Journal of Environmental Science and Water Resources Vol. 3(5), pp.104 - 109, June 2014 ISSN 2277 0704 2014 Wudpecker Journals Pollution assessment of sediment metals from the middle region of the Ogun River, Nigeria Diayi, M.A, Gbadebo, A.M. Department of Environmental Management & Toxicology, University of Agriculture, P.M.B. 2240, Abeokuta, Ogun-State, Nigeria. *Corresponding author E-mail: [email protected], +2348063517259 Accepted 15 April 2014 Metal concentrations were determined for sediment samples obtained from depths of 0 to 5cm, 5 to 10cm and 10 to 15cm at Lafenwa, Arakanga Old Scheme, Arakanga New Scheme and Oyan. Samples were obtained using Van Veen sediment grab after which they were stored in well labeled polythene bags. pH and conductivity, were determined in-situ using standard methods by American Public Health Association while Wakley and Black Method was used to determine organic carbon. Induced Couple Plasma Mass Spectrometry (ICP/MS) was used to determine the metal concentrations. Sediment metal concentrations from Lafenwa 0 to 5 cm (201 ppm), Arakanga 10 to 15 (263 ppm), Arakanga New Scheme 5 to 10 cm (135 ppm) and Arakanga New Scheme 10-15 cm (249 ppm) exceeded the Environment Canada Sediment Quality Guideline standard (123.00 ppm). Cr values from Lafenwa (81.00 ppm), Oyan 0 to 5 cm (44.00ppm), Oyan 5 to 10cm (45.00 ppm) and Oyan 10 to 15 cm (60.00 ppm) exceeded the standard limit (37.50ppm). Igeo result obtained showed very highly polluted status for Pb from Lafenwa 0-5cm (24.60). Similarly, contamination factor analysis also showed very highly polluted status for Pb (121.8) and Cu (9.2) from Lafenwa 0 to 5cm and Pb (5.5) from Lafenwa 5 to 10cm. Sediments from Lafenwa 0 to 5cm and Lafenwa 5 to 10 cm should be monitored frequently. Key words: Sediment, metal concentration, geochemical, Ogun River, pollution. INTRODUCTION Bottom sediments consist of particles that have been transported by water, air or glaciers from the sites of their origin in a terrestrial environment and have been deposited on the floor of a river, lake or ocean (Pravin et al., 2011). The continuous growth in human population and attendant sophistication in the commodities and materials consumed have led to the generation of substantial wastes of unprecedented quantities. The nature of wastes had moved from mere nuisance to being toxic and hazardous (Olatunji and Abimbola, 2010). According to Lin et al. (2003), Sediment plays an important role both as sink where heavy metals can be stored and as a source of heavy metals to the overlying water. Most heavy metals discharged into rivers are found to deposit in bottom sediments via the complex physical, chemical and biological processes. However, the accumulated heavy metals may be remobilized from sediments by natural and man-made processes, which can pose a risk to the aquatic ecosystem. Heavy metals have a great ecological consideration due to their toxicity and accumulation behavior (Purves, 1985). Metals in rivers, lakes or any aquatic environment can change both aquatic species diversity and ecosystem due to their toxicity and accumulative behavior. Sediments have recently been considered as diffuse sources of environmental contaminants (Baudo et al., 1990). Aquatic organisms such as fish are capable of accumulating heavy metals in their living cells to concentrations much higher than those present in water, sediment and microflora in their environment (Forstner and Wittmann, 1981). Heavy metals in fishes increase with the increment of metal levels in water, sediment and fish food organisms (Arvind, 2002). Heavy metals like Cu, Co, Zn, Fe and Mn at low concentrations are essential metals for enzymatic activity and many biological processes. Other metals like Cd, Pb, and Hg have no known essential role in the body of living organisms, and are toxic even at low concentrations. Copper is used as an algaecide to control algal growth. Since algae are at the base of the food chain, the amount of algal biomass present in an aquatic ecosystem will affect the amount of food available for aquatic animals including zooplankton, insects, fish and aquatic 105 J. Environ. Sci. Water Resources mammals. Copper affects olfaction (sense of smell) in fish by competing with natural odorants for binding sites, thereby affecting activation of the olfactory receptor neurons or by affecting intracellular signaling in the neurons (Baldwin et al., 2003). This reduces the ability of fish to detect predators which makes them vulnerable to predation. DWAF (1996) stated that Lead is bioaccumulated by bacteria, fresh water plants, invertebrates and fish. In the hematopoietic system, lead poisoning may result from; the impairment of heme (a precursor of haemoglobin) synthesis, an increased rate of red blood cell destruction and an inability of red blood cells to transport basic cell nutrients (sodium and potassium ions) into and out of the cells (Hasan et al., 1967). Cr is a human and animal carcinogenic agent; its biological effects depend on chemical form, solubility, and valence. Low concentrations of hexavalent chromium cause sublethal toxic effects in aquatic plants and animals (Frances, 2009). Health effects like mouth ulcer, nose bleeding, kidney disease, low white blood cell count, cancers and miscarriages were reported by Bradl (2005) as effects of hexavalent Chromium. Long-term arsenic concentration leads to thickening and discoloration of the skin, nausea and diarrhoea, decreased production of blood cells, abnormal heart rhythm and blood vessel damage (ATSDR, 1993). Domestic and human wastes are deposited into the river because of inadequate waste disposal systems. Vehicular movements are high especially around the Lafenwa area while fishing activities take place in all sampling locations. This research was carried out from January to March, 2012 along the middle region of Ogun River basin. The Ogun-River, located in Ogun-State, South West of Nigeria lies between latitude 6o35' and 8o58' North with Longitude 2o40' and 4o10' East. It rises from Iganran Hills, east of Shaki, Oyo state, South West, Nigeria (latitude 07o40' N and Longitude 03o20' E) (Jaji, et al., 2007). The entire river basin (Ogun River) occupies an area of approximately 23,700 sq.km (OORBDA, 1982). middle region of the Ogun River course between January and March, 2012. Five samples were collected per location/layer after which they were composited for each location/layer. High vehicular movements and indiscriminate dumping of municipal and human wastes as well as commercial activities and fishing were observed at the Lafenwa area. While Arakanga Old/New schemes and Oyan were located in serene environments with low domestic activities. Predominantly, fishing was observed as the major activity at those sites. Dams were also observed at the three locations (Arakanga Old Scheme, Arakanga Old Scheme and Oyan). Sediment samples which were collected with the aid of a Van Veen sediment grab. The sediments collected were transferred into polythene bags and placed in an ice chested cooler for onward transportation to the laboratory. pH and conductivity were determine using standard methods by APHA (1992). 10g of dried/2mm sieved sediment samples were place in a 50ml beaker containing 20ml of distilled water. The mixture was allowed to stand for 30 minutes after which the pH meter was inserted into the partly settled suspension for the pH values to be taken. The conductivity meter was also inserted for conductivity readings. Organic carbon was determined by Wakley’s and Black Method. At the laboratory, sediment samples were air dried and sieved using a 2mm sieve to remove coarse particles. The finer sediments (ie < 2mm) were taken subjected to the Induced Couple Plasma Mass Spectrometry (ICP/MS) for the determination of metal concentrations while the geochemical pollution indices were determined using the mathematical equation Igeo = log 2 (Cn/1.5Bn) introduced by Muller (1979). Sampling area RESULTS AND DISCUSSION Four sampling sites along the Middle Region of OgunRiver course namely; Lafenwa, Oyan, Arakanga Old Scheme and Arakanga New Scheme were surveyed. All sediment pH values obtained were alkaline with the highest pH observed at Arakanga New Scheme 0 to 5 cm (12.7) while the least was observed at Oyan 0-5 cm (8.12) as seen in Table 1. pH is critical to the release of metals because low pH can accelerate the release of metals like Pb, Cu, Hg, Mn and Cd. The highest conductivity value of 2273 µS/cm (Table 1) was recorded from Arakanga Old Scheme 10-15 cm while the least was obtained at Oyan 5-10 cm (68 µS/cm ) (Table 1). All sediment values obtained were sandy when subjected to particle size analysis (Table 1). From the sediment metal MATERIALS AND METHODS Experimental methods Sediments of depths 0 to 5cm, 5 to 10 cm, 10 to 15cm respectively were collected from different sections of the Quality assurance Three replicates were taken for every sample that was analyzed. A series of standard reference materials were used at the Acme Laboratory for and sediment samples. They include; STD OREAS45CA, STD DS9 and BLK. Diayi and Gbadebo. 106 Figure 1. Map of the Ogun River. Table 1. Levels (Mean) of physicochemical parameters of sediment samples obtained from the study area. Location pH µs/cm EC (%) Organic Carbon (%) Sand (%) Clay (%) Silt (%) Texture Lafenwa 0-5 cm Lafenwa 5-10 cm Lafenwa 10-15 cm Arakanga Old Scheme 0-5 cm Arakanga Old Scheme 5-10cm Arakanga Old Scheme 10-15 cm Arakanga New Scheme 0-5 cm Arakanga New Scheme 5-10 cm Arakanga Old Scheme 10-15 cm Oyan 0-5 cm Oyan 5-10cm yan 10-15cm 10.90 8.55 8.90 11.90 12.60 9.09 12.70 8.63 8.90 8.12 8.69 8.52 267.00 303.00 324.00 404.00 654.00 2273.00 476.00 573.00 150.00 79.00 68.00 73.00 0.60 2.59 4.59 1.00 0.80 0.80 0.80 2.19 2.79 1.00 1.20 2.99 96.40 98.20 98.20 98.20 98.20 98.20 98.20 100.00 91.00 100.00 100.00 98.20 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 1.80 0.00 0.00 0.00 3.60 1.80 1.80 1.80 1.80 1.80 1.80 0.00 7.20 0.00 0.00 0.00 Sand Sand Sand Sand Sand Sand Sand Sand Sand Sand Sand Sand analyses done using Induced Couple Plasma Mass Spectrometry (ICP/MS), all Cu values (Table 1) were lower than the Environment Canada Sediment Quality Guideline Standard (35.70 ppm) except that of Lafenwa 0 to 5 cm (413.50 ppm). All Hg values obtained were lower than the ECSQG standard (0.17 ppm). Zinc values from Lafenwa 0-5 cm (201 pppm) Arakanga 10-15 cm Old Scheme (263 ppm), Arakanga 5 to 10 cm New Scheme (135 ppm) and Arakanga New Scheme 10 to 15 cm (249ppm) were higher than the ECSQG standard (123 ppm). High conductivity values observed in those locations could have resulted in the accumulation of Zinc in the sediments sampled. 107 J. Environ. Sci. Water Resources Table 2. Trace metal values of sediments obtained from the study area. Location Lafenwa 0-5 cm Lafenwa 5-10cm Lafenwa 10-15 cm Arakanga Old Scheme 0-5 cm Arakanga Old Scheme 5-10 cm Arakanga Old Scheme 10-15 cm Arakanga New Scheme 0-5 cm Arakanga New Scheme 5-10 cm Arakanga New Scheme 10-15 cm Oyan 0-5 cm Oyan 5-10 cm Oyan 10-15 cm ECSQG Cu 413.50 17.70 8.50 4.90 2.60 33.60 2.30 14.70 33.20 7.10 7.20 7.60 35.70 Cd 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.60 Zn 201.00 68.00 42.00 41.00 8.00 263.00 9.00 135.00 249.00 12.00 12.00 13.00 123.00 Hg 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.17 Ni 9.90 4.60 4.30 3.40 2.30 11.90 1.80 7.60 11.10 7.30 7.80 8.30 NS Pb 2435.30 109.90 21.40 11.60 6.70 77.40 5.50 39.00 75.40 20.90 21.00 25.80 35.00 As 6.50 1.20 0.70 0.00 0.00 1.10 0.00 0.60 1.00 0.00 0.60 1.00 5.90 Pb 24.60 1.10 0.20 0.80 0.10 0.75 0.10 0.40 0.75 0.20 0.20 0.30 20.00 As 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 13.00 Cr 81.00 22.00 18.00 18.00 9.00 29.00 8.00 29.00 29.00 44.00 45.00 60.00 37.5 Mn 311.00 247.00 270.00 122.00 143.00 408.00 136.00 228.00 404.00 253.00 246.00 264.00 NS Note: ECSQG: Environment Canada Sediment Quality Guideline, NS: No Standard Table 3. Igeo values of sediments metal obtained from the study area Location Lafenwa 0-5 cm Lafenwa 5-10cm Lafenwa 10-15 cm Arakanga Old Scheme 0-5 cm Arakanga Old Scheme 5-10 cm Arakanga Old Scheme 10-15 cm Arakanga New Scheme 0-5 cm Arakanga New Scheme 5-10 cm Arakanga New Scheme 10-15 cm Oyan 0-5 cm Oyan 5-10 cm Oyan 10-15 cm Average Shale Value Cu 1.80 0.10 0.00 0.00 0.00 0.15 0.00 0.10 0.15 0.00 0.00 0.00 45.00 Cd 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.30 Zn 0.40 0.10 0.10 0.10 0.10 0.50 0.00 0.30 0.60 0.00 0.00 0.00 95.00 Hg 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.18 Ni 0.00 0.00 0.00 0.00 0.00 0.05 0.00 0.00 0.05 0.00 0.00 0.00 50.00 Cr 0.20 0.50 0.00 0.00 0.00 0.10 0.00 0.10 0.10 0.10 0.10 0.10 90.00 Mn 0.10 0.10 0.10 0.00 0.00 0.10 0.00 0.05 0.10 0.10 0.10 0.10 850.00 Note: ECSQG: Environment Canada Sediment Quality Guideline, NS: No Standard Table 4. Contamination Factor values of Sediments Obtained from the Study Area Location Lafenwa 0-5 cm Lafenwa 5-10cm Lafenwa 10-15 cm Arakanga Old Scheme 0-5 cm Arakanga Old Scheme 5-10 cm Arakanga Old Scheme 10-15 cm Arakanga New Scheme 0-5 cm Arakanga New Scheme 5-10 cm Arakanga New Scheme 10-15 cm Oyan 0-5 cm Oyan 5-10 cm Oyan 10-15 cm Cu 9.20 0.40 0.30 0.10 0.10 0.75 0.05 0.30 0.70 1.60 0.20 0.20 Cd 0.00 0.00 0.20 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Zn 2.10 0.70 0.00 0.40 0.10 2.80 2.80 1.40 2.60 0.10 0.10 1.30 Similarly, high Pb values were observed at Lafenwa 0-5 cm (2435.3 ppm), Lafenwa 5 to 10 cm (109.9 ppm), Hg 0.00 0.00 0.40 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Ni 0.20 0.10 0.00 0.10 0.05 0.20 0.00 0.150 0.20 0.15 0.20 0.20 Pb 121.80 5.50 0.10 0.60 0.30 3.90 0.30 1.90 3.80 1.05 1.05 1.30 As 0.50 0.10 1.10 0.00 0.00 0.10 0.00 0.05 0.10 0.00 0.50 0.10 Cr 0.90 0.20 0.05 0.20 0.10 0.30 0.10 0.30 0.30 0.50 0.50 0.10 Mn 0.40 0.30 0.20 0.10 0.2 0.50 0.20 0.30 0.50 0.30 0.30 0.30 Arakanga Old Scheme 10-15 cm (77.4 ppm), Arakanga New Scheme (39.00 ppm) and Arakanga NS (75.4 ppm) Diayi and Gbadebo. as seen in table 2. According to Jaji et al. (2007) water from the Oyan section of the Ogun River had a Pb value of 0.134 mg dm-3 which was higher than the WHO standard of 0.05 mg dm-3. Elsewhere from River Yauri, North- West Nigeria it was reported by Yahaya et al. (2012) that sediment Pb values were higher during the dry season with sampling point 3 (P3) having the highest value of 45.02 ± 1.04 µg/g. This high value observed was attributed to anthropogenic inputs like fertilizers and pesticides used in agricultural activities. All Arsenic values were lower than the ECSQG of 5.9ppm except that of Lafenwa 0-5cm (6.5ppm) (table 2). Chromium values from Lafenwa 0-5cm (81 ppm), Oyan 0-5 cm (44 ppm), Oyan 5 to 10 cm (45 ppm) and Oyan 10 to 15 cm (60 ppm), all exceeded the ECSQG standard of 37.50ppm as seen in Table 2. The order of metal concentration in the sediment was Mn>Pb> Zn> Cu> Cr >Ni >As > Hg =Cd. The highest concentration of metals from the locations was from Mn (3032 ppm) while Hg and Cd both accounted for the least concentrations of 0.00ppm. The mathematical equation Igeo = log 2 (Cn/1.5Bn) introduced by Muller (1979) was used to determine the geochemical pollution intensities for samples analysed. This index is classified into various classes for easy identification of sediment pollution status. Values between 0 to 1, are termed unpolluted while 1 to 2 can be classified as moderately to unpolluted, 2-3 is moderately polluted, 3 to 4 is classified as moderately to highly polluted, 4-5 is termed highly polluted while 5 and above is known as very highly polluted. From the result obtained in Table 3, all values for Cu, Cd, Zn, Hg, Ni, As, Cr an Mn fell into the ‘unpolluted’ category except for Lafenwa 0 to 5cm lead index (24.60) which rated ‘very highly polluted’. This result reveals that Lead is at a high risk to biota in the sediment of Lafenwa 0 to 5 cm. Since fishing is a common activity in this area, man could be affected when fishes containing high Pb values are consumed. From the Contamination Factor analysis, it was observed that Zn was moderately polluted at Lafenwa 0 to 5cm being 2.1 while Cu (9.2) and Pb (121.8) had very strong pollution status in that sediment layer. Similarly, Pb contamination factor value of 5.5 from Lafenwa 5 to 10cm sediment also showed very strong pollution status. Elsewhere, moderate to strong pollution status was observed for Pb (3.8) from Arakanga 10 to 15 cm while moderately polluted status were observed for Zn (2.8) and Pb (3.8) from Arakanga Old Scheme 10 to 15 cm, Zn (2.8) from Arakanga New Scheme 0 to 5 cm, and Zn (2.6) from Arakanga 10 to 15 cm. Medium pollution status were shown for Pb (1.1) from Lafenwa 10 to 15cm, Zn (1.4) from Arakanga New Scheme (5 to 10 cm), Pb (1.9) from Aarakanga New Scheme 10 to 15 cm, Cu (1.6), Pb (1.05) from Oyan 0 to 5 cm respectively, Pb (1.05) from Oyan 5-10 cm and Pb (1.30) from Oyan 10 to 15. 108 Conclusion Sediment from Lafenwa 0 to 5cm accounted for the highest metal concentrations for Pb, Cr, As, and Cu. This shows that there is high accumulation of toxic metals in this sediment. Since fishing is carried out in the Lafenwa area, it is important to carry out a proper assessment of the lead value in the fishes that are harvested for public consumption. Man can be affected when fish with high Pb content is consumed. Other sediments from Arkanga Old Scheme 10 to 15cm, Arkanga New Scheme 5 to 10cm, Arkanga New Scheme 10 to 15cm and Lafenwa 5 to 10 cm should be closely monitored as well owing to the high concentrations showed for Zn and Pb respectively. 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