European Journal of Scientific Research

ISSN 1450-216X Vol.74 No.2 (2012), pp. 186-204 EuroJournals Publishing, Inc. 2012 http://www.europeanjournalofscientificresearch.com

Spatial and Temporal Variations in Water and Sediment Quality of Ona River, Ibadan, Southwest Nigeria

Aina Olubukola Adeogun Corresponding Author, Hydrobiology and Fisheries Research Unit Department of Zoology, University of Ibadan, Ibadan, Nigeria Email: ainaadeogun@yahoo.com; aina.adeogun@.ui.edu.ng Tel: +2348055261105 Taofeek Ademola Babatunde Biology Department, Umaru Musa YarAdua University Katsina, Nigeria E-mail: babatundetaofeek@umyu.edu.ng Tel: +2348037851688 Azubuike Victor Chukwuka Ecology and Environmental Biology Unit, Department of Zoology University of Ibadan, Ibadan Nigeria Email: zubbydoo@gmail.com Tel: +2347030306066
Abstract The worldwide deterioration of surface water quality has become a growing threat to human society and natural ecosystems hence the need to better understand the spatial and temporal variabilities of pollutants within aquatic systems. This study was aimed at evaluating water and sediment parameters of Ona river to identify major pollutant sources using multivariate statistics. Accumulation Factor (AF) indicated that BOD and COD significantly built up with an accumulation factor of 7.70 and 4.83 respectively. Heavy metals Cu, Pb, Mn, Cd and Cr accumulated significantly in the sediment and water. The river recovered significantly from a number of physicochemical parameters: EC (58%), TDS (64%), TS (61%), Chloride (65%), COD (79%) and BOD had the highest recovery value of 87%. All the heavy metals measured showed a high level of recovery in both water and sediment except for Zn (41% in both water and sediment) and Fe (38%) in the sediment. Factor analysis (FA) showed that sediment factor accounted for 39.95% of the total variance in water quality, while the second factor, labelled as seasonal factor accounted for a complementary 21.94%. Discriminant analysis (DA) highlighted sediment factors as the major determinant of water quality, with seasonal factors playing an augmenting role.

Keywords: Physicochemical parameters, sediment quality, water quality, Ona river, accumulation factor, river recovery capacity,

Spatial and Temporal Variations in Water and Sediment Quality of Ona River, Ibadan, Southwest Nigeria

187

1. Introduction The widespread deterioration in water quality of inland aquatic systems have been reported in the last decade (Olajire et al., 2000; Heberer, 2002; Mara, 2003; Vi et al., 2009; Murray et al., 2010) and freshwater systems which constitute a large number of inland water ways (Sigee, 2005) play a major role in the assimilation and transportation of contaminants from a number of sources (Vutukuru, 2003; UN WWAP, 2003; Shell, 2004; Vi et al., 2009, Adeogun et al.,2011). It is in view of the limited supply of freshwater worldwide (Chinhanga, 2010) and the role of anthropogenic activities in the decline of water quality that the protection of the integrity of water resources have been given topmost priority in the 21st century (USEPA, 2007; Wei et al., 2008). This however cannot be achieved without a spatio-temporal evaluation of water and sediment quality of the aquatic systems of concern (Don Pedro et al., 2004). Environmental data acquired by investigating the dynamics of water quality may present complex patterns and variability which are dependent on a number of unpredictable factors. These factors may be geogenic or lithological, hydrological, meteorological and anthropogenic (Bricker and Jones, 1995; Shrestha and Kazama, 2007; Bu et al., 2010). The non-linear nature of environmental data makes spatial and temporal variations of water quality often difficult to interpret therefore creating a critical need to provide a representative and reliable estimation of the quality of surface waters (Dixon and Chiswell, 1996). Sequel to this challenge, the application of different multivariate statistical techniques such as Discriminant Analysis (DA), Principal Component Analysis (PCA) and Factor Analysis (FA) for the interpretation of complex data matrices and better understanding of the water quality variation have been developed (Vega et al., 1998; Lee et al., 2001; Wunderlin et al., 2001; Reghunath et al., 2002). This study was aimed at examining the impact of all sources of pollution on water and sediment quality of Ona River, and to identify the parameters responsible for spatial and temporal variability in water and sediment quality.

2. Materials and Methods 2.1. Study Area Ona river (7o 19-7o 42N; 3o 48- 3o 55E) is part of a dense network of inland watercourses that flows through Ibadan city southwards into the Lagos lagoon and industrial facilities located adjacent to this river include a food industry, beverage industry, agricultural production and processing industry. Effluents from these industries are connected by a network of canals that empty into this river. Six sampling points were chosen along the river course for this study. The coordinates of the sampling points were taken using GPS (Garmin GPS 12 x L). The first sampling point located upstream (UPS) had no industrial or domestic inputs impacting the water, thus suitable as a reference/ control point. The second sampling point was located at a site receiving domestic discharge (DDP). Two sampling points were also taken along Oluyole industrial estate where effluents from these industries are being discharged into the river respectively (EDP 1 and 2), while the last two sampling points were located downstream after the point of discharge (DSR, 1 and 2). The first two points were 3000m and 1500m respectively from the effluent discharge point. Effluent discharge points (EDP 1 and 2) were 600m apart within the effluent discharge area, while points downstream (DSR, 1 and 2) were 1500m and 3000m respectively away from the effluent discharge points.

188

Aina Olubukola Adeogun, Taofeek Ademola Babatunde and Azubuike Victor Chukwuka
Figure 1: Map of Ona River showing sampling points.

2.2. Collection of Samples Bi- monthly samples of water and sediment were collected between February and July 2010. Water samples for physicochemical and heavy metal analysis were collected in clean plastic bottles, prewashed, rinsed with deionised water and dried. At each sampling point, surface water was collected at the middle of the river. Samples were kept in the refrigerator prior to analysis. River sediment samples were collected with a Van Veen grab and stored in clean polythene bags to avoid contamination. Sediment samples were later air-dried in the laboratory, disaggregated and sieved to obtain clay fractions. The use of fine portions (clay fractions) was as a result of their role as metal accumulators, due to their net negative charge and participation in sorption and cation exchange processes (Ademoroti, 1996b). 2.3. Measurement of Physicochemical Parameters A total of 12 physicochemical parameters were measured namely Temperature, pH, Total Dissolved Solids (TDS), Electrical Conductivity (EC), Total Solids (TS), Total Suspended Solids (TSS), Chloride ion, Chemical Oxygen Demand (COD), Phosphate, Biochemical Oxygen Demand (BOD),Dissolved Oxygen (DO) and Nitrate. Physicochemical analysis of water samples was carried out using standard methods of water analysis (USEPA, 1979, Trivedi and Goyal, 1986, APHA-AWWA-WPCF, 1995). Parameters such as pH, Temperature, EC, DO and TDS were determined at the time of sampling in the field with a digital CS-C933T Multimeter (TOPAC INSTRUMENTS INC). COD was determined by the titrimetric method and BOD was determined using the incubation method oC for five days (APHA-AWWA-WPCF, 1995). Total Solids (TS) was determined using gravimetric at 20 procedures by evaporating a known volume of water to dryness in a pre-weighed crucible on a steam bath at 105oC. Phosphate w a s determined colorimetrically by the ascorbic acid- molybdenum blue method (Eaton and Franson, 2005). Chloride (Cl-) was analyzed by titrating a known volume of water sample with standardized 0.014N mercuric (II) nitrate solution. Nitrate was determined by the phenol disulphunic acid method (Marczenko, 1986).

Spatial and Temporal Variations in Water and Sediment Quality of Ona River, Ibadan, Southwest Nigeria
2.4. Analysis for Heavy Metals

189

Water samples for heavy metal analyses were filtered and digested with 10ml of concentrated analytical grade nitric acid to 250ml of water sample. The solutions were evaporated in a crucible to approximately 5ml, then filtered into 20ml standard flask and made up to the mark with distilled water (Ademoroti, 1996b). The water extract was analyzed for metals (Fe, Pb, Zn, Cd, Cu, Mn, and Cd). Heavy metals in sediment were extracted with concentrated nitric acid at the ratio of 2g of sediment sample to 5ml of acid. The mixture was gently heated in a water bath temperature of (105o C) until the sediment became bleached. The mixture was diluted to 20ml with distilled water decanted and filtered for analysis. Analysis of heavy metal content of water samples, sediment samples and effluent samples were carried out with a Perkin Elmer (Analyst 200 version 6.0) Atomic Absorption Spectrometry (AAS). 2.5. Statisitcal Analysis Data for physicochemical parameters and heavy metal concentrations of water and sediment samples were presented as mean values and analyzed using descriptive analysis. Prism Graph pad software version 5.0 was used for this analysis. The degree of contamination as a result of anthropogenic inputs was estimated by the Accumulation Factor (AF). AF is the ratio of the average level of a given parameter downstream (after a source discharge) to the corresponding average level upstream (before the source discharge) (Fakayode, 2005). Accumulation factor (AF) was calculated by dividing the average parameters downstream with upstream values (Fakayode, 2005). The degree of River Recovery Capacity (RRC) for Ona river was calculated using the formula adapted from Ernestova and Seminova (1994) as modified by Fakayode (2005) given as: RRC= (S0-S1)/S0 100 (Expressed in %) where: S0 is the level of a parameter downstream (i.e. immediately after the discharge point), S1 is the corresponding average level upstream where the water is relatively unpolluted. Multivariate analysis of variance (MANOVA) was used where several dependent variables were measured for each sampling unit instead of one variable. The objective of MANOVA was to investigate whether the mean vectors of water quality parameters across sampling points were the same or if the variables differed significantly across sampling points (Rencher, 2002; Johnson and Wichern, 2002). Data were further subjected to Factor Analysis (FA). Factor analysis is designed to transform the original variables into new uncorrelated variables called factors, which are linear combinations of the original variables. The FA is a data reduction technique and suggests how many varieties are important to explain the observed variances in the data. Principal components analysis (PCA) was used for extraction of the different factors. The axis defined by PCA is rotated to reduce the contribution of the less significant variables (Johnson and Wichern, 2002) Step-wise Discriminant Analysis (DA) which is also a multivariate statistical technique was used for spatio-temporal analysis of water quality data. Linear discriminant functions were used to describe or elucidate the differences between the sampling sites and the influence of season on water and sediment quality of each sampling site. The relative contribution of all variables to the separation of groups was highlighted (Rencher, 2002). Multivariate analysis was carried out with the computer program SPSS 18.0 for windows (SPSS Inc. USA).

190

Aina Olubukola Adeogun, Taofeek Ademola Babatunde and Azubuike Victor Chukwuka

3. Results 3.1. Physicochemical Analysis The man values of physicochemical parameters across sampling points are presented in Fig 2. Temperature, pH and DO demonstrated a seasonal cycle during the study period. High temperature values were o o recorded (29-30 C) between February and April (transition of dry to rainy season) and low values (26-28 C) were recorded between May and July (rainy season). Water pH ranged from 6.0-8.0 with the lowest value slightly below NESREA (2011) acceptable limits for surface waters. The pH values at the point of discharge showed an increasing tendency towards acidity from dry season into the rainy season while upstream and downstream values tended towards neutral pH during the rainy season. DO values were generally higher upstream and downstream, and lowest at the points of effluent discharge. There was however a progressive increase in DO values at all sampling points with transition into the rainy season. The highest values of TDS, EC, TS and TSS were recorded at the effluent discharge points in both dry and wet seasons (Fig 2). TS and TSS showed the highest values at the transitional period (March and April) between the dry season and wet season. There were considerably lower levels of chloride ions upstream compared to the points of effluent discharge points and downstream sites respectively (Fig 2) and lower values were recorded in the rainy season. COD and BOD values were markedly increased at the points of effluent discharge throughout the sampling period thus showing the contribution of effluent discharge to the increased values (Fig 2). Phosphate concentrations were significantly elevated at the effluent discharge points but did not show any significant difference in trend across seasons (Fig 2). Nitrate levels increased in water samples during the rainy season. Figure 2(a-l): Spatio-temporal variations of selected physicochemical parameters of Ona river.

Spatial and Temporal Variations in Water and Sediment Quality of Ona River, Ibadan, Southwest Nigeria

191

Figure 2(a-l): Spatio-temporal variations of selected physicochemical parameters of Ona river. - continued

192

Aina Olubukola Adeogun, Taofeek Ademola Babatunde and Azubuike Victor Chukwuka

3.2. Heavy Metals of Water Samples The heavy metal profile of water samples are presented in Fig. 3. Elevated levels of Cu were recorded at effluent discharge points but there was a marked increase in the rainy season compared to the dry season at all sampling points (Fig 3). Zn although elevated at the points of effluent discharge showed wider differences in values in the rainy season between the upstream value and point of domestic waste discharge (Fig 3). Although Pb showed higher levels in the rainy season compared to the dry season, the highest levels of Pb was detected at the onset of the rainy season (Fig 3). Mn, Cr and Fe showed a downward trend from the dry season into the rainy season while Cd showed its highest values in the dry season and onset of the rainy season (Fig 3).
Figure 3(a-g): Spatio-temporal variations of some heavy metals in water samples of Ona river

Spatial and Temporal Variations in Water and Sediment Quality of Ona River, Ibadan, Southwest Nigeria
Figure 3(a-g): Spatio-temporal variations of some heavy metals in water samples of Ona river - continued

193

3.3. Heavy Metals in Sediment Samples

The concentration of Cu and Cr in sediments was higher in the rainy season compared to the dry season. On the other hand the concentration of Cu upstream showed a decreasing trend with progression into the rainy season (Fig 4), while the concentration of Zn and Fe showed a general decrease from the dry to the rainy season with the higher values in the dry season (Fig 4). Although the concentration of Pb, Mn and Cd showed a fair trend across seasons, there was a significant increase (p<0.05) in the concentration of these metals at the point of domestic discharge (DDP) in the rainy season. Figure 4 (a-g): Spatio-temporal variations of some heavy metal samples of Ona river.

194

Aina Olubukola Adeogun, Taofeek Ademola Babatunde and Azubuike Victor Chukwuka
Figure 4 (a-g): Spatio-temporal variations of some heavy metal samples of Ona river. - continued

3.4. Index of Geoaccumulation (Igeo) The quantitative estimation of aquatic sediment contamination by metal was proposed by Mller (1979) in terms of the Igeo ( Index of Geoaccumulation), that is, the enrichment on a geological substrate. Geoaccumulation index (Igeo) is used to calculate metal concentrations in sediment by comparing observed concentrations with undisturbed or crustal sediment (control) levels using the expression: Igeo = ln (Cn/1.5Bn), where Cn is the measured content of element n, Bn is the geochemical background value of the same element (metal) n and Factor 1.5 is the possible variations of background data due to lithogenic impacts. The results were interpreted according to the geoaccumulation index classification table of Muller (1979) (Table 1) and the geoaccumulation index (Igeo) analysis for Ona river sediment is given in Table 2. Muller (1981) further classified Igeo as it relates to contaminant levels into 7 classes i.e. Class 0, Igeo<0 (unpolluted); Class 1, 0, Igeo<1 (unpolluted to moderately polluted); Class 2,1, Igeo<2 (moderately polluted); Class 3,2, Igeo <3 (moderately to strongly polluted); Class 4,3, Igeo<4 (strongly polluted); Class 5,4, Igeo<5 (strongly to very strongly polluted) and Class 6, Igeo>5 (very strongly polluted- depicting a 100-fold enrichment above the background values).The results for the geoaccumulation index revealed that 44.52% of the elements belonged to Igeo Class 4 (strongly contaminated) indicating that the sediments were strongly enriched with respect to Lead and Cadmium. Chromium and Manganese belonged to Igeo Class 3 (32.19%; moderately to strongly contaminated) showing tendencies toward strong contamination. Cu and Fe belonged to Igeo Class 2 (moderately contaminated; 21.23%) while Zinc had the lowest Igeo class of 1 (1.37%) indicating that Zn was within background levels or naturally occurring levels in the sediment.
Table 1: Description of sediment quality Igeo classification (Muller, 1979) Igeo Class 6 5 4 3 2 1 0 Contamination intensity Extremely contaminated Strongly to extremely strongly contaminated Strongly contaminated Moderately to strongly contaminated Moderately contaminated Uncontaminated to moderately contaminated Uncontaminated

Sedimentation Geoaccumulation factor >5 4-5 3-4 2-3 1-2 0-1 <0

Spatial and Temporal Variations in Water and Sediment Quality of Ona River, Ibadan, Southwest Nigeria
Table 2: Geoaccumulation index (Igeo) values of surface sediments of Ona river
Igeo 1.9 0.3 3.0 2.2 2.5 3.5 1.2 Sediment quality description Moderately contaminated Uncontaminated to moderately contaminated Strongly contaminated Moderately to strongly contaminated Moderately to strongly contaminated Strongly contaminated Moderately contaminated Heavy metals Cu Zn Pb Mn Cr Cd Fe

195

The Accumulation Factor (AF) and River Recovery Capacity (RRC) of the physicochemical parameters during the sampling period are presented in Table 3. The trend in accumulation factor of the parameters revealed that the COD and BOD of water downstream was about 5 and 8 times respectively more than values observed upstream. Other parameters showed an average accumulation factor of 2. COD and BOD showed the highest percentage recoveries of 79% and 87% while phosphate and nitrate showed the lowest recoveries of 47% and 42% respectively in water downstream. In other words there was a drop in COD and BOD values by 79% and 87% respectively in waters downstream compared to values at the discharge points or points of impact, while less than 50% of phosphate and nitrate introduced at discharge point was removed by self-purification downstream. Table 3: Accumulation Factor and River Recovery Capacity for physicochemical parameters of Ona river
EC
-I -1

TS TSS Cl-1 TDS (mg/l) (mg/l) (mg/l) (mg/l) ( cm ) AF 2.39 2.66 2.59 2.80 3.00 RRC% 58 64 61 64 65 AF: Accumulation factor, RRC: River recovery capacity.

P0 -3 (mg/l ) 1.9 47

COD (mg/l) 4.83 79

BOD (mg/l) 7.50 87

DO (mg/l) 0.39 -156

Nitrate (mg/l) 1.7 42

The Accumulation Factor and River Recovery Capacity for heavy metals in water and sediment are presented in Table 4. Pb was the highest accumulated metal in water and sediment downstream and was 21 and 17 times more than the average levels upstream whereas Cu, Mn, Cr and Cd showed an accumulation of about 10 times and 6 times more than average levels upstream for water and sediment respectively. All the metals, except Zn and Fe showed a recovery of >90% and >80% downstream for water and sediment respectively. Recovery values for Zn and Fe were 41% and 65% in water and 41% and 38% respectively in sediment indicating that there was little or no change in values downstream compared to values upstream especially for Zinc. Table 4: Accumulation Factor and River Recovery Capacity for heavy metals in water and sediment samples of Ona river. Pb 21.5 95 17.9 94 Mn 10.6 90 7.7 87 Cr 15 93 6.6 85 Cd 12 91.6 5.4 81 Fe 2.8 65 1.6 38

Cu Zn 11.4 1.6 AF Water column (mg/l) RRC 91 41 % 6.7 1.7 Sediment (g/g) AF 85 41 RRC AF: Accumulation factor, RRC: River recovery capacity %

196

Aina Olubukola Adeogun, Taofeek Ademola Babatunde and Azubuike Victor Chukwuka

3.5. Multivariate Analysis All studied variables were subjected to multivariate statistical techniques to explore temporal and spatial variations in parameters. The results of the multivariate analysis of variance (MANOVA) for water and sediment parameters are presented in Table 5. It can be inferred from this data that there was a significant difference in water and sediment parameters across the six sampling sites and across seasons (p<0.05). Table 5: Multivariate analysis (MANOVA) for spatial and temporal variations in water and sediment parameters of all sites of Ona river
Test Pillais Trace Wilks Lambda Hotellings Trace Roys Largest Root Pillais Trace Wilks Lambda Hotellings Trace Roys Largest Root Value 4.53 0.000 129.363 74.258 .977 .023 43.317 43.317 F 3.209 3.666 3.383 25.705 14.994 14.994 14.994 14.994 Sig. 0.000 0.000 0.003 0.000 .000 .000 .000 .000

Effect Spatial

Temporal

Factor analysis (FA) was carried out to identify the sources of variation in the water and sediment parameters. The Eigen-values for the different extracted factors, percentage variance accounted, cumulative percentage variance and component loadings are summarized in Table 6. A total of four factors were extracted, and 78.51% of the total variation was accounted for by these four factors. Factor 1 (sediment factor), accounting for 39.94% of the total variance, was highly correlated with concentrations of metals in water and sediment (Pb, Cr, Zn, Fe, Mn, Cu, and Cd in water, and Cr, Pb, Mn, Cu and Cd in sediment). Factor 2, designated as seasonal factors, accounted for 21.95% of the total variance and reflected the change in season by the positive correlations with TSS, Season, DO, COD and BOD and negative loadings for Zn_sediment, pH, Fe_sediment and Temperature. Factor 3, denoted as the mineral factor, was highly correlated with TDS and Chloride levels and accounted for 10.94% of the total variance in water quality. Factor 4 showed high positive loadings for TS and EC and was termed the conductivity factor, accounting for 5.68% of the total variance in water quality.

Spatial and Temporal Variations in Water and Sediment Quality of Ona River, Ibadan, Southwest Nigeria
Table 6: The varimax rotated factor loadings for water and sediment parameters of Ona river
Factor Pb Cr Zn Cr_sed Fe Mn Cu Cd Pb_sed Mn_sed Cu_sed Cd_sed BOD Zn_sed pH TSS Fe_sed Season DO COD Temp Nitrate Chloride TDS Phosphate TS EC 1 .947 .931 .904 .878 .866 .863 .834 .794 .781 .727 .682 .609 2 3 4

197

.824 -.809 -.808 .772 -.769 .750 .635 .596 -.560 .968 .711 .928 .878

% Variance Explained % Cumulative Variance

39.94 39.94

21.95 61.89

10.94 72.83

5.68 78.51

Rotation Method: Varimax and Kaiser Normalization. sed - sediment Note: Groups of values circled along the same column represent clusters of parameters with high significant loadings for each factor. The clusters were created by data rotation.

Spatial variations in water and sediment parameters were evaluated through step-wise Discriminant Analysis (DA). Five discriminant functions (DFs) were found to discriminate the quality of the six sampling sites used in this study (Table 7). Wilks Lambda test showed that all five functions were statistically significant (p<0.05). Furthermore, 93.8% of the total variance between the six sampling sites was accounted for by the first two DFs. The first DF accounted for 83.0% of the total spatial variance, and the second DF accounted for 10.8%. The relative contribution of each parameter is given in Table 7. The mean concentration of Pb in water, Pb in sediment and Cr in sediment showed a strong contribution in discriminating the six sampling sites and accounted for most of the expected spatial variations in the river, while other parameters exhibited a low contribution to the discriminant function. The second group of parameters (DF2) that accounted for the remaining spatial variations was Pb in sediment and Cd in sediment (Table 7).

198
Table 7:

Aina Olubukola Adeogun, Taofeek Ademola Babatunde and Azubuike Victor Chukwuka
Discriminant function coefficients for spatial variation in water and sediment parameters of Ona river
Function 3 2.404 -1.984 .571 -1.261 -9.824 .871 3.5 97.30

Parameter Pb Cu_sed Pb_sed Cr_sed Cd_sed Fe_sed % Variance % Cumulative Variance sed - sediment

1 -1.703 .153 3.119 7.435 .162 .325 83.0 83.0

2 3.126 -2.488 -3.187 -2.153 8.154 .783 10.8 93.8

4 1.351 1.477 -.956 -4.440 2.636 .291 2.3 99.60

5 .118 .478 -4.257 2.577 .905 .477 0.4 100

From the canonical discriminant plot (Fig 5), the industrial effluent discharge points (EDP 1 and 2) showed high positive loadings for factors represented by the first discriminant function (DF1) indicating that the effluent discharge points were highly characterized by elevated levels of Pb in water and sediment, and Cr in sediment. The sites upstream from the discharge points i.e. UPS and DDP depicted negative associations with these factors indicating that these sites were characterized by minimal levels of these metal contaminants. On the other hand, the domestic discharge point (DDP) showed high positive loadings for the factors represented by the second discriminant function (DF2) indicating that the DDP was characterized by elevated levels of Cd compared to EDP 1 and 2.

Figure 5: Discriminant plot for spatial variation in water and sediment parameters of Ona river

Spatial and Temporal Variations in Water and Sediment Quality of Ona River, Ibadan, Southwest Nigeria

199

Temporal variations in water and sediment parameters were also evaluated through Discriminant Analysis (DA). Data was subjected to DA after data was sorted into two seasonal groups, i.e. dry season and wet season. DA was conducted to assess whether there was a significant difference in seasonal trends and which parameters exhibited a seasonal trend or had strong associations with change in season. DF1 accounted for 100% of the total variance between seasons. Wilks Lambda test (p< 0.05) showed that this DF and its constituent variables with the highest contributions were able to significantly discriminate water and sediment parameters influenced by seasonal changes. Table 8 presents the standardized function coefficients, which highlight that Cr in sediment, Zn in water, and DO in were parameters that exhibited the highest change across seasons. Table 8: Discriminant Function Coefficients for temporal variation in water and sediment parameters of Ona river
Function 1 -.591 1.041 1.869 -1.818 100%

Parameters Temp DO Zn Cr_sed % Variance sed sediment

Discriminant plot for temporal variations (Fig 6) showed that the dry season was strongly characterized by increased temperatures and elevated levels of Cr in sediment while DO availability and temperature had strong positive associations with the wet season. Although Zn showed negative associations with both seasons, there was an increase in Zn from dry season to the wet season. Figure 6: Discriminant plot for temporal variations (Fischers linear discriminant functions) for water and sediment parameters of Ona river

200
4. Discussion

Aina Olubukola Adeogun, Taofeek Ademola Babatunde and Azubuike Victor Chukwuka

The descriptive analysis indicated that the change in each water and sediment parameter across sampling sites and seasons, showed elevated values at points of effluent discharge (EDP 1 and 2). This pattern clearly implicates unnatural sources and reports have it that although potentially harmful substances may have either natural or human-made sources or both, the contribution of some compounds of human origin to the natural environment far overshadows natural sources (Charkabi and Sakizadeh, 2006; Shrestha and Kazama, 2007; Najafpour et al., 2008; Bu et al., 2009). The accumulation factor of the physicochemical parameters (Table 3) clearly indicated elevated values downstream compared to the reference point upstream and is a clear pointer of anthropogenic impact. The River Recovery Capacity (RRC) values for these parameters indicated that the level to which the self-purification mechanism of the river was able to refresh water in the presence of pollutants was not very high. The observed values showed that about 60% of most of the physicochemical changes due to domestic and industrial input upstream was alleviated about 3000m downstream of the discharge points. This suggests that a longer stretch of un-impacted river will be required for higher recovery values. The low recovery values observed for phosphate and nitrate suggests that these substances are being released into the river in quantities that cannot be single- handedly removed by aquatic-plants and facultative algae which constitute part of the rivers selfpurification mechanism (Fakayode, 2005; Adeogun et al, 2011). The high levels of these nutrients clearly overwhelm the river recovery capacity thus indicating poor water quality. The high recovery of BOD, COD and Cl downstream may also be a pointer to the efficiency of the rivers aeration mechanism which is another means of self-purification (Ernestova and Semenova, 1994). The ability of river sediments to store metal contaminants of human origin has been reported (Salomons and Stigliani, 1995, Netpae & Phalaraksh, 2009) even in levels that sometimes outweigh the content of metal in water and fish (Klavin et al., 2000; Demark et al., 2006). The increased values of heavy metals downstream compared to average values upstream strongly implicate anthropogenic activity and this is confirmed by the accumulation factor reported for each metal downstream compared to upstream values (Table 4). Although all the heavy metals showed a level of accumulation downstream, Zn and Fe showed the least accumulation. This suggests a high abundance of these metals within this stretch of river studied hence there was no significant change in availability downstream compared to upstream values. The geoaccumulation index (Igeo), which is an index of metal enrichment in the sediment revealed the heavy metal concentration as Cd>Pb>Cr>Mn>Cu>Fe>Zn (Table 2). Metals such as Cd, Cr and Pb have higher possibilities of interacting with organic matter in the aqueous phase and settling, thus reflecting in the high concentration of these metals in the sediment (EC, 2002). This ability of sediments to store pollutants such as metals is a clear pointer of the role of sediment quality in assessing and evaluating metal contamination in natural waters (Wardas et al., 1996). The high recovery observed for most of the heavy metals i.e. >90 for water, and >80 for sediment may be attributed to the natural heavy metal removal mechanisms of river systems one of which entails redistribution and partitioning of the metals between water and sediment (Fakayode, 2005; Naji and Ismail, 2011). The low recovery values observed for Zn and Fe downstream compared to upstream values may be a reflection of their mobility within the river system (Thornton, 1983). Results of the factor analysis (FA) indicated that Factor 1 accounted for 39.94% of the total variations in water quality. This factor was labelled sediment factor because of the nature of positive loadings within the factor (Table 6). The second factor i.e. Factor 2 which was termed seasonal factor accounted for 21.95% of the total variations in water and sediment parameters. By comparing these two factors the FA depicts that the highest variations in water and sediment quality was as a result of non-seasonal factors, more specifically human factors. In other words, the all year round discharge of effluents impacts the sediment quality, which in-turn ensures a replenishment of contaminant levels within the water column. Sediments are an integral and inseparable part of the aquatic environment and play a very important role in the physicochemical and ecological dynamics of any aquatic system. Therefore, there is a higher tendency for metal deposits to be retained in sediments than for it to be released into the water column. This replenishing effect for most metals is to a large extent not dependent on seasonal changes. This is consistent with reports that

Spatial and Temporal Variations in Water and Sediment Quality of Ona River, Ibadan, Southwest Nigeria

201

anthropogenic discharges constitute a constant polluting source for aquatic systems (Singh et al., 2004; Karbassi et al., 2007; Najafpour et al., 2008). Factor 2, designated as seasonal factors, showed positive loadings for TSS, Season, DO, COD and BOD and negative loadings for Zn_sediment, pH, Fe_sediment and Temperature. The loadings of this factor suggest that the transition in seasons affects the water temperature and pH which in turn regulate the COD and BOD content (Jain, 2002; Bu et al., 2010).This factor also depicts that the levels of Zn and Fe in sediment had a strong negative relationship with seasonal changes. In other words, in transition from dry to wet season, these metals are mobilized from sediments into the water column thus resulting in a relative decrease in sediment concentrations compared to the initial concentrations. It has been reported that seasonal variations in precipitation, surface run-off, ground water flow, interception and abstraction strongly affect river discharge and, consequently the concentrations of pollutants in river water (Vega et al., 1998; Khadka and Khanal, 2008; Mtethiwa et al., 2008). Factor 3, named the mineral factor was highly correlated with TDS and Chloride levels. This factor is an essential feature of any water-body which represents mineral content resulting from the balance between dissolution and precipitation. It accounted for 10.94% of the total variance in water and sediment parameters. Factor 4 i.e. conductivity factor showed high positive loadings for TS (0.913) and EC (0.897) accounting for 5.68% of the total variance in parameters. This suggests that there is a strong relationship between TS and EC, and the relationship is not dependent on seasonal changes. Throughout the sampling period the EC at the effluent discharge points was above 1,200 S cm-1 (Fig 2). According to UNESCO/WHO/UNEP (1996) the conductivity of most freshwaters ranges from 10 to 1,000 S cm-1 but may exceed 1,000 S cm-1, especially in polluted waters, or those receiving large quantities of land run-off. Conductivity can be measured to establish a pollution zone, e.g. around an effluent discharge, or the extent of influence of run-off waters. The presence of heavy metals and other conducting species such as nitrate, phosphate and chloride could be responsible for elevated levels of EC downstream (UNESCO/WHO/UNEP, 1996). From the spatial discriminant analysis (DA), the first discriminant function (DF) accounted for 83.0% of the total spatial variance across the sampling sites (Table 7). The spatial DA using the first DF suggests that Pb in water, Pb in sediment and Cr in sediment were the most significant parameters that discriminated between the six sampling sites. The negative correlation of Pb in water (-1.703) and Pb in sediment (3.119) with the DF also brings out the inverse relationship between sediment contaminant and contaminant in the overlying water column. In other words there is a higher tendency for Pb to be retained in sediment than released into the water column. This agrees with reports that sediments hold a very large percentage of the total quantity of a metal present in an aquatic system (Netpae & Phalaraksh, 2009). Pb content in water might be due to terrestrial run off from sewage effluent, through seepage from waste sites (Fatoki et al., 2002) or runoff from agricultural fields where phosphorus fertilizers with lead impurities have been applied (Ramachandra, 2006). The positive association of the domestic discharge point (DDP) with Cd in sediment implicates inputs of Cd from domestic waste discharge into the river. Nodeberg et al., (2005) reported sewage from industrial and municipal areas as major sources of Cd into freshwater systems. From the temporal discriminant analysis (DA), only one DF accounted for 100% of the temporal variations in water quality across sampling sites. Zinc showed increased mobilization in water in the rainy season than in the dry season. On the other hand, Cr showed higher availability in the sediment in the dry season and lower availability in the rainy season. This is a depiction of the same trend by variables from different media. The increased mobilization of Zn in water means that there will be reduced levels in sediment, while the increased values of Cr in sediment indicate that there will be reduced values in the water column; although from the discriminant plot (Fig. 6) Zn had a stronger relationship with the rainy season than Cr. Some authors (Thornton, 1983; Alloway, 1990a; Kumar et al., 2010) have reported that Zn represents a group of metals that are easily mobilized from sediment deposits in the presence of seasonal factors, whereas Cr represent a group of metals that will require more rigorous geochemical factors for mobilization (EC, 2002; Nodberg et al., 2005). The presence of Cr in sediment as a significant variable in both spatial and temporal DA is an indication that Cr availability is affected by both anthropogenic and seasonal factors, but the results from the FA implies that anthropogenic effects outweighs the seasonal effects on metal availability in Ona river.

202

Aina Olubukola Adeogun, Taofeek Ademola Babatunde and Azubuike Victor Chukwuka

5. Conclusions This study has shown that the highest sources of variation in Ona river water and sediment quality are nonseasonal factors particularly anthropogenic factors. The level of pollution increased from the domestic discharge point to the industrial effluent discharge points. All sampled parameters indicated significant spatial variability and partial temporal differences. Multivariate analysis indicated that Ona river water quality is primarily influenced by industrial waste water discharge. Anthropogenic activities involving the discharge of industrial effluents into aquatic systems directly impact the sediments which in turn replenish contaminant levels in the water column. Moreso, the addition of excessive levels of naturally occurring compounds through domestic runoffs further degrades water quality which in turn erodes the availability of good quality water for humans and ecosystems. This may result in increased financial costs for human users (water purification process), and may lead to decreased species diversity and abundance in affected communities. Remediation activities should therefore be focused on reduction of river pollution through enforcement of regulations concerning treatment of industrial wastewater, although runoff from domestic activities should also be closely monitored to reduce their probable enhancement of heavy metal pollution. Acknowledgement The authors hereby acknowledge the MacArthur Foundation Startup Research Grant for female faculty for providing funds for this research.

References [1] Ademoroti, C.M.A. 1996b. Environmental Chemistry and Toxicology. Fodulex Press Limited Ibadan. pp 121. [2] Adeogun, A. O., A. V. Chukwuka and O. R. Ibor 2011. Impact of Abbatoir and Saw mill effluents on Water Quality of Upper Ogun River (Abeokuta). American Journal of Environmental Sciences 7(6):525-530. [3] Alloway, B. J. 1990a. Soil processes and the behaviour of metals. In: Alloway, B.J. (Eds.) Heavy Metals in Soils, New York, Blackie, John Wiley and Sons, Inc., pp.7-28. [4] APHA -AWWA-WPCF. 1995. Standard methods for the examination of water and waste water. American Public Health Association, American Water Works Association and Water Environment Federation, Washington, D.C. [5] Bricker, O. P., and B. F., Jones 1995. Main factors affecting the composition of natural waters. In: Salbu, B., Steinnes, E. (Eds.), Trace Elements in Natural Waters. CRC Press, Boca Raton, FL, 1-5. [6] Bu, H., X., Tang, S., Li and Q., Zhang 2010. Temporal and spatial variations of water quality in the Jinshui River of the South Qinling Mts., [7] Chinhanga, J.R. 2010. Impact of industrial effluent from an iron and steel company on the physicochemical quality of Kwekwe River water in Zimbabwe. International Journal of Engineering, Science and Technology 2 (7): 29-40 [8] Demark, A., F. Yilmaz, A.L. Tuna and N. Ozdemir, 2006. Heavy metals in water, sediment and tissues of Leuciscus cephalus from a stream in southwestern Turkey. Chemosphere, 63: 1451 1458 [9] Dixon, W. and B., Chiswell 1996. Review of aquatic monitoring program design. Water Resources 30(9): 1935-1948. [10] Don-Pedro K.N., E. O., Oyewo and A. A. Otitoloju 2004. Trend of heavy metal concentration in Lagos Lagoon ecosystem, Nigeria. West Afri. J. of Appl. Eco. 5:103-114. [11] European Commission (EC) 2002. Heavy Metals in Waste. Final Report DG ENV. E3. 86pp. [12] Ernestova, L. S., and I. V. Semenova 1994. The Self-purification Capacity of Natural Water as an Indicator of the Ecological State of a Water Body. Water Resources 21(2): 146-150. [13] Fakayode, S.O. 2005. Impact Assessment of Industrial Effluent on Water Quality of the Receiving Alaro River in Ibadan, Nigeria. Ajeam-Ragee 10:1-13. [14] Heberer, T. 2002. Occurrence, fate, and removal of pharmaceutical residues in the aquatic environment: a review of recent research data. Toxicol Lett., 131: 517

Spatial and Temporal Variations in Water and Sediment Quality of Ona River, Ibadan, Southwest Nigeria
[15] [16] [17] [18]

203

[19]

[20] [21] [22] [23] [24]

[25] [26] [27] [28] [29] [30]

[31] [32] [33]

[34]

[35] [36] [37]

[38] [39]

Jain, C.K., 2002. A hydro-chemical study of a mountainous watershed: The Ganga, India. Water Resources 36: 12621274. Karbassi, A. R.; J., Nouri, and G. O. Ayaz 2007. Flocculation of Cu, Zn, Pb, Ni and Mn during mixing of Talar River water with Caspian Seawater. Int. J. Environ. Res.1(1): 66-73 Khadka, R. B. and A. B. Khanal 2008. Environmental Management Plan (EMP) for Melamchi water supply project, Nepal. Environ. Monitor. Assess. 146 (1-3): 225-234 Kumar, R., C. S., Joseph, M. M., Gireesh, T. R. Kumar, K. R. Renjith, M. N., Manju, and N. Chandramohanakumar 2010. Spatial Variability and Contamination of Heavy Metals in the Inter-tidal Systems of a Tropical Environment. Int. J. Environ. Res. 4(4):691-700 Lee, J. Y.; Cheon, J. Y.; Lee, K. K.; Lee, S. Y.; Lee, M. H., (2001). Statistical evaluation of geochemical parameter distribution in a ground water system contaminated with petroleum hydrocarbons. J. Environ. Qual., 30: 1548-1563. Mara, D.D (2003). Domestic wastewater treatment in developing countries. 75pp Mtethiwa, A. H.; A., Munyenyembe, W., Jere, and E., Nyali 2008. Efficiency of oxidation ponds in wastewater treatment. Int. J. Environ. Res. 2 (2):149-152 Mller, G., 1979. Schwermetalle in den sedimenten des Rheins - Vernderungenseit 1971.Umschau 79:778-783. Mller, G., 1981. Die Schwermetallbelastung der sedimente des Neckars und seiner Nebenflusse: eine Bestandsaufnahme. Chemical Zeitung. 105:157-164 Murray, K.E., S. M., Thomas and A. A. Bodour 2010. Prioritizing research for trace pollutants and emerging contaminants in the freshwater environment: Environmental Pollution. 158: 3462-3471. Najafpour, S., A. F. M., Alkarkhi, M. O. A., Kadir and G. D. Najafpour 2008. Evaluation of spatial and temporal variation in river water quality. Int. J. Environ. Res., 2(4): 349-358. Netpae, T. and C. Phalaraksh 2009. Bioaccumulation of copper and lead in Asian Clam tissues from Bung Boraphet Reservoir, Thailand. Int. J.Agric. Biol., 11: 783786 Nordberg, G. F., B. A. Fowler, M. Nordberg 2005. Handbook on Toxicology of Metals. 3rd edition. 969pp OECD SIDS 2002. Potassium Hydroxide: UNEP Publications. ID: 1310-58-3 Olajire. A. A. and F. F. Imeokparia 2001. Water Quality Assessment of Osun River. Studies on Inorganic Nutrients. Environmental Monitoring and Assessment 69: 17-28. Reghunath, R., T. R. S. Murthy and B. R. Raghavan 2002. The utility of multivariate statistical techniques in hydrogeochemical studies: An example from Karnataka, India. Water Res. 36 (10): 2437-2442 Salomons, W. and W. M. Stigliani 1995. Biogeodynamics of pollutants in soils and sediments. Springer Verlag. Shell 2004. A Journal of effluent monitoring for the Shell Petroleum Development Company of Nig. Ltd. East Vol. 23. 28pp Shrestha, S. and F. Kazama 2007. Assessment of surface water quality using multivariate statistical techniques: A case study of the Fuji river basin, Japan. Environ. Model. Software 22(4): 464-475 Singh, K. P., A. Malik, D., Mohan and S. Sinha 2004. Multivariate statistical techniques for the evaluation of spatial and temporal variations in water quality of Gomti River (India): A case study. Water Res., 38 (18): 3980-3992. Thornton, I. (1983). Applied Environmental Geochemistry. Academic Press, London. Travedi, R. R. and P. K. Goyal 1986. Chemical and Biochemical Methods for Water pollution studies. Env.Pub. UNESCO-WHO-UNEP. 1996. Water Quality Assessments - A Guide to Use of Biota, Sediments and Water in Environmental Monitoring - Second Edition. Deborah Chapman. Eds. 609pp UN WWAP. 2003. United Nations World Water Assessment Programme. The World Water Development Report 1: Water for People, Water for Life. UNESCO: Paris, France. USEPA, 2007. Recent recommended water quality criteria. United States Environmental ProtectionAgency, http:// www.epa.gov/waterscience/criteria/wqcriteria.html

204
[40]

Aina Olubukola Adeogun, Taofeek Ademola Babatunde and Azubuike Victor Chukwuka
Vega, M., R. Pardo, E. Barrado and L., Deban 1998. Assessment of seasonal and polluting effects on the quality of river water by exploratory data analysis. Water Res. 32 (12): 35813592 Vi, J.C., C. Hilton-Taylor and S. N. Stuart (Eds.) 2009. Wildlife in a Changing World An Analysis of the 2008 IUCN Red List of Threatened Species. Gland, Switzerland: IUCN. 180 pp. Vutukuru, S. S. 2003. Chromium induced alterations in some biochemical profiles of the Indian major carps Labeo rohita (Hamilton). Bull Environ. Contam. Toxicol, 70:118-123. Wardas M, L. Budek and E. H. Rybicka 1996. Variability of heavy metals content in bottom sediments of the Wilga River, a tributary of the Vistula River (Krakow area, Poland). Applied Geochemistry 11:197-202. Wei, S., Y., J. C. W., Wang, G. J., Lam, M. K. Zheng, L. W. Y. So, Y. Yeung, L. Horii, H. Chen, N. Yu, N. Yamashita and P. K. S. Lam 2008. Historical trends of organic pollutants in sediment cores from Hong Kong. Mar. Pollut. Bull. 57: 758766. Wunderlin, D. A., M. P. Diaz, M. V. Ame, S. F. Pesce, A. C., Hued and M. A. Bistoni 2001. Pattern recognition techniques for the evaluation of spatial and temporal variations in water quality. A case study: Suquia river basin (Cordoba, Argentina). Water Res. 35(12): 2881-2894.

[41] [42] [43]

[44]

[45]