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Water Resources and Industry 19 (2018) 13–24

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Water Resources and Industry


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Water quality assessment of bitumen polluted Oluwa River, South-


T
Western Nigeria
⁎ ⁎
T.A. Ayandirana, , O.O. Fawolea, S.O. Dahunsib,
a
Department of Pure and Applied Biology, Ladoke Akintola University of Technology, Ogbomoso, Nigeria
b
Department of Biological Sciences, Landmark University, Omu-Aran, Kwara State, Nigeria

AR TI CLE I NF O AB S T R A CT

Keywords: This study was aimed at establishing a water quality database in the study area where none
Bitumen existed previously. Samples were taken from two different sites of River Oluwa, South-Western
Drinking water Nigeria. Physicochemical and biological factors and the metals for one year (April 2011–March
Health 2012) were evaluated using standard methods. All the physical parameters of the water samples
Nigeria
from the two sampling Sites did not show deviations from Nigeria Industrial Standard (NIS) for
Pollution
Standards
permissible levels of these parameters in drinking water. Virtually all heavy metals investigated
deviated from the permissible levels allowed by NIS, and WHO standards in drinking water. In
the same vein, all chemical parameters investigated during the dry season was significantly
different from rainy season except for BOD at P < 0.05. Isolated microorganisms include mem-
bers of the genera Bacillus, Micrococcus, Pseudomonas, Streptococcus, Proteus and Staphylococcus.
The public health implications of consuming water from this river are fully discussed.

1. Introduction

One of the globally recognized health-related programs and campaigns is the provision of potable and safe water especially in
rural communities [1] due to the important roles play by water in supporting life and wellness [2–7]. It has been reported an
estimated 1.1 billion people do not have access to adequate and uninterrupted water supplies which has been linked to about 4 billion
diarrhea outbreak and well over 5 million annual global deaths [8,9]. Researchers have reported the major causes of these shortfalls
in clean water supplies to be improper management, the upsurge in industrial developments and its attendant pollution menace,
alarming population growth, unfavorable policy implementation of water-related projects. All these factors are also known to ad-
versely affect the provision, availability, distribution, access, and quality of water and allied resources [10,11].
One of the yet to be achieved Millennium Development Goals (MDGs) set by the United Nations (UN) is to halve the number of
people without access to improved water sources by 2015 [7]. There is the need for immediate actions to arrest water shortage
especially in developing countries like Nigeria and others in Sub-Saharan Africa with high records of waterborne diseases like
cholera, typhoid, shigellosis, diarrhea, etc due to extreme poverty and lack of clean water [12,13]. In Nigeria alone, over 66 million
individuals lack access to good drinking water source and this has led to the upsurge in the consumption of water from diverse
sources most of which are polluted or contaminated [14,15] with attendant health issues.
Pollution of water bodies and the attendant reduction in quality is a major contributor to freshwater scarcity globally and this has
called for more integrated water management and monitoring [7]. Also, most rivers and streams have been plagued with enormous
microbial and sediment pollution which threaten the survival of life forms in such environment. The principal microbial water-borne


Corresponding authors.
E-mail addresses: toluexcel2005@yahoo.com (T.A. Ayandiran), dahunsi.olatunde@lmu.edu.ng (S.O. Dahunsi).

https://doi.org/10.1016/j.wri.2017.12.002
Received 1 June 2017; Received in revised form 1 December 2017; Accepted 7 December 2017
2212-3717/ © 2017 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/BY/4.0/).
T.A. Ayandiran et al. Water Resources and Industry 19 (2018) 13–24

Fig. 1. Map of study area (Ayandiran et al. [6]).

diseases are typhoid and paratyphoid fevers (Salmonellosis), cholera, bacillary dysentery (Shigellosis), infectious hepatitis, dra-
contiasis, schistosomiasis, etc. [16,17]. At the moment, there is no form of treated water supply in the area of study.
According to the USEPA, sediment contamination is the second leading cause of impairment to water bodies because suspended
sediment can directly impact aquatic organisms besides increasing the cost of water treatment in channel and reservoirs. Pollution of
water by petroleum and allied products is a universal environmental phenomenon in places where there is exploration or processing
of petroleum deposits [18]. Ondo State, South-Western Nigeria has a large deposit of natural bitumen and the exploration activities of
this resource have caused numerous pollution menaces to surrounding rivers and streams. Since the toxicity of a material is the most
common measure of its potential environmental impact, the environmental impacts of bitumen pollution on the physical environment
especially communities in Ondo State need be assessed. Therefore, the aim of this study was to evaluate the effects of bitumen
pollution on the water quality of Oluwa River as a continuation to the few preliminary studies available on the water of this
economically important river.

2. Materials and methods

2.1. Description of collection site

Ondo State is located in the south-western socio-political region of Nigeria within coordinates 6°35′19 N, 4°50′3 E and altitude
61 m. It is one of the largest agriculturally dominated areas especially with the presence of vast fresh and coastal water bodies which
is undoubtedly the largest in the country. One of the major sources of income for the state is the large deposit of bitumen whose

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T.A. Ayandiran et al. Water Resources and Industry 19 (2018) 13–24

exploration started in the 1960s. As shown in Fig. 1, Oluwa is an ancient and major river of immense agricultural, environmental
economic significance flowing through several communities within the Agbabu Bitumen settlement of Ondo State. The river con-
tinuously receives seepage of bitumen run-off as a result of the exploration besides other polluting activities (washing, bathing,
farming, etc.) that are daily carried out along its tributaries. The river interestingly serves these communities for different purposes
including fishing, irrigation and most importantly for drinking.

2.2. Surface water sampling

Pre-rinsed high-density PET screw-capped bottle (1-l capacity) was used in the sampling of surface water for physicochemical
analysis from the sampling points in the first week of every month (April 2011–March 2012). The sampling containers and stoppers
were thoroughly washed thrice with distilled water and once with the water from the river before the actual sample collection.
Surface water samples for Biological Oxygen Demand (BOD) and Dissolved Oxygen (DO) determinations were collected in two sets of
250 ml glass–stoppered-reagent bottles at each sampling Site [7,19]. The BOD samples were carefully filled without trapping air and
the bottle wrapped with dark polythene bags. This was to exclude light, the presence of which is capable of the production of DO by
autotrophs (algae), which may be present in the samples. The samples were all incubated for five days, at the end of which 2 ml of
Winkler solution I and II each was added to the samples using separate dropping pipettes so as to retard further biological activities.
The bottles were shaken thoroughly to precipitate the floc, which settled in the lower half of the bottles.

2.3. Sediment sampling

Sediment samples were collected by the grab method using Eckman grab sampler on 3–4 locations, representing approximately
2–3 cm of surficial bottom sediments, within each sampling Site, and wrapped with aluminum foil to avoid contamination, frozen in
an ice cooler and taken to the laboratory.

2.4. Analytical procedure

Determination of pH for all samples was done using the HI 9024-C, (Hanna Instruments Smithfield, RI, USA), while the tem-
perature was determined using the HI 98517, (Hanna Instrument). Salinity was determined by the HI 19311, (Hanna Instrument)
while electrical conductivity was measured using the HI 2315, (Hanna Instrument). Total dissolved solids (TDS) were analyzed in-situ
using the VSI 22 hand digital meters (VSI Electronics Private Limited, Punjab, India). Dissolved oxygen (DO) of samples was analyzed
using the azide modification of Winkler's method [20]. Determination of chloride was done by the titration method [20]. Ultraviolet
spectrophotometer (DR 2800, HACH, Washington, USA) was used in the determination of major anions as described by APHA [20]
and by Khan et al. [19]. In all, the blank, standard, and pre-analyzed samples were analyzed every 10 samples in order to ensure
reliability and reproducibility of samples [6,7]. For the evaluation of coliform bacteria, the most probable number (MPN) in water
samples was used [7]. Metals analyses using the Sens AA 3000 at. absorption spectrophotometer (AAS) (GBC, Australia) following the
method prescribed by APHA [20].

2.5. Microbial analysis

One (1.0) ml of water and 1 g of sediment sample were used in the microbial analyses. Samples were serially diluted, and
subsequently plated on Nutrient agar, MacConkey agar, Mannitol salt agar and Salmonella-Shigella agar. All the plates were in-
cubated in duplicate appropriately for between 24 and 48 h. Developed colonies were counted and recorded as numbers of colonies
formed per ml (Cfu/ml) of the sample [6,21]. The various distinct colonies were sub-cultured until pure cultures were obtained and
these were immediately transferred to slant bottles containing freshly prepared media. Identification of the individual colonies was
done by the morphological and biochemical techniques earlier described [22].

2.6. Statistical analyses

Data analysis was done using the Microsoft Office Excel 2007 software package with a significance level of P < 0.05 using the
analysis of variance (ANOVA). The mean values of the parameters analyzed were computed for each site and the standard deviations
show the variability between samples taken individually.

3. Results

3.1. Physical parameters

Mean monthly data for physical characteristics of water samples were analyzed and presented in Tables 1 and 2. Temperature
range for the water sample from Site A was 23.50– 26.50 °C with a mean value of 24.97 ± 0.03 °C. For Site B, the range recorded was
23.00–26.80 °C with a mean value of 25.38 ± 0.31 °C. There were no significant differences in the data obtained for the two Sites
(P > 0.05). Mean temperature variations for the rainy and dry season were 24.34 ± 0.71 °C and 26.00 ± 0.58 °C. There were sig-
nificant differences in the two seasons of the year (P < 0.05). pH for the water sample from Site A was found to be in the range of

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Table 1
Mean values of physicochemical characteristics and heavy metal concentrations of water from River Oluwa during sampling period.

Regulatory limits

Parameters Control Site A Site B NIS (2007) WHO (2011)

Temperature (°C) 23.06 ± 0.01 24.97 ± 0.03*


25.38 ± 0.31 *
Ambient –
pH 6.58 ± 0.04 6.87 ± 0.05* 6.78 ± 0.07* 6.5–8.5 6.5–8.5
Electrical Conductivity (µs cm−1) 0.11 ± 0.11 0.15 ± 0.01* 0.17 ± 0.02* 100 25.0
Alkalinity (CaCO3mg l−1) 53.38 ± 3.11 58.78 ± 0.48* 59.58 ± 2.11* – < 120
Total hardness (mgCaCO3l−1) 2.51 ± 0.14 4.01 ± 0.25* 4.26 ± 0.24* 150 100–150
Total Dissolved Solid (mg l−1) 270.10 ± 8.20 429.65 ± 21.44* 413.45 ± 16.30* 500 500
Total Suspended Solid (mg l−1) 6.00 ± 0.00 9.19 ± 0.26* 10.08 ± 0.35* 1500 < 1500
Biological Oxygen Demand (mgO2l−1) 1.80 ± 0.16 13.83 ± 0.23* 14.11 ± 1.07* – 10.0
Dissolves Oxygen (mgO2l−1) 6.21 ± 0.02 2.71 ± 0.22* 2.34 ± 0.15* – 6.0
Chemical Oxygen Demand (mg l−1) 5.81 ± 0.40 165.38 ± 3.41* 162.96 ± 2.81* 4 4
Chloride (mg l−1) 5.02 ± 0.01 7.03 ± 0.15* 7.31 ± 0.21* – 250
Nitrate (mg l−1) 1.02 ± 0.01 1.84 ± 0.79* 2.21 ± 0.96* 50 50
Sulfate (mg l−1) 7.23 ± 0.02 9.91 ± 0.41* 10.76 ± 0.32* 100 250
Phosphate (mg l−1) 0.6 ± 0.01 58.93 ± 3.23* 62.86 ± 3.08* – 0.05
Cadmium (mg l−1) 0.003 ± 0.03 0.12 ± 0.05* 0.09 ± 0.003* 0.003 0.003
Chromium (mg l−1) 0.03 ± 0.01 0.58 ± 0.05* 0.62 ± 0.07* 0.05 0.05
Lead (mg l−1) 0.02 ± 0.21 0.19 ± 0.01* 0.54 ± 0.21* 0.01 0.01
Zinc (mg l−1) 0.2 ± 0.01 2.79 ± 0.17* 3.02 ± 0.11* 0.3 0.1
Iron (mg l−1) 0.12 ± 0.01 0.06 ± 0.01* 0.15 ± 0.08* 0.3 0.3
Copper (mg l−1) 0.09 ± 0.01 0.13 ± 0.07* 0.14 ± 0.07* 1.0 2.0
Nickel (mg l−1) ND ND ND 0.02 0.02
Fluoride (mg l−1) 0.04 ± 0.02 0.22 ± 0.02* 0.24 ± 0.02* 1.5 1.5
Manganese (mg l−1) 0.10 ± 0.01 0.43 ± 0.02* 0.15 ± 0.04* 0.2 0.4

* Significant difference (P ≤ 0.05).

Table 2
Seasonal variations in the mean values of physical, chemical and heavy metal concentrations of water samples from River Oluwa.

Season Regulatory Limits

Parameters Dry Rainy P- value NIS (2007) WHO (2011)

Temperature (°C) 26.00 ± 0.58 a


24.34 ± 0.71 b
0.000 Ambient –
pH 6.81 ± 0.17a 6.84 ± 0.23a 0.760 6.5–8.5 6.5–8.5
Electrical Conductivity (µs cm−1) 0.18 ± 0.03a 0.15 ± 0.06a 0.200 100 25.0
Alkalinity (CaCO3mg l−1) 61.49 ± 5.61a 56.43 ± 3.80b 0.015 – < 120
Total hardness (mgCaCO3l−1) 4.73 ± 0.69a 3.54 ± 0.48b 0.000 150 100–150
Total Dissolved Solid (mg l−1) 457.49 ± 31.06a 383.12 ± 68.00b 0.003 500 500
Total Suspended Solid (mg l−1) 10.27 ± 0.79a 8.98 ± 1.05a 0.001 1500 < 1500
Biological Oxygen Demand (mgO2l−1) 14.80 ± 0.77a 14.37 ± 1.08a 0.171 – 10.0
Dissolves Oxygen (mgO2l−1) 2.93 ± 0.61a 2.12 ± 0.41b 0.001 – 6.0
Chemical Oxygen Demand (mg l−1) 169.14 ± 10.51a 159.15 ± 7.94b 0.017 4 4
Chloride (mg l−1) 7.53 ± 0.61a 6.80 ± 0.37b 0.002 – 250
Nitrate (mg l−1) 0.77 ± 0.23a 3.27 ± 3.89b 0.045 50 50
Sulfate (mg l−1) 11.15 ± 0.75a 9.52 ± 1.27b 0.001 100 250
Phosphate (mg l−1) 66.87 ± 8.15a 54.92 ± 10.15b 0.006 – 0.05
Cadmium (mg l−1) 0.08 ± 0.02a 0.08 ± 0.01a 0.746 0.003 0.003
Chromium (mg l−1) 0.65 ± 0.29a 0.50 ± 0.10a 0.114 0.05 0.05
Lead (mg l−1) 0.22 ± 0.05a 0.50 ± 0.12a 0.155 0.01 0.01
Zinc (mg l−1) 2.82 ± 0.27a 2.99 ± 0.66a 0.428 0.3 0.1
Iron (mg l−1) 0.16 ± 0.26a 0.06 ± 0.02a 0.206 0.3 0.3
Copper (mg l−1) 0.22 ± 0.34a 0.06 ± 0.03a 0.136 1.0 2.0
Nickel (mg l−1) ND ND ND 0.02 0.02
Fluoride (mg l−1) 0.26 ± 0.06a 0.19 ± 0.03b 0.002 1.5 1.5
Manganese (mg l−1) 0.48 ± 0.12a 0.46 ± 0.10a 0.651 0.2 0.4

Means for the same parameter in the same row having different superscripts are significantly different (P ≤ 0.05).

6.55–7.06 with a mean value of 6.87 ± 0.05 while that of Site B was recorded to be in the range of 6.49–7.37 with a mean value of
6.78 ± 0.07. Mean value of pH in the dry season was found to be 6.81 ± 0.17 while rainy season had 6.84 ± 0.23. Electrical
conductivity values for Site A was found to have a range of 0.058–0.210 µs cm−1 with a mean value of 0.150 ± 0.01 µs cm−1 while
that of Site B was found to have a range of 0.054–0.26 µs cm− 1 with a mean value of 0.17 ± 0.02 µs cm−1. Mean values for the dry
and rainy season were found to be 0.18 ± 0.03 µs cm−1 and 0.15 ± 0.06 µs cm−1 respectively. Alkalinity has values with a range of
57.20–63.20 CaCO3mg l−1 and a mean value of 58.78 ± 0.48 CaCO3mg l−1 for Site A. That of Site B had a range of 52.50–78.58

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CaCO3mg l−1 with a mean value of 59.58 ± 2.11 CaCO3mg l−1. Dry season had 61.49 ± 5.61 CaCO3mg l−1 while rainy season had
56.43 ± 3.8 CaCO3mg l−1. Total hardness has values between 2.80 and 5.00 CaCO3mg l−1 with a mean value of 4.01 ± 0.25 Ca-
CO3mg l−1 for Site A while Site B has values between 3.10 and 5.50 CaCO3mg l−1 with a mean value of 4.26 ± 0.24 CaCO3mg l−1.
Dry season and rainy season had mean values of 4.73 ± 0.69 CaCO3mg l−1 and 3.54 ± 0.48 CaCO3mg l−1 respectively. Total Dis-
solved Solids (TDS) has values ranging from 284.30 to 488.60 mg l−1 with a mean value of 429.65 ± 21.44 mg l−1 for Site A. That of
Site B was found out to have values ranging from 297.20 to 468.50 mg l−1 with a mean value of 413.45 ± 16.30 mg l−1. Values
recorded for dry season and rainy seasons were 457.49 ± 31.06 mg l−1 and 383.12 ± 68.00 mg l−1 respectively. Values recorded for
Total Suspended Solids (TSS) for Site A, ranged between 7.80 and 10.50 mg l−1 with a mean value of 9.19 ± 0.26 mg l−1. For Site B
the values ranged between 8.00 and 11.80 mg l−1with a mean value of 10.08 ± 0.35 mg l−1. Values recorded for dry and rainy
seasons were 10.27 ± 0.79 mg l−1 and 8.98 ± 1.05 mg l−1.

3.2. Chemical parameters

Biological Oxygen Demand (BOD) values ranged between 12.20 and 14.70 mgO2l−1 with a mean value of 13.83 ± 0.23 mgO2l−1
for Site A. Values for Site B was between 14.20 and 16.20 mgO2l−1 with a mean value of 14.11 ± 1.07 mgO2l−1; Dry season and
rainy seasons values are 14.80 ± 0.77 mgO2l−1 and 14.37 ± 1.08 mgO2l−1 respectively. Dissolved Oxygen (DO) concentrations
ranged between 1.80 and 4.00 mgO2l−1 for Site A with a mean value of 2.71 ± 0.22 mgO2l−1. The concentration of DO values at Site
B ranged between 1.60 and 3.30 mgO2l−1 with a mean value of 2.34 ± 0.15 mgO2l−1. Dissolved Oxygen values for dry and rainy
season were 2.93 ± 0.61 mgO2l−1 and 2.21 ± 0.41 mgO2l−1 respectively.
Values for Chemical Oxygen Demand (COD) for Site A were found to be between 148.0 and 180.50 mg l−1 with a mean value of
165.38 ± 3.41 mg l−1; Site B had values between 144.0 and 172.40 mg l−1 with a mean value of 162.96 ± 2.81 mg l−1 while the
mean value recorded for dry and rainy seasons were 169.14 ± 10.51 mg l−1 and 159.15 ± 7.94 mg l−1 respectively. Chloride had
values from 6.50 to 7.80 mg l−1 with a mean value of 7.03 ± 0.15 mg l−1 for Site A. That of Site B was found to be 6.00–8.50 mg l−1
with a mean value of 7.31 ± 0.21 mg l−1. Dry season value for chloride was recorded to be 7.53 ± 0.61 mg l−1 and that of rainy
season was 6.80 ± 0.37 mg l−1. Nitrate values were between 0.40 and 8.5 mg l−1 with a mean value of 1.84 ± 0.79 mg l−1 for Site
A. Site B had value range of 0.20–10.00 mg l−1 with a mean value of 2.21 ± 0.96 mg l−1. 0.77 ± 0.23 mg l−1 was recorded for dry
season while 3.27 ± 3.87 mg l−1 was recorded for rainy season. Sulfate had values from 7.20 to 11.52 mg l−1 for Site A with a mean
value of 9.91 ± 0.41 mg l−1. 8.50–11.80 mg l−1 with a mean value of 10.76 ± 0.32 mg l−1 was recorded for Site B. Dry season and
rainy season values were 11.15 ± 0.75 mg l−1 and 9.52 ± 1.27 mg l−1. Phosphate had values ranging from 40.20 to 71.20 mg l−1
with a mean value of 58.93 ± 3.23 mg l−1 for Site A. The value range of phosphate for Site B was 38.80–73.40 mg l−1 with a mean
value of 62.86 ± 3.08 mg l−1. Values recorded for dry and rainy season was 66.87 ± 8.15 mg l−1 and 54.92 ± 10.15 mg l−1
respectively.

3.3. Heavy metals

Analysis of heavy metal in the water samples from the two sampling Sites revealed varying degrees of concentration of these
metals. Cadmium recorded values between 0.05 and 0.096 mgl −1 with a mean value of 0.007 ± 0.05 mg l−1 for Site A; Site B
recorded values between 0.07 and 0.10 mg l−1 with a mean value of 0.09 ± 0.01 mg l−1. Dry and rainy season values were
0.08 ± 0.02 mg l−1 and 0.08 ± 0.01 mg l−1 respectively. The concentration of Chromium ranged between 0.38 and 0.80 mg l−1
with a mean value of 0.58 ± 0.05 mg l−1 at Site A. For Site B, it ranged between 0.42 and 0.93 mg l−1 with a mean value of
0.62 ± 0.07 mg l−1. Mean concentration of Chromium during dry and rainy seasons were 0.65 ± 0.29 mg l−1 and
0.50 ± 0.10 mg l−1 respectively. The concentration of Lead ranged between 0.11 and 0.25 mg l−1 with a mean value of
0.19 ± 0.01 mg l−1 for Site A. Concentration of lead at Site B ranged from 0.15 to 0.30 mg l−1 with a mean value of
0.54 ± 0.21 mg l−1. The concentration of Chromium during the Dry season was 0.22 ± 0.05 mg l−1 while rainy was
0.05 ± 0.12 mg l−1. The concentration of Zinc ranged between 2.00 and 4.20 mg l−1 with a mean value of 2.79 ± 0.17 mg l−1 for
Site A. Concentration of Zinc at Site B was between 2.65 and 3.82 mg l−1 with a mean value of 3.02 ± 0.11 mg l−1.
2.82 ± 0.27 mg l−1 and 2.99 ± 0.66 mg l−1 concentration of zinc was recorded for dry and rainy seasons respectively. The con-
centration of Iron ranged between 0.03 and 0.09 mg l−1 with a mean value of 0.06 ± 0.02 mg l−1 for Site A. 0.05–0.098 mg l−1 with
a mean value of 0.15 ± 0.08 mg l−1 for Site B. For dry and rainy seasons; 0.16 ± 0.26 mg l−1 and 0.06 ± 0.03 mg l−1 was recorded.
The concentration of Copper ranged between 0.03 and 0.95 mg l−1 with a mean value of 0.13 ± 0.07 mg l−1 for Site A.
Concentration of Copper for Site B ranged between 0.02 and 0.93 mg l−1 with a mean value of 0.14 ± 0.07 mg l−1. The con-
centration of copper during Dry season and rainy seasons was 0.22 ± 0.34 mg l−1 and 0.06 ± 0.03 mg l−1 respectively.
The concentration of Fluoride ranged from 0.16 to 0.30 mg l−1 with a mean value of 0.22 ± 0.02 mg l−1 for Site A. Concentration
of Fluoride at Site B ranged between 0.17 and 0.35 mg l−1 with the mean value 0.24 ± 0.02 mg l−1. The concentration of Fluoride
during the Dry and rainy season was 0.26 ± 0.06 mg l−1 and 0.19 ± 0.03 mg l−1 respectively. Manganese concentration ranged
between 0.30 and 0.55 mg l−1 with a mean value of 0.43 ± 0.02 mg l−1 for Site A. 0.20–0.68 mg l−1 with a mean value of
0.51 ± 0.04 mg l−1 for Site B. 0.48 ± 0.12 mg l−1 and 0.45 ± 0.10 mg l−1 was recorded as manganese concentration in the river for
dry and rainy seasons respectively. Results of the entire physical, chemical and heavy metals parameters analyzed revealed that there
were no significant differences in the two sampling Sites except for some chemical parameters and heavy metal. For the chemical
parameters, Total Suspended Solids and Biological Oxygen Demand were significantly different at P < 0.05 while the heavy metal
that was significantly different in the sampling Sites A and B was cadmium. Concentrations of all other heavy metals analyzed from

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Table 3
Concentration of heavy metals in sediment samples from study area.

Parameter Control Site A Site B P-value USEPA (1995)

−1 * *
Zinc (mg l ) 13.23 ± 0.12 71.33 ± 5.89 72.19 ± 4.00 0.646 15.00
Chromium (mg l−1) 5.3 ± 0.01 22.24 ± 2.85* 23.43 ± 2.11* 0.119 5.0
Cadmium (mg l−1) ND 7.81 ± 2.88* 8.99 ± 2.23* 0.134 0.3
Lead (mg l−1) 2.8 ± 2.01 13.01 ± 3.20* 13.00 ± 2.67* 0.119 5.0
Nickel (mg l−1) 4.00 ± 1.00 15.08 ± 1.22* 15.85 ± 1.52* 0.083 5.0
Copper (mg l−1) 3.12 ± 0.20 11.67 ± 0.83* 12.74 ± 0.78* 0.000 5.0
Manganese (mg l−1) 6.01 ± 1.00 34.83 ± 7.91* 36.99 ± 9.20* 0.536 5.0

* Significant difference (P ≤ 0.05).

the two sampling Sites were not significantly different. Moreover, all the physical parameters of the water samples from the two
sampling Sites did not show deviations from Nigeria Industrial Standard [23] for permissible levels of these parameters in drinking
water. However concentrations of some chemical parameters like Biological Oxygen Demand, Chemical Oxygen Demand, nitrite, and
sulfate showed deviations from the NIS [23], and WHO [24], permissible levels of concentration of these chemical parameters in
drinking water. Virtually all heavy metals investigated deviated from the permissible levels allowed by NIS [23], and WHO [24],
standards in drinking water except for copper, Iron, and fluorine. Analysis of physical parameters during the dry season was sig-
nificantly different (P < 0.05) from that of the rainy season except for pH and electrical conductivity (Table 2). In the same vein, all
chemical parameters investigated during the dry season was significantly different from rainy season except for BOD at P < 0.05.
Heavy metal analysis during the seasons did not differ significantly except for fluoride.

3.4. Sediment sample analysis

Sediment samples from the two Sites A and B (upstream and downstream) of River Oluwa were analyzed for some heavy metals.
The results were statistically compared between the Sites as well as the two seasons of the year. The result was also compared with
United State Environmental Protection Agency [25] safe limit of heavy metal concentrations in sediment of a water body. The heavy
metals analyzed in the sediment sample include zinc, chromium, cadmium, lead, nickel, copper and manganese as shown in Tables 3,
4. Cadmium concentration in the sediment from Site A ranged between 2.00 and 12.80 ppm with the mean value of 7.81 ± 2.88 ppm.
Site B, had values of cadmium between 6.00 and 13.00 ppm with a mean value of 8.99 ± 2.23 ppm. Dry and rainy season values for
cadmium were 10.18 ± 2.06 ppm and 6.62 ± 1.69 ppm respectively. Chromium concentration ranged between 18.40 and 24.20 ppm
with a mean value of 22.24 ± 2.85 ppm for Site A. 21.50–28.40 ppm was recorded as chromium value at Site B with a mean value of
23.43 ± 2.11 ppm. Chromium values for the dry and rainy season were 24.57 ± 2.16 and 21.10 ± 1.47 ppm respectively.
The concentration of Lead was within the range of 9.70–20.20 ppm with a mean value of 13.01 ± 3.29 for Site A, while lead
concentration ranged within 9.80–18.40 ppm with a mean value of 13.00 ± 2.67 at Site B. Dry and rainy season values for lead were
recorded to be 12.71 ± 0.95 ppm and 13.30 ± 4.11 ppm respectively. Zinc values recorded was within 62.50–85.60 ppm with a
mean value of 71.33 ± 5.89 ppm for Site A. Site B recorded value range for zinc to be between 66.20 and 79.20 ppm with a mean
value of 72.19 ± 4.00 ppm. 73.92 ± 4.75 ppm and 69.60 ± 4.25 ppm was recorded for zinc during dry and rainy seasons respec-
tively. Copper values for Site A ranged between 10.40 and 13.00 ppm with a mean value of 11.67 ± 0.83 ppm. Site B had values for
copper ranging from 11.40 to 14.40 ppm with a mean value of 12.74 ± 0.78 ppm. The dry and rainy season had values for copper as
12.74 ± 0.77 and 11.67 ± 0.84 respectively. Nickel values ranged between 12.20 and 16.20 ppm with a mean value of
15.08 ± 1.22 ppm for Site A. For Site B, value ranged between 13.10 and 17.70 ppm with a mean value of 15.85 ± 1.52 was recorded
for nickel. Dry and rainy season values for nickel were 16.39 ± 0.65 and 14.54 ± 1.35 ppm. Manganese had values between 12.30
and 39.40 ppm with a mean value of 34.83 ± 7.91 for Site A. Site B had 10.40–43.70 ppm with a mean value of 36.99 ± 9.20 ppm.
The values of manganese for the Dry and rainy season was recorded to be 39.88 ± 2.27 ppm and 31.14 ± 10.67 ppm respectively.

Table 4
Seasonal variations of the mean values of heavy metal concentrations in sediment samples from River Oluwa.

Parameter Dry Rainy P-value USEPA (1995)

−1 * *
Zinc (mg l ) 73.92 ± 4.75 69.60 ± 4.25 0.031 15.00
Chromium (mg l−1) 24.57 ± 2.16* 21.10 ± 1.47* 0.000 5.0
Cadmium (mg l−1) 10.18 ± 2.06* 6.62 ± 1.69* 0.000 0.3
Lead (mg l−1) 12.71 ± 0.95* 13.30 ± 4.11* 0.000 5.0
Nickel (mg l−1) 16.39 ± 0.65* 14.54 ± 1.35* 0.000 5.0
Copper (mg l−1) 12.74 ± 0.77* 11.67 ± 0.84* 0.000 5.0
Manganese (mg l−1) 39.88 ± 2.27* 31.14 ± 10.67* 0.016 5.0

* Significant difference (P ≤ 0.05).

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T.A. Ayandiran et al. Water Resources and Industry 19 (2018) 13–24

Table 5
Mean microbial count of microorganisms isolated from water and sediment (Ayandiran et al. [6]).

Water samples

Organism Count (× 102 Cfu/100 ml)

Bacillus species 156.20


Pseudomonas species 120.03
Streptococcus faecium 94.10
Micrococcus species 110.03
Staphylococcus aureus 94.10
Escherichia coli count 51.20
Coliform count 91.10

Sediment samples

Organism Control (× 104 Cfu g−1) Site A (× 104 Cfu g−1) Site B (× 104 Cfu g−1)

Pseudomonas species 6.39 ± 0.03 14.30 ± 1.40* 11.80 ± 1.06*


Proteus vulgaris 5.30 ± 0.02 9.93 ± 1.15* 10.10 ± 1.05*
Micrococcus species 2.55 ± 0.10 12.33 ± 1.33* 8.23 ± 1.02*
Staphylococcus aureus 5.30 ± 0.13 8.00 ± 1.01* 10.97 ± 1.22*
Bacillus species 9.19 ± 1.03 19.24 ± 2.10* 16.11 ± 2.02*
Streptococcus faecium 3.21 ± 0.01 10.51 ± 1.02* 12.01 ± 1.03*

* Significant difference.

3.5. Occurrence of bacterial isolates

As shown in Table 5, organisms belonging to 5 bacteria genera (Bacillus, Micrococcus, Pseudomonas, Staphylococcus and Strepto-
coccus) were isolated and identified from the water samples. Bacillus spp had the highest occurrence of 21.42%, followed by Mi-
crococcus spp with 14.14% and Pseudomonas with 7.14% while both S. aureus and Streptococcus faecium each had 3.57% occurrence.
Also, bacterial isolates belonging to 6 genera were isolated from the sediment. Among the sediment isolates, Micrococcus spp and
Proteus vulgaris had the highest occurrence of 10.71% followed by Bacillus spp 6.57% while Pseudomonas, S. aureus and S. faecium all
had 3.57% each.

4. Discussion

In this study, diurnal variations were observed and water temperature was found to be lower than atmospheric temperature at the
two Sites. This agrees with the works of previous authors [26–30]. This variation in temperature could be attributed to reduction in
water volume and more penetration of sunlight intensity during dry season. This is in agreement with the work of Jaji et al. [31] on
the assessment of water quality of Ogun river, Southwest Nigeria. However, temperature values obtained for the two sampling Sites
fell within the limit set by Nigeria Industrial Standard [23] and World Health Organisation [24]. Based on these guidelines, the mean
temperature of the two Sites does not appear to pose any threat to homeostatic balance of the water body in conformity with the
report of Jaji et al. [31]. Generally, the pH values for Sites A and B as observed in this study were within regulatory limits [23,24] and
are indicative of good water quality. The higher values of pH recorded for Site A (upstream) and during rainy season may be due to
pollutants which are washed into the storm and drains directly into the water body. This is in conformity with the submission of
Waziri et al. [32] on the assessment of the physicochemical characteristics of rain and runoff water in University of Maidugur-
i–Nigeria staff quarters. The authors found out that the pH of the runoff water ranged from 5.90 ± 0.18 to 6.71 ± 0.18 indicating
slight acidity while that of the rainwater ranged from 5.74 ± 0.51 to 5.97 ± 0.72 indicating some level of acidity. They finally
submitted that higher values recorded for the run-off water may be due to pollutants which are washed into the storm drains.
However, all the values fell within the WHO standard of 6.5–9.5. The pH values obtained in this study is slightly acidic for the
sampling Sites and the two seasons of the year. This also conforms with previous works [26–29,33,34]. These authors found that the
pH of surface water ranged between 6.5 and 8.5 and was within the standard regulatory limits.
There were no significant differences in the pH values obtained in the two sampling Sites and between the two seasons of the year.
This is in agreement with the work of Ewa et al. [35] on the impact of industrial activities on water quality of Omoku Creek. The
authors opined that the level of pH was high in the upstream and low at downstream. This implies that the Creek is acidic and this
affects the metal solubility and the hardness of the water. However, the variations observed for pH values in this study could be as a
result of agricultural activities near the river, runoffs, leachate seepages and temperature changes [36].
In this present study, the conductivity value obtained for the two Sites and throughout the two seasons of the year were within
standard regulatory limits [23,24,37]. Low concentration of conductivity might be responsible for the soft nature of the water.
However, in the rainy season, EC was lower than those observed in the dry season and this can be attributed to dilution of salts arising
from increased water volume in the river. This is in conformity with the submission of Phiri et al. [38,39]. Higher values of EC
observed in Site B and during dry season could be linked to the evaporation of water from the river especially Site B (downstream)

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T.A. Ayandiran et al. Water Resources and Industry 19 (2018) 13–24

than Site A (upstream) during dry season. This is in consonance with the work of Ololade and Ajayi [40], on the contamination
profiles of major rivers along the highways of Ondo State where they observed maximum values in properties like pH, EC, Cl-, SO42-,
PO43-, BOD and COD during dry season while minimum values were recorded during rainy season.
The alkalinity values obtained were still within regulatory limits (< 120 mg l−1) by WHO (2011). This result is in agreement with
the submission of Phiri et al. [38], where they recorded higher alkalinity levels in the dry season than in the rainy season sig-
nificantly. The higher level of alkalinity observed at Site B and dry season could be attributed to very low Dissolved Oxygen values
recorded in this study. It could also be as a result of domestic activities like cloth washing and bathing by villagers around the area.
These activities might have attracted aerobic micro-organisms which tend to degrade organic matter by making use of oxygen content
of the water. It could also be that in the absence of sufficient carbonic acids, the bicarbonate ion in the water dissociates to form
additional carbon dioxide and by so doing reduces the available Dissolved Oxygen [41,42]. Algae in the river exploit this carbon
dioxide for their photosynthetic needs at the cost of allowing a build-up of hydroxide ions to such an extent that the water becomes
quite alkaline [42]. Concentrations less than 100 ppm are desirable for domestic water supplies. The recommended range for
drinking water is 30–400 ppm [42]. Total hardness results obtained in this study were below regulatory standard by WHO and
Nigeria Industrial Standards (Table 1). Samples from sampling Site B also recorded higher values than that of Site A upstream but the
values were not significantly different. However, there was significant difference in the seasonal variation. Values obtained were
higher during the dry season than the rainy season. This result is in conformity with the submission of Ololade and Ajayi [40] who
obtained total hardness values lower than regulatory limits in their work on the contamination profile of major rivers along the
highways in Ondo State, Nigeria. However, generally accepted classification for hardness of water is 75–150 mg l−1 of CaCO3 for soft
water and 150 mg l−1 and above for hard water [43]. Oluwa River could, therefore, be said to be soft.
Total Solids (Dissolved and Suspended) in water vary considerably in different geological regions owing to differences in the
solubility of minerals [34]. The result of Total Dissolved solids obtained in this study for the two sampling Sites A and B respectively
was within regulatory standard set by NIS [23], and WHO [24]. These values were not significantly different. However, higher values
of Total Dissolved Solids were obtained in the dry season remarkably than in the rainy season, and the seasonal variation of the TDS
was significantly different. The result obtained in this study for Total dissolved solids disagrees with the submission of Ololade and
Ajayi [40] who recorded Total Dissolved Solids for river Oluwa to be between 325 and 1410 mg l−1 in their work on the con-
tamination profile of major rivers along the highway in Ondo State, Nigeria. The high value of TDS obtained during the dry season
could be attributed to higher concentration of transported loads of organic matter since evaporation of the water body set in during
dry season. However, lower TDS value obtained during the rainy season could be as a result of several physicochemical reactions such
as sedimentation, coagulation, fixation among other factors like oxidation and precipitation [44]. The amount of solids present in a
water body can be used to estimate the pollution load as a result of both organic and inorganic contaminants present.
The BOD results obtained in this study were found to be higher than the regulatory limit of (6.0 mgO2l−1) set by NIS [23], and
WHO [24]. However, high BOD recorded in this study suggested that Oluwa River is grossly polluted organically. According to
Oluyemi et al. [45], BOD values higher than 6.0 mg l−1 implied that the water is highly polluted by organic matter and may not
support aquatic life well enough. Also, Chapman [46], opined that a water body is polluted if the average value of BOD recorded for
such water body exceeds the recommended maximum allowable concentration (RMC 3.0–6.0 mgO2l−1) of European Union for good
quality water.
Moreover, the result obtained in this study revealed that Dissolved Oxygen values for the two Sites were below the recommended
6.0 mgO2l−1 of WHO [24]. Omole and Longe [47], submitted that the standard value of Dissolved Oxygen that can sustain aquatic
life is stipulated at 5.0 mgO2l−1, a concentration below this value adversely affect aquatic biological life, while concentration below
2 mgO2l−1 may lead to death of most fishes. However, low value of Dissolved Oxygen recorded in this study especially at Site B could
be attributed to anthropogenic and domestic activities of villagers on the water body and the breakdown of organic matter by aerobic
microbes which in turn makes use of the oxygen required for this process from the surrounding water and by so doing reduce
drastically the total oxygen content of the water body.
The Dissolved Oxygen values of Site B, obtained in this study conforms with those reported for many other polluted Nigerian
waters including (4.00–7.50) mgO2l−1 for Luubara creek in Niger Delta [48]; 1.20–9.40 mgO2l−1 documented by Victor and Ono-
mivbori [49], for some polluted water bodies in Nigeria. According to United State Department of Agriculture [50], the level of
Oxygen depletion depends primarily on the amount of waste added, the size, velocity and turbulence of the stream and the tem-
perature of the water. Frequent deaths of fish in water have been established not to often come from toxicity matters but from deficit
of consumed oxygen from biological decomposition of pollutants [42].
The COD results recorded in this study for the two Sites A and B and for the two seasons of the year were higher than the
regulatory (4.0 mg l−1) limit set by NIS [23], and WHO [24]. There were no significant differences between the sampling Sites
(P > 0.05), but there were significant differences in the seasonal variation of the (COD) values (P < 0.05). However low DO, high
BOD and High COD result obtained for the sampling Sites and during the two season of the year revealed that Oluwa River is grossly
polluted. The result obtained for DO, BOD and COD in this study conformed to the submission of Etim and Adie [34], in their work on
the assessment of qualities of surface water, sediment and aquatic fish from selected major rivers in South-Western Nigeria. They
reported dissolved oxygen from the following rivers Asejire, Ori, Ona, Ogun, Ogunpa, Eleyele, Majidun and Lagos to be 2.24, 2.89,
1.04, 5.54, 6.68, 1.73, 2.02 and 5.50 mg l−1 respectively. The values recorded for chloride, nitrate, sulfate and phosphorus in-
vestigated in this study from the two Sites did not differ significantly (P > 0.05). The values obtained from Site B for all the in-
vestigated nutrients were higher than those recorded for Site A. This could also be as a result of human anthropogenic and domestic
activities and reduction in water volume especially during dry season since Site B is shallower than Site A.
Seasonal variation in the values of chloride, nitrate, sulfate and phosphorus investigated differs significantly. The values recorded

20
T.A. Ayandiran et al. Water Resources and Industry 19 (2018) 13–24

were higher in the dry season than what was obtained in the rainy season except for nitrate which recorded a low value during dry
season. This is in accordance with the submission of Phiri et al. [38], who recorded higher values of nitrate during the rainy season
than in the dry season in the rivers in urban areas of Malawi. This observation could be as a result of usage of fertilizer on the farming
areas at the banks of the river.
However, chloride, nitrate and sulfate values recorded in this study were found to be below the recommended regulatory limit in
water (250 mg l−1, 50 mg l−1 and 250 mg l−1 respectively) set by WHO [24], and Nigerian Industrial Standards, while Phosphate
values recorded were higher than the regulatory limits of 0.05 mg l−1 set by NIS [23], and WHO [24]. Nitrate is an essential plant
nutrient and its level in natural waterways are typically low (less than 1 mg l−1) [51]. An excessive amount of nitrate can cause water
quality problems, accelerate eutrophication, as well as contribute to the illness known as methemoglobinemia [52]. Although, the
low values recorded for chloride, nitrate and sulfate fell below regulatory limits set by WHO [24]. A serious health hazard can occur
in case of bioaccumulation of highly toxic nitrate in the intestinal tracts of infants [40], especially those who drink from the river
water. Human Infants below the age of six months who drink water containing excess of Maximum Contaminant Level (MCL) of
10 mg l−1 could become seriously ill and if untreated, may die [25].
In addition to the levels of Nitrate (NO3-) and phosphate (PO43-) obtained in this study are exceedingly too high even for irrigation
purpose, if the guideline values of < 0.5 mg l−1 for NO3- and < 0.05 mg l−1 for PO43- respectively is to comply with FEPA [53]. The
Oluwa River water is not equally suitable for livestock watering and recreational activities, if the guideline values of < 0.5 mg l−1 for
NO3- and 0.05 mg l−1 for phosphate is to be complied with. Moreover, the phosphate levels recorded in this study are generally high
which could explain the observed proliferation of blue-green algae on the banks and surface of the water. Persistence of high
concentrations of phosphate in surface water body can reduce its recreational use and also endanger aquatic life [45]. The low
content of chloride in this study may arise as a result of various soluble salts and animal manure, which might have entered the river
via run-offs from nearby farms. This manure is also a potential source of sulfate [54]. The implication of this in drinking water will
lead to heart and kidney diseases and cause impair health [54].
Contamination of aquatic ecosystems by heavy metals has long been recognized as a serious pollution problem. Metals, released
into surface water, tend to accumulate in sediments through adsorption and precipitation processes. From the water, the fish absorb
the metal by means of gills or epithelial tissue and bioaccumulate it in the body [55–59]. Heavy metals (Cd, Cr, Pb, Zn, Fe, Cu, F and
Mn) concentrations in water samples analyzed were high in the two Sites except for fluorine, iron and copper when compared with
NIS [23]) and WHO [24], standard regulatory limits. However, the values obtained showed that the concentrations of all the metals
investigated were higher at Site B than that of A (B > A). The reason for this could be as a result of anthropogenic activities of
villagers and domestic activities as well as farming activities around Site B. This observation is in consonance with earlier submissions
[30,34,40,42,54] who observed higher levels of heavy metals in polluted rivers in Southwest region of Nigeria.
Seasonal variation in the levels of heavy metals in Oluwa River revealed that the concentration of metals investigated were higher
during the dry season except for lead and zinc, while lower concentration were observed during the rainy season. This trend could be
attributed to the evaporation of water from river during dry season and subsequent dilution due to precipitation and run-offs from
surrounding farmland during the rainy season. Similar observations have been reported by Patil et al. [60,61]. Generally, higher
levels of cadmium, chromium, lead, zinc iron, copper, fluorine and manganese observed in Site B follows the trend (Zn > Cr >
Pb > F > Fe > Mn > Cu > Cd). The observed trend is similar to the work of Etim and Adie [34], on assessment of qualities of surface
water, sediments and aquatic fish from selected major rivers in Oyo, Ogun and Lagos States, South-Western Nigeria in the order
Pb > Cu > Co > Ni > Cr > Cd. The observed trend is also similar to the submission of Kuforiji and Ayandiran [30], who observed
higher concentration of heavy metals in River Owo in the following trend (Fe > Cu > Cr > Pb > Cd). Moreover, zinc was observed to
have highest concentration while cadmium recorded the lowest concentration in the two Sites in Oluwa River. Comparatively with
regards to the effect of season on heavy metals concentrations in Oluwa River, zinc had the highest concentration during the dry
season and cadmium had the least concentration. This could be as a result of presence of zinc in large amount in natural water and as
a result of presence of domestic sewage, deterioration of galvanized iron, leaching of brass [42,54,62]. Oluwa River observed in this
study could also be as a result of presence of bitumen in Oluwa River. Adebiyi and Omole [63], subjected Nigerian Bitumen com-
ponent (Asphaltene, Oil and Resin) to trace metal analysis and they observed that the component contain high concentrations of zinc,
nickel, vanadium and iron. Zinc is one of the earliest known trace metals and a common environmental pollutant which is widely
distributed in the aquatic environment [42]. Studies have shown that it could be toxic to some aquatic organism such as fish [57–59].
It has been found to have low toxicity effect in man. However, prolonged consumption of large doses can result in health implications
such as fatigue, dizziness, neutropenia [64]. The result obtained for zinc as the highest metal concentration in this study is in
agreement with the work of Uzoekwe and Oghosanine [28]. Although cadmium was recorded to be the heavy metal with the lowest
concentration in Oluwa River, its concentration in large amount constitutes a serious health hazard. Sources of cadmium in water
include weathering of minerals and soils, run-offs from industries containing Cd-laden materials [42]. This statement justified the
reason why cadmium was observed in this study to be the heavy metal with the lowest concentration both in water and sediment
since there are no industries at Agbabu village or near Oluwa River. The possible accumulation of cadmium in man is mainly in the
kidney and liver. Its high concentration lead to chronic kidney dysfunction, inducing cell injury and death by interfering with calcium
(Ca) regulation in biological system in man, fish and other aquatic organism [7]. The result obtained for cadmium as a lowest
concentration of heavy metals conforms to previous submissions [28,30,34,40] that reported low concentration of cadmium in
different rivers of Nigeria. Chromium concentration in Oluwa River was also higher than 0.05 mg l−1 recommended by WHO [24],
and NIS [23]. High concentration of chromium next to zinc observed in this study might be as a result of the metal being one of the
constituents of bitumen which is a major pollutant of the river in an elemental characterization of Nigerian Bitumen by total re-
flection X-ray fluorescent which showed Fe, Cr and Mn to be part of its component [65]. Concentration of lead recorded in this study

21
T.A. Ayandiran et al. Water Resources and Industry 19 (2018) 13–24

was also higher than the regulatory standard of 0.01 mg l−1 set by WHO [24], and NIS [23]. Lead is ubiquitous in our environment
with diverse pollution sources. It could also be as a result of lead being one of the constituent of bitumen which is a pollutant in
Oluwa River. Most natural bitumen contain sulphur and several heavy metals such as Nickel, Vanadium, Lead, Chromium, Mercury,
Arsenic, Selenium and other toxic element [6]. The United States Environmental Protection Agency has classified lead as being
potentially hazardous and toxic to most forms of life [25].
Lead toxicity studies conducted on female animals revealed mostly miscarriages, premature delivery and potent mortality [66]. A
concentration of lead 0.1 mg l−1 is detrimental to fetus and children with possible development of neurological problem [67]. Pb
usually accumulates in the skeleton where it causes health defects which include sub-encephalopathic, neurological, and behavioral
effects [62]. Pb when present in the food chain can result in bioaccumulation, thereby becoming harmful to man's health [56].
Furthermore, concentration of iron recorded in this study was lower than the standard limit of (0.3 mg l−1) set by NIS [23], and WHO
[24]. Iron concentration was higher at Site B, than Site A. The differences in the level of Fe in the water across the two Sites were not
significant. The geochemical and biochemical processes in the aquifers within the area according to Tay et al. [68] may be re-
sponsible for the differences. Sources of iron in the river could also be as a result of it being one of the components of bitumen.
Adebiyi et al. [65] carried out an elemental characterization of the Nigerian bitumen by total reflection x-ray fluorescence which
shows Fe, Cr and Mn to be part of its component. Sources of iron in water may also be from dissolved rock and soil and anthropogenic
sources of iron such as leached corrosive iron materials in rural and urban settlement [31,62]. However, iron is an important metal in
both plants and animals especially in the cellular processes [7]. Insoluble Fe3+ is reduced to soluble Fe2+ in water by bacterial
reduction. Iron is found in natural fresh and groundwater but has no health-based guideline, although high concentrations give rise to
consumer complaint due to its ability to discolor aerobic waters at concentrations above 0.3 mg l−1 [24]. The concentration recorded
for copper at the two sampling Sites and the seasons of the year was lower than the regulatory standard of 2.0 and 1.0 mg l−1 set by
NIS [23], and WHO [24], respectively. Copper is both an essential nutrient and a drinking water contaminant [24]. Copper con-
centration often increases in systems with high carbonate waters with an alkaline pH as observed in this study. NIS [23], and WHO
[24] however submitted that high concentration of these metals in humans can lead to adverse gastro-intestinal response. The
concentration of fluoride recorded in this study at the two Sites A and B and the two seasons of the year was also lower than the
regulatory limit of (− 1.5 mg l−1) and (1.5 mg l−1) set by NIS [23], and WHO [24], respectively. Fluoride was recorded in the study
to be below the regulatory limit, it could pose a health risk if it bio-concentrate in fish tissues and in turn bio-accumulate over time in
man who is at the top of the food chain. Epidemiological evidence has revealed that content ration of fluoride above 1.5 mg l−1 carry
an increased risk of dental fluorosis, and progressively higher concentration leads to increased risk of skeletal fluorosis
Results obtained in this study for manganese concentration in the two Sites, and during the two season of the year were higher
than the regulatory limits of 0.4 mg l−1 and 0.2 mg l−1 set by NIS [23], and WHO [24], respectively. The result obtained for
manganese in this study is in agreement with the submission of Lawson [42], where he obtained mean manganese level above the
recommended or acceptable level for unpolluted water. High concentration of this metal especially during the dry season and at Site
B could be as a result of the anthropogenic activities at Site B and dilution due to rainfall during the rainy season. Another reason
could be the presence of the metal as one of the constituents of bitumen which is a major pollutant in the water body as well. Adebiyi
et al. [65] in an elemental characterization of the Nigerian bitumen by total reflection x-ray fluorescence showed Fe, Cr and Mn to be
part of bitumen. Manganese is known to naturally occur in many surface water and groundwater sources, particularly in anaerobic or
low oxidation conditions [24]. It functions as co-factor in the synthesis of urea from ammonia, amino acid and fatty acid metabolism
and glucose oxidation. Values of manganese above the recommended guideline of 0.4 mg l−1 [24] in water will elicit health impact.
The symptoms in man include problem with central nervous system, euphoria, insomnia, serious headache and palsy of feet.
Comparison of heavy metal content in sediment in different aquatic ecosystem may be a convenient way of assessing the pollution
status of an environment. Sediment as an indicator of pollution remains an important component of the aquatic ecosystem because it acts
as reservoir for heavy metals [69]. Moreover, the concentrations of all the heavy metals (Zn, Cr, Cd, Pb, Ni, Cu and Mn) investigated in the
sediment of Oluwa River were higher than those of heavy metals in sediment of flowing streams and rivers and static lakes and ponds set
by USEPA [25]. All the metals investigated in the sediment samples from the two Sites A and B revealed that the concentrations of all the
metals except Lead (Pb) were higher at Site B than those of Site A. there were no significantly differences in the concentrations of the
metals between the Sites (P > 0.05) except for copper which differs significantly (P < 0.05). variations in the concentration of the heavy
metal in Sediment investigated revealed that higher concentrations of the metals investigated were observed in the dry season while lower
concentrations were observed during the rainy season except for lead which showed higher concentration during the rainy season. The
statistical analysis carried out revealed that there were significant differences in the concentration of heavy metals investigated in the
sediment during the two seasons of the year (P < 0.05). This implies that the metals are not firmly bounded within the crystal structure of
the minerals comprising the sediment and were largely affected by dilution due to rain [70].
This observation could probably be due to dilution by rainwater which influences concentration and heavy metal mobility. This
observation is in agreement with the submission of Fagbote and Olanipekun [70], on the evaluation of the status of heavy metal
pollution of sediment of Agbabu bitumen deposit area, Nigeria. They observed that the mean concentration of Cu, Mn, Cr, Zn, Pb, Cd,
Ni and V were higher in the dry season than in the rainy season. The increased level of metals at Site B and during the dry season is of
environmental significance. This is because, it indicates the continual input or increase in anthropogenic metal burden into the
environment, majority of which may persist and thus becomes toxic not only to aquatic lives but also to humans who are at the top of
the food chain.
Zinc was found in this study to have the highest concentration in the sediment of Oluwa River while cadmium was recorded to
have the least. The concentration of the heavy metals followed the trend Zn > Mn > Cr > Ni > Pb > Cu > Cd. The high mean
concentration of these metals especially zinc, manganese, Nickel and chromium in sediment samples of Oluwa River, may be due to

22
T.A. Ayandiran et al. Water Resources and Industry 19 (2018) 13–24

bitumen deposit in Agbabu village and Oluwa River which flows through the village. This is in agreement with the submission of
Adebiyi et al. [65] who in an elemental characterization of the Nigerian bitumen by total reflection x-ray fluorescence showed Fe, Cr
and manganese to be some of the constituents of bitumen. Adebiyi and Omole [63], also submitted that Nigerian bitumen compo-
nents (asphaltene, oil and resins) when subjected to trace metal analysis were found to contain high concentrations of zinc, nickel,
vanadium and iron. The result obtained for heavy metal in the sediments of Oluwa River in this study is also in agreement with the
submission of Ololade and Ajayi [40], where they reported that contamination of heavy metal in the sediment of major rivers along
the highways in Ondo State follows the order Zn > Pb > Cu > Cd which is similar to what was obtained in Oluwa river sediment.
The result recorded for lead at Sites A and B showed no significant difference, it could be that the metal probably originated from
many sources. These sources include contamination by bitumen, run-offs due to rainwater and anthropogenic activity such as
Agriculture which is noticed upstream (Site A). High concentration of lead observed in the sediment during the rainy season (Table 4)
which was significantly different to what was observed in the dry season implies that the metal is firmly bounded within the crystal
structure of the minerals comprising the sediment and are not largely affected by dilution due to rain [70].

5. Conclusion

From the studies, surface water and sediment of Oluwa River was found to be grossly polluted with organics and heavy metals as
evident in high COD and BOD and low DO observed in this study. The high increase in heavy metal concentration above the
regulatory limits of WHO, NIS and USEPA, in the surface water as well as the sediment of Oluwa River has really implicated the water
body as being polluted. Higher concentrations of the metals investigated especially downstream (Site B) revealed that villagers
depend on the river water for domestic use which includes bathing, washing and drinking or for agricultural uses like fishing and
farming. Probably the presence of bitumen in the water body also influenced high concentrations of these metals most especially zinc.
Villagers making use of the water body may indeed be exposed to some health risks. With all these revelations, Oluwa River is said to
be highly polluted especially with heavy metals and it is not recommended as a drinking water for human consumption.

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