the area,
so as to guide against the spread of diseases and sudden deaths. The
aim of this study is to determine the concentrations, contamination,
bioavailability and risks associated with heavy metals in soils, stream
sediments, tailings and plants in the area.
2. Methods and materials
2.1. Study area
Anka the study region is located in Zamfara state, Northwest Nigeria
(12°15′27.05″N; 5°51′27.01″E). It is one of the most prominent mining
areas in the country (Fig. 1). The study area has a tropical climate, with a
mean temperature of 31.8 °C with the most elevated temperature of the
year observed in April and the least observed in January. The mean
precipitation in the territory is 71.83 mm with the highest rainfall of
255 mm in August and none in January, February, and December. It
spreads over a land mass of 2746 km2 and a population of 142,280.
The major villages in this area are Sunke, Mallamawa, Kawaye, Bagega,
Dareta, Tungar Kudaku, Abare, Waramu, Bidan Zaki and Tungar Daji.
The area is underlain by the Proterozoic Anka schist belt (ASB) situated
toward the western portion schist belt of Nigeria. The Precambrian
migmatitic-gneisses and metasediments of the ASB are also intruded
by Older Granites and amphibolites (Danbatta et al., 2009; Fitches
et al., 1985; Holt, 1982; Holt et al., 1978). Mining process in a typical
gold mining and processing area in Nigeria are grinding, washing,
drying, amalgamation with Hg and melting of the amalgam to extract
the gold (Nnaji and Omotugba, 2016).
2.2. Sample collection
For this study a total of 82 samples which include: 42 soils (collected
at 25 cm depth), 22 stream sediments, 13 mine tailings and 5 plants
(Zea mays and Sorghum bicolor) were collected in January 2017. At
each sampling point, composite samples of 1 kg of soils, stream
sediments and mine tailings were collected. Likewise, whole plants
were gathered up for this survey. Control samples were gathered from
an area where excavation is not outstanding. All samples were retained
in a clean and unused ziplock bag. These were transported to the lab
where they were further treated. In the laboratory, plants were washed
with ultrapure water to remove dirt. Subsequently, all the samples were
air-dried at room temperature to complete dryness. Dried samples were
then powdered, using a clean China clay mortar and pestle and were
sieved using a mechanical sedimentological sieve to collect fine
particles for chemical analysis. Crop samples were oven-dried at
105 °C for 1 h and then at 70 °C to constant weight. Then, crop samples
were comminuted using a pulveriser, grounded to pass through 100
meshes using a nylon sieve, and stored in closed polyethylene bags for
further analysis. Five grams of all samples were weighed using electrical
weighing balance and held back in clean ziplock bags for onward
transmission into the laboratory for chemical analysis.
2.3. Chemical and mineralogical analysis
The total concentrations of As, Co, Cr, Cu, Ni, Pb, Sb, Zn and Fe in soil,
stream sediments and mine tailings samples were acid-digested with
HCl–HNO3–HClO4, and the plant samples were digested by means of
the dry ashing method (Lin et al., 2015), and determined using Agilent
HPLC-ICPMS. High performance liquid chromatography or high
pressure liquid chromatography (HPLC) is a chromatographic method
that is employed to separate a mixture of compounds in analytical
chemistry to identify, quantify or purify the individual components of
a mixture (Thomas, 2019). Total Cd in the soils and plants were digested
by HF–HNO3–HClO4 and analyzed by an inductively coupled plasma-
mass spectrometer (ICP-MS, Agilent 7500a, Palo Alto, CA, USA). All
analysis was carried out in the State Key Laboratory of Environmental
Geochemistry, Institute of Geochemistry, Guiyang, China. Quality
assurance and quality control were determined by method blanks,
duplicates, and certified reference materials (CRM) (sediment and soil
CRM: GBW07305, GBW07405). Recovery from CRM sediment
(GBW07305) was between 90% and 120%, from CRM soil
(GBW07405) between 92% and 112%. The relative percentage
difference was b6% for duplicate samples. The detection limit of As, Cd,
Co, Cr, Cu, Hg, Ni, Pb, Sb, Zn and Fe were 0.20 μg/g, 0.02 μg/g, 0.10 μg/
g, 1.00 μg/g, 0.20 μg/g, 0.01 μg/g, 0.20 μg/g, 0.50 μg/g, 0.05 μg/g,
2.00 μg/g and 0.01% respectively. Major oxides in the samples were
analyzed using X-Ray Fluorescence ARL Quant'x EDXRF spectrometer.
Major oxides analyzed include: Al2O3, CaO, CuO, TFe2O3, K2O, MgO,
MnO, Na2O, P2O5, TiO2 and Loss on Ignition (LOI) with a detection
limit of 0.01%. Mineralogical analysis for soils, stream sediments, rocks
and mine-tailings were carried using ARL™ Equinox 6000 X-Ray
diffractometer.
 A.J. Adewumi, T.A. Laniyan / Dr.Science of the Total Environment 718 (2020) 137235 3

Fig. 1. Location map of the study area.

2.4. Data processing 2.5.1. Geo-accumulation index (Igeo)

All data obtained in the study were subjected to processing
using Statistical Package for Social Sciences (SPSS) version 22,
Microsoft excel and SURFER softwares. Bivariate correlation,
hierarchical cluster analysis (HCA) and factor analysis (FA) were
carried out to decipher potential sources of heavy metals in
media from the area.
2.5. Assessment of contamination
Contamination assessments of samples were carried out using
the Geo-accumulation index (Igeo), Enrichment Factor (EF),
Contamination Factor (CF), Pollution Load Index (PLI), and
Contamination Degree (CD).
The Geo-accumulation index (Igeo) was employed to measure the
contamination of a specific metal in soils by evaluating metal
enrichment above baseline or background values (Wang et al., 2017).
The Geo-accumulation index was computed according to Eq. (1)
(Muller, 1969). The classes of Igeo according to Muller (1969) are:
Igeob0 (unpolluted); 0 ≤ Igeob1 (unpolluted to moderately polluted);
1 ≤ Igeob2 (moderately polluted); 2 ≤ Igeob3 (Moderately to heavily
polluted); 3 ≤ Igeob4 (Heavily polluted); 4 ≤ Igeob5 (Heavily to
extremely polluted) and Igeo≥5 (Extremely polluted).
Cn
Igeo ¼ log2 ð1Þ
1:5  Bn
Cn is the metal concentration in the sample and Bn is the concentration
of metal in the background sample. The constant 1.5 is introduced to
4 A.J. Adewumi, T.A. Laniyan / Dr.Science of the Total Environment 718 (2020) 137235

minimize the force of possible variances in the background values 2.5.6. Contamination load index (CLI)
which may be attributed to lithologic variations in the deposits. Degree of plant contamination for each metal was determined using
contamination load index (CLI). Eq. (6) was used to assess the CLI level
2.5.2. Enrichment factor (EF) in crops.
Enrichment Factor (EF) of an element in the analyzed samples was
based on the standardization of a measured element against a reference C Crop
CLI ¼ ð6Þ
element. A reference element is often the one characterized by low MPC
occurrence variability, such as the most commonly used elements: Al,
Fe, Ti, Si, Sr, K, etc., (Duzgoren-Aydin, 2007; Sezgin et al., 2003; Li where Ccrop is the heavy metal concentrations in the edible portion of
et al., 2001). Fe was used as normalizer in this study. The EF calculation plants, and MPC is the maximum permitted concentration of heavy
is shown in Eq. (2). metal in crops (Codex Alimentarius Commission, 2001). If CLI of a
heavy metal in one crop becomes N1, it shows that crop is contaminated
Metal with the metal (Moradi et al., 2015).



RE Soil
EF ¼
ð2Þ
Metal 2.6. Bioacccumulation and translocation of heavy metals


RE Background
Bio-accumulation factor (BAF) is an indicator of the ability of crop to
where RE is the Reference metal concentration accumulate a particular metal with respect to its concentration in the
Five contamination categories are recognized on the basis of the soil substrate (Ghosh and Singh, 2005). It is computed as indicated in
enrichment factor: EF b 2 states deficiency to minimal enrichment, Eq. (7):
EF = 2–5 moderate enrichment, EF = 5–20 significant enrichment,
EF = 20–40 very high enrichment and EF N 40 extremely high C Plant
BAF ¼ ð7Þ
enrichment (Duzgoren-Aydin, 2007; Sezgin et al., 2003). C Soil

2.5.3. Contamination factor (CF) where CPlant and Csoil represent the heavy metal concentrations in the
The assessment of soil contamination was also carried out using the edible portion of plants and soil, respectively.
contamination factor (CF) in Eq. (3). The CF is the single element index, Trace element translocation in plants from shoot to root was
and all four classes are recognized (Hakanson, 1980). These are: CF ≤ 1 measured using translocation factor (TF) given in Eq. (8).
(Low contamination factor); 1 ≤ CF˂3 (Moderate contamination factor);
Cs
3 ≤ CF˂6 (Considerable contamination factor), and 6 ≥ CF (Very high TF ¼ ð8Þ
Cr
contamination factor).

Contamination Factor where Cs and Cr are metal concentration in (μg/g) in the shoot and root
Metal Concentration respectively. When TF N 1, plants translocate metals effectively from
¼ ð3Þ root to the shoot (Baker and Brooks, 1989).
Concentration of Element in Background Soils

2.7. Weathering index

2.5.4. Contamination degree
Chemical index of weathering is an improved measure of the level of
The sum of contamination factors for all elements examined
weathering experience by a material relative to its parent rock. The
represents the CF of the environment (Hakanson, 1980). The CD is
value of this index increases as the degree of weathering increases,
targeted at providing a criterion of the level of overall pollution in
and the difference between CIW index values of the silicate parent
surface layers in a particular sampling site. The CD is classified into
rock and soil or sediment reflects the amount of weathering
four groups. Formula for calculating CD is shown in Eq. (4).
experienced by the weathered material (McLennan et al., 1993). CIW
Categorizations of the CD are: CD b 8 (low degree of pollution);
for samples were estimated using Eq. (9):
8 ≤ CD˂16 (Moderate level of pollution); 16 ≤ CD˂32 (Considerable
degree of pollution); CD ≥ 32 (Very high degree of pollution).
Al2 O3


CIW ¼  100 ð9Þ
n Al2 O3 þ CaO þ Na2 O
C if
X
Cd ¼ ð4Þ
i¼1
From this formula, chemical index of weathering, values in the range
of 50 to 60 indicates incipient weathering, values between 60 and 80
where Cd is the Contamination Degree and CF is the Contamination
indicate intermediate weathering, and values above 80 indicate
Factor.
extreme weathering.
2.5.5. Pollution load index (PLI)
2.8. Ecological risk assessment
Each sampling point was evaluated for the extent of metal pollution
by employing the method based on the pollution load index (PLI)
The ecological risk index is applied to evaluate heavy metal pollution
developed by Tomlinson et al. (1980), in Eq. (5).
in soil to associate ecological and environmental effects with their
p
n
ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi toxicology and the toxic-response factor (Tri) of Cu, Zn, Cd, Cr, Ni, and
Pollution Load Index ðPLIÞ ¼ CF 1  CF 2  CF 3  …CF n ð5Þ
Pb is 5, 1, 30, 2, 5, and 5 (μg/g) respectively (Hakanson, 1980). ERI is
expressed in Eq. (10). The classifications of the ERI are: EiRb40 (slight
where n is the number of metals studied and CF is the contamination
ecological risk); 40NEiRb80 (medium ecological risk); 80NEiRb160 (high
factor calculated as reported in Eq. (4). The PLI provides simple but
ecological risk); 160NEiRb320 (higher ecological risk) and EiRN320
comparative means for evaluating a site quality, where a value of PLI b 1
(highest ecological risk).
denote perfection; PLI = 1 present that only baseline levels of pollutants
are present and PLI N 1 would indicate deterioration of site quality
(Tomlinson et al., 1980). EiR ¼ T iR  C if ð10Þ
 A.J. Adewumi, T.A. Laniyan / Dr.Science of the Total Environment 718 (2020) 137235 5

where Tr is toxic-response factor and CF is the pollution of a single emission factor in m3/kg (Table 1). EF, ED, BW and AT are as specified
element factor. earlier in Eq. (12) above.
Potential Ecological Risk Index (PERI) is employed to determine
semi-quantitative evaluation of regional pollution level. It can be 2.9.3. Dermal contact with soil
expressed in Eq. (11) (Wang et al., 2015). The classifications of RI are: The equation for calculating average daily intake of heavy metal via
RI˂50 (Slight risk index); 150 N RI˂300 (Medium risk index); dermal contact with soil is shown in Eq. (14):
300 N RI˂600 (High to higher risk index) and RI ≥ 600 (Highest risk
index). C s  SA  FE  AF  ABS  EF  ED  CF
ADI dems ¼ ð14Þ
BW  AT
m
EiR
X
RI ¼ ð11Þ where ADIdems is the exposure dose via dermal contact in mg/kg/day.
i¼1
CS is the concentration of heavy metal in soil in mg/kg, SA is exposed
skin area in cm2, FE is the fraction of the dermal exposure ratio to soil,
where ERi is the potential ecological risk of a single element. (TR for
AF is the soil adherence factor in mg/cm2, ABS is the fraction of the
Zn = 1, Cr = 2, Cu = 5, Pb = 5, Cd = 30).
applied dose absorbed across the skin. EF, ED, BW, CF and AT are as
specified earlier in Eq. (12). Table 1 shows the exposure parameters
2.9. Health risk assessment
used for the health risk assessment for standard residential exposure
scenario through different exposure pathways.
The potential exposure pathways for heavy metals in contaminated
soils are calculated based on recommendations by several American
2.9.4. Non-carcinogenic risk assessment
publications. ADI (mg/kilo-day) for the different pathways were
Non-carcinogenic hazards are characterized by a term called the
calculated utilizing the following exposure Equations to as prescribed
hazard quotient (HQ). HQ is a unitless number that is expressed as the
by (USEPA, 1989).
probability of an individual suffering an adverse effect. It is defined as
the quotient of ADI or dose divided by the toxicity threshold value,
2.9.1. Ingestion of heavy metals
which is referred to as the chronic reference dose (RfD) in mg/kg-day
The equation for calculating average daily intake of heavy metal via
(Table 2) of a specific heavy metal as shown in Eq. (15) (USEPA, 1989):
ingestion of soil is shown in Eq. (12):

C  IR  EF  ED  CF ADI
HQ ¼ ð15Þ
ADIing ¼ ð12Þ RfD
BW  AT

where ADIing is the average daily intake of heavy metals ingested from
soil in mg/kg−day, C = concentration of heavy metal in mg/kg of soil. IR
in mg/day is the ingestion rate, EF in days/year is the exposure
frequency, ED is the exposure duration in years, BW is the body weight
of the exposed individual in kg, AT is the time period over which the
dose is averaged in days. CF is the conversion factor in kg/mg (Table 1).
For n number of heavy metals, the non-carcinogenic effect to the
population is as a result of the summation of all the HQs due to
individual heavy metals. This is believed to be another term called the
Hazard Index (HI) as identified by the USEPA document (USEPA,
1989). Eq. (16) shows the mathematical representation of this
parameter:

n n
2.9.2. Inhalation of heavy metals X X ADI k
HI ¼ HQ k ¼ ð16Þ
The equation for calculating average daily intake of heavy metal via k¼1 k¼1
RfDk
inhalation of soil is shown in Eq. (13):
where HQk, ADIk and RfDk are values of heavy metal k. If the HI value is
C s  IRair  EF  ED
ADIinh ¼ ð13Þ less than one, the exposed population is unlikely to experience adverse
BW  AT  PEF
health effects. If the HI value exceeds one, then there may be concern for
where ADIinh is the average daily intake of heavy metals inhaled from potential non-carcinogenic effects (USEPA, 1989).
soil in mg/kg−day, CS is the concentration of heavy metal in soil in
mg/kg, IRair is the inhalation rate in m3/day, PEF, is the particulate 2.9.5. Carcinogenic risk assessment
For carcinogens, the hazards are calculated as the incremental
probability of an individual developing cancer over a lifetime as a result
Table 1
Exposure parameters used for the health risk assessment through different exposure
of exposure to the potential carcinogen. The equation for calculating the
pathways for soil and water (DEA, 2010). excess lifetime cancer risk is as shown in Eq. (17):
S/N Parameters Unit Child Adult References n
X
1. Body weight (BW) kg 15 70 DEA, 2010 Riskpathway ¼ ADI k CSF k ð17Þ
2. Exposure factor (EF) Days/year 350 350 DEA, 2010 k¼1
3. Exposure duration (ED) Year 6 30 DEA, 2010
4. Ingestion rate (IR) mg/day 200 100 DEA, 2010 where Risk is a unitless possibility of an individual developing cancer
5. Inhalation rate (IRair) m3/day 10 20 DEA, 2010 over a lifetime. ADIk (mg/kg/day) and CSFk (mg/kg/day)−1 are the
6. Skin surface area (SA) cm2 2100 5800 DEA, 2010
average daily intake and the cancer slope factor, respectively for the
7. Soil adherence factor (AF) mg/cm2 0.2 0.07 DEA, 2010
8. Dermal absorption factor None 0.1 0.1 DEA, 2010
kth heavy metal, for n number of heavy metals (Table 2). The slope
(ABS) factor converts the estimated daily intake of the heavy metal averaged
9. Dermal exposure ratio (FE) None 0.61 0.61 DEA, 2010 over a lifetime of exposure directly to the incremental risk of an
10. Particulate emission factor m3/kg 1.3 × 109 1.3 × 109 DEA, 2010 individual developing cancer (USEPA, 1989).
(PEF)
The total excess lifetime cancer risk for an individual is finally
11. Conversion factor (CF) kg/mg 10−6 10−6 DEA, 2010
12. Average time (AT) calculated from the average contribution of the individual heavy metals
For-carcinogens Days 365 × 70 365 × 70 DEA, 2010 for all the pathways using the following Eq. (18):
For non-carcinogens 365 × ED 365 × ED DEA, 2010

DEA: Department of Environmental Affairs. RiskðtotalÞ ¼ RiskðingÞ þ RiskðinhÞ þ Riskdermal ð18Þ

6 A.J. Adewumi, T.A. Laniyan / Dr.Science of the Total Environment 718 (2020) 137235

Table 2
Reference doses (RfD) in (mg/kg-day) and Cancer Slope Factors (CSF) for the different heavy metals (DEA, 2010).

S/N Metal Oral RfD Dermal RfD Inhalation RfD Oral CSF Dermal CSF Inhalation CSF References

1. As 3.00E-04 3.00E-04 3.00E-04 1.50E+00 1.50E+00 1.50E+01 DEA, 2010

2. Pb 3.60E-03 – – 8.50E-03 – 4.20E-02 DEA, 2010; Luo et al., 2012
3. Hg 3.00E-04 3.00E-04 8.60E-05 – – – DEA, 2010
4. Cd 5.00E-04 5.00E-04 5.70E-05 – – 6.30E+00 DEA, 2010
5. Cr(VI) 3.00E-03 – 3.00E-05 5.00E-01 – 4.10E+01 DEA, 2010
6. Co 2.00E-02 5.70E-06 5.70E-06 – – 9.80E+00 DEA, 2010
7. Ni 2.00E-02 5.60E-03 – – – – DEA, 2010
8. Cu 3.70E-02 2.40E-02 – – – – DEA, 2010
9 Zn 3.00E-01 7.50E-02 – – – – DEA, 2010

DEA: Department of Environmental Affairs.

where Risk (ing), Risk (inh), and Risk (dermal) are risks contributions
through ingestion, inhalation and dermal pathways. Both non-
carcinogenic and carcinogenic risk assessment of heavy metals are
calculated using RfD and CSF values derived largely from the
Department of Environmental Affairs (South Africa) and USEPA as
shown in Table 2.
3. Results
3.1. Distribution of heavy metals in soils, stream sediments, mine tailings
and plants
Results of heavy metals in soils of Anka area are presented in Table 3.
The mean value of As, Cd, Co, Cr, Cu, Ni, Pb, Sb, Zn, Hg and Fe are 0.64 μg/
g, 0.03 μg/g, 7.98 μg/g, 42.55 μg/g, 27.15 μg/g, 15.26 μg/g, 131.76 μg/g,
0.53 μg/g, 47.14 μg/g, 0.85 μg/g and 1.75% respectively (Table 3). All
metals in soils of the area are above their concentrations in the
background samples. Zinc is above the average shale values and average
crustal values while it is below the USEPA (2002) standards. The
concentrations of major oxides are: SiO2 -79.88%; Al2O3 – 9.54%; CaO –
0.35%; Fe2O3 – 2.32%, K2O – 1.88% and MgO – 0.31% (Fig. 2).
Concentrations of heavy metals in stream sediments in the study
area are presented in Table 3. The mean concentration of As, Cd, Co,
Cr, Cu, Ni, Pb, Sb, Zn, Hg and Fe are 15.46 μg/g, 0.10 μg/g, 19.74 μg/g,
111.82 μg/g, 320.05 μg/g, 1.77 μg/g, 39.24, 39.24 μg/g, 2234.02 μg/g,
367 μg/g, 42.55 μg/g, 2.12 μg/g and 4.39%. These values are above the
background values except Fe which is below its concentration in the
control sample. The concentrations of As, Cr, Co, Cu, Hg, Pb and Sb values
are above the USEPA (2002) standards while Cd, Ni, Zn and Fe are below
the average shale, average crustal value and USEPA (2002) standards.
The mean concentrations of major oxides are: SiO2 -62.74%; Al2O3 –
15.74%; CaO – 1.65%; Fe2O3 – 7.04%, K2O – 2.36% and MgO – 1.34%
(Fig. 2).
Results of heavy metals in mine tailings of Anka area are
presented in Table 3. The mean concentration of As, Cd, Co, Cr, Cu,
Ni, Pb, Sb, Zn, Hg and Fe are 4.78 μg/g, 0.67 μg/g, 28.59 μg/g,
96.94 μg/g, 675.26 μg/g, 80.56 μg/g, 2802.56 μg/g, 20.24 μg/g,
119.16 μg/g, 1.25 μg/g and 4.97%. These values are likewise above
the background values concentration in the control sample.
Heavy metals in the samples are above the USEPA (2002)
standards. The mean concentrations of major oxides are: SiO 2 -
48.50%; Al2 O3 – 16.84%; CaO – 4.92%; Fe2 O3 – 11.44%, K 2O – 1.82%
and MgO – 5.22%.
Mean heavy metal concentrations in plants of the area are shown in
Table 3. The mean concentrations in roots of plants in the region are: As:
0.79 μg/g; Co: 7.96 μg/g; Cr: 20.83 μg/g; Cu: 16.26 μg/g; Ni: 29.28 μg/g;
Pb: 105.75 μg/g; Zn: 42.49 μg/g. The mean concentrations in shoots of
plants in the area are: As: 0.99 μg/g; Co: 4.57 μg/g; Cr: 21.83 μg/g; Cu:
20.83 μg/g; Ni: 23.59 μg/g; Pb: 120.43 μg/g; Zn: 52.49 μg/g. The mean
concentrations in leaves of plants in the area are: As: 1.04 μg/g; Co:
4.11 μg/g; Cr: 30.65 μg/g; Cu: 30.91 μg/g; Ni: 35.49 μg/g; Pb:
102.24 μg/g; Zn: 70.83 μg/g. The mean concentrations in grains of plants
in the area are: As: 0.62 μg/g; Co: 2.84 μg/g; Cr: 13.90 μg/g; Cu: 14.81 μg/
g; Ni: 21.47 μg/g; Pb: 71.12 μg/g; Zn: 29.32 μg/g. The concentrations of
heavy metals in plants of the area are above the recommended limit
sets by FAO (2007).

Table 3
Mean heavy metal concentrations in soils, stream sediments, mine tailings and plants of the study area.

As Cd Co Cr Cu Hg Ni Pb Sb Zn Fe
μg/g μg/g μg/g μg/g μg/g μg/g μg/g μg/g μg/g μg/g %

Soil 0.64 0.03 7.98 42.55 27.15 0.85 15.26 131.76 0.53 47.14 1.75
Stream Sediments 15.46 0.10 19.74 111.82 320.06 2.12 39.20 2234.02 3.67 42.55 4.39
Mine tailings 4.79 0.68 28.63 96.95 675.26 1.25 80.57 2802.56 20.24 119.20 4.97
Background 0.09a 0.16 2.16 5.39 6.11 0.03 2.57 25.19 0.005 5.66 3.61
1.32b 0.02 3.65 10.21 15.62 0.04 14.11 45.07 0.090 10.02 4.56
Average shale valuec 13.00 0.30 19.00 90.00 45.00 68.00 20.00 1.50 95.00 4.72
Average crustal valuesc 2.50 0.08 26.60 135.00 27.00 59.00 11.00 0.20 72.00 6.71
Iludun-Oro (Oyebamiji et al., 2018) – – – 14.76 45.28 – 21.53 107.22 – 48.17 5.17
Enyigba (Nnabo 2015) 11.30 1.62 4.88 – 57.33 – 8.79 23.84 – 16.09 –
Ijana (Abiya et al., 2019) – 0.13 – 0.15 0.63 – 0.08 0.22 – 0.70 –
USEPA (2002) 0.11 0.48 – 11.00 270.00 – 72.00 200.00 1100 –
Plants Roots 0.79 – 7.94 20.83 16.26 – 29.28 105.75 – 42.49
Shoots 0.99 – 4.57 21.83 20.83 – 23.59 120.43 – 52.49
Leaves 1.04 – 4.11 30.65 30.91 – 35.49 102.24 – 70.83
Grains 0.62 – 2.84 13.90 14.81 – 21.47 71.12 – 29.32
FAO (2007) 0.10 – 0.10 1.30 0.60 – 0.11 0.20 – 0.60

The bolden data are higher than their concentrations in background sample
a
Soil background value.
b
Sediment background value.
c
Rudnick and Gao (2003).
 A.J. Adewumi, T.A. Laniyan / Dr.Science of the Total Environment 718 (2020) 137235 7

Fig. 2. Major and minor oxides in soils, stream sediments and mine tailings in Anka area.

3.2. Mineralogical composition and weathering index of soils, stream
sediments and mine tailings
Mineralogical composition of soils, stream sediments and mine
tailings in the Anka area as revealed by XRD analysis (see Suppl. Data
7–16). The results revealed that the major minerals in soils of the area
are quartz, microcline, albite, muscovite and kaolinite (see Suppl. Data
7–10) while in stream sediments of this area, quartz, albite, microcline,
muscovite, orthoclase, kaolinite, diopside and anorthite are the major
mineralogical constituents (Suppl. Data 11–14). The main minerals in
mining. Chemical weathering of these minerals release metals
constituents in soils, sediments and tailings into the environment.
Therefore it plays a major role in the degradation of the ecosystem.
3.3. Contamination assessment of soils, stream sediments, mine tailings and
plants
The mean Geo-accumulation (Igeo), contamination factor (CF) and
enrichment factor (EF) for heavy metals in soils, stream sediments
and mine tailings are shown in Table 4. The mean Igeo for As, Cd, Co,
Cu, Ni, Pb, Sb, Zn, Hg and Fe in soils are 2.25, −3.00, 1.31, 2.40, 1.57,
1.99, 1.81, 6.15, 2.48, 4.23 and −1.63 while in stream sediments the
mean Igeo for As, Cd, Co, Cu, Hg, Ni, Pb, Sb, Zn and Fe is 2.97, 1.74,
1.56, 2.87, 3.78, 5.14, 0.89, 5.05, 4.77, 1.55 and −0.64 respectively. For
mine tailings, the mean Igeo for As, Cd, Co, Cu, Hg, Ni, Pb, Sb, Zn and
Fe are 1.28, 4.51, 2.39, 2.67, 4.85, 4.38, 1.93, 5.38, 7.23, 5.39, 2.99 and
−0.47 each.
The mean CF for As, Cd, Co, Cu, Hg, Ni, Pb, Sb, Zn and Fe in soils are
7.12, 0.19, 3.70, 7.90, 4.45, 28.33, 5.94, 5.24, 106.00, 8.33 and 0.49
while in stream sediments the mean CF for As, Cd, Co, Cu, Hg, Ni, Pb,
Sb, Zn and Fe is 11.72, 5.00, 5.41, 1s0.96, 20.50, 53.00, 2.78, 49.57,
40.78, 4.25 and 0.97 each. For mine tailings, the mean Igeo for As, Cd,
Co, Cu, Hg, Ni, Pb, Sb, Zn and Fe are 3.63, 34.00, 7.85, 9.50, 43.24,
31.25, 5.71, 62.19, 224.89, 11.9 and 1.09 each.
The average EF for As, Cd, Co, Cu, Hg, Ni, Pb, Sb, Zn and Fe in soils are
14.67, 0.39, 7.63, 16.29, 9.17, 58.45, 12.25, 10.80, 218.67, 17.19 and 1.00
while in stream sediments the mean EF for As, Cd, Co, Cu, Hg, Ni, Pb, Sb,
Zn and Fe is 12.17, 5.20, 5.62, 11.38, 21.29, 55.05, 2.89, 51.49, 42.36, 4.42
and 1.00 each. For mine tailings, the mean EF for As, Cd, Co, Cu, Hg, Ni,
Pb, Sb, Zn and Fe are 3.33, 31.20, 7.20, 8.72, 39.67, 28.67, 5.24, 57.06,
206.34 and 1.00 respectively.
The Pollution load index (PLI) and contamination degree (CD) for
soils, stream sediments and mine tailings are shown on Table 4. For
soils, stream sediments and mine tailings in the area are 1.44, 1.57 and
1.54 respectively while contamination degree (CD) for soils, stream
sediments and mine tailings are 177.69, 204.94 and 435.26 each.
Contamination assessment of plants (Table 5) showed maize (Zea
mays) and Sorghum (Sorghum bicolor) have contamination value N1 in
Cr, Co, Ni, Cu, Zn, As and Pb. This showed that crops in the area are
contaminated by heavy metals released from human activities in the
area.

Table 4
Mean Geo-accumulation (Igeo), Contamination Factor (CF) and Enrichment Factor (EF), Contamination Degree (CD), Pollution Load Index (PLI) of heavy metals in soils, stream sediments,
mine tailings and plants in Anka area.

Media As Cd Co Cr Cu Hg Ni Pb Sb Zn Fe CD PLI

Igeo Soil 2.25 −3.00 1.31 2.40 1.57 4.23 1.99 1.81 6.15 2.48 −1.63 – –
Stream sediment 2.97 1.74 1.86 2.87 3.78 5.14 0.89 5.05 4.77 1.51 −0.64 – –
Mine tailings 1.28 4.51 2.39 2.67 4.85 4.38 1.93 5.38 7.23 2.99 −0.47 – –
EF Soil 14.67 0.39 7.63 16.29 9.17 58.45 12.25 10.80 218.67 17.19 1.00 – –
Stream sediment 12.17 5.20 5.62 11.38 21.29 55.05 2.89 51.49 42.36 4.42 1.00 – –
Mine tailings 3.33 31.2 7.20 8.72 39.67 28.67 5.24 57.06 206.34 10.92 1.00 – –
CF Soil 7.12 0.19 3.70 7.90 4.45 28.33 5.94 5.24 106.00 8.33 0.49 177.69 1.44
Stream sediment 11.72 5.00 5.41 10.96 20.50 53.00 2.78 49.57 40.78 4.25 0.97 204.94 1.57
Mine tailings 3.63 34.00 7.85 9.50 43.24 31.25 5.72 62.19 224.89 11.90 1.09 435.26 1.54
CLI Plants 6.20 – 28.40 10.69 24.68 – 195.18 355.60 – 48.87 – – –
8 A.J. Adewumi, T.A. Laniyan / Dr.Science of the Total Environment 718 (2020) 137235

Table 5
Bioaccumulation of heavy metals in plants.

Sampling point Plants Cr Co Ni Cu Zn As Pb

Bagega CLI Maize (Zea mays) 20.08 15.69 43.51 6.08 63.37 25.11 91.72
BAF 0.45 1.08 0.71 0.96 0.88 1.08 0.56
TF 0.69 0.96 0.78 1.43 1.02 1.68 0.66
Dareta CLI Sorghum (Sorghum bicolor) 34.77 18.09 45.76 48.58 86.38 22.64 91.35
BAF 0.87 0.79 0.65 0.82 0.88 1.29 0.89
TF 1.49 0.66 0.69 1.55 1.68 0.55 1.25
Dareta CLI Maize (Zea mays) 28.97 16.38 24.96 19.28 28.94 19.19 42.86
BAF 0.97 0.87 1.36 0.89 0.91 1.05 0.91
TF 1.32 1.15 1.09 1.11 1.07 1.26 1.28
Bidan Zaki CA Maize (Zea mays) 22.08 14.62 19.26 23.89 50.51 16.76 381.08
BAF 0.74 0.51 0.71 0.53 1.09 0.51 0.25
TF 0.79 1.15 1.50 1.16 1.16 3.00 1.35
Kawaye CLI Maize (Zea mays) 1.61 2.71 2.07 6.95 14.24 1.19 14.93
BAF 1.05 1.27 1.06 1.05 1.13 1.41 1.05
TF 2.26 1.16 0.86 1.21 1.07 1.38 1.54

CLI: Contamination Load Index; BAF: Bioaccumulation Factor; TF: Transfer Factor.
CLI N1 implies contamination of plant by the specific metal. BAF and TF N indicate mobility of metal from soil to plants.

3.4. Weathering indices of soils, stream sediments and mine tailings
Weathering indices of soils, stream sediments and mine tailings are
presented in Fig. 3. Chemical index of weathering (CIW) for soil, stream
sediments and mine tailings are 87.15, 83.02 and 74.65 respectively,
which pointed to extreme and intense weathering of the media.
Ni, Cu, Zn, As and Pb in sorghum (Sorghum bicolor) is 1.49, 0.66, 0.69,
1.55, 1.68, 0.55 and 1.25 respectively. For maize (Zea mays) in Dareta,
TF for Cr, Co, Ni, Cu, Zn, As and Pb is 1.3, 1.15, 1.09, 1.11, 1.07, 1.26 and
1.28. In Bidan Zaki, TF for Cr, Co, Ni, Cu, Zn, As and Pb in maize (Zea
mays) is 0.79, 1.15, 1.50, 1.16, 1.16, 3.00 and 1.35 respectively. In
Kawaye, BAF for Cr, Co, Ni, Cu, Zn, As and Pb in maize (Zea mays) plant
is 2.26, 1.16, 0.86, 1.21, 1.07, 1.38 and 1.54 respectively.

3.5. Mobility of heavy metals in plants

The bioaccumulation factor (BAF) and transfer factor (TF) of plants
in the area is presented in Table 5. In Bagega area, BAFs in maize (Zea
mays) are: Cr - 0.45; Co – 1.08; Ni – 0.71; Cu – 0.96; Zn – 0.88; As –
2.08 and Pb – 0.56 while the BAF for Cr, Co, Ni, Cu, Zn, As and Pb in
sorghum (Sorghum bicolor) is 0.87, 0.79, 0.65, 0.82, 0.88, 1.29 and 0.89
respectively. For maize (Zea mays) in Dareta, BAF for Cr, Co, Ni, Cu, Zn,
As and Pb is 0.97, 0.87, 1.36, 0.89, 0.91, 1.05 and 0.91. In Bidan Zaki,
BAF for Cr, Co, Ni, Cu, Zn, As and Pb in maize (Zea mays) is 0.74, 0.51,
0.71, 0.53, 1.09, 0.51 and 0.25 respectively. In Kawaye, BAF for Cr, Co,
Ni, Cu, Zn, As and Pb in maize (Zea mays) plant is 1.05, 1.27, 1.06, 1.05,
1.13, 1.41 and 1.05 respectively.
In Bagega area, TFs in maize (Zea mays) are: Cr - 0.69; Co – 0.96; Ni –
0.78; Cu – 1.43; Zn – 1.02; As – 1.68 and Pb – 0.66 while the TF for Cr, Co,
3.6. Bivariate correlation (BC), hierarchical cluster analysis (HCA) and
factor analysis (FA)
Bivariate correlation of heavy metals in soils, sediments, and mine
tailings are shown in Suppl. 1-3. For soils, bivariate correlation (Suppl.
Data 1) showed that there is a positive and strong correlation between
As and Cd [r = 0.675]; As and Zn [r = 0.950]; As and Fe [r = 0.566]; Cd
and Sb [r = 0.550]; Cd and Zn [r = 0.500]; Co and Cr [r = 0.642]; Co and
Ni [r = 0.824]; Cr and Cu [r = 0.572]; Cr and Ni [r = 0.757]; Cu and Pb
[r = 0.910]; Cu and Zn [r = 0.811]; Pb and Zn [r = 0.964] and, Sb and Fe
[r = 0.830].
For stream sediments there is positive and strong correlations
(Suppl. Data 2) between As and Cd [r = 0.581]; As and Co [r =
0.810]; As and Cr [r = 0.809]; As and Cu [r = 0.663]; As and Ni [r =

Fig. 3. Risk Index (RI), Potential Ecological Risk Index (PERI) and chemical index of weathering of metals in soils, stream sediments and mine tailings of Anka area.
 A.J. Adewumi, T.A. Laniyan / Dr.Science of the Total Environment 718 (2020) 137235 9

0.872]; As and Pb [r = 0.586]; As and Sb [r = 0.612]; As and Fe [r =
0.970]; Cd and Co [r = 0.631]; Cd and Cr [r = 0.861].
For mine tailings, bivariate correlation showed that there is a strong
and positive correlation (Suppl. Data 3) between As and Cd [r = 0.879];
As and Cd [r = 0.654]; As and Cr [r = 0.545]; As and Cu [r = 0.911]; As
and Ni [r = 0.575]; As and Pb [r = 0.771]; As and Sb [r = 0.919]; As and
Zn [r = 0.797]; As and Fe [r = 0.919]; As and Ni [r = 0.575]; As and Pb
[r = 0.771]; As and Sb [r = 0.919]; As and Zn [r = 0.797]; As and Fe [r =
0.596].
Hierarchical cluster analyses (HCA) for heavy metals in soils and
stream sediments are divided into two groups (Suppl. Data 18). In
group 1 are Cd, As, Sb, Fe, Co, Ni, Cr, Cu and Zn while in group 2 is Pb.
For mine tailings, HCA revealed that there are 3 groups. In group 1 are
Fe, Cd, As, Co, Sb, Cr, Ni and Zn while in group 2 is Cu and group 3 is
Pb (Suppl. Data 18).
Factor analysis (Suppl. Data 4–6) showed that heavy metals in soils
are grouped into 3 factors. In factor 1, As, Cd, Co, Cr, Cu, Ni, Pb and Fe
have values N0.50 while in factors 2 and 3, As and Zn have values
N0.50 respectively. For stream sediments, heavy metals are grouped
into three components. In factor 1, Cd, Cu, Pb, and Sb have values
N0.50 while in factor 2, Co, Cr, Ni, and Zn have a value N0.50 while in
factor 3, only Zn have values N0.50. For mine tailings, heavy metals
have three components. In factor 1, As, Cd, Cu, Pb and Sb have loadings
N0.50 while in factor 2, Co, Cr, and Ni have values larger than 0.50. In
factor 3, none has values N0.50.
3.7. Ecological risk
The Risk Index (RI) (Fig. 3) ranges from 5.25 to 124.78 with Pb
having the highest RI and Zn with the least RI. The overall Potential
Ecological Risk Index (PERI) for soil is 230.30. For stream sediments,
the risk index ranges from 5.21 to 602.73 with Cd having the highest
risk index and Zn with the least RI. The PERI for stream sediments is
1152.59. Mine tailings revealed RI from 5.93 to 479.41 with Pb having
the highest RI and Zn with the least RI. PERI for stream sediments is
1004.64. This implied that Pb and Cd of in the area pose great challenge
to the ecological system in the area.
3.8. Health risk of HM in soils, stream sediments, mine tailings and plants
(THQ)
Non-carcinogenic health risk in soils, stream sediments and mine
tailings in children and adults is presented in Table 6. For children,
hazard index (HI) through oral ingestion, inhalation and dermal contact
with heavy metals in soils are 7.06, 1.2E-04 and 23.04 with a total HI are
30.11 while in stream sediments HI through ingestion, inhalation and
dermal contact are 92.98, 3.06E-04 and 57.99 respectively with a total
of 150.98. For mine tailings, HI through ingestion, inhalation and dermal
contact are 108.96, 3.84E-04 and 83.16 each with a total of 192.11. For
adults, HI through oral ingestion, inhalation and dermal contact with
heavy metals in soils are 3.56, 3.48E-05 and 6.10 with a total HI are
9.66 while in stream sediments HI through ingestion, inhalation and
dermal contact are 37.44, 1.03E-07 and 33.72 respectively with a total
of 71.16. For mine tailings, HI through ingestion, inhalation and dermal
contact are 41.77, 8.464E-05 and 46.28 each with a total of 88.05.
According to the USEPA (1989) people are at a risk of non-
carcinogenic health risk if HI is N1 through different pathways. It is
observed that non-carcinogenic health risk in this area are propelled
by oral ingestion and dermal contact with contaminated environmental
media from this area.
The carcinogenic health risk in soils, stream sediments and mine
tailings in children and adults is presented in Table 6. For children,
hazard index (HI) through oral ingestion, inhalation and dermal contact
with heavy metals in soils are 1.92E-03, 5.14E-02 and 1.76E-11 with a
total HI are 5.33E-02 while in stream sediments HI through ingestion,
inhalation and dermal contact are 2.59E-02, 8.71E-03 and 4.35E-10
respectively with a total of 8.97E-01. For mine tailings, HI through
ingestion, inhalation and dermal contact are 3.18E-02, 1.09E+01 and
4.02E-07 each with a total of 1.13E+01. For adults, HI through oral
ingestion, inhalation and dermal contact with heavy metals in soils are
1.09E-03, 8.93E-03 and 2.94E-12 with a total HI are 1.00E-02 while in

Table 6
Hazard quotient and hazard index of heavy metals in soils, stream sediments and mine tailings through different pathways.

Non-carcinogenic Carcinogenic

HQ As HQ Pb HQ Cd HQ Cr HQ Co HQ Hg HQ Ni HQ Cu HQ Zn HI HQ As HQ Pb HQ Cd HQ Cr HQ Co HI

Child
S OI 0.27 4.68 6E-3 1.81 0.05 3.6E-2 0.09 0.09 0.02 7.06 6.9E-6 1.4E-3 4.7E-4 – – 1.9E-3
IN 8.7E-8 – 1.9E-8 5.9E-5 5.9E-5 1.4E-6 – – – 1.2E-4 6.8E-7 5.1E-2 6.1E-8 1.7E-5 1.3E-5 5.1E-2
DC 0.03 – 9E-4 – 22.93 4.6E-3 0.05 0.02 0.01 23.04 1.8E-11 – – – – 1.76E-11
Total 0.30 4.68 8E-3 1.81 22.98 4.1E-2 0.14 0.11 0.03 30.11 7E-6 5.3E-2 4.7E-4 1.7E-5 1.3E-5 5.3E-2
SS OI 6.59 79.34 3E-2 4.77 0.13 0.09 0.25 1.11 0.02 92.98 1.7E-4 2.5E-2 1.2E-3 – – 2.5E-2
IN 2.2E-6 – 7.4E-8 1.6E-4 2E-4 3.5E-6 – – – 3.1E-4 1.7E-5 8.7E-1 2.6E-7 4.5E-5 3.2E-5 8.7E-3
DC 0.84 – 3E-3 – 56.71 0.01 0.12 0.22 0.009 57.99 4.4E-10 – – – – 4.4E-10
Total 7.43 79.34 3E-2 4.77 56.84 0.10 0.39 1.33 0.029 150.98 1.9E-4 8.9E-1 1.2E-3 4.5E-5 3.2E-5 8.9E-1
MT OI 2.04 99.53 0.17 4.13 0.18 0.05 0.52 2.33 0.05 108.96 5.3E-5 3.1E-2 1.1E-3 – – 3.2E-2
IN 6.7E-7 – 4.9E-7 1.4E-4 2E-4 2.0E-6 – – – 3.4E-4 5.2E-6 1.1E+1 1.7E-6 3.9E-5 4.8E-5 1.1E+1
DC 0.26 – 0.02 – 82.15 6.8E-3 0.24 0.46 0.03 83.16 4.0E-7 – – – – 4.0E-7
Total 2.30 99.53 0.19 4.13 82.33 0.06 0.75 2.79 0.08 192.11 5.8E-5 1.1E+1 1.1E-3 3.9E-5 4.8E-5 1.1E+1

Adults
S OI 0.19 1.92 3.2E-3 1.28 0.02 2.9E-3 0.04 0.09 1.6E-3 3.56 2.7E-7 8.2E-4 2.7E-4 – – 1.1E-3
IN 1.6E-8 – 8.9E-9 1.3E-5 2.2E-5 4.4E-7 – – – 3.4E-5 1.8E-8 8.9E-2 1.6E-9 4.5E-6 5.6E-6 8.9E-3
DC 0.01 – 2.2E-4 – 6.04 7.2E-4 0.02 0.02 9.6E-3 6.10 2.9E-12 – – – – 2.9E-12
Total 0.19 1.92 3.4E-3 1.28 6.06 3.6E-3 0.06 0.11 1.1E-2 9.66 2.9E-7 9.7E-3 2.7E-4 4.5E-6 5.6E-6 1E-2
SS OI 3.09 32.33 0.01 1.34 0.04 7.3E-3 0.11 0.34 3.7E-3 37.44 1.1E-4 6.9E-3 1.2E-3 – – 8.2E-3
IN 3.9E-7 – 2.6E-8 6.7E-5 3.6E-5 1.1E-6 – – – 1.0E-7 5.9E-6 2.9E-1 1.6E-8 1.6E-5 5.6E-6 2.9E-1
DC 0.26 – 0.001 – 33.23 1.8E-3 0.03 0.16 9.3E-3 33.72 1.1E-11 – – – – 1.1E-11
Total 3.33 32.33 0.01 1.34 33.27 9.1E-3 0.14 0.50 1.3E-2 71.16 1.1E-4 3.0E-1 1.2E-3 1.6E-5 5.6E-6 3.0E-1
MT OI 0.05 41.03 0.07 0.10 0.09 4.3E-3 0.10 0.31 1.1E-2 41.77 2.6E-5 8.9E-3 4.6E-4 – – 9.4E-3
IN 1.1E-7 – 1.1E-7 6.3E-5 2.2E-5 6.6E-7 – – – 8.5E-5 5.9E-7 8.6E-1 1.4E-7 8.8E-6 1.6E-5 8.6E-1
DC 0.12 – 0.01 – 45.81 1.1E-3 0.18 0.13 2.6E-2 46.28 5.7E-8 – – – – 5.7E-8
Total 0.17 41.03 0.08 0.10 45.89 5.4E-3 0.28 0.44 3.7E-2 88.05 2.7E-5 8.7E-1 4.6E-4 8.8E-6 1.5E-5 8.7E-1

S - Soil; SS – Stream sediments; MT: Mine tailings; OI: Oral ingestion; IN: Inhalation; DC: Dermal contact; HQ: Hazard quotient; HI: Hazard index.
Bolden data indicate that HQ and HI are higher that the recommended value for carcinogenic (N10-4) and non-carcinogenic (N1) health risks.
10 A.J. Adewumi, T.A. Laniyan / Dr.Science of the Total Environment 718 (2020) 137235

stream sediments HI through ingestion, inhalation and dermal contact
are 8.24E-03, 2.96E-01 and 1.06E-11 respectively with a total of 3.03E-
01. For mine tailings, HI through ingestion, inhalation and dermal
contact are 9.41E-03, 8.60E-01 and 5.66E-08 each with a total of
8.69E-01. According to USEPA (1989) people are at a risk of carcinogenic
health risk if HI is between 10−4 and 10−8 through different pathways.
In this study, that carcinogenic health danger in this area are increased
by oral ingestion and inhalation of contaminated environmental media.
For plants, the targeted hazard quotient (THQ) carcinogenic effect
through ingestion of heavy metals in sorghum by children and adults
are 1.83 and 0.43 while for maize the effect ranges between 4.00E-02
and 20.40 for children while it ranges between 2.00E-02 and 4.15 for
adults. For non-carcinogenic effect through ingestion of metals in
sorghum by children and adults are 6.63 and 4.32 while for maize the
effect ranges between 0.17 and 45.51 for children while it ranges
between 0.10 and 47.38 (Table 7).
4. Discussions
of As, Cd, Co, Cu, Ni, Pb, Sb and Zn in mine tailings were above this limit
while As, Cd, Cr, Cu, Ni and Pb in the tailings are higher than the
recommended limits set by USEPA (2002). High abundance of Cr in
soils, sediments and tailings may be linked to the mining of chromite
deposits found in the area. Overall, the concentrations of heavy metals
in the media from this area pose great threat to the surroundings. In
plants from the area, As, Co, Cr, Cu, Ni, Pb and Zn are of higher
concentrations than the limit sets by FAO (2007). Many studies across
the world have reported significant heavy metals concentrations in
soils (Lee et al., 2005; Zhou et al., 2007; Oyebamiji et al., 2018), stream
sediments (Yacoub et al., 2012; Kraus and Wiegand, 2006; Kartal
et al., 2006), mine tailings (Ngole-Jeme and Fantke, 2017; Romero
et al., 2006) and plants (Chibuike and Obiora, 2014) in areas around
mining sites. Elevated abundance of toxic metals in media from this
area poses great threat to the environment (Yacoub et al., 2012) and
consumption of contaminated plants will contribute significantly to
the deterioration of human health in the area (Chibuike and Obiora,
2014).

4.1. Heavy metals in environmental media 4.2. Contamination of soils, sediments, tailings and plants

This study was carried out to ascertain the degree of toxic metals in
environmental media from the study area. The concentrations of As, Co,
Cr, Cu, Ni, Pb, Sb, Hg and Zn are above those in the background samples
(Table 3). The concentration of Cu, Pb and Sb are greater than average
crustal values listed by Rudnick and Gao (2003). The high
concentrations of these metals in soils of the area may be due to
intensive artisanal mining of gold and associated chalcopyrite and lead
sulphide in the area. Chromium (Cr) and Pb in soils of the area are
more eminent than those reported by Oyebamiji et al. (2018) in soils
of Iludun-Oro while Co, Ni, Pb and Zn are greater than those reported
in soils of Ijana area as listed by Abiya et al. (2019). Furthermore, As
and Cr is greater than the limits set by USEPA (2002) for metals in
soils. The average concentration of As, Co, Cr, Cu, Pb and Sb in sediments
are higher than those in average shale while As, Cd, Cr, Pb and Sb in the
stream sediments are higher than the average crustal value of metals
(Rudnick and Gao, 2003). Compared with USEPA (2002) standards, As,
Cr, Cu and Pb have higher concentrations in sediments. In mine tailings,
the average concentration of Co, Cr, Cu, Ni, Pb, Sb and Zn are higher than
those reported in average shale (Rudnick and Gao, 2003). Compared
with average crustal values (Rudnick and Gao, 2003), the concentration
Contamination assessment (Table 4) was utilized to show the level
of metal contamination of student environmental media. Geo-
accumulation index (Igeo), revealed that the soils of the area are
unpolluted by Cd and Fe (Table 4). According to Muller (1969)
classifications, soils in this area are also moderately polluted by Co, Cu,
Ni, and Pb while they were moderately to heavily polluted by As, Cr
and Zn. The soils are heavily to extremely polluted by Hg while it is
extremely polluted by Sb. Igeo also revealed that stream sediments
from the area are unpolluted by Fe, but are unpolluted to moderately
polluted by Ni and Zn. They are moderately polluted Cd and Co while
they are moderately to heavily polluted by As and Cr but are heavily
polluted by Cu. Also, the sediments are heavily to extremely polluted
by Sb while they are extremely polluted by Hg and Pb (Muller, 1969).
For mine tailings, Igeo showed that they are unpolluted by Fe while
they are moderately polluted by As and Ni. Also, the tailings are
moderately to heavily polluted by Co, Cr and Zn while they are heavily
to extremely polluted by Cd, Cu and Hg. The media is also extremely
polluted by Pb and Sb. Studies have shown that soils, sediments, and
tailings have high accumulation of toxic metals around gold mining
and processing areas (Abiya et al., 2019; Nurcholis et al., 2017). High

Table 7
Targeted Hazard Quotient (THQ) for carcinogenic and non-carcinogenic health effects of heavy metals in children and adults.

Location Plants Cr Co Ni Cu Zn As Pb Total

Carcinogenic
Bagega Maize (Zea mays) Children 1E-1 1E-2 3E-3 2E-3 2E-1 4E-2 8E-1 1E+0
Adult 4E-2 2E-2 2E-2 2E-2 5E-2 3E-2 2E-1 4E-1
Dareta Sorghum (Sorghum bicolor) Children 3E-1 5E-2 2E-2 8E-2 4E-1 2E-2 8E-1 2E-1
Adult 9E-2 1E-2 3E-2 2E-2 7E-2 1E-2 2E-1 4E-1
Dareta Maize (Zea mays) Children 2E-1 8E-3 6E-2 1E-2 5E-2 1E-2 2E-1 5E-1
Adult 6E-2 3E-3 1E-2 5E-3 1E-2 1E-2 4E-2 2E-1
Bidan Zaki Maize (Zea mays) Children 6E-1 2E-2 2E-1 5E-2 2E-1 6E-2 2E+1 2E+1
Adult 4E-2 8E-4 7E-3 7E-3 2E-2 3E-2 4E+0 4E+0
Bidan Zaki Maize (Zea mays) Children 2E-3 3E-4 7E-4 1E-3 7E-3 1E-2 3E-2 4E-2
Adult 1E-3 2E-4 3E-4 1E-3 1E-3 1E-2 8E-3 2E-2

Non-carcinogenic
Bagega Maize (Zea mays) Children 1E+0 5E-2 5E-3 1E-2 4E-1 1E-1 2E+0 4E+0
Adult 2E-1 4E-2 7E-3 4E-3 4E-1 1E-1 2E+0 5E+0
Dareta Sorghum (Sorghum bicolor) Children 3E+0 1E-1 4E-2 2E-1 9E-1 8E-2 2E+0 7E+0
Adult 7E-1 1E-1 3E-1 2E-1 8E-1 6E-2 2E+0 4E+0
Dareta Maize (Zea mays) Children 2E+0 3E-2 2E-2 5E-2 1E-1 5E-2 4E-1 3E+0
Adult 5E-1 3E-2 2E-1 3E-2 8E-2 4E-2 4E-1 2E+0
Bidan Zaki Maize (Zea mays) Children 1E+0 7E-3 9E-2 6E-2 3E-1 1E-1 4E+1 5E+1
Adult 3E-1 6E-3 7E-2 6E-2 3E-1 8E-2 4E+1 5E+1
Bidan Zaki Maize (Zea mays) Children 6E-2 2E-3 1E-3 5E-3 2E-2 7E-2 6E-2 2E-1
Adult 3E-3 7E-4 1E-3 4E-3 2E-2 3E-2 5E-2 1E-1

Bolden data indicate that THQ are higher that the recommended value for carcinogenic (N10-4) and non-carcinogenic (N1) health risks.
 A.J. Adewumi, T.A. Laniyan / Dr.Science of the Total Environment 718 (2020) 137235
contamination of soils, sediments and tailings pose great threat to the
well-being of the ecosystem and consequently people living in the area.
The enrichment factor (EF) of metals showed in Table 4 revealed
that Cd and Fe are minimally enriched in the soil while they are
significantly enriched by As, Co, Cr, Cu, Ni, Pb and Zn. The soils are
extremely enriched by Hg and Sb. The high enrichment of Pb, Hg and
Sb in soils of this area may be attributed to artisanal gold mining and
processing in this area. Mercury amalgam is used for gold processing
in this area and might have contributed to its concentration in the
soils. It had been discovered that Pb, Zn, Cd, As and Cu are major toxic
metal associated gold mining (Gerson et al., 2018). Stream sediments
in the area are minimally enriched by Fe while they are moderately
enriched by As and are significantly enriched by Co, Cr, Ni and Zn.
Also, the sediments are extremely enriched by Hg and Sb. Waste
water from gold processing in the area are highly laden with Hg
which poses serious threat to the environment (Adewumi and
Laniyan, 2020). Toxic metals find their ways into rivers and significantly
accumulate in stream sediments from soils, tailings and rocks around
mining environment. Mine tailings from the area are lowly enriched
by Fe while they are moderately enriched by As. Likewise, the tailings
are significantly enriched by Co, Cr, Ni, and Zn but are very highly
enriched by Cd, Cu, and Hg. Also, they are extremely enriched by Pb
and Sb. Waste rocks are stockpiles of heavy metals around mining
areas which might pose serious hazards to human health and
agricultural productivity (Chileshe et al., 2019).
To further ascertain the extent of media contamination by metals,
contamination factor (CF) was employed (Table 4). For soils, Cd and
Fe pose low contamination while Co and Ni cause considerable
contamination. As, Cr, Hg, Pb, Sb and Zn pose very high contamination.
For stream sediments, only Fe poses a low contamination while Ni
pose moderate contamination. Also Cd, Co, and Zn pose considerable
contamination. Furthermore, As, Cr, Cu, Hg, Pb and Zn caused very
high contamination. For mine tailings, Fe pose moderate contamination
while As and Ni, pretend considerable contamination but Cd, Co, Cr, Cu,
Hg, Pb, Sb and Zn pose very high contamination. (Table 4).
Contamination degree (CD) of soils, sediments and tailings revealed
that metals pose a very high degree of contamination in these media
(Table 4). Pollution load index (PLI) further showed that all the media
are highly polluted by metals and is causing deterioration of the site
quality. As for plants, contamination load index (CLI) (Table 4) showed
that heavy metals (Cr, Co, Ni, Cu, Zn, As and Pb) in maize (Zea mays)
from Bagega, Dareta, Bidan Zaki and Kawaye are above 1, and revealed
that they are contaminated by these metals. Consumption of these
contaminated plants may trigger severe health issues in the community.
Several studies such as that of Ngole-Jeme and Fantke (2017), Song et al.
(2015) and Meunier et al. (2010) revealed that soils and plants around
mining areas are usually contaminated by heavy metals. Elevated
concentrations of toxic metal and their contamination in this area
might have been caused by leaching and aerial dispersion from the
tailings to surrounding environment. Surrounding ecosystems are at
greater risk of heavy metal exposure from contaminated soil, sediments,
tailings and plants.
4.3. Bioavailability of metals in plants
In Bagega area of Anka, only Co and As are mobile from the soil to the
maize (Zea mays) while in sorghum (Sorghum bicolor) of Dareta area
only As is mobilized from the soil to the plant (Table 5). In Dareta area
of Anka, only Ni and As are mobile from soil to the maize plant (Zea
mays). All heavy metals were mobilized from soil to maize (Zea mays)
plant in parts of Bidan Zaki which is near to the mines. In areas not
close to the mines, no metal was selectively mobilized from soil to
maize (Zea mays) plant and established that plants growing close to
the mines are mobilized heavy metals than plants raised in areas far
from the mines. The study further showed that in Bagega area of
Anka, Cu, Zn and As are mobile from roots to shoots of the maize (Zea
11
mays) plants while in sorghum (Sorghum bicolor) of Dareta area only
Cr, Cu, Zn and Pb were mobilized from root to the shoot (Table 5). In
Dareta area of Anka, all metals were mobilized from root to the shoot
of the maize plant (Zea mays). All heavy metals except Cr were
mobilized from root to the shoot of the maize (Zea mays) plant in
parts of Bidan Zaki close to the mines while in areas not close to the
pits all metals except Ni were selectively mobilized from root to the
shoot of maize (Zea mays) plant (Table). Maize (Zea mays)
bioaccumulates heavy metals more than other plants in this area and
may be useful in remediating contaminated soils. Maize (Zea mays)
and Sorghum (Sorghum bicolor) translocate metals in the area due to
the high moisture content that these plants have. Studies such as that
of Chibuike and Obiora (2014) have revealed that heavy metals
bioaccumulate in plants around mining sites and their consumption
poses great problem to the health of people living around this area.
4.4. Sources of metals
Bivariate correlation (Suppl. Data 1–3) revealed that metals in soils,
stream sediments and mine tailings were from similar geogenic and
anthropogenic sources, particularly mining and mineral processing.
Factor analysis (Suppl. Data 18) of heavy metals in soils showed that
Pb, Cu, Fe, Cd, Cr, Zn, As and Sb are mainly from mining and mineral
processes activities in the area, while Ni and Co are from both geogenic
and anthropogenic sources. FA of metals in stream sediments showed
that Fe, Zn, As, Cu, Pb, Sb, and Cd are from mining and mineral
processing while Ni, Co and Cr are from mixed sources. For mine
tailings, FA showed that Ni, Co, Fe, Cr and Zn are from mafic-
ultramafic rocks while As, Cu, Pb, Cd and Sb are from gold bearing quartz
veins. Hierarchical cluster analysis (HCA) while other metals in soils and
stream sediments (Suppl. Data 18) of the area might have originated
from geogenic and mining sources, Pb might have originated from
mining and mineral processing of galena (PbS) and gold bearing quartz.
For mine tailings (Suppl. Data 18), HCA revealed that Fe, Cd, As, Co, Sb,
Cr, Ni and Zn are from similar geogenic sources and Cu might have
been released from different source mainly from chalcopyrite (CuS)
mined in the area, while Pb have been leached out from PbS. Mercury
in soils, sediments and tailings in this area are mainly from gold mining
and processing in the area. Extreme and intense weathering also play
significant role in the release of heavy metals in the media.
4.5. Risk assessment of metals in media
Risk assessment is the overall process of identifying the nature of
hazards and their level of risk in the environment (CCOHS 2019)
which can be inferred from theoretical analysis. The effects of prolonged
exposure of various plants and animals to toxic metals have been
reported by Fayiga et al. (2004), Franco-Hernandez et al. (2010),
Chibuike and Obiora (2014), Emamverdian et al. (2015), Sobolev and
Begonia (2008), and Eisler (2004). Ecological risk assessment showed
that Zn, Cr, and Cu pose slight ecological risk in soils of the area, while
Pb and Cd pose high and medium ecological risks respectively. Overall
potential ecological risk index (PERI) showed the metals poses medium
ecological risk. In stream sediments and mine tailings, Zn and Cr pose
slight ecological risk while Cu, Pb and Cd pose high and highest
ecological risks. PERI (Fig. 3) showed that all the metals in the sediments
pose higher ecological risks. As stated by Finnegan and Chen (2012),
plant development is prompted by low concentrations of As, since few
plants are lenient to high concentrations of the metal. At small
accumulations, Ni has a vital role in various plant morphological and
physiological functions Sreekanth et al. (2013), but high Ni aggregations
affects root growth, photosynthesis, mineral nutrition and enzymatic
action and would therefore affect vegetation increase. Cobalt and Zn
would also affect seed germination (Ngole-Jeme and Fantke, 2017).
Non-carcinogenic health risks of heavy metals in soils for children
and adults showed that the total hazard index is greater 1 and is
12 A.J. Adewumi, T.A. Laniyan / Dr.Science of the Total Environment 718 (2020) 137235
aggravated by oral ingestion of Pb and Cr, and dermal contact with the
contaminated soils triggered by Co. For stream sediments, the overall
health risk index is N1 for both adults and children. It is mainly increased
by oral ingestion of As, Pb, Cr and Cu. Dermal contact with contaminated
sediments aggravated by Co played a significant role in the process. For
mine tailings, non-carcinogenic health risk in children and adults are
higher than 1. In children, it is mainly driven by oral ingestion of As,
Pb, Cr and Cu, and dermal contact with Co played a great role in
increasing non-carcinogenic health risks. In this study, it was observed
(Table 6) that children in the area are more exposed to non-
carcinogenic health diseases than adults. This is not only because of
their low immune system (WHO, 2011), but also due to the increased
participation of the kids in artisanal mining and mineral processing in
the area (Adewumi et al., 2019). Studies in the area have shown that
increase in metals, especially Pb in the blood (Ogabiela et al., 2011),
nail and hairs (Adewumi et al., 2019) of children in the area. For plants,
total hazard quotients (THQ) showed that ingestion of maize (Zea mays)
and sorghum (Sorghum bicolor) contaminated by Cr and Pb contribute
significantly to high non-carcinogenic health risk in the area (Table 7).
It showed that children are more exposed to this risk by consuming
the Cr and Pb contaminated plants while adults face this risk through
consumption of Pb laden plants (Table 7). Human exposure to extreme
levels Hg destroys the brains, kidneys and developing foetus leading to
irritability, tremors, impaired vision, memory loss, lung damage, skin
rashes etc. (UNEP/OCHA, 2010).
Carcinogenic health risk (Table 6) showed that the total hazard
quotient for heavy metals in mine tailings and soils for adult and
children are N10−2 and is aggravated by oral ingestion of Pb and Cd,
and inhalation of Pb laden tailings and soil. For stream sediments, oral
ingestion of sediments contaminated by As, Pb and Cd, and inhalation
of Pb laden sediments by children and adults may also prompt
carcinogenic health issues in them. As with the non-carcinogenic,
children in the area are more prone to carcinogenic health issues
compared to the adults. Total hazard quotients (THQ) for metals in
plants revealed that oral ingestion of contaminated crops in the area
may aggravate and contribute significantly to carcinogenic health issues
in both adults and children (Table 7). As at 2010, about 335 cases of
strange ailments were reported in local clinics in Anka area following
the outbreak of Pb poisoning (Igwe, 2010). Out this total number, a
total of 163 lives were lost and children accounts for 68% of the deaths.
It was reported by Doctors Without Borders that this epidemic was
observed in communities around artisanal mining sites. Furthermore
it was also reported the 60% of illegal miners are women and children
(Igwe, 2010). According to Ogabiela et al. (2011) and Adewumi et al.
(2019), there is bioaccumulation of toxic metals in the bloods, hairs
and nails of children in this area. Numerous studies explaining the
health effects associated with exposure of humans to heavy metals
exist (Jaishankar et al., 2014; Singh et al., 2011; Alissa and Ferns,
2011). Soaring vulnerability of humans to As is connected with skin
destruction, elevated risk of cancer, and challenges with circulatory
system (Scragg, 2006). Cadmium and Pb are carcinogenic and extended
subjection to low concentrations could lead to kidney disorder, lung
problem, and weak bones for Cd, and nervous damage in the case of
Pb. Cobalt has been implicated in cardiomyopathy and lung irritation.
Chromium may lead to gastrointestinal, nasal and lung chagrin,
ulceration of stomach and small intestines, dermatitis, and decreased
sperm counts (ATSDR, 2016a). Dermatitis, lung sensitivity and cancer
are health orders associated with unrestricted Ni consumption. The
most commonly described adverse health consequences of Cu and Zn
are gastrointestinal discomfort including distaste, spewing, and/or
stomach pain but irritation of the respiratory structure is also mundane
(ATSDR, 2016b). These difficulties are likely to be encountered by
natives close to mining sites because of the higher assemblages of
heavy metals and metalloids in this area, in contrast to the others.
Ingestion of surface tainted plants contributes remarkably to exposure
to Cd, Cu, Mn, Pb and Zn. Bearing in mind that crops eaten by man are
grown on these media by some inhabitants, total day-to-day
consumption of the metals could actually be greater than what is
given in our study.
5. Conclusions
This study was carried out to determine the concentrations,
contamination, bioavailability and risks related to metals in soils, stream
sediments, mine tailings and plants of Anka area, Zamfara state,
Northwest Nigeria. It was observed that toxic metals in the studied
environmental media are above recommended standards and are
highly contaminated with them. The polluted media pose very high
ecological and health risks. The findings revealed that geogenic
processes aggravated by mining activities may cause great threats to
the environment and human health especially children. Future research
should endeavour to carry out epidemiological studies with respect to
contamination of environmental media. This will greatly assist the
Government and other policy makers make necessary laws to mitigate
the impacts of mining on the ecosystem.
Declaration of competing interest
The authors declared that there is no conflict of interest attached to
this manuscript.
Acknowledgements
The authors appreciate the efforts Oladoyin Ayodeji Felix and
Mustapha Haske for their supports during sample collections. We also
thank the Zamfara State Ministry of Environment. The Emir of Anka
and the village heads of Kawaye, Bagega, Dareta, and Bidan Zaki are
appreciated for their supports. We also appreciate Professor Xiao
Tangfu, Dr. Ning Zengping, Dr. Liu Yizhang, Dr. Atta Ratsool and Ma Liam
for their assistance during the first author visit to the State Key
Laboratory of Environmental Geochemistry (SKLEG), Institute of
Geochemistry, Chinese Academy of Science, Guiyang, Guizhou Province,
China. We appreciate the Management of Achievers University, Owo,
Ondo State, Nigeria for approving the visit of the first author to SKLEG.
Funding
This research was sponsored by the opening fund of State Key
Laboratory of Environmental Geochemistry (SKLEG), Institute of
Geochemistry, Chinese Academy of Science, Guiyang, Guizhou Province,
China. The grant number is SKLEG2017910.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.scitotenv.2020.137235.
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