Professional Documents
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Amoakwah 2020
Amoakwah 2020
Amoakwah 2020
Journal
To cite this article: Emmanuel Amoakwah , Shamim Ahsan , Mohammad Arifur Rahman , Eric
Asamoah , D. K. Asamoah , Mursheda Ali & Khandakar Rafiq Islam (2020): Assessment of Heavy
Metal Pollution of Soil-water-vegetative Ecosystems Associated with Artisanal Gold Mining, Soil
and Sediment Contamination: An International Journal, DOI: 10.1080/15320383.2020.1777936
Introduction
AGM is one of the most important economic activities in Ghana. Several southern Ghana
river basins, which are characterized by a wide range of habitats and ecosystems with
varying degrees of species diversity, are rich in alluvial gold deposits. Most of the AGM
activities are undertaken in rivers and small streams, as well as along the riverbanks.
Amalgamation is the preferred gold recovery method employed by nearly all artisanal
gold miners because it is a very simple and economic technique. However, the impact of
extensive and unregulated use of Hg in gold extraction may be responsible for pollution in
terrestrial ecosystems.
CONTACT Khandakar Rafiq Islam islam.27@osu.edu Ohio State University South Centers, 1864 Shyville Rd., Piketon,
OH, USA
© 2020 Taylor & Francis
2 E. AMOAKWAH ET AL.
Figure 2. Distribution of mercury in the soil, sediment, water and plants from artisanal gold mining
activities.
Mining activities, in general, use large volumes of fresh water to process ores. In Ghana,
AGM wastewater containing toxic compounds is often discharged directly into river and
stream systems. Moreover, excessive gold mining activities can wash away soil into nearby
freshwater systems, especially rivers, streams, lakes, ponds, and wells. Waste from gold
mining process such as waste rocks are known to contain Hg, Cd, Pb, Al, and other heavy
metals (Da Silva et al. 2004). Eventually, water-soluble heavy metals can contaminate both
surface and groundwater systems and, consequently, plant systems (Figure 2). Heavy metals
distribution, especially Hg in the terrestrial ecosystems, are quite complex and involve
different chemical species such as methyl mercury (MeHg), which is more mobile than ionic
Hg (Hg0). The humic acid in soil often enhances the solubility of Hg0 (Melamed et al. 1997).
The soluble Hg-complex is relatively low interactive with the sediments-water interface and
often prone to spread within the aquatic environment.
The Cd, Pb, Al, and Hg are not essential for plant growth, as they do not perform any
physiological functions in plants. In contrast, Fe, Cu, and Zn are essential elements required
for plant growth and metabolism, but these elements can easily lead to pollution when their
concentrations are more than the permissible levels (Garrido et al. 2002; Rascio and Izzo
2011).
Several studies have reported the presence and accumulation of heavy metals in surface
water of pristine environments and major mining areas in southern Ghana (Hadzi,
Essumang, and Adjei 2015). Mean concentration of Fe was reported as 1.75 mg/kg and
Hg was 0.001 to 0.45 mg/kg at the AGM sites. Likewise, Akoto et al. (2017) reported
a contamination of surface soils with heavy metals in the Kumasi metropolis of Ghana.
The geo-accumulation indices for Zn, Cd, Hg, and Pb were calculated as moderate-to-
extreme levels. Recently, Gyamfia et al. (2019) reported that the soil was extremely polluted
with Fe, Pb, Zn, As, Mn, and Cu in the Kokoteasua region of Ghana. Moreover, the potable
4 E. AMOAKWAH ET AL.
water was unsuitable for drinking in several adjacent locations of AGM due to high levels of
As and Zn. NKansah et al. (2017) indicated an accumulation of heavy metals in indigenous
plants growing in the AGM areas of Ghana.
To date, several studies have reported about the assessment of soil, sediments, water, and
vegetative systems accumulated with heavy metals in southern Ghana. However, those
studies did not elaborately identify and link the source-sink relationships of heavy metals
among soil-water-vegetative ecosystems. Source-sink relationship indices such as the geo-
accumulation index determines the metal level of contamination or accumulation with
reference to background levels of the same element in the environment. The enrichment
factor is an indication of the enrichment of a selected metal with reference to background
metals, such as Fe, which complements the geo-accumulation index by indicating the
source of enrichment as either natural or anthropogenic. Likewise, the bio-accumulation
factor is often used to evaluate the level of contamination in soil, sediment, and plants.
Considering all these concerns and consequences, the need to assess the contamination
of soil, sediments, surface and groundwater, and plants becomes imperative in terms of
their heavy metals load in the AGM areas of southern Ghana. The objectives of our study
were to (1) assess the concentration of Fe, Cu, Zn, Pb, Cd, and Hg in soil, stream sediments
and water, well water, and plants in the Obuasi AGM and processing sites and (2) evaluate
the extent of environmental pollution in response to AGM impacts on soil-water-vegetative
ecosystems in southern Ghana.
Figure 3. Location of sampling sites in artisan gold mining areas in southern Ghana.
were collected in dry, clean sterilized 500-mL plastic bottles. Corn plant samples were
collected from agricultural fields, and the naturally grown ferns were sampled from the edge
of the AGM site and agricultural fields.
The field-moist soil and sediments were air-dried at room temperature (~25°C) for seven days,
ground, and 2-mm sieved to remove small stones and visible organic debris. Stream and well-water
samples were filtered to remove suspended solids, followed by short-term storage at 4°C prior to
chemical analysis. The corn and fern samples were oven-dried at 55°C until a constant weight was
obtained, ground with a clean porcelain mortar and pestle, and 250-µm sieved to obtain homo
geneous samples prior to chemical analysis.
A 10 g sample of finely ground soil and sediments were placed into a 50 mL plastic tube
with 25 mL of hot water, then shaken at 250 rpm on a mechanical shaker (Agitatore model
709/O, ASAL Srl, Italy) for a period of 30 min, followed by filtration with a Whatman filter
paper to obtain clear aliquots for soluble heavy metals analysis. For total heavy metals
6 E. AMOAKWAH ET AL.
analysis, 1.0 g of finely ground sample of soil and sediments was placed into a 50 mL Pyrex
glass tube with a mixture of 10 mL of concentrated HClO4, 10 mL concentrated HCl, and
0.2 mL of 30% H2O2. The wet digestion was performed on an Al block hot plate under
a fume hood at 185°C for 10 min. After cooling, the digested aliquot was diluted with
distilled, deionized water, followed by filtration with white ribbon filter paper (Macherey–
Nagel, Germany, 640 m, Ø 125 mm, Cat No. 203 210). Similarly, a 1.0 g processed sample of
corn or fern was digested using 10 mL of concentrated HNO3 and 5 mL of 30% H2O2. After
cooling, the digested aliquot was diluted with distilled, deionized water, followed by
filtration with white ribbon filter paper to obtain clear aliquots. The reagents used were
obtained from Surechem Products Ltd, Suffolk, England.
Soil and sediment pH were determined (water-soil 1: 2.5) using a pH glass electrode
(Model 520 A, Orion, Boston, MA, USA). Similarly, the electrical conductivity (ECe) of soil
in distilled water suspension (1:1) was measured by using an EC electrode. The pH and ECw
of well and stream waters were directly measured by glass electrode and EC meters. Heavy
metals were analyzed from hot water extracted and digested soil, sediments, plants, and
waters by using Inductively Coupled Plasma-Emission spectrometry (ICP-OES: Varian
vista MPC, Varian, Palo Alto, California, USA). The measurements were carried out in
three replications to obtain a greater precision. While the detection limits of Fe, Cu, Pb, Cd,
Zn and Hg in soil, sediments and corn and fern were 0.1, 0.1, 0.2, 0.2, 0.1 and 0.2 mg/kg, the
detection limits of Fe, Cu, Pb, Cd, Zn and Hg in water was 0.02, 0.02, 0.03, 0.01, 0.02,
0.01 mg/L, respectively. After every 10 samples, a QC/QA sample, made from certified
standard solution, was analyzed to check the analytical quality with a relative standard
deviation of QA/QC samples were 1 to 4.5%. Analytical quality control was maintained by
analyzing certified reference material NIST 1944 (Waterway sediment). Replicated analysis
of this reference material showed a recovery of 95 ± 17%. Analytical precision as determined
by QA/QC procedures, reagent blanks, and internal standards, was better than ±10%.
�
�
Cχ
Whereby, Fe is chosen as a natural element of reference, Sample is the ratio between
� �
CFe
Cχ
concentration of the element “X” and that of Fe in the sediments, CFe Crust is the ratio
between concentration of the element “X” and that of Fe in unpolluted reference baseline.
The Igeo factor is widely used in the assessment of contamination by comparing the
levels of heavy metals obtained to background levels originally used with soil and sediments
(Atiemo et al. 2011).
SOIL AND SEDIMENT CONTAMINATION 7
Where the Cn is the measured concentration (mg/kg) of the heavy metal and the Bn is the
geochemical background value of the heavy metal. Due to the conceivable variations in the
background values, the factor 1.5 was used for small anthropogenic impacts on a given
heavy metal in the environment.
The BCF is an important parameter for the soil-plant transfer of hazardous contaminants
such as heavy metals in terrestrial ecosystems (Yang et al. 2018).
Statistical analysis
The data were compared among samples by one-way analysis of variance using SAS to evaluate
the impact of AGM activities on soil-water-vegetative ecosystems. For all statistical analyzes,
the F-protected significant differences between and among samples were performed based on
p ≤ 0.05 using the Least Significant Difference (LSD) test, unless otherwise mentioned.
Figure 4. Artisan gold mining activities on pH and electrical conductivity of the soil, sediment, and water
ecosystems (mean values were presented with standard errors).
that of the Hg and Cd contents in the soil, the Fe content was highest followed by Cu, Zn,
and Pb than that of the Hg and Cd in the sediments. On average, the Fe followed by Zn, Pb,
and Cd contents were higher, except Cu and Hg, in the sediments than in the soil.
Our results on the chemical contaminants in the soil and sediments were evaluated by
comparison with the soil and sediment quality guidelines of the United States EPA (Table 1).
Except Cd in sediment, the concentration of heavy metals in both soil and sediments were
higher than the maximum permissible limit recommended by U.S. EPA (U.S. EPA 2002).
Moreover, the measured heavy metals contents were higher than the average background
values in the continental crustal abundance reported for West Africa (Taylor 1964). Our
results suggested that both the soil and sediments were polluted with heavy metals that can
be attributed to the AGM activities currently accruing in and around southern Ghana.
The enrichment factor (EF) and geo-accumulation index (Igeo) were used to evaluate the
anthropogenic impact on the soil and sediments via AGM activities (Table 2). Both heavy
metals pollution indicators were classified on standardized classification procedures (Buat-
Menard and Chesselet 1979; Martin and Meybeck 1979; Muller 1969). The results of EF and
SOIL AND SEDIMENT CONTAMINATION 9
Table 1. Total concentration of metals in soil and sediment along with the maximum permissible limit of
U.S. Environmental Protection Agency (EPA). Mean values were presented with standard errors.
Metals Soil Sediment
Background value
Maximum permissible (mg/kg)
Mean conc. Maximum permissible limit Mean conc. limit U.S. EPA** Continental crustal abun
(mg/kg) U.S.EPA* (mg/kg) (mg/kg) (mg/kg) dance-West Africa***
Fe 175.2 ± 10.2 - 320.9 ± 19.5 - 5
Cu 250.9 ± 28.9 16.4 201.1 ± 64.1 25 71
Zn 137.6 ± 10.4 24.7 143.5 ± 6.4 123 35
Pb 57.2 ± 13 3.9 74.7 ± 5.6 10 14
Cd 2.0 ± 0.91 0.48 4.1 ± 0.77 6 0.11
Hg 8.6 ± 5.3 - 8.3 ± 0.91 - 0.1
* U.S. EPA (2002).
** Mortuza and Al-Misned (2017).
*** Taylor (1964).
Table 2. Classes of pollution indices (enrichment factor, EF and geo-accumulation index, Igeo).
EF* Soil quality Igeo** Soil quality
<2 Depletion to minimal enrichment <0 Unpolluted
2–5 Moderate enrichment 0–1 Unpolluted to moderately polluted
5–20 Significant enrichment 1–2 Moderately polluted
20–40 Very high enrichment 2–3 Moderately to heavily polluted
>40 Extremely high enrichment 3–4 Heavily polluted
4–5 Heavily to extremely polluted
>5 Extremely polluted
* Buat-Menard and Chesselet (1979).
** Ismaeel and Kusag (2012).
Igeo indicated that both the soil and sediments were moderately contaminated by Pb and
extensively contaminated by Cd and Hg, suggesting anthropogenic impacts via ASM
activities were responsible for their dispersal and pollution. Results presented in Table 3
show that the degrees of contamination were 54.5 (EF) and 23.3 (Igeo) for soils, while the
degrees of contamination for sediments were 25.8 (EF) and 18.4 (Igeo). Among the heavy
metals, the Hg had a significantly higher impact in polluting the environment. Results on
degrees of contamination indicated that soils were contaminated more with the heavy
metals, especially Cd and Hg, compared to the sediments in AGM areas. The degrees of
contamination showed that soils were loaded with heavy metals in the order of
Cu>Zn>Pb>Cd>Hg; conversely, the sediment heavy metals show a slightly different pattern
in the order of Cu>Zn>Cd>Pb>Hg.
The pH directly or indirectly affects the migration and transformation, and many
reaction pathways of heavy metals retained by soils and sediments (Zhao et al. 2012),
which mostly controlled the mobility and adsorption of heavy metals in soil. The lower
the pH (acidic), the higher the mobility of heavy metals in soil due to the formation of metal
ions. In contrast, metals tend to form hydroxide complex at pH above 7. The heavy metals
discharged from AGM areas into the water systems enriched the soil and sediments by
adsorption, complexation, flocculation, and sedimentation (Wang et al. 2016). In our study,
the enrichment of heavy metals in soil and sediments followed a slightly different trend,
which was due to pH fluctuations as sediments were overlaid by water column and
continuous soil-water-air interactions.
Table 4. Soluble heavy metals concentration in well water and stream water along with U.S.
Environmental Protection Agency (U.S. EPA) maximum permissible limit. Mean values were pre
sented with standard errors.
Well water Stream water
Metals (mg/L) (mg/L) Maximum permissible limit U.S.EPA* (mg/L)
Fe 0.80 ± 0.01 1.78 ± 0.98 0.3
Cu 0.40 ± 0.07 0.31 ± 0.12 1.0
Zn 0.26 ± 0.14 0.17 ± 0.03 5.0
Pb 0.36 ± 0.05 0.03 ± 0.001 0.015
Cd 0.01 ± 0.002 0.02 ± 0.001 0.005
Hg <0.01 <0.01 0.002
* U.S. EPA (2018). Hg: Detection Limit: 0.01 mg/L
SOIL AND SEDIMENT CONTAMINATION 11
Table 5. Total concentration of heavy metals in corn and fern samples with their bio-contamination
factors (BCF). Mean values were presented with standard errors.
Metals Corn Fern WHO/FAO
Mean conc. Mean conc. Maximum permissible limit*
(mg/kg) BCF (mg/kg) BCF (mg/kg)
Fe 8.00 ± 0.24 0.05 32.0 ± 2.23 0.18
Cu 20.40 ± 2.11 0.08 10.00 ± 1.20 0.04 40.0
Zn 95.10 ± 4.52 0.69 137.58 ± 5.12 1.01 60.00
Pb 4.30 ± 0.45 0.08 4.90 ± 1.12 0.09 2.00
Cd 0.20 ± 0.02 0.10 0.50 ± 0.04 0.25 0.10
Hg 8.80 ± 0.64 1.03 32.0 ± 2.25 3.73 0.03
Contamination intensity 2.02 5.30
* WHO/FAO (2007).
Figure 5. Artisan gold mining activities on partition, fate, and distribution of heavy metals in soil-plant-
water ecosystems in southern Ghana.
SOIL AND SEDIMENT CONTAMINATION 13
Table 6. Comparison of average heavy metals concentrations with other published reports related to
artisanal gold mining pollution (mg/kg or mg/L).
Sample Fe Cu Zn Pb Cd Hg Country Reference
Soil - 27.15 47.14 131.76 0.03 0.85 Nigeria (Adewumi and Laniyan, 2020)
Soil - 0.629 0.700 0.216 0.130 - Nigeria (Abiya et al. 2018)
Soil - 36.67 22.55 4.60 0.07 - Niger (Dan-Badjo et al. 2019)
Soil - 316.0 124.4 244.4 0.29 - Kenya (Odumo et al. 2018)
Soil 113.06 3.02 4.44 2.69 3.15 0.26 Nigeria (Eludoyin et al. 2017)
Soil 175.2 250.9 137.6 57.2 2.0 8.6 Ghana This work
Sediment - 320.6 42.55 2234.02 0.10 2.12 Nigeria Adewumi and Laniyan, 2020
Sediment - 82.8 99.7 130.2 0.21 - Kenya (Odumo et al. 2018)
Sediment - 5.10 236 15.5 - - Senegal (Niane et al. 2014)
Sediment - 69.0 1415 1545 - - Congo (Atibu et al. 2016)
Sediment - 24.196 46.662 5.856 0.128 0.106 Cameroon (Mandeng et al. 2019)
Sediment 320.9 201.1 143.5 74.7 4.1 8.3 Ghana This work
Surface water 1.79 5.92 6.45 0.06 - - Nigeria Adewumi and Laniyan, 2020
Surface water - 1.028 3.18 0.014 - 0.006 Nigeria (Ishola and Abdulgafar 2014)
Pond water - 0.004 0.01 0.005 - - Niger (Dan-Badjo et al. 2019)
Ground water - 0.003 0.134 0.002 - - Niger (Dan-Badjo et al. 2019)
Ground water 0.52 4.16 4.23 0.05 - - Nigeria Adewumi and Laniyan, 2020
Well water 0.80 0.40 0.26 0.36 0.01 <0.01 Ghana This work
Stream water 1.78 0.31 0.17 0.03 0.02 <0.01 Ghana This work
Plant (Roots) - 16.26 42.49 105.75 - - Nigeria Adewumi and Laniyan, 2020
Plant (Shoots) - 20.83 52.49 120.43 - - Nigeria Adewumi and Laniyan, 2020
Plant (Root) - 0.602 1.205 0.202 - - Nigeria (Abiya et al. 2018)
Plant (Shoot) - 0.590 1.017 0.134 - - Nigeria (Abiya et al. 2018)
Corn (seed) 8.0 20.40 95.10 4.30 0.20 8.80 Ghana This work
Fern 32.0 10.0 137.58 4.90 0.50 32.0 Ghana This work
soils, sediments, water, and plants of this study were much higher than that reported results.
This was possibly due to the difference in geology and the extent of mining operations
around the sampling stations.
Conclusions
Results suggest that AGM activities affected soil-water-vegetative systems with heavy metals
contamination. When compared with U.S. EPA limits, direct and indirect discharges of ore
waste and other mining byproducts released or disposed by AGM activities have directly
affected stream water, soil and sediments, and, consequently, plants. The Hg levels, both in
soil and sediments, were significantly higher compared to continental crust levels in that
region, suggesting that AGM activities in southern Ghana are responsible for polluting the
soil and sediment systems. The high enrichment of Cd and Hg in both soil and sediments
suggests anthropogenic inputs and impacts based on the EF and Igeo results. Likewise, the
stream water was higher in Hg and Cd than the maximum permissible limits allowed by
U.S. EPA and would have an adverse effect on public health from drinking it directly or
ingesting crops that water had been used to irrigate. The transfer of heavy metals from soil
to plants indicated that the transformation of Hg was significantly higher in both corn and
fern. There could be a potential risk to public and animal health systems from the
consumption of Hg-contaminated fern and corn products. However, fern had the higher
absorption capability for all the heavy metals, especially Hg, compared to corn. Our study,
nevertheless, provides information on the heavy metals’ contamination of vegetative sys
tems via soil-stream systems as a result of AGM activities. It was recommended that future
studies should consider crops, vegetables and fishes from the same sampling areas in the
14 E. AMOAKWAH ET AL.
assessment of heavy metals to assess potential risk of public and animal health.
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