Research Journal of Chemical Sciences ___ ______________________________ ______ ____ ___ ISSN 22 31 - 606X Vol. 3 ( 3 ), 70 - 75 , March (201 3 ) Res. J. Chem. Sci. International Science Congress Association 70 Assessment of Some Trace Metals Content of Oreochromis niloticus Obtained from River Okpokwu, Apa Benue State, Nigeria Abah J. * , Ubwa S.T., Onyejefu D.I. and Nomor S.A. Department of Chemistry, Benue State University, P.M.B. 102119, Makurdi NIGERIA Avail able online at: www.isca.in Received 5 th February 201 3 , revised 13 th February 201 3 , accepted 28 th February 201 3 Abstract This study was conducted with the aim of determining the concentrations of As, Mn, Cu, Pb, Cd and Fe in whole Oreochromis niloticus (tilapia) and its fresh water habitat using recommended analytical procedures and compare the results with WHO‟s permissible limits. Samples of fresh water and the fish were collected weekly at the peak of rainy and dry s easons in the study area (October, 2010 and February, 2011) respectively at three locations; Auke, Odejo and Ochalanya along the river. Across the sampling points, the results obtained using Unicam Solar (32) Atomic Absorption Spectrophotometer showed that the trace metal contents of Oreochromis niloticus varied between 0.050.01g/g As to 0.380.04g/g Fe in October, 2010 and 0.090.03g/g As to 0.280.02g/g Fe in February, 2011. The water levels of the trace metals ranged from 0.060.02g/L As to 1.240. 05g/L Fe in October, 2010 and 0.040.01g/L As to 0.590.10g/L Fe in February, 2011. There were positive correlations between the concentrations of the trace elements in the whole fish and river water. T - test analyses of the levels of the trace metals be tween the sampling periods were statistically significant (P < 0.05). The levels of the trace metals recorded in this study were below WHO‟s permissible limits. Therefore, the water and Oreochromis niloticus obtained from the study area have not become con taminated by the trace metals studied. However, periodic review should be sustained to monitor possible accumulations of the heavy metals in future due to the proliferation of anthropogenic activities around river Okpokwu. Key w ords: Agrochemicals, o reochr omis niloticus , t race m etals, r iver o kpokwu . Introduction Trace metals are natural components of the environment but they have become a matter of great concern because of the continuous increase in concentration of these metals in our environment. The p ollution of water bodies in the urban, industrial and agricultural areas has resulted to increased concentration of heavy metals and minerals in the internal body of fish 1 . This situation was further aggravated by the rapid growth of population, increased urbanization and expansion of industrial activities, exploration and exploitation of natural resources as well as the modern agricultural practices and lack of environmental regulations 2 - 4 . As heavy metals cannot be degraded, they are deposited, assimilate d or incorporated in water, sediment and aquatic animals 5 and present great dangers to organisms in the food chain. Research works have shown that heavy metals can be bio - accumulated and biomagnified via the food chain and finally assimilated by human cons umers with the attendant adverse health effects 6 . As a consequence, fish are often used as indicators of heavy metals contamination in the aquatic ecosystem because they occupy high trophic levels and are important food source 6,7 . Unacceptable levels of le ad and mercury were reported in the study on tissues of African catfish, Clarias gariepinus from River Niger 8 . Similarly, the levels of lead, copper and zinc reported in the study on Nile tilapia, Oreochromis niloticus caught from River Delimi, Jos were to o high for frequent human consumption 9 . It has been observed that the functioning of the natural ecosystems is increasingly being affected by human activities. Research work has shown that it is difficult to find a river or other water bodies whose natural regime has not been modified by man‟s activities 10 . The unsanitary habits of depositing industrial wastes at dumps without adequate treatment or directly into the aquatic environment is a common sight in many industrial cities in Nigeria 11 . Among the rura l populace also, there has been indiscriminate usage of different agrochemicals in farm lands at the banks of rivers which provide sources of water to the host communities for domestic and agricultural purposes. The result is that toxic and hazardous mater ials including heavy metals are transported to several water bodies (rivers, streams, lake, and ponds) with potential effects on aquatic organisms. Over the years there has been a remarkable degradation in the quality of River Okpokwu and its portability due to the proliferation of chemical - based agriculture, mining and block industry activities in the major settlements along the rivers. Agricultural contamination of many resources through fallout, drainage and runoff erosion is highly probable in rivers within the vicinity of intensive agricultural activities. Furthermore, there is no clear documentation of any effect of anthropogenic activities around River Okpokwu. Thus, this study provides a baseline data of the levels of some heavy metals in Oreochrom is niloticus and water from River Okpokwu and the result formed Research Journal of Chemical Scienc es ___ _ _ _______________________________ ______________ _ ________ ISSN 22 31 - 606X Vol. 3 ( 3 ), 70 - 75 , March (201 3 ) Res. J. Chem. Sci. International Science Congress Association 71 basis for monitoring the pollution by the heavy metals in River Okpokwu. Material and Method s The Study Area: River Okpokwu is one of the relief features in Apa LGA of Benue State, Nigeria. I t is located on longitude 7.80 o E and latitude 7.58 o N. The River is located 4km away from Ugbokpo, Apa Local Government Headquarters. River Okpokwu meets river Ochekwu at Odejo, Agatu LGA and they flow into River Benue at Ocholonya, also in Agatu LGA. Unlik e other rivers within the locality, River Okpokwu never dries up completely during dry season. The volume and size of the river increase very rapidly during rainy season. Thus, it sustains high agricultural and fishing activities. Near the source of this r iver, there is high gravel mining activity while along the river, there are high chemical - based farming activities and block industries. These activities constitute potential sources of surface and underground water pollution. Samples Collections and Pres ervation: A total of eighteen (18) samples each of Oreochromis niloticus (Tilapia) and water were collected from three locations; Auke, Odejo and Ocholonya in River Okpokwu during the months of October, 2010 and February, 2011. These periods were chosen to represent the peaks of rainy and dry seasons in the study area. Oreochromis niloticus is a surface feeder and it feeds from its water habitat. The fish were collected and transported to the laboratory in ice boxes and rinsed with deionized water and froze n at - 10 o C prior to analyses 12 . The samples were preserved in a refrigerator at 5 o C 1 . Water samples were collected at each extremity and median part of the river by immersion of polythene bottles to approximately 30cm below the water surface and allowed t o overflow. All containers used for sampling and storage were thoroughly washed with solution of detergent and distilled water. They were then soaked in 10% “Analar” nitric acid overnight followed by rinsing with distilled water to remove trace elements co ntamination 13 . Samples Preparations and Analyses : Water Sample: Raw water was subjected to wet digestion. 100ml unfiltered water was measured into a 250ml beaker and 20ml “Analar” nitric acid solution plus 10ml of 50% hydrochloric acid solution were adde d. The acidified water was then evaporated to almost dryness on a hot plate and 5ml of 50% hydrochloric acid was again added and heated for 15 minutes. The beaker was removed and cooled to room temperature before transferring the content into a 100ml volum etric flask and made up to the mark with distilled water 13 . The digested water was filtered and analyzed for the levels of As, Mn, Cu, Pb, Cd and Fe using Unicam Solaar (32) Atomic Absorption Spectrophotometer (AAS). Oreochromis niloticus : The fishes were discaled and inviscerated and then transferred to electric oven at 40 o C. They were dried in the oven at this temperature for 24hours and then pulverized in a clean dry porcelain mortar 12 . The pulverized fish samples were dried further for 1hour at reduced temperature of 20 o C and put into clean dried bottles 14 . 3.00g of the dried fish samples were weighed into a silica crucible and ashed in a muffle furnace at a temperature of 600 o C for 5hours 14,1 . The ashes were cooled to room temperature and filtered to r emove particles and then transferred into a 250ml conical flask. Thereafter, 20ml of concentrated HNO 3 was added and then diluted to 50ml with deionised water and swirled gently. The volume was made up to 100ml marks in a volumetric flask with deionised wa ter and analyzed for heavy metals as in the water. Data Handling: The data generated were subjected to t - test (p 0.05) to determine the significance of mean metal concentrations between the sampling periods. Correlation analysis was also carried out to assess the relationship between fish metals content and those of its water habitat. Results and Discussion The results in t able - 1 presents the concentrations (g/g) of the trace metals in Oreochromis niloticus (tilapia) obtained from River Okpokwu in th e months of October, 2010 and February, 2011. Across the sample locations, A s and Mn concentrations in Oreochromis niloticus ranged from 0.050.02 to 0.110.03(g/g) and 0.080.04 to 0.170.02(g/g) in October, 2010 and while the concentrations in Februar y, 2011 revealed 0.090.03 to 0.160.04(g/g) and 0.190.02 to 0.220.03(g/g) respectively. Copper (Cu) concentrations varied between 0.100.03 to 0.150.02(g/g) and 0.140.02 to 0.230.03(g/g) during the same period respectively. Cadmium (Cd) was not d etected in the fish but Pb concentrations ranged from 0.030.01 to 0.050.02(g/g) and 0.050.02 to 0.080.01(g/g), Fe concentrations varied between 0.310.05 to 0.380.03(g/g) and 0.210.08 to 0.280.02(g/g) in the months of October, 2010 and February , 2011 respectively. T - test analyses of the variations of paired mean (October, 2010 and February, 2011) are statistically significant (P 0.05). The overall mean concentrations of the trace metals recorded in the fish in this study ( f igure - 1) showed very high level of iron in October. Generally, the results of the mean concentrations of the trace metals were higher in February than October. This may be due to the effect of bioaccumulation over the periods that the fish lived and fed in its water habitat. Studies have shown that direct absorption and bioaccumulation of toxic heavy metals are common in aquatic environment where organisms are exposed to the same concentrations of the substances present in the water environment 15 . The concentrations (g/l) of the trace metals in the river water (Table - 2) showed that arsenic (As) varied between 0.060.02 to 0.090.04(g/l) in October, 2010 and 0.020.01 to 0.050.01(g/l) in February, 2011. The other results showed that Mn ranged from 0.260.05 to 0.340.08(g/ l), Cu varied between 0.540.05 to 0.740.02(g/l), Pb varied between 0.060.01 to 0.310.02(g/l) and Fe ranged from 1.030.02 to Research Journal of Chemical Scienc es ___ _ _ _______________________________ ______________ _ ________ ISSN 22 31 - 606X Vol. 3 ( 3 ), 70 - 75 , March (201 3 ) Res. J. Chem. Sci. International Science Congress Association 72 1.240.05(g/l) in October, 2010. Similar results in February, 2011 revealed 0.200.03 to 0.410.04(g/l) Mn, 0.250.06 to 0. 370.08(g/l) Cu, 0.120.03 to 0.160.04(g/l) Pb and 0.400.03 to 0.590.10(g/l) Fe. Cadmium (Cd) was also not detected in the water. The overall mean concentrations of the trace metals in the river water ( f igure - 2) revealed significantly (p 0.05) hi gher levels of iron and copper in October, 2010. This may be attributed to the input by surface run - off through quarry sites, agricultural fields and domestic wastes located along the river. Furthermore, the high iron and copper levels of the river may als o depend on hydrological situation. In a study on the distribution pattern of trace metal pollutants in the sediments of an urban wetland in Southwest coast of India it was observed that trace metals are among the most common environmental pollutants and t heir occurrence in waters indicate the presence of natural or anthropogenic sources 16 . It has also been reported that heavy metals or their compounds may be discharged from industries, farmlands, municipal urban water runoffs, and agricultural activities i nto surface water and can cause pollution 17 . Most of the iron in river is particle - bound which suggests why the total iron content of the river water is influenced by the amount of suspended solids in the water and by the concentration of iron on these par ticles. Copper is an essential trace element used in pesticides formulations. The agricultural fields along the river received different types of pesticides during pests control of the cropping season. Thus, during the peak of raining season where the rive r water was very high and received maximum effluents from drainages through farms and quarry industries; the flood events mobilised varying degree of contaminants into the river so that concentration peaks may occur. Heavy metals are highly persistent and can easily enter a food chain and accumulate until they reach toxic levels. In February however, the rain fall has stopped and the volumes of effluents discharge into the river via surface run off have reduced. Consequently, substantial amount of the chemi cal residues initially washed into the river during rainfall settled at the bottom sediment of the river and less contents are possible in the river water. This may be responsible for the general lower levels of most of the trace metals recorded in the riv er water in February. The concentrations of the trace metals in Oreochromis niloticus are positively correlated with the heavy metals in water ( t able - 3). This suggests that the water metals content have significant effect on the availability of the trace metals to the fish and hence, the bioaccumulation into the tissues. The results of the bio - accumulation factors of the trace metals ( f igure - 3) revealed very high absorption of arsenic in both October, 2010 and February, 2011. This may present serious he alth challenge to the consumers of Oreochromis niloticus in the study area. Fish, shellfish, meat, poultry, dairy products and cereals have been reported as the main sources of dietary intake of arsenic. However, the arsenic content of fish and shellfish u sually involves organic compounds (e.g. arsenobetaine) that are of low toxicity 18 . A report of the World Health Organisation indicated that the International Agency for Research on Cancer (IARC) classified arsenic and arsenic compounds as carcinogenic to h umans ( g roup 1), which means that there is sufficient evidence for their carcinogenicity in humans 19 . Generally, the levels of the trace metals recorded in this study were below the WHO‟s Permissible Limits of 0.05mg/L As, 1.0mg/L Cu, 0.01mg/L Pb, 0.30mg/L Fe and 0.10mg/L Mn for water and 0.03mg/g Cu , 0.10mg/g Fe, 0.02mg/g Pb and 0.01mg/g Mn for fish respectively 20 . Table - 1 Concentrations (g/g) of the trace metals in Oreochromis niloticus obtained from river Okpokwu in October, 2010 and February, 2011 Heavy Metals Auke Odejo Ocholonya Oct. 2010 Feb. 2011 Oct. 2010 Feb. 2011 Oct. 2010 Feb. 2011 As 0.11 a 0.03 0.16 b 0.04 0.05 a 0.02 0.09 a 0.03 0.07 a 0.03 0.11 b 0.02 Mn 0.17 a 0.02 0.21 b 0.06 0.13 a 0.01 0.22 b 0.03 0.08 a 0.04 0.19 b 0.02 Cu 0.13 a 0.05 0.17 b 0.04 0.10 a 0.03 0.14 b 0.02 0.15 a 0.02 0.23 b 0.03 Cd - - - - - - Pb 0.05 a 0.02 0.07 b 0.03 0.04 a 0.02 0.08 b 0.01 0.03 a 0.01 0.05 b 0.02 Fe 0.31 a 0.05 0.21 b 0.08 0.38 a 0.03 0.28 b 0.02 0.37 a 0.06 0.27 b 0.04 „„ - ‟‟ = Not detected. T - test of paired mea n (October, 2010 and February, 2011) with different alphabets are statistically significant (P 0.05). Data presented are mean SD of replicate analyses (n=4). SD = standard deviation Research Journal of Chemical Scienc es ___ _ _ _______________________________ ______________ _ ________ ISSN 22 31 - 606X Vol. 3 ( 3 ), 70 - 75 , March (201 3 ) Res. J. Chem. Sci. International Science Congress Association 73 Table - 2 Concentrations (g/L) of the trace metals in water obtained f rom river Okpokwu in October, 2010 and February, 2011 Auke Odejo Ocholonya Heavy Metals Oct. 2010 Feb. 2011 Oct. 2010 Feb. 2011 Oct. 2010 Feb. 2011 As 0.06 a 0.02 0.02 b 0.01 0.07 a 0.03 0.05 a 0.01 0.09 a 0.04 0.04 b 0.01 Mn 0.34 a 0.08 0.20 b 0.03 0.31 a 0 .02 0.41 b 0.04 0.26 a 0.05 0.36 b 0.03 Cu 0.54 a 0.05 0.35 b 0.02 0.59 a 0.04 0.37 b 0.08 0.74 a 0.02 0.25 b 0.06 Cd - - - - - - Pb 0.31 a 0.02 0.16 b 0.04 0.08 a 0.01 0.13 b 0.02 0.06 a 0.01 0.12 b 0.03 Fe 1.06 a 0.05 0.40 b 0.03 1.03 a 0.02 0.58 b 0.03 1.24 a 0.05 0.5 9 b 0.10 „„ - ‟‟ = Not detected. T - test of paired mean (October, 2010 and February, 2011) with different alphabets are statistically significant (P 0.05). Data presented are mean SD of replicate analyses (n=4). SD = standard deviation Table - 3 Correlatio n Coefficient of the Concentrations of the Trace Metals in the River Water and Oreochromis niloticus As Mn Cu Pb Fe As 1.0000 Mn 0.7327 1.0000 Cu 0.4989 0.9554 1.0000 Pb 0.8788 0.9687 0.8520 1.0000 Fe 0.3931 0.9138 0.9930 0.7843 1.0000 Figure - 1 Overall mean concentrations (ppm) of the trace matals in Oreochromis niloticus Figure - 2 Overall mean concentrations (ppm) of the trace matals in the river water Research Journal of Chemical Scienc es ___ _ _ _______________________________ ______________ _ ________ ISSN 22 31 - 606X Vol. 3 ( 3 ), 70 - 75 , March (201 3 ) Res. J. Chem. Sci. International Science Congress Association 74 Figure - 3 Bio - accumulation factors of the trace metals in Oreochromis niloticus , Bio - accumulation factor = Metal concentration in fish / Metal concentration in river water Conclusion The results of this study revealed variable concentrations of As, Mn, Pb, Cu and Fe in Oreochromis niloticus (Tilapia) and water obtained from river Ok pokwu in October, 2010 and February, 2011. The water recorded elevated levels of the trace metals in October which may due to the high surface runoff of effluents from agricultural lands, quarry industries and domestic waste into the river. The fish conten ts of the trace metals were higher in February, probably due to the effect of bioaccumulation over the periods of its habitation and feeding in the water environment. However, the levels of the trace metals recorded in this study were below the WHO‟s Permi ssible Limits. Accordingly, the water and Oreochromis niloticus from the study area have not become contaminated by the trace metals studied. Therefore, periodic review should be sustained to monitor possible accumulations of the trace metals in future due to the proliferation of anthropogenic activities around river Okpokwu. Acknowledgement The authors are thankful to the management of Sheda Science and Technology Complex (SHESTCO), Abuja for providing the required laboratory facilities and skills for the analyses. References 1. Farkas A., Salanki J. and Varanka I., Heavy metal concentrations in fish of lake Balaton, lakes and reservoirs: research and management, 5, 271 - 279 (2000) 2. Gupta A., Rai D.K., Pandey R.S. and Sharma B., Analysis of some heavy metals i n the riverine water, sediments and fish from river Ganges at Allahabad , Environ. monit. assess ., 157, 449 - 458 (2009) 3. 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