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Chemosphere 169 (2017) 281e287

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Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Water contamination with heavy metals and trace elements from


Kilembe copper mine and tailing sites in Western Uganda;
implications for domestic water quality
Mwesigye R. Abraham*, Tumwebaze B. Susan
School of Forestry, Environment and Geographical Sciences, Makerere University Uganda, P.O. Box 7062, Kampala, Uganda

h i g h l i g h t s

 Kilembe tailings contain Co, Ni, Cu, and As which exceed world crust concentrations.
 Kilembe mine contributed Co, Ni and Cu into river Nyamwamba, a public water source.
 Geologic weathering appeared to contribute Fe, Al and Mn into public water sources.
 Concentrations of Al, Fe and Co in some domestic water samples exceeded thresholds.

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

Article history: The mining and processing of copper in Kilembe, Western Uganda, from 1956 to 1982 left over 15 Mt of
Received 4 June 2016 cupriferous and cobaltiferous pyrite dumped within a mountain river valley, in addition to mine water
Received in revised form which is pumped to the land surface. This study was conducted to assess the sources and concentrations
1 November 2016
of heavy metals and trace elements in Kilembe mine catchment water. Multi-element analysis of trace
Accepted 15 November 2016
elements from point sources and sinks was conducted which included mine tailings, mine water, mine
leachate, Nyamwamba River water, public water sources and domestic water samples using ICP-MS. The
Handling Editor: Martine Leermakers study found that mean concentrations (mg kg1) of Co (112), Cu (3320), Ni (131), As (8.6) in mine tailings
were significantly higher than world average crust and were being eroded and discharged into water
Keywords: bodies within the catchment. Underground mine water and leachate contained higher mean concen-
Kilembe mine trations (mg L1) of Cu (9470), Co (3430) and Ni (590) compared with background concentrations
Copper (mg L1) in un contaminated water of 1.9, 0.21 and 0.67 for Cu, Co and Ni respectively. Over 25% of
Trace elements household water samples exceeded UK drinking water thresholds for Al of 200 mg L1, Co exceeded
Drinking water
Winsconsin (USA drinking) water thresholds of 40 mg L1 in 40% of samples while Fe in 42% of samples
exceeded UK thresholds of 200 mg L1. The study however found that besides mining activities, natural
processes of geological weathering also contributed to Al, Fe, and Mn water contamination in a number
of public water sources.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction surface environment (Hudson-Edwards and Edwards, 2005).


Oxidation of sulphide ores, particularly those rich in pyrite at the
Mining and milling operations, together with grinding, surface of the earth, introduces high concentrations of metals,
concentrating ores and disposal of tailings, provide obvious sources sulphuric acid (hydrogen ions) and sulphate ions into waters fed by
of contamination in the surface environment, along with mine and mine discharge (Lowson, 1982; Nordstrom, 1982; Fuge et al., 1993).
mill waste water (Adriano, 1986). Mine spoil is a rich source of The generation of acidic drainage and the release of water con-
potentially toxic metallic and metalloid elements to the earth's taining high concentrations of dissolved metals from mine wastes
are an environmental problem of international scale (Blowes et al.,
2003). Acidic waters can be responsible for the pollution and
degradation of groundwater, streams, rivers and complete river
* Corresponding author. basins (Nieto et al., 2007).
E-mail address: mwesigye@caes.mak.ac.ug (M.R. Abraham).

http://dx.doi.org/10.1016/j.chemosphere.2016.11.077
0045-6535/© 2016 Elsevier Ltd. All rights reserved.
282 M.R. Abraham, T.B. Susan / Chemosphere 169 (2017) 281e287

Heavy metals and trace elements are of major concern because (upstream), zone 2 encompassed the Kilembe mine and tailing sites
of their persistent and bio-accumulative nature and they may pose while zone 3 was located downstream of the mine and tailing de-
a potential health risk to residents in the vicinity of mining areas posits. Sampling was conducted between June and September
(Myung, 2001). In Kilembe area, the mining and processing of 2014.
copper between 1956 and 1982 left a legacy of metalliferous ma-
terial such as tailings, rock fill and rock waste dumped within a
mountain river valley. Previous studies in the greater Rwenzori 2.2. Sample collection and analysis
region (Hartwig et al., 2005, Owor et al., 2007) have all found
elevated concentrations of heavy metals and trace elements such as 2.2.1. Water sampling and analysis
Cu, Co, Ni and Zn in lake George waters, sediments and tap water A total of 61 water samples were collected from the Kilembe
supplies around Kasese town, all of which receive water inputs valley along River Nyamwamba (n ¼ 24), River Rukoki and other
from River Nyamwamba. Mwesigye et al. (2016) found the toe nails tributaries (n ¼ 11) and from public water sources which included
of Kilembe mine residents to contain concentrations of Cu, Co and tap water (n ¼ 6), gravity flow water (n ¼ 2), streams (n ¼ 5) and
Ni which were several folds the mean Cu concentrations in toe nails community water wells (n ¼ 1). Additional samples were collected
of people who lived outside the Kilembe mine environment, sug- from household water containers (n ¼ 12). Water samples from R.
gesting exposure. However, inadequate information is available on Nyamwamba were collected at an interval of 500 m from upstream
the concentrations of heavy metals and trace elements in most Kilembe mine to downstream, covering a distance of about 13 km.
public water sources around Kilembe mine area and within the At every sample point along River Nyamwamba, 4 water samples
river basin. The aim of this study was therefore to investigate the were collected from different points across the river width at a
point-sources of heavy metals and trace elements within Kilembe depth of more than 10 cm below the river surface and homogenised
mine catchment, and to assess the concentration of the elements in in one water container measuring 1 L. Water from streams was
public water sources and domestic waters. collected from at least 2 sample points at a depth exceeding 5 cm
below the surface and homogenised while water from domestic
water containers, public wells and tap water were collected into the
2. Materials and methods sampling container without homogenisation. All water samples
were filtered using a 0.45 mm syringe filters to remove suspended
2.1. Site description solids and stored in plastic bottles before analysis. Samples for
heavy metal and trace element analysis were acidified using 2 mL of
Kilembe mine is located 10 km west of Kasese town on the 0.2 M HNO3 to prevent sorption on containers. The elements in
slopes of the Rwenzori Mountain in Western Uganda. The study acidified water were analysed by inductively coupled plasma mass
area covered Kilembe valley, an area bisected by River Nyamwamba spectrometry (ICP-MS) for a wide range of elements. Field mea-
which originates from the Rwenzori mountain range (Fig. 1). The surements of water parameters were taken for pH, electrical con-
study area was divided into 3 distinct zones. Zone 1 was the upper ductivity and total dissolved solids using a Hanna multi-parameter
course of the R. Nyamwamba before it reaches Kilembe mine instrument model HI9828.

Fig. 1. Map of study area.


M.R. Abraham, T.B. Susan / Chemosphere 169 (2017) 281e287 283

2.2.2. Tailings and sediments sampling and processing 2.2.6. Social survey
A total of 22 sediment samples were collected from R. Nyam- A social survey was conducted involving 60 randomly selected
wamba from sites where water samples were collected by scraping households who were interviewed on sources of domestic water,
the river bed with a plastic scoop, in the top 5 cm. At least 4 sedi- access and use of Kilembe mine waters and River Nyamwamba.
ment sub samples were collected from each sample point and
homogenised. Of the total sediment samples, 17 were collected 2.3. Statistical analysis
from the mining zone and downstream while 5 were collected from
upstream the mine (control). The samples were stored in plastic Survey data was assessed for precision and entered into SPSS
bags and transported to Makerere University where they were air version 16 to generate descriptive statistics. Data for tailings and
dried in the lab for 2 weeks, sieved to less than 2 mm and stored in water were analysed using Pearson's correlation, to determine
plastic zip-lock bags. Six mine tailing samples were taken from whether there was a linear association between the trace elements.
different tailing sites and processed as sediment samples. A two sample t-test was conducted to assess differences between
Following importation to UK, tailings and sediments (c. 0.2 g) were trace elements in contaminated and control samples of water and
fully digested in perfluoroalkoxy (PFA) vials using 2.5 mL hydro- sediments using Minitab version 14. All the statistical tests were
fluoric acid (HF; 40% Analytical Reagent-AR), 2.0 mL HNO3 (70%, conducted at a 5% significance level.
Trace analytical grade-TAG), 1.0 mL HClO4 (70%, AR) and 2.5 mL
Milli-Q water in a 48-place Teflon-coated graphite block digester 3. Results and discussion
(Model A3, Analysco Ltd, UK).
3.1. Sources of trace elements in Kilembe catchment waters
2.2.3. Determination of trace elements in all samples
The concentrations of 28 elements, including Al, Fe, Zn, Cu, Co, 3.1.1. Erosion of tailings
Ni, and Pb were determined using ICP-MS (Model iCAP-Q, Thermo- Trace element concentrations in Kilembe mine tailings are
Fisher Scientific, Bremen, Germany) in three modes with ‘in-sample shown in Table 1. Tailing sites 1, 2, 3, and 5 (Fig. 1) were located
switching’: standard mode and kinetic energy discrimination with uphill which exposed them to frequent erosion by precipitation
either He or H2 as the cell gas to reduce polyatomic interferences. water downhill into surrounding soils and into River Nyamwamba.
Internal standards included Sc (10 mgL1), Ge (10 mgL1), Rh The tailings exhibited erosion rills and large gulley created by
(5 mgL1) and Ir (2 mgL1) in 2% TAG HNO3. External multi-element running water, an indication of dispersion into the environment
calibration standards (Claritas-PPT grade CLMS-2, Certiprep) downhill. Tailing sites 2 and 4 were located along the banks of River
included elements in the concentration range 0e100 mg L1. Nyamwamba, and are constantly eroded into the river water. All the
tailing sites contained elevated concentrations of Cu, Co, Ni and As
compared with world average crust.
2.2.4. Quality assurance
Bird (1968) and Davis (1967) identified the primary sulphides at
For quality control, tailing and sediment samples were prepared
Kilembe as pyrite (FeS2), chalcopyrite (CuFeS2) and pyrrhotite
and tested in duplicate. The reagents used for sample preparation
(Fe(1x)S. Rare minerals included linnaeite (Coþ2Coþ32S4), sphaler-
were analytical grade (AR) or trace analytical grade (TAG) supplied
ite((Zn,Fe)S), diegenite (Cu9S5), pentlandite (Fe,Ni)9S8) and molyb-
by Fisher Scientific, UK. Digestion blanks as controls were included
denite (MoS2). Therefore the high concentrations of Cu, Co, Zn, Fe
in all samples tested. Certified reference materials included Mon-
and Ni found in tailings conform to the known area mineralogy.
tana soil (NIST 2711). The average recovery of heavy metals and
Along River Nyamwamba, water and sediments collected within
trace elements in NIST 2711 (%) were As (95), Cd (126), Co (78), Cu
a distance of less than 5 cm from tailing boundaries were strongly
(93), Fe (92), Mn (82), Ni (85), Pb (122), Zn (100). Laboratory work
acidic with mean pH of 3.5 and contained Cu, Co and Ni concen-
was conducted from the School of Biosciences, University of Not-
trations that were several times the concentrations of the elements
tingham, UK.
in water samples collected at distances exceeding 4 m from tailing
boundary. This suggested that tailing erosion led to dissolution of
2.2.5. Enrichment factors in sediments the trace elements into river water, increasing trace element con-
Several authors (Schiff and Weisberg, 1999; Baptista et al., 2000) centrations and acidity. Concas et al. (2006) also found that tailings-
have successfully used iron to normalise trace metal contents in waters interaction causes contaminants dispersion along the
sediments to differentiate natural sources from anthropogenic stream course both by dissolution and solid transport and all the
sources. Enrichment factors in sediments were used to assess the processes lead to increment of trace elements in water.
level of contamination and possible anthropogenic contributions in
sediments using the equation; 3.1.2. Underground mine waters and leachate
m
 Water pumped from the Kilembe underground mine and
Fe sample leachate from Kilembe mine ore processing centre exhibited
EF ¼ M
(1)
FE background elevated concentrations of trace elements compared with back-
ground waters collected upstream, 4 km from ore processing
where m is the elemental concentration e.g. Cu in a sediment centre. The mean concentration (mg Kg1) of Cu was 9500, Co was
sample, Fe is the concentration of iron in the sample, M is the 3430, Ni was 600, Fe was 1350, Al was 4700 while Mn was 5800 in
elemental concentration in background sediments while FE is the the mine water and leachate compared with elemental concen-
concentration of Fe in background sediments. Background values trations in the un contaminated waters (mg kg1) which were 1.5,
were the averages of upstream sediment elemental concentrations 0.21, 0.67, 185, 204 and 23.1 for Cu, Co, Ni, Fe, Al and Mn respec-
which were 30,000 mg kg1 for Al, 700 mg kg1 for Mn, 12 mg kg1 tively. The mean electrical conductivity and total dissolved solids of
for Co, 16 mg kg1 for Ni, 21 mg kg1 for Cu, 54 mg kg1 for Zn and mine water and leachate were over 38 times the background water
15 mg kg1 for Pb. According to Zhang and Liu (2002), EF values levels while the mean pH was strongly acidic at 3.9 compared with
between 0.5 and 1.5 indicate that the metal is entirely from natural uncontaminated water whose pH averaged 6.7. Water discharged
sources while EF greater than 1.5 suggests possible anthropogenic from the highly contaminated sources into River Nyamwamba
sources. contributed to heavy metal and trace element concentrations and
284 M.R. Abraham, T.B. Susan / Chemosphere 169 (2017) 281e287

Table 1
Heavy metals and trace elements concentrations in tailings (units ¼ mg kg1).

Al Cr Mn Fe Co Ni Cu Zn As Ag Pb

Tailing sites1 33,354 152 876 54,043 79.7 101 2267 29.6 11.7 0.35 6.33
2 37,397 121 945 52,209 101 164 165 52.6 6.30 0.23 13.3
3 37,779 136 1428 42,094 148 156 1100 68.3 2.90 0.16 7.01
4 28,044 113 809 49,797 152 125 10,217 36.2 5.01 0.79 4.80
5 29,953 97.4 727 52,088 78.2 119 691 50.9 13.6 0.63 21.8
6 32,277 107 800 58,019 110 118 5472 41.1 11.9 0.88 16.2
World average crusta 100 350e2000 1e15 20 20e75 70 1.8 0.06 15a
a
Kabata-Pendias (2011).

increased the acidity in River Nyamwamba water. Increased pH 2


levels and elevated concentrations of heavy metals and trace ele- 1.8
ments were observed in River Nyamwamba at the onset of the 1.6
mining zone and further downstream, underscoring the impact of

Enrichment factors
1.4
Kilembe mine on River Nyamwamba water quality. McGregor et al.
1.2
(1998) and Nordstrom et al. (2000) also found that highly acidic
1
mine waters containing high concentrations of trace elements were
generated around metal mining and smelting sites where sulphide 0.8
containing ores were processed. Nordstrom et al. (2000) identified 0.6
sulphuric acid generation by pyrite oxidation, concentration of Hþ 0.4
and other ions by evaporation, consumption of Hþ during oxidation 0.2
of Fe(II) to Fe(III), and acid production during efflorescent mineral 0
formation as being largely responsible for increased acidity. Al Mn Co Ni Cu Zn Pb
Trace elements in sediments

3.1.3. Trace elements in sediments Fig. 2. Enrichment factors of heavy metals in sediments.
The concentrations of heavy metals and trace elements in sed-
iments are shown in Table 2. The sediments from underground
mine water and leachate exhibited high concentrations (mg kg1) Fig. 2. Enrichment factors for Cu and Co were considerably high,
of Cr (117), Mn (1890), Fe (55100), Co (620), Ni (187), Cu (4010) and exceeding 1.5. Basing on findings of Zhang and Liu (2002), Co and
As (15) compared with mean trace element concentrations found in Cu in the sediments were of anthropogenic origin. For all the ele-
background sediments from upstream water which contained (mg ments, enrichment factors were in the decreasing order
kg1) Cr (34), Mn (687), Fe (35200), Co (12), Ni (16), Cu (20) and As Cu > Co > Pb  Zn  Ni  Al > Mn, following the organometallic
(1.1). The concentrations of Cu, Ni, Pb and Zn in sediments regis- complexes of the Irwing-William series (Coquery and Welbourn,
tered significant increase along the mine area and downstream, 1995), attributed to trace elements strength to form complexes
suggesting elemental inputs into sediments from mine water and with organic matter. Strong and positive Pearson's correlations
eroded tailings. The concentrations of Cu and Co in upstream sed- were observed between all the trace elements in sediments e.g Fe
iments (zone 1) were significantly lower than concentrations of Cu and Al (p < 0.001, r ¼ 0.816), Al and Co (p < 0.001, r ¼ 0.706), Cu and
(p ¼ 0.005) and Co (p ¼ 0.009) along the mine area and down- Al (p < 0.001, r ¼ 0.605), Co and Mn (p < 0.001, r ¼ 0.663), Ni and
stream (Zone 2 and 3). The increase in concentrations of Cu and Co Mn (p < 0.001, r ¼ 0.553), Ni and Co (p < 0.001, r ¼ 0.913), Cu and Co
in sediments along the mine area and downstream could be largely (p < 0.001, r ¼ 0.943), Zn and Co (p < 0.001, r ¼ 0.674), Zn and Ni
attributed to tailing erosion into river water and inputs from mine (p < 0.001, r ¼ 0.882), Fe and Ni (p < 0.001, r ¼ 0.869), Fe and Cu
water and leachate. The reduction of trace element concentrations (p < 0.001, r ¼ 0.633). The strong and positive correlations between
further downstream can be explained by dilution of River Nyam- the elements suggested strong adsorption on aluminosilicate
wamba water with uncontaminated water from tributaries. minerals (Rubio et al., 2000), adsorption and co-precipitation on Fe
The enrichment factors (equation (1)) for trace elements in and Mn oxy-hydroxides (Banks et al., 1997; Holmstrom and
sediments along the mine area and downstream are shown in Ohlande, 2001) and organic matter (Forstner and Wittmann, 1981

Table 2
Heavy metals and trace elements concentrations in sediments along R. Nyamwamba and mine water (units ¼ mg kg1).

Element Upstream (background) n ¼ 4 Mine and tailing zone n ¼ 11 Downstream n ¼ 7 Underground and leachate sediments
Mean ± SD Mean ± SD Mean ± SD Mean ± SD

Al 30,000 ± 3900 31,000 ± 2700 46,000 ± 35000 30,100 ± 3070


Cr 34.1 ± 2.8 37.3 ± 10 54 ± 24 116 ± 15
Mn 687 ± 160 702 ± 88 862 ± 500 1890 ± 1000
Fe 36,000 ± 9000 36,100 ± 9100 4550 ± 24,000 55,100 ± 21070
Co 12.1 ± 3 20.6 ± 11 28 ± 16 620 ± 522
Ni 16.1 ± 2 18.2 ± 5.3 23.7 ± 12 187 ± 100
Cu 20.1 ± 4 39.1 ± 20 47.8 ± 30 4110 ± 3486
Zn 53.5 ± 3.5 58 ± 7.4 73.9 ± 49 149 ± 99
As 1.11 ± 0.3 1.2 ± 0.4 1.3 ± 0.7 14.8 ± 11
Ag 0.1 ± 0.04 0.1 ± 0.01 0.1 ± 0.1 0.25 ± 0.1
Cd 0.1 ± 0.31 0.1 ± 0.0o6 0.22 ± 0.2 0.38 ± 0.3
Pb 14.1 ± 2.1 15 ± 1.3 24.9 ± 24 19.2 ± 6.8
M.R. Abraham, T.B. Susan / Chemosphere 169 (2017) 281e287 285

and Xiangdong et al., 2001). However, sediments could easily


release trace elements adsorbed back to aquatic systems hence
turning back from sink to source of heavy metals for fluvial systems
by diffusion at the wateresediment interface (Blasco et al., 2000),
bioturbation (Zoumis et al., 2001) or re-suspension due to dredging
(Van Den Berg et al., 1999). Desorption of trace elements and heavy
metals from sediments could have contributed to the fluctuations
observed in trace element concentrations along the mine area and
downstream.

3.1.4. Natural inputs


The concentration of trace elements in River Nyamwamba water
and its tributaries are shown in Table 3. Although there were no
mining activities upstream of River Nyamwamba, 50% of the water
Fig. 3. Heavy metal concentrations in water along River Nyamwamba.
samples collected (n ¼ 4) exhibited Al concentrations measuring
216 mg L1 and 214 mg L1, exceeding UK drinking water thresholds
of 200 mg L1 while the Al concentration in the remaining 50% of drinking water thresholds for Fe (200 mg L1) while water samples
water measured 190 mg L1and 197 mg L1, close to the UK drinking along the mine and tailing sites exceeded drinking water thresh-
water threshold. Iron (Fe) concentrations in the upstream water olds for Fe and Co in 42% and 25% of samples respectively.
ranged between 179 and 192 mg L1, close to the UK drinking water An increase in concentrations of Cu, Co, Ni, Mn, Fe and acidity in
threshold for Fe which is 200 mg L1. Water in tributaries flowing River Nyamwamba water was evident at the start of the mining and
into River Nyamwamba, located outside the mine and tailing zone tailing zone (Fig. 3 sample point 8) and further downstream which
(n ¼ 8) also contained elevated concentrations of heavy metals, could be attributed to (i) heavy metal inputs from metal-rich mine
exceeding recommended drinking water thresholds for Fe (38%), Ni waters and leachate (ii) the oxidation and release of heavy metals
and Mn (13%). Heavy metals and trace elements found upstream of and trace elements from tailing sites and tailing-rich sediments.
River Nyamwamba (before the mining and tailing zone) and in the Gunsinger et al. (2006) observed that conventional sub-aerial
tributaries possibly originated from geological weathering, attrib- tailings disposal method exposes sulphide-bearing tailings to at-
uted to area mineralogy and geology. Solomons and Forstner (1984) mospheric O2, resulting in the oxidation of residual sulphide min-
found the natural sources of heavy metals in water to be weath- erals and the release of Hþ, SO4, Fe, and other metals to the tailings
ering and dissolution of minerals while Klavins et al. (2000) pore waters. Singer and Stumm (1970) also explained in details the
established that geochemical factors and the abundance of sedi- reactions which lead to the oxidation of pyrite in the presence of
mentary deposits in the drainage basins contributed to heavy metal oxygen, releasing heavy metals and acidity in water.
concentrations in drainage basins. Although Al and Fe concentrations in upstream waters were
high, they dropped sharply along the mine zone when pH fell below
6, which was in agreement with Lee et al. (2002) who also observed
3.2. Water quality in Kilembe mine area
the reduction of Al 3þ in water at pH 5.5 which was attributed to
formation of solid Al(OH)3. Aluminium could also form Al-
3.2.1. Water quality of River Nyamwamba
hydroxysulfate precipitate following the sorption of SO2 4 on the
The concentrations of heavy metals in River Nyamwamba water
surface of Al (OH)3 at lower pH levels (Munk et al., 2002). However
are shown in Fig. 3. The concentrations of Mn, Co, Ni, Cu and Zn in
occasional increments of Al were observed downstream, possibly
upstream waters were significantly lower than concentrations
due to increases in pH following dilution of acidic river water with
along the mine area and downstream (p < 0.001) implying signif-
near neutral waters from tributaries. The decrease in Fe concen-
icant contribution of copper mining area (Zone 2 Fig. 1) to water
tration as pH became strongly acidic concurred with previous
trace element concentrations. Aluminium concentration upstream
studies (Bingham et al., 1996; Lee et al., 2002) who found the
of river Nyamwamba was significantly higher than concentrations
precipitates of schwermannite Fe8O8(OH)6(SO4)$nH2O and ferri-
along the mine area and downstream (p ¼ 0.006) suggesting that a
hydrite 5Fe2O3$9H2O to form in mine waters having a pH between
significant proportion of the element was of geologic weathering
2.8 and 4.5. However downstream River Nyamwamba, the con-
origin rather than being mainly anthropogenic from copper mining
centration of Fe increased, suggesting reduced precipitation of Fe
activities. The reduction of Al in water along the mining zone
into colloids, possible desorption of the Fe from colloids and pre-
suggested precipitation of the element from the water into sedi-
cipitates and inputs of Fe from River Nyamwamba tributaries some
ments. All the water samples downstream (n ¼ 7) exceeded Win-
of which contained Fe in the range of 270e400 mg kg1.
sconsin (USA) drinking water thresholds for Co (40 mg L1) and UK

Table 3
Concentration of heavy metals and trace elements in River Nyamwamba water and its tributaries (units ¼ mg L1).

Zone Upstream (n ¼ 4) Mining and tailing zone (n ¼ 11) Downstream Tributaries (n ¼ 8)


Mean ± SD Mean ± SD Mean ± SD Mean ± SD

Element
Al 204 ± 12.8 100 ± 16 98.5 ± 15 73 ± 75
Mn 23.1 ± 2.3 63.2 ± 11 100 ± 9.6 37 ± 33
Fe 186 ± 6.5 185 ± 74 265 ± 26 188 ± 128
Co 0.21 ± 0.02 35.6 ± 9.2 55 ± 5.4 0.53 ± 0.3
Ni 0.67 ± 0.25 8.8 ± 1.8 12 ± 0.8 0.98 ± 0.91
Cu 1.9 ± 0.51 59 ± 8.5 61 ± 3.6 2.1 ± 1.1
Zn 4.1 ± 1.3 10 ± 4.2 14 ± 6.2 6.2 ± 2.6
As 0.12 ± 0.01 1.5 ± 4.2 0.15 ± 0.01 0.13 ± 0.05
Pb 0.35 ± 0.1 0.3 ± 0.2 0.4 ± 0.4 0.27 ± 0.2
286 M.R. Abraham, T.B. Susan / Chemosphere 169 (2017) 281e287

The concentration of Mn in River Nyamwamba water upstream have originated from rusted steel pipes which formed the water
were relatively lower but increased along the mine and tailing distribution network.
zone, suggesting inputs of Mn from tailings (Table 1) and mine One underground water well sampled contained high concen-
water. Manganese could not precipitate in River Nyamwamba wa- tration of Mn (649 mg L1) and Fe (2612 mg L1) which exceeded
ter where the maximum pH observed was 6.8, because Mn requires recommended drinking water thresholds. The water well received
elevated pH greater than 8 for oxidation of soluble Mn (II) to water from underground sources, indicating the possibility of
insoluble Mn (IV) (Stumm and Morgan, 1981; Hallberg and Johnson, ground water contamination from geological weathering or disso-
2005) hence the relatively steady increase along the mine area and lution. Trace elements analysis in household water samples
downstream. Pearson's correlation of heavy metals in water were (n ¼ 12) revealed that Fe concentrations in 42% of the samples
positive and strong e.g Al and Co (p < 0.001, r ¼ 0.807), Al and Ni ranged between 231 and 7179 mg L1, exceeding UK thresholds of
(p < 0.001, r ¼ 0.860), Cu and Al (p < 0.01, r ¼ 0.996), Mn and Co 200 mg L1 Cobalt concentration in 25% of domestic water samples
(p < 0.001, r ¼ 0.993), Mn and Cu (p < 0.001, r ¼ 0.885), Ni and Mn ranged between 46 and 66 mg L1, exceeding Wisconsin (USA)
(p < 0.001, r ¼ 0.988), Fe and Ni (p < 0.001, r ¼ 0.867), Fe and Cu thresholds of 40 mg L1. Aluminium in 25% of domestic water
(p < 0.001, r ¼ 0.967), Ni and Cu (p < 0.001, r ¼ 0.870), Zn and Cu samples ranged between 1316 and 4835 mg L1, exceeding UK
(p < 0.001, r ¼ 0.934). Similar correlation trends were observed in drinking water thresholds of 200 mg L1. The high concentrations of
sediments, suggesting similar mechanisms of metal retention in Al, Fe and Mn in domestic water supplies requires further investi-
water and sediments, perhaps adsorption on organic matter and gation because Jones et al. (1974) showed that metals like Al, Fe and
complexes of Fe, Al and Mn. In addition, the correlations suggest Mn in surface water require filtration in pore size membranes
possible oxidation of tailing residues derived from pentlandite, smaller than 0.45 mm to define dissolved concentrations, since even
linnaeite, sphalerite, diegenite and chalcopyrite and subsequent 0.1 mm membranes may allow Fe colloids to pass through and be
adsorption of trace elements on precipitates of Al, Mn and Fe (Munk analysed as part of dissolved phase (Kimbal et al., 1992).
et al., 2002; Bingham et al., 1996; Lee et al., 2002).

4. Conclusions
3.2.2. The quality of domestic water and public water sources
A survey conducted (section 2.2.6) found that 51% of households The study identified Kilembe mine water, ore processing centre
depended on tap water for domestic water supplies, 38% collected leachate and tailing sites as the main sources of heavy metals and
water from River Nyamwamba while 11% depended on community trace element contamination in surface water within Kilembe mine
water wells and gravity water supply systems. The concentrations catchment. These sources were largely responsible for the increase
of heavy metals and trace elements in River Nyamwamba are in concentrations of Cu, Co, Ni, Pb and As in catchment waters
shown in Fig. 3 while concentrations in other public water sources especially river Nyamwamba with Co concentrations which
and domestic water samples are shown in Table 4. exceeded Wisconsin (USA) drinking water thresholds of 40 mg L1
The concentration of Al, Mn, Fe, Zn, Cu, Co and Ni in tap water in 53% of River Nyamwamba water along the mine zone and
supplies increased gradually along the length of water distribution downstream. Tap water supplies were contaminated with heavy
network, but the concentrations did not exceed drinking water metals and trace elements through old leaking pipes although the
thresholds. The increase of the heavy metals in piped networks concentrations did not exceed drinking water thresholds. Natural
suggested leakage of the elements into piped water supplies, sources of geological weathering and area mineralogy too appeared
possibly through old and visibly leaking steel pipes that formed the to contribute to heavy metal concentrations in water. Over 50% of
tap water distribution network. Failures in water distribution sys- water samples upstream of River Nyamwamba contained Al con-
tem such as low water pressure, intermittent service and ageing of centrations which exceeded UK drinking water thresholds of
infrastructure can result in the declining quality of the water supply 200 mg L1, even though there were no mining activities. In addi-
(WHO and UNICEF, 2000) and this could be due to back siphonage tion, Fe and Mn in 25% of water samples from tributaries exceeded
(Trussell, 1998). Back siphonage occurs when the pressure drops drinking water thresholds of 200 mg L1 (UK) and 400 mg L1 (WHO)
sufficiently to cause a vacuum effect in the pipe which can then respectively. Therefore both mining and natural (geological) pro-
draw in contaminants surrounding the pipe through leaks in the cesses appeared to expose local people to heavy metal and trace
pipes or through cross-connections (Geldreich, 1996; Mermin et al., element contaminated water. Cobalt in 25% of domestic water
1999; Kelkar et al., 2001). Additional inputs of Fe in tap water could samples exceeded UK drinking water thresholds of 40 mg L1,

Table 4
Concentrations of heavy metals and trace elements in public water sources and domestic water within Kilembe mine catchment (units ¼ mg L1).

Sources Tap water (n ¼ 6) Water well (n ¼ 1) Gravity flow water Domestic water Drinking water thresholds
(mg L1)
Element Range Mean ± SD Range Mean ± SD Range Mean ± SD

Al 0.12e51.3 24.8 ± 20 21.9 14e15.3 14.7 ± 1 2.4e4835 699 ± 1419 200c


Cr 0.0e0.58 0.27 ± 0.18 0.34 0.22e0.24 0.23 ± 0.01 0.32e5.54 0.92 ± 1.5 100b
Mn 0.3e3.4 1.64 ± 1.1 649 2.91e4.59 3.75 ± 1.2 0.57e254 61.1 ± 76.3 400a
Fe 0.9e121 62.8 ± 61 2612 17.8e23.4 20.6 ± 4 4.5e7179 885 ± 2063 200c
Co 0.02e1.21 0.34 ± 0.44 2.43 0.27e2.39 1.3 ± 1.5 0.03e66.1 20.4 ± 23.4 40d
Ni 0.02e1.1 0.48 ± 0.37 1.21 0.57e1 0.8 ± 0.3 0.6e16 5.6 ± 5.73 70a
Cu 0.3e6.5 3.1 ± 2.54 2.37 2.66e3.3 2.9 ± 0.5 2.9e119 36.1 ± 47 2000a
Zn 0.0e82.2 30 ± 32 5.88 27.4e174 101 ± 104 4.8e104 47.1 ± 49.1 3000a
As 0.0e0.2 0.08 ± 0.04 0.91 0.05e0.06 0.05 ± 0.01 0.06e0.82 0.21 ± 0.24 10a
Cd 0.0e0.01 0.01 ± 0.01 0 0.01e0.01 0.01 ± 0 0.0e0.07 0.03 ± 0.02 3a
Pb 0.0e0.57 0.25 ± 0.19 0.22 0.29e0.58 0.44 ± 0.21 0.19e3.2 0.66 ± 0.85 10a
a
WHO (2008).
b
US EPA (2016).
c
Drinking water inspectorate UK (2010).
d
Wisconsin Department of Natural Resources (2011).
M.R. Abraham, T.B. Susan / Chemosphere 169 (2017) 281e287 287

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