Chemosphere 211 (2018) 834e843

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

Determination of levels of some metal contaminants in the freshwater

environments of Osun State, Southwest Nigeria: A risk assessment
approach to predict health threat
Yinka Titilawo a, c, *, Abiodun Adeniji a, b, Mobolaji Adeniyi d, Anthony Okoh a
a
SAMRC Microbial Water Quality Monitoring Centre, University of Fort Hare, Alice 5700, South Africa
b
Department of Chemistry, University of Fort Hare, Alice 5700, South Africa
c
Department of Biology/Microbiology/Biotechnology, Federal University, Ndufu-Alike, Ikwo, Abakaliki, Ebonyi State, Nigeria
d
Department of Biological Sciences, Osun State University, Osogbo, Osun State, Nigeria

h i g h l i g h t s

Fe, Cu, Mn, Al, Cr and Zn were identified as possible hazards.

HQ and HI fell below the recommended criteria.

Selected metal contaminants revealed no significant difference.

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

Article history: This study evaluated levels of heavy metals and macro-elements in ten major rivers in Osun State,
Received 27 February 2018 Southwest Nigeria. Triplicate water samples collected from selected rivers were analyzed for metal
Received in revised form pollutants by atomic absorption spectrophotometry. Concentrations were obtained as follows: iron: 60
9 July 2018
e960 mg L1; manganese: ND e 3 mg L1; chromium 0e2100 mg L1; aluminium: 0e800 mg L1; copper: 0
Accepted 31 July 2018
Available online 1 August 2018
e1350 mg L1; zinc: 10e650 mg L1; calcium: 6400e232000 mg L1 and magnesium: 2000e71000 mg L1
but lead was not detected. While most of the parameters fell within the threshold values for drinking
Handling Editor: Martine Leermakers water, iron, chromium, aluminium and calcium exceeded at some locations. The pollution order of the
rivers, especially with heavy metals had the order: R8 > R3 > R2 > R5 > R10 > R6 > R4 > R1 > R7 > R9;
Keywords: which implies that R8 and R3 are the most polluted. The health risk assessment results revealed that
Freshwater bodies hazard quotient and hazard index were below the acceptable limit of 1.0, suggesting no substantial non-
Heavy metals carcinogenic effect would arise from individual exposure to the elements. However, the carcinogenic
Environmental pollutants risks were 3.18  106 and 4.43  106 for adults and children, respectively at R8, implying that 1 person
Average daily dose
in 314,206 adults and 225,836 children drinking from the water may be at risk of having cancer corre-
Hazard index
spondingly. Hence, there is need to moderate the levels of these pollutants in these waterbodies to
Health risk assessment
safeguard public health.
© 2018 Published by Elsevier Ltd.

1. Introduction increase in anthropogenic activities as well as natural processes

Water is a vital resource to the health, well-being and existence
of humans. However, freshwater is a finite resource; without which
it's availability in adequate quantity and quality, sustainable
development will be practically impossible (UNEP/WHO, 1996). The
* Corresponding author. SAMRC Microbial Water Quality Monitoring Centre,
University of Fort Hare, Alice 5700, South Africa.
E-mail addresses: olayinkatemi@yahoo.co.uk, olayinkatemi@yahoo.uc.uk
(Y. Titilawo).
such as precipitation inputs, erosion, weathering of crustal mate-
rials and degradation of surface waters have rendered most aquatic
milieus unsuitable for their multi-purpose usage (Furhan et al.,
2004). “Heavy metals” are the metallic elements with somewhat
high densities; they are in most cases toxic even at low concen-
trations (Lenntech, 2004; Dinis and Fiuza, 2011). They include lead
(Pb), cadmium (Cd), zinc (Zn), silver (Ag) chromium (Cr), copper
(Cu) iron (Fe) and the platinum group elements (Farlex, 2005;
Duruibe et al., 2007). They are among the most common environ-
mental pollutants, and their occurrence in waters and biotic

https://doi.org/10.1016/j.chemosphere.2018.07.203
0045-6535/© 2018 Published by Elsevier Ltd.
 Y. Titilawo et al. / Chemosphere 211 (2018) 834e843 835

communities could be from natural or anthropogenic sources.
While the main natural sources of metals in waters are chemical
weathering of minerals and leaching, the anthropogenic sources
are associated mainly with industrial and domestic effluents, urban
storm, water runoff, landfill, atmospheric sources, wastes from
rural areas mining of coal and ore, smelting of copper and the
preparation of nuclear fuels (Baby et al., 2010; Ibeto et al., 2012).
Surface water contamination by heavy metals remains a serious
ecological challenge. Although, trace metals such as iron, copper
and zinc are micro-nutrients, yet their detrimental effects on the
physiology of the living organisms at higher concentrations cannot
be underestimated (Baby et al., 2010; Nair et al., 2010; Manoj et al.,
2012). However, several heavy metals including cadmium and lead
are highly toxic at relatively low concentrations, and their accu-
mulation in the body tissues over long period can become nuisance
to human health. Some enter into natural waters at increased
concentrations through the discharge of sewage, industrial effluent,
mining and refining operations, and at these levels could have se-
vere toxicological effects on aquatic environments and humans,
and pose significant health hazards when absorbed by plants (El
Bouraie et al., 2010; Lokhande et al., 2011). Through precipitation
and atmospheric deposition, significant amounts also enter the
hydrological cycle and may eventually find their ways to human
body through food, water, air or skin absorption. They accumulate
in the soft tissues and become toxic when they are not metabolized
by the body (Baby et al., 2010; El Bouraie et al., 2010).
The global challenge of water pollution by heavy metals has now
become a major quality issue in most regions of the world espe-
cially in the developing countries where monitoring and mainte-
nance of water quality, and sanitation facilities do not correspond
with population growth and increased urbanization (Akoto et al.,
2008; Ahmad et al., 2010; Ghorade et al., 2014). In most parts of
Nigeria, information on heavy metal pollution of surface and
ground waters have been documented (Agbaire and Obi, 2009;
Akubugwo et al., 2012; Daso and Osibanjo, 2012; Kuforiji and
Ayandiran, 2013). Surface water sources in Osun State, Southwest
Nigeria are increasingly witnessing incessant pollution due to
indiscriminate and excessive discharge of domestic, agricultural
and industrial wastes into the rivers (Olafisoye, 2011; Godwin et al.,
2015). Other factors contributing to the immense contamination of
water sources in the region include urbanization, poor land use
patterns, imprudent use of agrochemicals among others (Olajire
and Imeokparia, 2001; Oyekunle et al., 2011).
Prior environmental studies in the state focused on the physi-
cochemical and bacteriological qualities (Olajire and Imeokparia,
2001; Olafisoye, 2011; Oginni and Ojoawo, 2014; Ogunbode et al.,
2016; Titilawo et al., 2015, 2018), polycyclic aromatic hydrocar-
bons (Adekunle et al., 2017) and heavy metal contamination
(Oyekunle et al., 2011; Adeyeye and Ayoola, 2013; Aladesanmi et al.,
2014; Jeje and Oladepo, 2014; Godwin et al., 2015) of some
environmental samples. Unfortunately and to the best of our
knowledge, the study has not been thoroughly investigated in most
of the major rivers in the state. Therefore, it will be hard to give
holistic report on the environmental and health statuses of surface
waters in the state. It is in this light that the present study was
conducted to assess some macro elements and indices of heavy
metals in ten major rivers across the geographic borders of the
state, with a view to determine their health impacts on the sur-
rounding communities.
2. Materials and methods
2.1. Description of the study areas
Osun State is an inland state in the south-western part of Nigeria
with a population of 3,416,959 people. Its capital city is located in

Osogbo with coordinates 7 30ʹN4 30ʺE (NBS, 2012). The name of
the state was derived from Yoruba goddess of a popular natural
spring (River Osun). Hence, it was formerly nicknamed “State of the
Living Spring”. It has 30 local government areas and 3 senatorial
districts, and is surrounded in the East, West, North and South by
Ondo, Oyo, Kwara and Ogun states, respectively. Although, rivers in
the state are impounded for water supply for the domestic use of
the people of the state, however, due to erratic supply in some parts
of the state, many are now relying on the underground, rain and
surface waters for their daily needs, especially in the rural areas
(Adedeji and Ajibade, 2008; Oginni and Ojoawo, 2014; Ogunbode
et al., 2016). Table 1 shows the sampling sites, activities and
geographic co-ordinates.
2.2. Sample collection
Composite water samples were collected in triplicates into pre-
cleaned polypropylene bottles from each of the ten rivers at 10 cm
depth to the surface and labelled accordingly (Nekhavhambe et al.,
2014; Olusola and Festus, 2015). All apparatus used were initially
washed with detergents, soaked in 2 M nitric acid for 24 h to avoid
interference with contaminants and washed thoroughly again.
They were rinsed using tap water and then double distilled water
before being oven-dried at 105  C (Voica et al., 2012; Olusola and
Festus, 2015). The water was acidified with 2 mL of analytical
grade nitric acid in order to preserve metals and avoid precipitation
(Kar et al., 2008) and adsorption on walls of the sampling bottles
(Manoj et al., 2012). The water samples were filtered and stored at
5  C for onward transportation to the laboratory for analysis
(Salano, 2013).
2.3. Sample digestion for heavy metal analysis
Water samples were digested by adding 5 mL conc. HNO3 to

Table 1
Sampling sites description.

Site code Site name Activities GPS coordinates

R1 Erinle-Ede Fishing, animal rearing irrigation, tourism and domestic purposes 7 44ʹ44ʺN; 4 29ʹ22ʺE
R2 Ido Osun Animal rearing, fishing, irrigation domestic and recreational purposes 7 49ʹ 01ʺN; 4 26ʹ41ʺE
R3 Osun-Osogbo Farming, fishing, habitation, tourism and worship shrine 7 46ʹ 04ʺN; 4 34ʹ00ʺE
R4 Oba-Iwo Fishing, domestic and recreational purposes 7 38ʹ 01ʺN; 4 11ʹ20ʺE
R5 Ejigbo Farming, fishing and domestic use 7 54ʹ0ʺN; 4 18ʹ54ʺE
R6 Ilobu-Okinni Car washing, swimming and domestic use 7 50ʹ06ʺN; 4 29ʹ14ʺE
R7 Asejire-Ikire Fishing, irrigation, domestic and industrial activities 7 25ʹ44ʺN; 4 13ʹ14ʺE
R8 Shasha Fishing, farming, palm oil processing and domestic purposes 7 22ʹ32ʺN; 4 28ʹ11ʺE
R9 Ila-Oke Ila Farming, irrigation, fishing and domestic activities 8 01ʹ50ʺN; 4 59ʹ03ʺE
R10 Inisha-Okuku Fishing, irrigation and domestic activities 8 01.32ʺN; 4 42ʹ11ʺE

Source: Titilawo et al. (2015).

836 Y. Titilawo et al. / Chemosphere 211 (2018) 834e843
each 100 mL aliquot of the thoroughly mixed sample in 125 mL
conical flask. The solution was evaporated to about 20 mL on hot
plate. Another 5 mL conc. HNO3 was added and the mixture heated
until digestion was completed. Additional 10 mL conc. HNO3 was
added and the content was filtered using Whatmann No. 1 filter
paper and made up to 100 mL with double distilled water as
described by Ayenimo et al. (2005). Double distilled water and ni-
tric acid were used for the preparation of reagent blank solutions
(Joseph et al., 2017).
Flame Atomic Absorption Spectrophotometer (Bulk Scientific
VGP 210 Model) was employed in the analysis of digested water
samples and blanks for iron, manganese, chromium, aluminium,
copper, zinc, lead, calcium and magnesium using appropriate lamp
for each metal (Manoj et al., 2012; Joseph et al., 2017). Separate
calibration curve for each metal was plotted with standard solu-
tions of different concentrations (0, 2, 4, 6, 8, 10 mg L1). The so-
lutions were prepared by serial dilution of their respective stock
solutions (1000 mg L1) (Adenike, 2014; Tesfamariam and Younis,
2016). Acceptable correlation coefficient for the calibration curves
was R  0.990 (Cortes et al., 2012; Voica et al., 2012; Adeniji et al.,
2017). Digested water samples and blanks were analyzed in tripli-
cates. Concentrations of metals in both the samples and blanks
were determined by extrapolation on the calibration graphs pre-
pared. Errors due to impurities in the reagents were eliminated by
subtracting the blank results from those of the samples (Adenike,
2014; Joseph et al., 2017). The instrument detection limits (IDLs)
and limits of quantification for the experiment were estimated as
three and ten times the signal to noise ratio of the lowest calibra-
tion standard respectively (Nkabinde et al., 2018). The calculated
values were very consistent with the values reported by Oyekunle
et al. (2011). Supplementary Table 1 shows the working wave-
lengths for the metals of interest (Reza and Singh, 2010).
2.4. Health risk assessment
2.4.1. Non-carcinogenic risk assessment
Iron, copper, manganese, aluminium, chromium and zinc were
identified as potential hazards in the rivers under investigation.
Hence, exposure assessment was conducted to estimate the extent
of exposures by humans to the metal contaminants in the study
sites. This was achieved by calculating the average daily dose (ADD)
of the metals taken by adults and children in the study areas. ADD
for the two age groups were separately estimated owing to their
physiological and behavioural variations (Wang et al., 2005;
Kamunda et al., 2016).
The estimation of exposure depends on a number of factors
including the level of the contaminant in the environmental media,
rate of consumption in the particular medium (either directly by
inhalation, or indirectly by ingestion), frequency and duration of
exposure, as well as body weight of the exposed person. ADD was
therefore calculated using equation (1) below:
C  IR  ED  EF  CF
ADD ¼ (1)
BW  AT
where ADD is the average daily dose, which is the amount of metal
contaminant (mg/kg/day). C is the concentration of heavy metals
previously detected in the surface water (mg/L); IR is the con-
sumption rate of the water being studied (3.45 and 2.0 L/day for
adults and children, respectively); ED is the exposure duration (70
years for adults and 10 years for children); EF is the frequency of
exposure (365 days/year); CF is the conversion factor (106); BW is
the average body weight (60 kg for adults and 25 kg for children)
and AT is the average time, which is equal to 25,550 days for adults
(i.e 70 years  365 days/year) and 3650 days for children (i.e.
10 years  365 days/year) (Roychowdhury et al., 2003; Dinis and
Fiúza, 2011; Wongsasuluk et al., 2014; Bortey-Sam et al., 2015).
The probability of any chronic toxicity was thereafter evaluated
by calculating the HQ of the ADD, a non-carcinogenic risk value for
each metal contaminant. HQ is assumed to be the threshold value
below which no adverse health effects would be expected to occur.
This was done by comparing the individual exposure to the
contaminant with an oral reference dose (RfD), a principal toxicity
factor obtained from animal studies as shown in equation (2) below
(Dinis and Fiúza, 2011; Bortey-Sam et al., 2015; Kamunda et al.,
2016).
HQ ¼ ADD=RfD (2)
where HQ is the non-carcinogenic effect due to long time exposure
(unitless) and RfD is the oral reference dose for each heavy metal
that a person is likely to be exposed to per day over his entire
lifetime without any experience of injurious health effect (mg/kg/
day). In this study, HQ was estimated for only four heavy metals for
which RfD values were available (Supplementary Table 2) and the
reference doses (for humans) were multiplied by ten, so as to take
care of any uncertainty (Arizhibowa, 2011; Bortey-Sam et al., 2015;
Wei et al., 2015; Kamunda et al., 2016). A total hazard ratio, called
hazard index (HI) was also determined as the sum of HQs for the
four heavy metals in each study site (Eq. (3)). No adverse human
health effects would be expected to occur if HQ or HI value is equal
to or less than 1.0, but any value above 1.0 suggests a significant risk
level (IRIS, 2009; Dinis and Fiúza, 2011; Wei et al., 2015; Yahaya
et al., 2017). Kamunda et al. (2016) suggested four possible levels
of risk with respect to HQ and HI. The risk is negligible when the
value is below 0.1; low when it is between 0.1 and 1; medium when
it varies from 1 to 4 and high when it exceeds 4.
X
HIi ¼ HQi (3)
2.4.2. Carcinogenic risk assessment
Carcinogenic risks are calculated as possibility of an individual
developing cancer incrementally, consequent upon his exposure to
a potential carcinogenic compound over a lifetime. This is done by
multiplying the cancer slope factor (CSF), another principal toxicity
factor (also known as carcinogen potency factor) with lifetime
average daily dose (LADD) of ingesting the compound in water as
shown in Eq. (4) below (Dinis and Fiúza, 2011; Kamunda et al.,
2016).
Carcinogenic risk ¼ LADD  CSF (4)
Overall carcinogenic risk is thereafter computed as addition of
the risk values for all the potential carcinogens of concern in the
investigation. ADD previously calculated using Eq. (1), is in this case
regarded as the lifetime average daily dose for a particular carci-
nogenic compound or metal. The risk value is considered insignif-
icant when it is  106 and significant if it is  104. The cancer risk
is very high when it reaches 103 (Man et al., 2013; Wei et al., 2015).
In the present investigation, carcinogenic risk assessment was only
estimated for chromium, subject to availability of CSF (Table 6).
2.5. Data analysis
Statistical analysis was performed using statistical package for
social sciences [(SPSS) IBM version 24 software]. One-way analysis
of variance (ANOVA) was used to test the significance of differences
in the concentrations of the metal contaminants with respect to
different sampling sites whereas the relationship among the
 Y. Titilawo et al. / Chemosphere 211 (2018) 834e843 837

elements was assessed using Pearson correlation. Results were

28789e195087
considered significant at P < 0.05 and 0.01 as appropriate.

6400e232000
2000e71000

3599e27870
60e960

0e2100

0e1350
10e650
ND e 3
3. Results and discussion

0e800
Range

ND
3.1. Determination of the metallic elements

93331 ± 12414
65475 ± 8113
26695 ± 4070

11666 ± 1552
0e232000
The results of the analysis of metals analyzed in the water

200 ± 18

192 ± 44

407 ± 97
310 ± 53
1.4 ± 0.3

52 ± 20
samples drawn from all the ten locations are presented in Table 2.

Mean

ND
Six of the heavy metals determined were frequently detected in all
the sampling sites except in R9 where manganese was not found.

49067 ± 19406
39500 ± 14110
89723 ± 34242
11215 ± 4280
It is noteworthy that lead (Pb) was below detection limit in all the

273 ± 263
333 ± 284
390 ± 120

3e49067
107 ± 13
study sites. The dominance level of metals found in the water

50 ± 45
samples collected from the ten locations in descending order is

3±0
R10

ND
presented as follows: calcium > magnesium > cop-

173147 ± 34832

195087 ± 46007
per > zinc > iron > chromium > aluminium > manganese. This in-

21450 ± 10983

27870 ± 5751
dicates that heavy metals with highest and lowest concentrations

6.7e173147
were copper and manganese respectively (Table 2).

107 ± 18

187 ± 79
150 ± 72
40 ± 20
7±3

ND
R9
3.1.1. Iron

106015 ± 31441
Iron, the most abundant element by weight on earth (32.1%),

50667 ± 20663
53000 ± 9866

13252 ± 3930
and the fourth most abundant element in earth's crust (Kumar

1350 ± 629

1.7e53000
507 ± 149
367 ± 113
and Puri, 2012) was detected in all the water samples in the

1.7 ± 0.7

37 ± 15
present investigation between 60 and 960 mg L1, with a mean

87 ± 7

ND
value of 200 ± 18 mg L1 (Table 2). The observed experimental

R8
values were mostly below USEPA permissible limit of 300 mg L1

91268 ± 14033
42133 ± 6933
48333 ± 6741

11409 ± 1754
which is considered safe for drinking in all the locations except R2

1.3e48333
213 ± 213
403 ± 105
and R3 that had mean values of 368 ± 216 mg L1 and

1.3 ± 0.9
93 ± 20
17 ± 12
73 ± 7
835 ± 63 mg L1 respectively, indicating that the rivers might not

ND
R7
present any serious aesthetic challenge. Values higher than

21600 ± 6417

28789 ± 9301
1000 mg L1 are toxic to aquatic lives (Fatoki et al., 2002; Daso and

6167 ± 2455

3599 ± 1163
467 ± 225
350 ± 159

2e21600
Osibanjo, 2012; Idoko et al., 2012).

90 ± 21
33 ± 24
2 ± 0.6
80 ± 0
Given its natural abundance in the earth, the concentrations

ND
R6

recorded in this study could be due to the interaction of rainwater

with soils and rocks, releasing ferrous iron into the environmental

107733 ± 19029

126965 ± 29660
18000 ± 10214

15871 ± 3708
waters rather than any anthropogenic source (Idoko et al., 2012).

1.3e107733
560 ± 170
387 ± 190
Average heavy metal concentrations (mg L) in selected rivers of Osun State, Southwestern Nigeria.

This is because the metal of interest is reportedly available in

1.3 ± 0.9
120 ± 0

90 ± 27
73 ± 29

Nigeria soils, lagoons and aquatic lives in high quantity (Asaolu

ND
R5

and Olaofe, 2004; Nwajei and Gagophien, 2000). Other sources

of iron in the study sites, especially in R3 may include contribu- 159091 ± 15343
114400 ± 7632
43833 ± 7507

19886 ± 1918
100 ± 10E-15

tions from waste discharge, cookware, steel, cast and galvanized

1.3e114400
360 ± 164

iron pipes used for water supply in the capital city, as well as old
307 ± 30
1.3 ± 0.3
73 ± 7
17 ± 3

roofing sheets that may be eroding due to rainfall in the area

ND
R4

(Roberts, 1999; Baby et al., 2010; Eletta, 2012; Godwin et al., 2015).
Moderate level of iron in water is desirable because it is an
31467 ± 11175

37676 ± 13183
4667 ± 1764

4710 ± 1648

essential element in human nutrition, and required for the syn-

1.3e31467
367 ± 111
835 ± 63

273 ± 56

thesis of haemoglobin in the red blood corpuscles (Vetrimurugan

1.3 ± 0.3
47 ± 15
20 ± 0

et al., 2017). It also supports growth and metabolic processes of

ND
R3

both humans and animals (Tria et al., 2007; WHO, 2008; Kumar
45867 ± 13461

54875 ± 17059

and Puri, 2012; Edward et al., 2013). High concentration of iron

7667 ± 2906

6859 ± 2132

in water generally causes inky flavour, bitter, astringent and dis-

0.7e45867
368 ± 216

663 ± 356
247 ± 96
0.7 ± 0.3

colouring taste, plumbing fixtures and scaling which encrusts

37 ± 18
27 ± 7

pipes (Saeed and Shaker, 2008; Hassan, 2012). At toxic levels, iron
ND
R2

can bring about damage of the cells in the heart, liver, gastroin-
43824 ± 16383
18667 ± 8583
24333 ± 7753

testinal tract, cardiovascular system and kidneys, leading to car-

5478 ± 2048

diac arrest, depression, coma, convulsions and various respiratory

1e24333
413 ± 18
223 ± 19
120 ± 0
1 ± 0.6

disorders (Roberts, 1999; Baby et al., 2010; Idoko et al., 2012).

53 ± 3
13 ± 7

ND
R1

3.1.2. Manganese
Mean concentration
Total concentration

Manganese is one of the most abundant metals in the earth's

ND: Not detected.
Metals (mg L1)

crust, usually occurring with iron. It is an important micronutrient

Magnesium
Manganese

Aluminium
Chromium

for normal physiological operations in humans and animals. In

Calcium
Copper

algae and green plants, it is required for the reduction of nitrates,

Range
Table 2

Lead
Zinc
Iron

and deeply involved many enzymatic activities in higher animals.

Deficiency of Mn in mammals may result in serious reproductive,
838 Y. Titilawo et al. / Chemosphere 211 (2018) 834e843
nervous and skeletal disorders (Salano, 2013; Oyekunle et al., 2011;
Edward et al., 2013). Usually, the greatest exposure to manganese is
from food (WHO, 2008). In the current investigation, the levels of
Mn ranged from not detected to 3 mg L1 (mean ¼ 1.4 ± 0.3 mg L1)
(Table 2). The levels of manganese were generally lower than the
WHO permissible limit of 400 mg L1 (WHO, 2008), suggesting that
waters from the rivers may be less likely to support algae growth
and will possibly have desirable taste (Jeje and Oladepo, 2014). The
results were similar to those reported by Oginni and Ojoawo (2014),
although lower compared to many other past studies (Oyekunle
et al., 2011; Singare et al., 2012; Edward et al., 2013; Aladesanmi
et al., 2014; Jeje and Oladepo, 2014; Tesfamariam and Younis,
2016). Higher levels of manganese can cause black stains on fab-
rics, enamel and porcelain (Vetrimurugan et al., 2017).
3.1.3. Chromium
Chromium is used mostly in the manufacture of some products
such as pigments for paints, metal alloys, cement, rubber and paper
(Jeje and Oladepo, 2014). Other sources of Cr in the environment
include plastics, dyes, printing ink, cutting oils, photographic ma-
terials, detergents, wood preservatives, erosion of rocks, power
plants, liquid fuels, brown and hard coal, industrial and municipal
wastes, laundry chemicals, road run off due to tire wear, corrosion
of bushings, brake wires and radiators. In the present study, con-
centrations of chromium ranged from 0 to 2100 mg L1. Of the ten
sampling sites, three (R2, R3 and R9) had levels within the WHO
permissible limit of 50 mg L1 (WHO, 2008; Oyekunle et al., 2011),
whereas others exceeded (Table 2). The presence of Cr in envi-
ronmental waters is usually linked with industrial waste discharge
(Dawaki et al., 2013). Higher concentrations of chromium in the
study locations implies that the rivers are heavily polluted, and
hence unsuitable for human consumption (Hilgenkamp, 2006;
Salano, 2013; Saeed and Shaker, 2008; Adeleken and Abegunde,
2011; Lokhande et al., 2011).
Highest mean concentration of Cr (1350 ± 629 mg L1) recorded
at R8 was found consistent with the findings of Jeje and Oladepo
(2014), who detected chromium as high as 6500 mg L1 in the
aquatic resources within the locality, suggesting a need for strict
control of pollution activities in the area. Previous studies in the
area suggested that solid wastes including hospital, domestic,
electronic, industrial and constructive wastes, which are indis-
criminately disposed could be leaching into the surrounding sur-
face waters (Oluyemi et al., 2010; Aladejebi et al., 2015). Part of the
Cr concentrations obtained from this location could also be asso-
ciated with effluent contribution from the palm oil mills in the
community (Ohimain et al., 2012). The toxic effect of Cr on plants is
evident when the roots remain small, leaves become narrow with
reddish brown discoloration and small necrotic blotches (Lokhande
et al., 2011). Exposure to chromium (especially chromium VI) can
result in many health defects including lung cancer, skin ulcers and
irritation, malignant neoplasia, chromium dermatitis, damage of
liver, kidney, circulatory and nerve tissues (Sarkar, 2005). The heavy
metal is known to often accumulate in aquatic organisms, conse-
quently biomagnifying in the food chain (Lenntech, 2011; Jeje and
Oladepo, 2014).
3.1.4. Aluminium
Aluminium is the third most abundant element in the earth
crust and not very soluble in water, having a background concen-
tration of 10e400 mg L1 in river freshwater (Tria et al., 2007;
Singare et al., 2012). The present study reveals aluminum concen-
tration in the samples varying from 0 to 800 mg L1. The lowest
(7 ± 3 mg L1) and highest (273 ± 263 mg L1) mean concentrations
were recorded at R9 and R10 respectively. The tolerant limit of
200 mg L1 set by WHO was exceeded at R10 only, indicating the
suitability of the waters in almost all the sites for use with respect
to aluminium. Any concentration in excess of this target value could
result in the deposition of aluminium hydroxide flocs in water
distribution systems, undesirable turbidity and worsening of its
discoloration by iron (WHO, 2008). The levels of aluminium
recorded in this study may largely be attributable to natural sour-
ces. The high concentration at R10 could have resulted from
indiscriminate disposal of domestic wastes (Table 1) (Aladesanmi
et al., 2014). Although, it was previously believed that aluminum
was not quite harmful, yet available evidence in the recent times is
implicating the metallic element in causing disorders in humans. It
could readily find its way into surface and groundwaters from soils
and sediments by leaching.
Oral exposure to aluminium at high concentrations can bring
about bone and brain diseases, and as well affect the kidneys
negatively. Possible toxicity of aluminium, especially to some
selected plant species and aquatic organisms, which depends
mostly on its available chemical form in the aquatic ecosystem has
been reported (Singare et al., 2012). Exposure routes to aluminium
include the use of food additives, antacids, buffered aspirin, as-
tringents, nasal sprays, and antiperspirants; through drinking wa-
ter, automobile exhaust, tobacco smoke; aluminum foil, aluminum
cookware, cans, ceramics, and fireworks (Baby et al., 2010; Ibeto
et al., 2012). Sources of aluminium in freshwaters include domes-
tic wastes, manufacturing processes involving metals and the
dumped sewage sludge (El Bouraie et al., 2010).
3.1.5. Copper
Copper occurs naturally in its native state, but also found in
many minerals. It is both an essential nutrient and a drinking-water
contaminant. It is required for the production of red blood cells and
strengthening of immunity, and its absence can result in nutritional
anaemia in the human body (Edward et al., 2013; Vetrimurugan
et al., 2017). Copper concentrations in drinking water vary widely,
with the primary source most often being the corrosion of interior
copper plumbing (Idoko et al., 2012). In this study, the average Cu
content ranged from 0 to 1350 mg L1 (Table 2). The observed values
mostly fell below the WHO permissible limit of 2000 mg L1,
implying no likelihood of health-based difficulties associated with
the metal (WHO, 2008).
Highest mean concentration (663 ± 356 mg L1) was obtained at
R2, which is predominantly an agricultural area, thereby suggesting
the possible influence of agrochemical run-offs from farms on the
level of water contamination in the locality (Dawaki et al., 2013).
Copper levels above 5000 mg L1 can impair the taste of water
whereas concentration higher than 1000 mg L1 can result in the
stain of sanitary wares and laundry materials (WHO, 2008). The
levels recorded in the study locations could generally be as a result
of corrosion of plumbing pipes in the homes, wearing away of
natural deposits and accumulation of agricultural and domestic
wastes (Idoko et al., 2012; Edward et al., 2013). High level of copper
can cause detrimental effects including irritation of nose, mouth
and eyes, nausea, vomiting, diarrhoea, lesions in gastro intestinal
tract (Saeed and Shaker, 2008). Very high amount is toxic and may
cause damage to liver and/or kidney (Idoko et al., 2012; Edward
et al., 2013; Vetrimurugan et al., 2017). Copper contamination af-
fects fish adversely with the gill being an important site for the
entry of copper, among other sites such as liver, stomach and in-
testine (Vinodhini and Narayanan, 2008).
3.1.6. Zinc
Zinc is an essential trace element for plants, animals and
humans. It is found virtually in all foods and potable waters in the
form of salts or organic complexes (Salano, 2013; Swaminathan
et al., 2011). It helps in the development of embryo, reproductive
 Y. Titilawo et al. / Chemosphere 211 (2018) 834e843
organs and performance of body's normal metabolic activities.
There may be onset of low fertility, loss of taste, stunted growth and
hypogonadism when deficient (Edward et al., 2013). Low level of
zinc can as well weaken resistance of the body against diseases
(Vetrimurugan et al., 2017). In the present investigation, the highest
and lowest amounts of Zn were detected at R7 and R9 with mean
values of 403 ± 105 mg L1 and 150 ± 72 mg L1 respectively
(Table 2), although they all fell below the USEPA and WHO target
value of 5000 mg L1 (Oyekunle et al., 2011; Daso and Osibanjo,
2012; USEPA, 2012). Excessive levels above the standard limit
may affect the potability of water, especially making the taste un-
acceptably sharp and bitter, even as the appearance becomes
opalescent (WHO, 2008; Idoko et al., 2012).
Toxicity of zinc to man is rare but at concentrations of about
40,000 mg L1, it may induce symptoms of irritability, muscular
stiffness and pain (Al-Weher, 2008; Salano, 2013). Sources of zinc in
natural waters may be from geological rock weathering or other
anthropogenic inputs such as industrial and domestic wastewater
discharges, and from animals as observed in some of our sampling
sites (Kori-Siakpere and Ubogu, 2008; Oyekunle et al., 2011;
Ibemenuga, 2013). Other sources in soils and waters include dis-
charges of smelter slag and wastes and the use of commercial
products such as fertilizers, paints and wood preservatives con-
taining zinc (Salano, 2013; Lew, 2008; Saeed and Shaker, 2008; El
Bouraie et al., 2010).
3.1.7. Lead
Lead is a naturally occurring metal used in many industrial ac-
tivities (Ibeto et al., 2012). It is a very soft metal and was principally
used in pipes, drains, soldering materials, batteries, cable coverings,
plumbing, fuel additives, PVC plastics, x-ray shielding, crystal glass
production, pesticides and as paint pigments (Baby et al., 2010). It
was however not detected in all the river water samples examined
in this study. This was in agreement with the report of Adeyeye and
Ayoola (2013) on heavy metal content of African Catfish in Eko-
Ende Dam, Ikirun, Osun Central, Nigeria. Although, that was con-
trary to the findings of Oluyemi et al. (2010), who detected Pb as
high as 6690 mg L-1 in the Shasha River and other three towns in Ife
North Local Government Area of the state. Similar results were
published on the sediment quality of Asejire Reservoir (R7) where
high levels of Fe and Pb were documented (Godwin et al., 2015).
The disparity in the levels detected could be linked with human
activities in the surroundings of the rivers investigated at the
particular period of study, which vary from one location to location,
and season to season (Binns et al., 2003; Dawaki et al., 2013). Also,
its non-detection does not really mean it was actually absent in the
river waters but that it was obtainable in extremely trace concen-
trations below the detection limit of the analytical instrument
(Adekunle et al., 2017). Lead is a known human carcinogen that is
very toxic to aquatic organisms and humans, even at trace level
(Idoko et al., 2012). Exposure to Pb, even in low concentrations
could result in many health effects with target body organs and
systems including bones, brain, blood, kidneys, gastrointestinal
tract, thyroid gland and reproductive system (Baby et al., 2010;
Ibeto et al., 2012; Edward et al., 2013; Jeje and Oladepo, 2014;
Vetrimurugan et al., 2017).
3.1.8. Calcium
Calcium is an essential element naturally found in surface and
ground waters. It exists mainly in the water bodies as alkali metal
(Grochowska and Tandyrak, 2009), and its presence is largely
linked to decomposition of aluminosilicates. When found in higher
concentration, it might have been washed out from minerals such
as magnesite, gypsum, limestone, magnesium limestone, amongst
839
others (Ko
zí
sek, 2003; Gałczyn  ska et al., 2013; Potasznik and
Szymczyk, 2015). Other factors governing its availability in sub-
stantial amount in the aquatic environments include weather
conditions, geological structure, type and class of soil, land use
type, water supply intensity and type, runoffs and plant cover
(Wons et al., 2012; Potasznik and Szymczyk, 2015). It is however
very uncommon to detect calcium in abundance as a result of
environmental pollution (Ko
zí
sek, 2003). Although, higher levels of
calcium are not generally considered a health concern, yet a
maximum level of 50,000 mg L1 has been recommended in
drinking water. Higher concentration than this could result in the
formation of excess calcium carbonate deposits in the plumbing
system or may decrease the cleansing power of soaps. Levels below
5000 mg L1 can result in oligotrophy, a condition that does not
support plant and animal lives adequately. Calcium concentrations
as high as 400,000 mg L1 could be detected in seawater (Goldstein,
2008; Li and Migliaccio, 2011), however the amount in freshwater
bodies as recommended by Indian Council of Medical Research
(ICMR) should not exceed 200,000 mg L1 (Olajire and Imeokparia,
2001).
In this study, calcium level as cation varied between 6400 and
232,000 mg L1, with an average concentration of
65,475 ± 8113 mg L1 (Table 2). The amounts of calcium were higher
than 5000 mg L1 needed for the survival of biota in the water
bodies in all the ten locations. Highest mean levels were deter-
mined and recorded in the order 114,400, 107,730 and
173,150 mg L1 at R4, R5 and R9, indicating enrichment of calcium
based minerals in those regions and also implying that water at the
three locations may not support laundry work and may deposit
excess CaCO3 in the plumbing pipes if used for public water supply
(DWAF, 1996). It is needed in the cell membranes of plants for
structural reasons, helps in the metabolic processes and water
transport in plants, and as well contributes immensely to the
accumulation of oxalate in them. It also induces coagulation of soil
colloids and support crumb-like structure of soil (Pulikowski et al.,
2006; Orzepowski and Pulikowski, 2008; Potasznik and Szymczyk,
2015).
Calcium is one of the most dominant mineral elements in the
bone and teeth structure of humans and animals. In fact, drinking
water rich in calcium reduces the chance of having cardiac disorder
or any heart related issue. It also reduces neuromuscular excit-
ability, enhances contraction of muscle and heart, coagulation of
blood, along with the intracellular information transmission
(Khopkar, 1993; Ko
zí
sek, 2003; Sanjoy and Rakesh, 2013). Ingestion
of calcium may inhibit heavy metals absorption in the body and
could prevent certain types of cancer. Although, very high con-
centration of the element may adversely affect the absorption of
other essential minerals (Nova Scotia Environment, 2008), yet its
deficiency could as well lead to osteoporosis and osteomalacia.
Hypertension is another unusual but proven likely effect of low
calcium in the body (Ko
zí
sek, 2003).
3.1.9. Magnesium
Magnesium is an important element that exists naturally in the
water bodies. It is usually found with calcium as an alkali metal
from similar sources in the aquatic milieu (Grochowska and
Tandyrak, 2009). Its level in the present investigation ranged
from 2000 to 71,000 mg L1, having a mean value of
26,695 ± 4070 mg L1 (Table 2). Highest desirable limit of magne-
sium in drinking water has been set at 50,000 mg L1 by WHO and
ICMR, although levels below 150,000 mg L1 could still be tolerated.
Its levels in all the areas studied fell within the desirable limits
(Sanjoy and Rakesh, 2013). Magnesium, which is a component of
chlorophyll, is a natural antagonist of calcium (Ko

zí
sek, 2003). The
840 Y. Titilawo et al. / Chemosphere 211 (2018) 834e843

water containing as much as 500,000 mg L1 of the metal is usually
found unpleasant in taste by average individuals (Nova Scotia
Environment, 2008).
Magnesium acts as an activator and a cofactor for over 300
enzymatic reactions and as well supports intensive growth in plant
(Potasznik and Szymczyk, 2015). Very low levels of the metallic
element could increase risk of having a number of pathological
conditions that include motor neurone disease, diabetes mellitus of
type II and osteoporosis possibly, vasoconstrictions, acute
myocardial infarction, hypertension, cardiac arrhythmia, athero-
sclerotic vascular disease, as well as eclampsia in pregnant women
(Innerarity, 2000; Saris et al., 2000; Ko
zí
sek, 2003). Since calcium is
found in higher level than magnesium in the earth crust, concen-
tration of the latter is usually detected in lower concentration in the
water bodies. The ratio of calcium to magnesium in both ground
and surface waters could be up to 10, although it is commonly
found in the neighbourhood of 4. The Ca/Mg ratio in the study sites
ranged from 0.77 to 8.07, with a mean value of 2.45. The ratios were
higher than 4 in four of the ten rivers, inferring low mineralisation
in most of the water bodies, with three sites (R1, R7 and R8) having
values below 1. Higher concentrations of calcium at R4, R5 and R9
could be attributed to anthropogenic inputs such as municipal
waste discharge, and the agricultural land use activities in the areas
(Potasznik and Szymczyk, 2015).
3.2. Statistical analysis
Table 3 presents the Pearson correlation matrix among the
metallic contaminants of interest in the water samples analyzed.
The results showed that positive correlation at a significant level of
p  0.05 existed between copper and the duo of manganese and
aluminium. At the same level, manganese correlated positively
with aluminium, just as zinc also does with aluminium. Similarly,
zinc was observed to be strongly correlated with both copper and
manganese (p  0.01 level), suggesting that they might have orig-
inated from common sources in the environment (Oyekunle et al.,
2011). The one way ANOVA performed on the triplicate concen-
trations of the selected metal contaminants revealed no significant
difference across the sampling sites, except iron (F ¼ 11.163,
r ¼ 0.000) and chromium (F ¼ 4.144, r ¼ 0.004). The mean level of
iron recorded at R3 (835 ± 63 mg L1) was statistically higher than
the amounts detected in other studies. Similarly, the maximum
mean values concentrations of chromium obtained at R8
(1350 ± 629 mg L1) was significantly different from others. In both
cases, permissible values for the contaminants in drinking water
were exceeded, raising a concern for the health of those using the
river waters in those locations, especially for domestic purposes
(Supplementary Table 3).
3.3. Health risk assessment
The data gathered in this study revealed that HQs for the four
metallic elements were below the benchmark of 1.0 in all locations,
both for the adults and children. Likewise, the estimated hazard
index was also generally low, suggesting that no significant non-
carcinogenic effect would arise from individual exposure to these
elements in the ten rivers being investigated (Tables 4 and 5). In the
same vein, the carcinogenic risk values estimated for chromium

Table 3
Pearson correlation matrix among the metals of interest in the selected river water samples.

Pearson Correlation Iron Copper Manganese Aluminium Chromium Zinc

Iron 1
Copper 0.069 1
Manganese 0.069 0.406* 1
Aluminium 0.072 0.378* 0.376* 1
Chromium 0.140 0.168 0.286 0.005 1
Zinc 0.194 0.478** 0.646** 0.450* 0.110 1
*
Correlation is significant at the 0.05 level (2-tailed).
**
Correlation is significant at the 0.01 level (2-tailed).

Table 4
Hazard quotient (HQ) for adults.

Metals R1 R2 R3 R4 R5 R6 R7 R8 R9 R10 Range Mean

Iron e e e e e e e e e e e e
Copper (108) 5.94 9.54 5.27 5.18 8.05 9.33 3.07 7.28 2.68 4.79 2.68e9.54 6.113 ± 0.76
Manganese (1011) 4.11 2.88 5.34 5.34 5.34 11.43 5.34 6.98 0 12.32 0e12.32 5.91 ± 1.16
Aluminium e e e e e e e e e e e e
Chromium (108) 10.22 7.03 8.95 14.05 17.25 24 17.88 259 7.67 9.58 7.03e259 37.54 ± 24.64
Zinc (109) 4.28 4.73 5.24 5.88 7.42 9.33 7.73 7.03 2.88 7.48 2.88e9.33 6.2 ± 0.61

Total (107) 1.66 1.71 1.48 1.98 2.61 3.43 2.17 2.67 1.06 1.51 1.06e26.67 4.43 ± 2.48

Table 5
Hazard quotient (HQ) for children.

Metals R1 R2 R3 R4 R5 R6 R7 R8 R9 R10 Range Mean

Iron e e e e e e e e e e e e
Copper (108) 8.27 13.27 7.33 7.2 11.2 9.33 4.27 10.1 3.73 6.67 3.73e13.27 8.14 ± 0.94
Manganese (1011) 5.71 4 7.43 7.43 7.43 11.43 7.43 9.71 0 17.14 0e17.14 7.77 ± 1.43
Aluminium e e e e e e e e e e e e
Chromium (108) 14.2 9.8 12.5 19.6 24 24 24.9 360 10.7 13.3 9.8e360 51.3 ± 34.35
Zinc (109) 5.96 6.58 7.29 8.18 10.3 9.33 10.76 9.78 4 10.4 4e10.76 8.26 ± 0.7.13

Total (107) 2.31 2.37 2.06 2.76 3.62 3.43 3.03 3.71 1.48 2.1 1.48e37.11 6.03 ± 3.46
 Y. Titilawo et al. / Chemosphere 211 (2018) 834e843
Table 6
Chromium cancer risk assessment.
Age Categories R1 (107) R2 (108) R3 (107) R4 (107) R5 (107)
Adults 1.26 8.64 1.1 1.73 2.12
Children 1.75 12 1.53 2.4 2.95
Total 3.01 20.7 2.63 4.13 5.07
were generally lower than the standard limit in all the locations
except at R8, where it was as high as 3.18  106 and 4.43  106 for
adults and children, respectively, above the acceptable level
(Table 6). This implies that 1 person in every 314,206 adults and
225,836 children, respectively may be at risk of cancer in the area.
Hence, the regulatory authorities in the state are thus implored to
do everything possible to reduce the level of this carcinogen in R8
and its environments in order to safeguard the health of people
who depend on the river for domestic usage, especially children in
the rural areas.
4. Conclusion
The levels of the metal contaminants investigated in ten of the
major rivers in Osun State, Southwest Nigeria revealed some
heights of pollution. The results showed that the average concen-
trations of the metals in water samples from the selected rivers
varied considerably and decreased in the order of
Ca > Mg > Cu > Zn > Fe > Cr > Al > Mn > Pb. These findings support
many of the previous reports from aquatic environments in the
state and other parts of Nigeria. The concentrations of Fe (at R2 and
R3), Cr in seven locations (with exception of R2, R3 and R9) and Al
(at R10) were conspicuously higher than the permissible limits
stipulated for drinking water, whereas others were moderate. Lead
was not detected in any of the sampling locations. The order in
which the rivers were polluted is thus presented:
R8 > R3 > R2 > R5 > R10 > R6 > R4 > R1 > R7 > R9; with R8 and R3
recording the highest levels of contaminants. Thus, efforts should
be made to ensure they are kept below acceptable limits. Results of
the human health risk assessment indicated that the probability of
non-carcinogenic effect arising from individual exposure to toxic
metals in the rivers is less likely, but carcinogenic risk was evidently
high at R8, suggesting that an average of 1 person in every popu-
lation of 314,206 adults and 225,836 children correspondingly may
be at risk of having cancer in the surrounding communities of R8. It
is therefore very pertinent to stress that infants and young children,
particularly those in the rural areas would be at greater risk, as a
result of their frequent usage of untreated river waters for drinking
and other domestic purposes and should be protected. Appropriate
measures should be taken to address indiscriminate disposal of
solid, industrial, agricultural and domestic wastes into/nearby the
water bodies in some parts of the state. Furthermore, environ-
mental policies should be enhanced and campaigns carried out to
educate the public on the need to also protect and preserve aquatic
ecosystems and their resident biota.
Conflicts of interest
We declare that there is no conflict of interest concerning the
publication of this paper.
Acknowledgements
Special thanks to the South African Medical Research Council,
Water Research Commission of South Africa and University of Fort
Hare for supporting this study.
841
R6 (107) R7 (107) R8 (106) R9 (108) R10 (107) Range (108) Mean (107)
2.12 2.2 3.18 9.43 1.18 8.6e318 4.53 ± 3.04
2.95 3.06 4.43 13.1 1.64 12e443 6.31 ± 4.23
5.07 5.26 7.61 22.6 2.82 21e761 10.8 ± 7.26
Appendix A. Supplementary data
Supplementary data related to this article can be found at
https://doi.org/10.1016/j.chemosphere.2018.07.203.
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