International Journal of Animal and Veterinary Advances 1(2): 54-58, 2009 ISSN: 2041-2908 © M axwell Scientific Organization, 2009 Submitted Date: July 27, 2009 Accepted Date: August 19, 2009 Published Date: October 30, 2009 Level of Heavy Metals in Freshwater Crab (Cardisoma guahumi) Obtained from Ahmadu Bello University Reservoir, Zaria Nigeria 1 D.S. Abolud e, 2 O.A. Davies and 1 D.W. Avong 1 Department of Biological Sciences, Ahmadu Bello University, Zaria, Nigeria. 2 Department of Fisheries & Aquatic Environment, Rivers State University of Science and Techno logy , Port Harcourt. Nigeria Abstract: The levels of Calcium (Ca), Potassium (K), M anganese (M n), Iron (Fe), Lead (Pb), Zinc (Zn ), Bromine (Br), Arsenic (A s), Rubidium (Rb), Strontium (Sr), Vanadium (V), Niobium (Nb) and Zirconium (Zr) in crabs Cardisoma guahumi has been evalua ted. Th e crabs we re collected in the A hma du B ello U niversity Reservo ir and analysed for the above metals using Energy Dispersive X-Ray Fluorescence (EDXRF) Technique. The data indicated variable levels of some of the metals in the crab samples. Enrichments of some of the metals were higher than others, in some stations and on the different body comp onents. The most concentrated was calcium (46500±16300ppm) while the least concentration was obtained in Niobium (29.3ppm ). Correlation co efficient betw een the various stations and betw een the various bo dy co mpo nents shows significant differences (P#0.05). Concentrations of some metals in Ahm adu B ello University Reservo ir, Zaria were found to be higher than the WHO recommended safe reference values. The high level of some of the metals in the crab C. guahumi suggested that the crab can be used as bio-indicator. Key w ords: Concen tration, freshwater crab, heavy m etals and ma n-made reservo ir INTRODUCTION Heavy metals contamination in wa ter may arise in many ways. Some of them are being mobilized by man to the atmosphere and hydrosphere at rates compared to and sometimes exceeding those by weathering process. The several human activities that may result to water pollution include agriculture, irrigation, fire, urbanization, mining and industrialization (Goudie, 1990). These activities have been docu men ted to have im pacted neg atively in some specified Nigerian surface waters especially in the Niger-Delta region (Izonfuo and Bariwe ni, 2001). Also these activities have affected the soils of industrial areas in southern Nigeria (Olajire et al., 2003). As a consequence, mod ifications of their co ncen trations in aquatic organism s are to be expected (Abubakar and Garba , 2006). Anthropogenic heav y me tals follow ing their introduction to water bodies through atmospheric fallout or through the use of domestic antiseptic soaps and pesticides in our farms are washed into the water and concentrated by aquatic organisms (Goldb erg, 1972). Discharge of industrial wastes also constitute about 62% of total source of heavy metal such as Lead (Pb), Zinc (Zn), Copper (Cu), Nickel (Ni), Cadm ium (Cd ), Chromium (Cr) and Manganese (M n) which are respo nsible not on ly for degrading the water quality of a river or sea but for killing a number of aquatic organisms (Abubakar and Garba, 2006). These metals are toxic after large accumulation in the body of flora and fauna and later pass on through the food chain from fish to man (Ayodele and Abubakar, 2001). Although some of these metals may be essential, some may be hazardous for human metabolism especially when their concen tration is high (Sheriff et al., 1979). The presence of heavy metals in aquatic animals is becoming a threat, thereby making them unfit for human consumption. Heavy metals found in crustac eans are known to affect the enzyme balance as well as demobilize them (Herkovits et al., 1996 ). Baseline inform ation on the pond ecosystem status in the northe rn parts of Nigeria including Zaria is scanty, as a result, it leads to a few published works on water chemistry, quality and management (Balarabe, 2001). The objectives of the rese arch w ork are to determine the types of metals and the levels of their concentration obtained in crabs found in the Ahmadu Bello University freshwater Reservoir. MATERIALS AND METHODS Study Area: Kubanni Reservoir: Zaria, one of the largest cities in Kaduna State, Nigeria is situated in the northern guinea savannah zone. It possesses a tropical continental climate with distinct wet and dry seasons Kubanni Rive r is located in Zaria. The river lies approxim ately betw een latitude 11º8'N , 11º10'N and longitude 7º41'E, 7º42'E on the Zaria sheet no 102 of Nigerian ordinance survey map. The Kubanni River drains this area in a dendritic pattern, with its major drainage artery dissecting Zaria. Its wa terway is made up of about 157 channels which drain the entire basin as the river flows in a north-south, East direction at the ge ntle Corresponding Author: D.S. Abolude, Department of Biological Sciences, Ahmadu Bello University, Zaria, Nigeria 54 Int. J. Anim. Veter. Adv., 1(2): 54-58, 2009 gradients carrying along its course superficial deposits of alluvial sands, silts, eroded detritus, younger laterite and organic matter derived from the catchment zones (Abolude, 2007 ). The Kubanni River takes off from the Kampa gi hills at an elevation of the approximately 711meters, it thus acquires enough inertia and gravitational force for the drainage of the entire basin before empting its bed-load finally into the Galma River a major tributary of the Kad una R iver (Abolude, 2007 ). Along its course, the Kubanni waterw ay meanders through deep gullies created by the weathering of granite basement rock (Ewa et al., 1999 ). Altho ugh most of the channels which v ary co nsiderably b oth from station to station and from time to time are seasonal flowing m ostly during and shortly after the rains, the flood plains re main wet due to the shallow water table and perhaps because of the various recharge sources through the unconsolidated surface layers underlain by impervious bedrocks (Thomas, 1976). There is therefore sufficient water for seaso nal irrigation and dam emb ankmen t. Upstream, there is a dam across its valley (A.B.U. Reservoir) which is used by the A hma du B ello U niversity com mun ity and p artly by the peo ple in Sam aru Zaria for its water supply. Downstream, attempt to conserved river water include construction of earth or sand barrages or by artificially the enlarging and deepening pools (Adakole, 1995). There are two major uses of the river, Agriculture (irrigation, Fishing and watering cattle) and dom estic (drinking, washing and bathing). Heaps of refuse dumps, human faeces, cattle dump could be found on the slopes of the Kubanni River valley. Both municipal and industrial effluents are ch annelled into the river without respect to their quality. Station 5: Site chosen along same axis o ccup ied by Centre for Energy Research and raining (CER T). It is a point along the Kubanni River just before the entry point of sewage (from the treatme nt plant of the A hma du B ello University) into the K ubanni R iver. Selection of Sampling Stations: Five (5) established sampling stations were selected and marked along the Kubanni Reservoir from the point Kub anni River enters into the Reservoir to the across the dam, titled station 1-5. These sampling stations were selected to reflect progression of pollution. The stations are as described. Elemental Analysis: Heavy metal composition and concentration of the crab samples collected from the reservoir were determined using Energy D ispersive XRay Fluorescence (EDXRT) Technique at the Centre for Energy Research and T raining (CE RT ), Ahmad u Bello University, Zaria. Station 1: Sampling point close to the Institute of Development Research (IDR), takes care of agricultural, domestic and other wastes from the university. It is the point wh ere Ku banni R iver enters the Reservoir. Method of Eleme ntal An alysis: Pellets of 19 mm diameter were prepared from 0 .3-0.5g pow der m ixed w ith three drops of organic liquid binder and pressed afterwards at 10 tons with a hydraulic press. Measuremen ts were performed using an annular 25 mCi 1 0 9 Cd as the excitation source, that emits Ag-K Xrays [22.1 KeV] in which case all elements with lower characteristics excitation energies were accessible for detection in the samples. The system consists furthermo re of a Si (Li) detector, with a resolution of 170 eV for the 5.90 KeV line, coupled to a computer controlled ADCcard. Quantitative analysis of the samples was carried out using the Emission Transmission (E-T) method, for which a number of quantification methods has been developed and applied (Leroux and Mahmoud, 1996; Giauque et al., Collection of Crab: Crab samples were collected from the described established stations on Kubanni R eservoir using Ma li traps which w ere set and left for at least three (3) days. They were placed in clean polythene bags and taken to the laboratory. Laboratory Analysis: Crab Weighing and Measurement The collected crab specimens were weighed using the electronic Mettler Ba lance (Model P1200N ). The length [from the tip of the first claws stretched to the other claws), body width and d epth w ere measured w ith a pair of Van ier calliper. Drying: The crab samples were dried in an oven (Gakenkamp oven] at 110ºc. Separation of body com ponents: The crab sample was separated into four various pa rts, which are the claws, the legs back carapa ce and front carapace. Preparation of Crab Powder: Each crab sample was ground manually to powder with an agate mortar and pestle to grain size of less than 125:m forms with pretreated mortal and pestle. Cleaning of the mortal and pestle took p lace after each crushing to pow der form to avoid contamination (Prendez and Carrasco, 2003). The crab powder were bagged into coded new plastic bags and sealed, then taking for analysis for heavy metals. Station 2: Samp ling point halfway betw een w here Kubanni River and Kud ungi Stream enters the Reservoir. It takes care of agricultural, chemicals and other wastes from the adjacent farmland. Station 3: Samp ling point below where Kudungi Stream enters the adjacent farmland. Station 4: The sou thern end point of AB U R eservoir. It takes care of the wastes from the adjacent farmland settlements. 55 Int. J. Anim. Veter. Adv., 1(2): 54-58, 2009 1979; Markowicz, 1979; Tang et al; 1986; Markowicz and Van Grieken, 1993; Kump, 1996; Bernasconi et al., 1996). These quantification methods provide different approaches to correct the matrix absorption as well as enhancement effects. In this work quantification was carried out using a modified version of E-T method (Kump, 1996; Angeyo et al., 1998; Funtua, 1999a; 1999b) and it involves the use of pure target material (Mo) to measure the absorption factor in the sample. The Mo target serves as a source o f mon ochromatic X-rays, which are excited throug h the samp le by primary radiation and then penetrate the sample on the w ay to the detector. In this way, the absorption factor is experimentally determined which the program uses in the quantification of concentration of the elemen ts. In addition, the contribution to the Mo-K peak intensity by the Zr-K is subtracted for each sample. Sensitivity calibration of the system was performed using thick pure m etal foils (T i, Fe, Co, Ni, Cu, Z n, Zr, Nb, Mo, Sn, Ta, Pb) and stable chemical compound (K 2 CO 3 , CaCO 3 , Ce2 O 3 , W O 3 , ThO 2 , U 3 O 8 ). The spectra for the sam ples w ere collected for 3000 s with the 1 0 9 Cd source and 2000 s for the 5 5 Fe source and the spectra were then evaluated using the AXIL-QX AS program (Bernasconi, 1996 ). least (36100±144ppm ). More ov er, wh ile the highest (465000±163ppm) Ca claw was obtained at Station 3, the least (318000±108ppm) was obtained at Station 1. The correlation coefficient shows significant difference (P#0.05) in the various body components and also in each station there is significant difference (P#0.05) in the body components. The distribution of Ca in the body componen ts were: back carapace > claws > legs > front carapace. Ca is the major constituent that makes up the carapac e (shell). M anganese (Mn, ppm ): Manganese was only obtained at Station 5 but was not obtained from the legs of Crabs at Station 5. The concentration ranged from 2400 ± 1125 to 2910 ± 1130 ppm. There was no significant difference (P$0.05) between Mn obtained from the body componen ts. Iron (Fe, ppm ): Fe was not found in all the stations except in Station 2, 3 and 5. Even in these three stations, Fe was not found in all the body components. The Iron concentration obtained ranged from 1390±95 to 2900 ±467ppm. W hile the highest Fe concentration on the back carapace (2900±467 ppm) was obtained at Stations 2, the least (2260±840ppm ) was at Station 3. The highest (2310±695ppm) Fe in legs was obtained at Station 2, the least (1390±95ppm) was obtained at Station 5. While the highest (2880±874ppm) Fe in claws was obtained at Station 2, the least (1660±120ppm) was obtained at Station 5. So also the highest (2570±606ppm) Fe in front carapace was obtained at Station 5, the least (2030±467ppm) was obtained at Station 2. The correlation coefficient show s that there was no significant difference (P$0.05) between the stations or in the body com ponents of each station. 109 Cd source was use d for the analysis of K , Ca, T i, V, Cr, Fe, Co, Ni, Cu, Zn, Ta, W, Ga, As, Se, Pb, Br, Rb, Sr, Th, Y, U, Zr, Nb, and Mo. RESULTS The results of the analysis using Energy Dispersive X-Ray Fluorescence Technique are as presented in the Table 1. The result shows the level of concentration of the metals in the crab Cardisoma guahumi obtained in the Reservo ir from different sampling stations. Som e metals were not detected in som e of the sampling stations w ith the exception o f Ca and Sr. the trend or the metal accumulation in the crab C. guahumi is Nb< Zr< Rb < Br <As < Pb < Z n < Sr < M n < Fe < V < K< Ca. This is not in support of the fact that the crude generalization order of metals toxicity w as reported as Co < N i < Cr <Pb < Zn < Cd < Cu < Ag < Hg (R iley and Skirrow, 1974 ). Lead (Pb, ppm ): Lead was only obtained at Station 5 and only in the claws with concentration of 238±16ppm. Zinc (Zn, ppm ): Zinc was obtained at Stations 3 and 5. At Station 3, it was o btained in the front carapace with a concentration of 498±58ppm and in Station 5 in the back carapace (442±1 5ppm ) and legs (304±05ppm). Potassium (K, ppm ): Potassium was not detected in all the stations, it was found only at Station 5. At Station 5, K was found in the claws with concentration of (34300±9990ppm) and legs with (32400ppm). The correlation coefficient show s significant difference in concentration of the two body compo nents that w ere obtained (P#0.05). Bromine (Br, p pm ): Bromine was only obtained at Station 5 in the claws with concentration of 85±5ppm. Arsenic (As, ppm ): Arse nic w as obtained at Station 5 only. It was obtained in the back carapace with concentration of 160±10ppm. Calcium (Ca, pp m): Calcium w as w idely distributed in all the body com ponents examined from all the stations. The concentration of Ca ranged from 20 3000± 100 to 465000± 163ppm. W hile the highest concentration of Ca in the front carapace (354000±159ppm) was obtained at Station 1, the least (203000±100ppm) was obtained at Station 2. The highest concen tration (463000 ±108ppm) of Ca back carapace was obtained at station 1, but Station 5 had the Rubidium (Rb, ppm ): Rubidium was obtained at Station 5 only from the back carapace with a concentration of 75.6±31.1 ppm concentration. Strontium (Sr, ppm ): Strontium was widely distributed in all the body components examined from all the stations (Table 1). The conc entration rang ed from 380±46 to 1610±57ppm. The correlation coefficient shows significant difference (P#0.05) in the various stations and 56 Int. J. Anim. Veter. Adv., 1(2): 54-58, 2009 Table 1:Elemental composition of the anatomical components of the crab (Ca rdisom a gu ahu mi) o b ta in fr om A B U R es er vo ir (i n p p m) Station 1 Station 2 Station 3 ----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------Element CF CB CW L CF CB CW L CF CB CW L K BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL Ca 35400 463000 318000 364000 203000 437000 401000 344000 314000 420000 465000 454000 ±159 ±164 ±108 ±145 ±100 ±151 ±147 ±136 ±161 ±147 ±163 ±165 Mn BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL Fe BDL BDL BDL BDL 2030 2900 2880 2310 BDL 2260 BDL 2620 ±467 ±467 ±874 ±695 ±840 ±94 Pb BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL Zn BDL BDL BDL BDL BDL BDL BDL BDL 498±58 BDL BDL BDL Br BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL As BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL Rb BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL Sr 918±35 1100±39 1290±41 1010±35 683±28 1500±48 1190±43 1150±39 972±4 11470±49 1610±57 1470±56 V BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL Nb BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL Zr BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL Table 1: (Continuted) Station4 Station5 ------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------CF CB CW L CF CB CW L BDL BDL BDL BDL BDL BDL 34300±9990 32400 278000± 1 41414000±160 338000±119 287000±144 243000±137 361000±44 436000±15 4444000±153 BDL BDL BDL BDL 2400±1125 2650±110 2910 ±1130 BDL BDL BDL BDL BDL 25070±606 BDL 1660±120 1390±95 BDL BDL BDL BDL BDL BDL 238±16 BDL BDL BDL BDL BDL BDL 442±15 BDL 304±5 BDL BDL BDL BDL BDL BDL 85±5 BDL BDL BDL BDL BDL BDL 160±10 BDL BDL BDL BDL BDL BDL BDL 75.6±±31 BDL BDL 1040±37 1420±48 1400±41 1090±43 957±35 380±46 1450±42 1340±36 BDL BDL BDL BDL BDL BDL 7710±212 BDL BDL BDL BDL BDL BDL BDL 2 9 .3 ± 5 BDL BDL BDL BDL BDL BDL BDL BDL 3 0 .5 ±4 CF = C arapa ce fron t, CW = claw s, PP M = Pa rt per m illion, CB = C arapa ce bac k, L = legs, B DL = B elow detectio n limit also in each station crab, there is significant difference (P#0.05) observed in the body components. While the highest Sr concentration in the front carapace (1040±37ppm) was obtained at Station 4, the least (683±28ppm) was obtained at Station 2. Moreover, the highest (1500±48ppm) Sr back carapace was obtained at Station 2, the least (380±46ppm) was obtained at Station 5. So also, while the highest (1610±57ppm) Sr claw was obtained at Station 3, the least (1190±43ppm) was obtained at Station 2. In addition, the highest (1470±56ppm) Sr in legs was obtained at station 3, the least (1010±35.2ppm) was obtained at Station 1. concentration of 1610ppm does not exceed the WHO limit of 2433ppm, but Lead with concentration of 238ppm exceeded the WH O limit of 10ppm. Iron also with highest concentration of 2880±874ppm exceeded the W HO limit of 1220ppm. Aquatic organisms were reported to be selective in metal accum ulation due to toxicity effects (Ayodele and Abu bakar, 2002). The mode of action of heav y me tals on biological systems is thought to be through enzymes systems, although extra ordinary concentrations may result in direct tissue damage (Abubakar and Garba, 2006). Some aquatic animals can regulate their body burden, crab Carcinus maenus can regulate its body level of Zn, after exposure to sea water containing 500 times the normal concentration of Zn, with the concentration by 2 and 4 factors respectively (Abubakar and Garba , 2006). Regulation of metal body burden by aquatic organisms can be through three principal mechanisms, via gut, urine and diffusion through the body surface. Crustaceans excre te Zn, Cu, Co, Mn, and Hg in the urine (Bernard and Lane, 1961).This could be responsible for the low detection of Z n and other m etals. Vanadium (V, ppm ): Vanadium was obtained at Station 5 only in the claws with 7710±212ppm concentration. Niobium (Nb, pp m): Niobium was only obtained at Station 5 in the claws with 29.3±5ppm concentration. Zirconium (Zr, ppm): Zirconium was only obtained at Station 5 in the legs w ith 30.5±4ppm c oncentration. DISCUSSION CONCLUSION Calcium and Strontium were obtained in all the stations and in all the body components because they constitute the major part of the elements that make up the shell of all crustaceans. Most of the metals detected did not exceed the tolerable limit. Zinc with the highest concentration of 498±158 ppm does not exceed the WHO limit of 500 ppm . Also Strontium with the highest The result of the analysis has shown that crab Cardisoma guahumi can be used as bio-indicator as it contains variable levels of the metals analysed with high enrichment of Ca, Fe, Pb, and Sr observed. In orde r to reduce excessive discharge of m etals into the rese rvoir there should be reduction of farming activities around the 57 Int. J. Anim. Veter. Adv., 1(2): 54-58, 2009 reservoir. Furthermore, the consum ption of crab C. guahumi obtained from Station 5 by humans m ay pose risk from ingestion of tox ic metals at unacceptable concentration. matrices by X-ray fluorescence with incoherent scattered radiation as an internal standa rd. Anal. Chem., 51: 512-516. Goldberg, E.D., 1972. The Changing Chemistry of the Oceans (D. Drysseu and Jagnereds). Wiley Inter science Division, New Y ork, pp: 250-255. Goudie, A., 1990. The Human Impact on the Natural Env ironm ent. 3rd Edn. The M IT Press Cambridge, Massach usetts. Herkovits, J., C.S. Perez -Coll and F.O. Herkovits, 1996. Ecotoxicity in the Recognista River. Province of Buenos Aires, Argentina. A Preliminary study. Environ. Health Perspect., 104(2): 183. Izonfuo, L.W. and A. Bariweni, 2001. The Effects of Urban Runoff water and Human activities on some physico-chemical parameters of the Epe Creek in the Niger-Delta. J. Appl. Sci. Environ. Management, 5(1): 47-55. Kump, P., 1996. QAE S. Quantitative Analysis of Environmental Samples, Instruction Manual, Ljubljana. Leroux, J. and M. M ahmoud, 1996. X-ray quantitative analy sis by an emission-transmission, method. Anal. Chem., 38: 76-82. Markowicz, A.A., 1979. A method for correction for absorption matrix effects in samples of intermediate thickness in EDXRF analysis. X-ray Spectrum, 8: 14-18. Markowicz, A.A. and R.E. Van Grieken, 1993. Quantification in XR F Analysis of Interm ediate Thickness Samples. In: Handbook of X-ray Spectroscopy. R.E. Van Grieken and A.A. Markowicz. (Eds). Marcel Decker Inc. New Y ork. pp: 339-358. Olajire, A.A., E.T. Ayodele, G.O. Oyediran and E.A. Olugbemi, 2003. Levels and Speciation of Heavy Metals in Soils of Industrial Southern Nigeria. Environ. Monitoring Assessment, 85(2):135-155. Prendez, M. and M.A. Carrasco, 2003. Elemental composition of surface waters in the Antarctic Peninsula and interaction s with the environmen t. Environ. Geochem. Health, 25: 347-363. Riley, J.P. and G. Skirrow, 1974. Chemical Oceanography, 2 n d Edn. Vol. 1, Bergmann Press, London, pp: 489-491. Sheriff, M.K., R.M. Aw adallah and A.E. Moham ed, 1979. Determination of trace elements of Egyptian Crops by INAA. J. Radioanal Chem. 53: 145-151. Tang, S.M., P. Kump, C.T. Yap and M.G. Bilal, 1986. Calculation of relative fluorescence intensity for annular source geom etry by Monte Carlo method. XRay Spectrum. 15: 289-293. Thomas, M.F., 1966. Some Geomorphological Implications of Deep W eathering Patterns in Crystalline Rocks in Nigeria. Tans. Inst. Br G eorg., 40: 173-193. In: Horizontal and vertical distribution of selected metals in the Kubanni River, Nigeria as Determined by Neutron Activation Analysis. Ewa, I.O.B ., M.O.A. Oladipo and L.A. Dim, (Eds.). 1991. Commun. Soil Sci. Plant Anal., 30(7-8): 1081-1090. REFERENCES Abolude, D.S., 2007. Water quality and metal concentration in sediments and fish from Ahmadu Bello University Reservoir, Zaria Using Neutron Activation An alysis and Atomic Absorption Spectrophotometer. Unpublished Ph.D. Thesis, Department of Biolo gical Sciences A hma du B ello University, pp: 6-30. Abu bakar, M. and S. Garba, 2006. Level of havy mtals in terrestrial crabs. Best J., (4): 47-80. Adakole, J.A., 1995. The effects of pollution on a stretch of River Kubanni, Zaria. Unpublished M.Sc. Thesis Deptartment of Biological Science, ABU Zaria, Nigeria. pp: 121. Angeyo, K.H., J.P. Patel, J.M . Mangala and D.G.S. Naroya, 1998. Optimization of X-ray fluorescence elemental analysis an example from Kenya. Appl. Rad. Isot., 49: 885-891. Ayodele, J.T. and M. Abubakar, 2001. Chromium and C o p p e r i n w a t e r , se d im e n t s a n d th e ir bioaccumulation by freshwater Bivalves in Tiga Lake, Kano-Nigeria. J. Environ. Sci., 5(1): 177-184. Ayodele, J.T. and M . Abub akar, 2002. Trace Metal Determination in Sediment and in two species of freshwater molluscs in Tiga Lake, Kano Nigeria. Nig. J. Basic Appl. Sci., 2(1): 81-90. Balarabe, M.L., 2001. Effect of Limnological characteristic on Zooplankton composition and distribution in Dumbi and Kwangila Ponds, Zaria, Nigeria. Ph.D. Thesis, Department of Biological Sciences, Ahmadu Bello University. pp: 7-21. Bernard, F.J. and C.E. Lane, 1961. Regulation of body metal burden by crustaceans crabs. Biol. B ull. Mar. Lab. Wood H ole, 121: 438. Bernasconi, G.B., 1996. AXIL-QX AS, Instruction Manuals IAEA , Vien na. Bernasconi, G.B., S.A. Bamford, B. Dosan, N. Haselberger, A. Markowicz, A. Mahmoud and V . Valcovic, 1996. Applicability of annular source excited systems in quantitative XRF analysis. X-ray Spectrum, 23: 65-70. Ewa, I.O.B ., M.O .A. O ladipo and L .A. D im, 1999. Horizontal and vertical distribution of selected metals in the Kubanni R iver, Nigeria as determined by Neutron Activation analysis. Co mm un. Soil Sci. Plant Anal., 30(7-8): 1081-1090. Funtua, I.I., 1999a. Analysis of Nb-Ta ores by energy dispersive X-ray fluorescence spectrometry. J. Trace Microprobe. Tech., 17(2): 189-195. Funtua, I.I., 1999b. Application of the transmission emission method in EDXRF for the determination of trace elements in geological and biological materials. J. Trace Microprobe Tech., 17(3): 293-297. Giauque, R.D., R.B. Garreth and L.Y. Goda, 1979. Determination of trace elements in light element 58