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DOI: http://dx.doi.org/10.4314/gjes.v12i1.1

GLOBAL JOURNAL OF ENVIRONMENTAL SCIENCES VOL. 12, 2013: 1-11 1 COPYRIGHT© BACHUDO SCIENCE CO. LTD PRINTED IN ISSN 1596-6194 www.globaljournalseries.com , Email: [email protected] HEAVY METAL PROFILES IN VARIOUS MATRICES OF THE BONNY/NEW RIVER ESTUARY, , NIGERIA

B. B. BABATUNDE, F. D. SIKOKI, M. C. ONOJAKE, R. U. AKPIRI AND D. AKPULOMA

ABSTRACT

A study of the concentrations of Ca, Mg, K, Zn, Pb, Cd, Co, Cr, Cu, Fe, Ni and Na in the sediment, sea water, fish and crab of the Bonny/New Calabar River Estuary in Niger Delta, Nigeria was carried out using atomic absorption spectrophotometer A100 for two consecutive years. The contamination levels of the respective metals varied between 2011 and 2012and the range of mean values for all metals in mg/kg were presented along with variations at statistically significant level (P <0.05) between the two years studied. Only K, Zn and Co exhibited variation in their concentrations in water samples between the two years at a statistical significant level (P <0.05) probability. In sediment, only Cr varied between the two years at a statistically significant level (P = 0.05). All metals concentrations were higher in sediment than in water samples.Bioaccumulation factor (BF) indicated a more potent source of metals from sediment than water with organisms accumulating Zn, Fe and Ni in the magnitude of 10, 6 and 5 times more from sediment than from water. Some metals were more accumulated in fish than crab and vice versa. The evidence of elevated levels of heavy metals in sediment and bioaccumulation in biota in the studied area may poise a wanton threat to the health of inhabitants whose diet is predominantly fish. This calls for regular monitoring to avert potential public health problems arising from consumption of metals in seafood.

KEYWORDS: Heavy metals, Matrices, bioaccumulation, Bonny River, Niger Delta, Nigeria.

INTRODUCTION many years (Akpomuvie, 2011). The Bonny estuary, location of the present study, is one of a The Niger Delta accounts for over 90% of network of creeks in the Niger Delta region that Nigeria’s foreign exchange earnings through oil empties directly into the Atlantic Ocean at Bonny and gas export. However, it suffers extensive Island. It is tidal and thus receives a high influx of environmental pollution, such as heavy metal and sea water most of the year (DublinGreen, 1988). hydrocarbon contamination as a consequence of Large scale oil and gas production, oil and gas exploration and exploitation, industrial industrialization and urbanization characterise the production and urbanization, which together have study location with reported impacts from oil significantly impacted its ecological systems for spills, gas flares, industrial discharges,

B. B. Babatunde, Centre for Marine Pollution Monitoring and Seafood Safety, University of , Port Harcourt, IAEAFGN Project, RAF/700 9. F. D. Sikoki, Centre for Marine Pollution Monitoring and Seafood Safety, University of Port Harcourt, Port Harcourt, IAEAFGN Project, RAF/7009. M. C. Onojake, Centre for Marine Pollution Monitoring and Seafood Safety, University of Port Harcourt, Port Harcourt, IAEAFGN Project, RAF/7009. R. U. Akpiri, Centre for Marine Pollution Monitoring and Seafood Safety, University of Port Harcourt, Port Harcourt, IAEAFGN Project, RAF/7009. D. Akpuloma, Centre for Marine Pollution Monitoring and Seafood Safety, University of Port Harcourt, Port Harcourt, IAEAFGN Project, RAF/7009.

2 B. B. BABATUNDE, F. D. SIKOKI, M. C. ONOJAKE, R. U. AKPIRI AND D. AKPULOMA agricultural runoff and domestic effluents and al. (2004) on lower Bonny River, Omoigberale leachates (Jamabo and Chinda, 2010). The and Ogbeibu (2005) on Ase River, Southern estuary also supports marine transportation by Nigeria. The use of fish and invertebrates as heavy vessels conveying goods and services to bioindicators of water quality has also been and from a petroleum tank farm, Port Harcourt advocated by some workers (Yamazaki et wharf, cement and flour factories, among others, al.1996). This is because they produce evidence in addition to heavy traffic of fast speed boats for of relatively stable concentration compared with communal transportation. water analysis that indicates only short term Despite these activities, artisanal conditions. Fufeyin(1998) investigated trend of fisheries in the estuary largely support the heavy metal concentrations in Lagoon livelihood of its inhabitants who have little or no ecosystem, Nigeria, and reportedthat the knowledge of the extent of contamination in the concentration of the metals detected in the estuary. Fish remains an important part in the lagoon sediments, water and animal samples diet of Nigerians, especially for riverine collected from zones of the lagoon that received communities such as the inhabitants of the study most of the industrial effluents, generally had area, with seafood being served at almost every higher concentration than samples collected from meal. In Nigeria, especially in rural and fishing zones which received fewer or no industrial communities, fish constitute approximately 75% effluents. Davies et al.(2006) in the studies on of animal protein consumed (Edun et al., 2010). heavy metal load in water and sediment and Fish is consumed either freshly prepared or bioaccumulation of heavy metals in periwinkle smoked. Shellfish, especially the (Tympanotonusfuscatusvar. radula) from Elechi Tympanotonus species, are used largely as a Creek, Niger Delta, reported that the sediment condiment in most meals eaten in the Niger Delta concentrated more heavy metals than the water, (Gomna and Rana, 2007). while periwinkles accumulated more of these In Africa and developing world where metals than found in its environment. environmental protection laws have sparingly Bonny/New Calabar River Estuary been enforced, industrial and domestic wastes system is vital to the people of Niger delta and containing toxic and hazardous substances other surrounding regions. It is perhaps one of including heavy metals are dumped the largest arms of the River Niger discharging indiscriminately into water bodieswhich directly into the Atlantic Ocean.and it is believed eventually settle in bottom sediments (Oguzie to also be the most environmentally stressed 2002). According to Bineyet al.(1994), microbial (DublinGreen 1994).Artisanal fishery is a and redox processes may change the properties common sustenance to inhabitants on its banks. of sediments and affect the composition of Several independent researchers have reported interstitial water, while reworking of the at different times the heavy metal load in this sediments by organisms will also bring sediments Estuary (Chindahet al. 2004; Davies et al.2006; to the surface, where a significant fraction of Obireet al. 2003). However, there has been no heavy metals will be released. A good knowledge coordinated approach to monitor heavy metal of the distribution of heavy metals in water and levels in the estuary, hence the present study aim sediments plays a key role in detecting the to determine the levels of heavy metal pollution in sources of pollution in aquatic systems (Idodo the sediment, sea water, fish and crab of Bonny Umeh and Oronsaye 2006). Bottom sediments Estuary to establish changes over a period of two are particularly useful to monitor heavy metal years and evaluate bioaccumulation patterns of pollution in aquatic ecosystems because they metals in biota as part of an ongoing monitoring serve as a sink for archiving contaminants. exercise along Nigeria’s coastline for integrated Several workers have investigated the catchment management supported by concentration of heavy metals in the coastal international funding agencies. rivers with Atlantic tidal effect in Nigeria.A good account of such studies in the Niger Delta is MATERIALS AND METHODS given in the work of Asonye et al. (2007) in which Study Area heavy metal load of several rivers in Nigeria were The study area stretched from lower reported.Generally, heavy metal concentration reach of Bonny River at Bonny town by Peterside have been reported to be low in Nigerian water community to Choba town in the upper reach of bodies by earlier workers, notable among which the New Calabar River. The entire stretch from are Obireet al. (2003) on Elechi Creek, Chindahet the Bonny to Choba is largely influenced by the

HEAVY METAL PROFILES IN VARIOUS MATRICES OF THE BONNY/NEW CALABAR RIVER ESTUARY 3 tidal cycles, about 20km, lies between longitude washed plastic polythene bottle and digested in a 7ᴼ 00’’ to 7 ᴼ15’’ E and latitude 4 ᴼ 25’’ to 4 ᴼ 45’’ N. 100ml solution of conc. HNO and HCl acids (1:1 3 The tidal amplitude is generally high and above ratio). The mixture was vigorously shaken in a 2m at the Bonny terminaljetty. However, the mechanical shaker and then filtered through No water level increases and decreasesdepending 42 Whatchman filter paper (IdodoUmeh and on the lunar cycle. At high tides, salinity Oronsaye, 2006). All acid used were of analytical increases and decreases at low tides. Sea grade quality and control was assured by the use influence is experienced more at high tide regime of procedural blanks and spikes. The spike than at low tide, when the effect decreases recovery for each element was greater than 94%. especially within the upper limits when fresh All samples were run in triplicates and the relative water input dominates the zone. standard deviation for the triplicate analysis was The fanshaped Niger Delta, which is the less than 10%. Standard solutions of the metals third largest in the world after the Mississippi were prepared from their 1000 ppm stock (USA) and Pantanal (SouthWest Brazil), lies solutions for calibration between latitudes (4° and 6°) north of the equator and longitudes (5° and 9°) east of the Greenwich Sample analysis Meridian. The predominant coastal vegetation of The concentrations of the metals (Ca, Mg, K, Zn, the Bonny River due to its tidal influence is the Pb, Cd, Co, Cr, Cu, Fe, Ni and Na) were mangrove, whose main species are the red and determined using a Varian Atomic Absorption white mangroves which form more than nineteen Spectrophotometer (Perkin Elmer Analyst AA 200 percent (19%) of the saline swamps (Nwilo and equipped with a high sensitivity nebulizer). A one Badejo, 2008). The white mangroves occur way analysis of variance was performed to scattered among the red mangroves and thrive in compare the difference in concentration between less waterlogged places. The Bonny river the two years for sediment and water samples. system is characterized by the interaction of an Metal concentrations in crab and fish were estuarine and highly saline seawater located compared using multiple bar charts. seaward of the river mouth (typical of the Niger Bioaccumulation factor (BF) was calculated to Delta coastal region), and influenced by tide and determine the level of heavy metal accumulation winddriven surface currents. The coastal areas in the tissue of the organism using the formula of Bonny River play host to many fishing below, settlements while the river itself is a major BF = Concentration of metals in seafood (mg/kg)______navigational channel for oil vessels, countless Concentration of metals in water/sediment (mg/kg) outboard engine boats, maritime and oilrelated Where: activities. BF is the ratio of metals concentration in seafood tissues to the concentration in wateror sediment Sampling and sample preparations calculated using Microsoft Excel package 2010. Grab bottom sediment samples were collected quarterly over a two year period (20112012) Results and Discussions. using and kept in plastic containers which had Results of trace metals analysis in water, previously been treated with 10% nitric acid for sediments, Fish and Crab from the Bonny/New 24 hours and rinsed with deionized water. The Calabar River Estuary system are presented in samples were transported to the Laboratory and Table 1 and Figs. 13. The range values and the stored frozen. The samples were later ovendried test of statistical significance between heavy to constant weight at 105 °C, ground to powder concentrations of the two years of sampling are and then sieved through a 650m stainless sieve presented in Table 1 and bioaccumulation factors to remove ungrounded matter. 10grams of the in Table 2. sieved sediments was weighed into an acid

4 B. B. BABATUNDE, F. D. SIKOKI, M. C. ONOJAKE, R. U. AKPIRI AND D. AKPULOMA

Table 1: Range values and P values of heavy metal concentrations in water and sediment from the Bonny/New Calabar Estuary system for 2011/2012 Metal Water Sediment 2011 2012 P values 2011 2012 P values

Ca 4.810.8 3.110.6 0.178 3.110.5 7.510.9 0.530 Mg 51.452.7 50.257.1 0.421 50.653.3 52.253.4 0.199 K 20.730.3 19.838.1 0.011* 18.728.3 18.357.1 0.199 Zn 0.10.6 0.12.5 0.002* 1.53.3 0.26.0 0.303 Pb 0.20.3 0.20.3 0.702 0.20.6 0.20.9 0.131 Cd 0.090.1 0.020.2 0.628 0.00.1 0.010.3 0.430 Co 0.20.4 0.40.6 0.027* 0.40.7 0.30.7 0.470 Cr 1.11.9 0.12.9 0.111 0.81.8 1.03.8 0.005* Cu 0.40.5 0.31.2 0.642 1.41.9 0.42.2 0.343 Fe 0.44.5 0.31.3 0.170 0.438.0 0.638.7 0.822 Ni 0.10.4 0.10.3 0.396 0.20.7 0.20.8 0.912 Na 0.66.7 3.15.1 0.633 4.123.3 5.118.7 0.916 *Statistically significant

Table 2: Concentration factors of metals in fish and crab with reference to water and sediment.

CF = Concentration factor Medium Ca Mg K Zn Pb Cd Co Cr Cu Fe Ni Na CF fish/water 0.19 0.98 0.73 0.94 0.90 0.09 1.50 1.48 0.11 0.08 1.14 0.34 CF crab/water 0.17 0.94 0.82 0.21 1.17 1.06 1.15 0.70 1.06 0.53 3.13 0.64 CF fish/sediment 0.25 0.99 0.78 10.08 2.12 0.14 2.53 1.66 0.23 1.02 1.96 1.22 CF crab/sediment 0.21 0.95 0.87 2.25 2.76 1.64 1.94 0.79 2.28 6.85 5.40 2.28

HEAVY METAL PROFILES IN VARIOUS MATRICES OF THE BONNY/NEW CALABAR RIVER ESTUARY 5

60 2011 50 2012 40 30 20 mg/l 10

Concentration in Concentration 0 -10 Ca Mg K Zn Pb Cd Co Cr Cu Fe Ni Na Metals

Fig. 1: Mean heavy metal concentration in water from the Bonny/New Calabar River Estuary system (n = 5).

60 2011 2012 50

40

30

20

10

Concentration in mg/g in Concentration 0 Ca Mg K Zn Pb Cd Co Cr Cu Fe Ni Na Metals

Fig. 2: Mean heavy metal concentration in sediment from the Bonny/New Calabar River Estuary system (n = 6).

6 B. B. BABATUNDE, F. D. SIKOKI, M. C. ONOJAKE, R. U. AKPIRI AND D. AKPULOMA 70 FISH 60 CRAB 50

40

30

20

10 Concentration mg/g in Concentration 0 Ca Mg K Zn Pb Cd Co Cr Cu Fe Ni Na -10

Metals

Fig. 3: Mean heavy metal concentration in fish and crab from the Bonny/New Calabar River Estuary system (n = 3).

Water a statistical significant level of P < 0.05 (P = Calcium concentrations in water ranged 0.0112) indicating increase in 2012. Zinc from 4.810.8 mg/L in 2011 and 3.110.6 mg/L in concentrations recorded a wider range in 2012 2012 with 2011 recording a higher average value (0.12.5 mg/L than 2011 (0.10.6 mg/L) at a of 7.8±1.1 mg/L than 2012 (5.2±1.4 mg/L) but the statistical significant level (P = 0.002441).The difference was not statistically insignificant at (P statistical significance at (P <0.05) indicated an > 0.05) and the values were well within stipulated increase in 2012 which was not as a result of limits of 5– 500mg/L by US EPA (2004) and chance but possible anthropogenic input. Mean WHO, (2006). Concentrations of Mg, K, Fe, Ni valuesrecorded for Zn were 0.8±0.2 and 0.3±0.1 and Na were slightly higher in 2011 than 2012 in 2011and 2012 respectively. Furthermore, Zn but none recorded statistical significant variation values recorded in water samples during the two value at P > 0.05 probability level between years showed levels higher than stipulated limits concentrations of the two years. Magnesium of 0.001 mg/L for drinkable water by WHO concentrations ranged from 51.452.7 mg/L in (2006).Elevated levels of Zn have been shown to 2011 and 50.257.1 mg/L in 2012 with average adversely affect growth, survival, and values of 51.7±0.3 and 52.9±1.4 in 2011 and reproduction animals (Eisler 1993). 2012 respectively and its concentrations did not The concentration of Pb was higher than vary significantly between the two years (P = stipulated limits of 0.01 mg/L for safe drinkable 0.4211). The concentrations of K ranged from water by WHO, (2006) ranging from 0.20.3 mg/L 20.730.3 mg/L in 2011 and 19.857.1 mg/L in in both 2011 and 2012 with statistical insignificant 2012 with mean values of 25.8±1.8 and 31.8±1.9 variation at P >0.05 probability level. Adverse mg/L in 2011 and 2012 respectively. The effects caused by Pb to aquatic organisms concentration of K vary between the two years at include loss of sodium, reduced capability, and

HEAVY METAL PROFILES IN VARIOUS MATRICES OF THE BONNY/NEW CALABAR RIVER ESTUARY 7 developmental problems and distorted algal of low level heavy metal concentrations in growth (Freda 1991).Cadmium concentrations surface water in the study area and Niger Delta ranged from 0.090.1 mg/L in 2011 and 0.020.2 (Abu and Egenonu2008; Asonye et al. 2007; mg/L in 2012 with mean values of 0.1±0.001mg/L Chindah et al. 2004; Ubalua et al. 2007), some of and 0.1±0.003 mg/L in 2011 and 2012 the toxic metals such as Pb, Cd, Zn, Ni and Cr respectively. Its concentration did not vary were higher than stipulated limits by WHO, between the two years at a statistically significant (2006) and require continuous monitoring to level (P =0.6281). However, Cd values were detect malicious increases as a result of higher than 0.003 mg/L stipulated by WHO anthropogenic input and avert possible public (2006) as a safe limit in drinkable water. health implications of these metals on consumers Cadmium is an important factor in aquatic of water and seafood from the study area. monitoring studies, because it has been found to be toxic to fish and other aquatic organisms. It is Sediment one of the most toxic elements with widespread The concentrations of all the metals carcinogenic effects in humans, widely distributed measured in sediment apart from Co and Na, in the aquatic environment and bioaccumulates were slightly higher in 2012 than 2011. However, at all trophic levels, accumulating in the livers and only Cr recorded significant variation in its kidneys of fish (Sindayaigaya, et al. 1994). Cobalt concentration between the two years Table 1. concentrations ranged from 0.20.4 in 2011 and Calcium ranged from 3.110.5 mg/kg in 2011 and 0.40.6 in 2012. Its concentration varied between 7.510.9 mg/kg in 2012 with mean values of the two years at a statistical significant level (P 6.1±1.1 and 9.7±0.6 mg/L in 2011 and 2012 =0.0270) with 2012 recording higher mean respectively.Magnesium concentrations ranged values of 0.5±0.04 mg/L than 0.3±0.003 in 2011. from 50.653.3 mg/kg in 2011 and 52.253.4 Chromium values were higher in 2012 than 2011 mg/kg in 2012 with mean values of 52.3±0.4 and and higher than stipulated limit of (0.05 mg/L) by 53.0±0.1 mg/kg in 2011 and 2012 respectively. WHO (2006). Its concentrations ranged from 1.1 Potassium ranged from 18.728.3 mg/kg in 2011 1.9 mg/L in 2011 and 0.13.8 mg/L in 2012 with and 18.338.1 mg/kg in 2012 with mean values of mean values of 1.8±0.2 and 2.1±0.6 mg/L in 24.2±1.5 and 28.1±3.3 mg/kg in 2011 and 2012 2011 and 2012 respectively. Chromium in its respectively. Zinc ranged from 1.53.3 in 2011 hexavalent form has been known as a and 0.26.0 in 2012 with mean values of 2.7±0.9 carcinogen and implicated in many health effects and 2.8±0.7 mg/kg in 2011 and 2011 in animals (WHO 2006). Copper concentrations respectively. Lead concentrations ranged from ranged from 0.40.5 in 2011 and 0.31.2 in 2012 0.20.6 mg/kg in 2011 and 0.20.9 mg/kg in 2012 with mean values of 0.4±0.02 and 0.5±0.2 in with mean values of 0.6±0.1 and 0.3±0.06 mg/kg 2011 and 2012 respectively. All copper values in 2011 and 2012 respectively. Cadmium ranged were below permissible limits of 2 mg/L by WHO from below detection limit to 0.1 mg/kg in 2011 (2006) and US EPA (2004) and its concentrations and 0.010.2 mg/kg in 2012 with mean values of did not vary at a statistical significant level 0.06±0.02 and 0.1±0.03 mg/kg in 2011 and 2012 between the two years studied (P = 0.6420). respectively. The concentration of Fe was higher in The concentrations of Co ranged from 2011 than 2012 but not at a statistically 0.40.7 mg/kg in 2011 and 0.30.4 mg/kg in 2012 significant level. It ranged from 0.44.5 mg/L in with mean values of 0.5±0.05 mg/kg and 2011 and 0.31.3 mg/L in 2012 with mean values 0.5±0.06 mg/kg in 2011 and 2012 respectively. of 2.0±0.8 and 0.8±0.2 mg/L. Nikel Chromium ranged from 0.81.8 mg/kg in 2011 concentrations ranged from 0.10.4 mg/L in and 1.02.9 mg/kg in 2012 with mean values of 20111 and 0.10.3 mg/L in 2012 with mean 1.1±0.2 mg/kg and 2.0±0.3 mg/kg in 2011 and values of 0.3±0.04 and 0.2±0.01 in 2011 and 2012 respectively. The concentrations of Cu and 2012 respectively. Mean concentration of Ni was Fe in 2011 and 2012 ranged from 1.41.9 and only slightly higher in 2012 (P = 0.3960). Sodium 0.42.2 mg/kg, 0.438.0 and 0.638.7 mg/kg concentrations recorded ranged values from 0.6 respectively with mean values of 0.9±0.3 and 6.7 mg/L in 2011 and 3.15.1 in 2012 and mean 0.5±0.09 mg/kg, 25.6±7.4 and 29.9±5.9 mg/kg for values of 3.81.0 and 4.40.4 mg/L in 2011 and Cu and Fe in 2011 and 2012 respectively while 2012 respectively. Although the results of surface that of Ni and Na ranged from 0.20.7 and 0.20.8 water concentrations of heavy metals observed in mg/kg, 4.123.3 and 5.118.7 mg/kg respectively the present study agrees with the general opinion with mean values of 0.4±0.09 and 0.5±0.08

8 B. B. BABATUNDE, F. D. SIKOKI, M. C. ONOJAKE, R. U. AKPIRI AND D. AKPULOMA mg/kg, 13.8±3.2 and 12.8±1.8 mg/kg for Ni and fish from water was Na in 2011 and 2012 respectively. Co>Cr>Ni>Mg>Zn>Pb>K>Na>Ca>Cu>Cd>Fe Sediments are described as sink for and in crab the accumulation of metals was in the contaminants. In the present study, all metals order of magnitude concentrations were higher in sediments than in Ni>Pb>Co>Cd>Cu>Mg>K>Cr>Na>Fe>Zn>Ca. surface water, however, only Zn, Fe and Na Some of the metals such as Ni, Na, Fe, Cu, Cd, recorded higher concentrations in sediment than Pb and K were better accumulated in crab with surface water at statistically significant level (P = three times more Ni in crab than in fish.However, 0.00351). Some studies have reported similar some of the metals such as Cr, Co and Zn were results for metals studied in the present research better bioaccumulated in fish than in to range higher in sediment than surface water in crab.Bioaccumulation of metals was generally the Bonny/New Calabar Estuary system and higher in both organisms when sediment was the Niger Delta (Chindah et al. 2004, 2009). medium of evaluation with metals such as Zn, Fe However, the general results obtained in this and Ni bioaccumulating in the magnitude of 10, 6 study for heavy metal concentrations in and 5 times higher in the organisms.This may be sediments were higher than that of other studies as a result of higher metal concentrations in in the Niger Delta (Davies et al. 2006; Horsfall sediment and the biology of the organisms and Spiff 2002; Iwegbue et al. 2007; Obire et al. studied which typifies bottom feeders. The order 2003). of magnitude of metal accumulation in fish from sediment was in the sequence Fish and Crab Zn>Co>Pb>Ni>Cr>Na>Fe>Mg>K>Ca>Cu>Cd Results of the analyses of heavy metals while the pattern in crab was in fish and crab showed variability in the Fe>Ni>Pb>Na>Cu>Zn>Co>Cd>Mg>K>Cr>Ca. concentrations of the metals in the two animals The bioaccumulation patterns observed in the Fig. 3. The concentration of Ca, Mg, Zn and Cr present study shows that even in similar media, recorded higher values in crab than in fish. different organisms may bioaccumulate However, the differences in the concentrations of contaminants differently and there may be these metals in the two organisms was not specific factors influencing selective statistically significant at P > 0.05 probability level bioaccumulation of metals in the organisms (P = 0.2612). The concentrations of K, Cd, Pb, which is beyond the scope of the present Ni, Cu, Fe and Na were higher in fish than in study.However, according to Eneji et al. (2011), crab. However, only the concentrations of Fe and the rate of bioaccumulation of heavy metals in Na were higher at statistically significant level (P aquatic organisms depends on the ability of the = 0.01128). Mean values of heavy metal organisms to digest the metals and the concentrations in fish and crab are presented in concentration of such metal in the river. Also it Fig. 3. Fish samples showed Mg to record the has to do with the concentration of the heavy highest concentration, followed by Ca and K metal in the surrounding soil sediments as well while Co recorded the least mean concentration as the feeding habits of the organism. Fig. 3. In crab also, Mg recorded the highest Furthermore, some of the factors may include, followed by K, Ca and Fe while Ni recorded the age of fish, lipid content in the tissue and mode of least mean concentration Fig. 3. All metals feeding are significant factors that affect the except Ni in crab recorded mean values higher accumulation of heavy metals in fishes. Similar than reported elsewhere in the Niger Delta studies have reported similar bioaccumulation (Agbozu et al., 2007; Chindah et al. 2009; Davies patterns of metals in different organisms in the et al. 2006; Obire et al. 2003;Ubalua et al. 2007; Bonny/New Calabar River Estuary (Chindah et al. Uyimadu et al. 2008,) and higher than stipulated 2009; Davies et al. 2006) and elsewhere in the limits for safe consumption of seafood by WHO Niger Delta (Olowoyo 2011) and River Benue (2006). (Eneji et al. 2011). Seafoods have been recognized as good Heavy metals have multiple effects in accumulators of organic and inorganic pollutants biological systems depending on the oxidation which are finally transferred to other animals state, the formation of complexes and including humans through the food chain. biotransformation of elemental species. Health Bioaccumulation of metals showed different effects of heavy metals such as Pb, Zn, Cr, Cd patterns in fish and crabstudied Table 2. The and Cu in humans have been demonstrated in order of magnitude of accumulation of metals in acute toxicity, neurotoxicity and nephrotoxicity

HEAVY METAL PROFILES IN VARIOUS MATRICES OF THE BONNY/NEW CALABAR RIVER ESTUARY 9 (Katz and Salem 1993; ATSDR 200; Stift et al. Akpomuvie, O. B., 2011. Tragedy of commons: 2000; WHO 2011) while Pb is a confirmed Analysis of oil spillage, gas flaring and carcinogen (Martin and Griswold 2009; WHO sustainable development of the Niger 2011).Some observed effects of Ni in aquatic Delta of Nigeria. Journal of Sustainable environments include tissue damage, Development . 4, 20010. genotoxicity and growth reduction. Mollusks and crustaceans are more sensitive than other Asonye, C. C., Okolie, N. P., Okenwa, E. E and organisms (Onojake and Frank 2012). Iwuanyanwu, U. G., 2007. Somephysico chemical characteristics and heavy metal CONCLUSIONS profiles of Nigerian rivers, streams and waterways. African Journal of Heavy metals from different sources are Biotechnology. 6, (5): 617624. prevalent in coastal areas of the Bonny River, Southeastern Niger Delta. The present study ATSDR., 2000. Toxicological profile for showed that sedimentary heavy metals, surface chromium. Atlanta, Georgia, United water heavy metals, heavy metals in crab and States Department of Health and Human fish in stations from the study area were of mixed Services, Public Health Service, Agency biogenic, anthropogenic and industrial sources. for Toxic Substances and Disease Heavy metal concentrations showed slight Registry. increase over 24 months of monitoring in water and sediment samples with statistical significance Biney, C. A., Amuzu, A. T., Calamari, D., Kaba, in the variation of some of them at (P<0.05) N., Mbome, I. L., Neave, H., Chumba, P. B. O., probability. The higher concentrations of heavy Osibanjo, O., Radegonde, R and MAH.Saad., metals in sediment showed reiterated the general 1994. Review of heavy metals in the African believe that sediment are a sink and archive for aquatic environment. Ecotoxicology and contaminants. Environmental Safety. (28): 134159. In all, crab and fish had the tendency to bioaccumulate metals with preferences for some Chindah, A. C., Braide, A. S and Sibeudu, O. C., depending source (water or sediment) in which 2004. Distribution of hydrocarbons and heavy Zn, Fe and Ni bioaccumulated at magnitude of metals in sediment and a crustacean 10, 6 and 5 times higher in organisms from (Penaeusnotialis) from the Bonny sediment than water. Bioaccumulation of metals River/New Calabar River Estuary, Niger in edible organisms is a threat to human health Delta. African Journal Environmental since the metals will be ultimately transferred to Assessment and Management. (9): 117. humans along the food chain with possibilities of increase concentration of tissue burden which Chindah, A. C., Braide, S. A., Amakiri, J and may become fatal. Continuous monitoring to Chikwendu, S. O. N., 2009. Heavy Metal detect dangerous increases is therefore Concnetrations in Sediment and advocated. Periwinkle –Tympanotonusfuscastusin the Different Ecological Zones of Bonny ACKNOWLEDGEMENT River System, Niger Delta, Nigeria. Open The authors wish to acknowledge the support of Journal of Environmental. Pollution and the International Foundation for Science (IFS) Toxicology.1, 93106. Stockholm, Sweden, through a grant to Babatunde B B(W/52461) and International Davies, O. A., Allison, M. E and Uyi, H. S., 2006. Atomic Energy Agency (IAEA) through a Bioaccumulation of heavy metals in Technical Cooperation (RAF7/008 &009). water, sedimentand periwinkle (Tympanotonusfuscatusvar radula)from REFERENCES the Elechi Creek, Niger Delta. Afri.J. of Biotech. (5): 968973 Agbozu, I. E., Ekweozor, I. K. E and Opuene, K., 2007. Survey of heavy metals in the catfish DublinGreen, C. O., 1988. Some textural Synodontisclarias. International Journalof characteristics and organic content of Environmental Science and Technology recent sediments in the Bonny estuary, 4, (1): 937. Niger Delta. Technical Paper 67.

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