International Journal of Advances in Science and Technology, Vol. 4, No.

2, 2012

Arsenic and Heavy Metals in waters of Oluyole NE, Ibadan SW, Nigeria
Laniyan, T.A.
1

Department of Earth sciences, Olabisi Onabanjo, University, Ago-Iwoye ttlaniyan@yahoo.com,

Abimbola, A. F.
2

Department of Geology, University of Ibadan, Ibadan af.abimbola@mail.ui.edu.ng

Omosanya, K.O.
1

Department of Earth sciences, Olabisi Onabanjo, University, Ago-Iwoye 3 Cardiff University, School of Earth, Ocean and Planetary Sciences kamaloomosanya@yahoo.com , Tel: +2348034454405

Abstract
Increase in population and domestic activities had led to the problem of high rate of weathering, disposal and inability to control industrial wastes in Ibadan metropolis which may cause contamination of available drinking water by heavy metals such as Arsenic. Hence, the need to evaluate the impact of different heavy metals especially arsenic (As) and weathered rocks on the various water sources (spring (5), swamp (10), stream (10), and groundwater (12)) with effluent (14) in the study area. Rock samples (Banded gneiss, Augen gneiss and Quartzite) were picked and water samples collected in a 100ml plastic bottle and acidified with two drops of concentrated acetic acid. All metal contents were determined with ICP-OES and ICP-MS Code (4A-4B) was used for the rock. Geochemical analyses revealed quartzite with the highest arsenic concentration (0.8ppm), Hydrogeochemical results of the water types reveal dominance of Fe and K in all the media sampled. However, high arsenic content was recorded (0.03-0.20mg/l) in the effluents. Water sources in Oluyole and its environs are prone to Arsenic contamination from both leaching of the weathered bedrock and indiscriminate discharge of wastes and effluents.

Keywords: Arsenic, Water, Wastes, Contamination, Effluents, Quartzite.

Introduction
Inadequate hygienic infrastructural facilities with no actual waste dump site (Tijani, et al., 2004) had led to leaching of soluble metals from waste due to persistent discharge of toxic wastes (Cyle, et al 2006, Adeniji, 2009) into the waters. This subsequently led to high contamination of waters by trace elements (IPCC, 2001, 2007) such as arsenic (As) (Ulker, et al, 2010). Arsenic, a known human carcinogen occurs naturally in soil and minerals and may get into waters from effluent run-off and leaching by man (Cullen and Reimer, 1989, Riedel 1994, EPA 2000Seth et al (2002). The metal has harmful effects on both human health and environment, even at low concentration (Nriagu, 1994, Chowdhury, 2000, Chwirka et al. 2000, DeMarco et al 2003, Wasserman, et al., 2004, Patlolla, et al., 2005). However, water-borne arsenic poses a significant threat to human and ecosystem worldwide (Nriagu, 1994). In Bangladesh, more than 10million tube wells used by about 30 to 40

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International Journal of Advances in Science and Technology, Vol. 4, No.2, 2012 million people have been recorded to have high concentration of As and all the inhabitants that depend on these wells have been diagnosed of the attendant health effects (Wasserman, et al., 2004). Over the last ten years, arsenic has been discovered in groundwater in about 70 countries, and it is likely that many other areas with elevated arsenic in groundwater will be found in future (Ravenscroft, 2007). Due to the threat to humans, the World Health Organization (W.H.O) and the US Environmental Protection Agency (US EPA) implemented a reduction of the arsenic maximum contamination level (MCL) in drinking water from 50 to 10 g/l in 2006 (US EPA 2006). Information about the distribution of arsenic in water in Nigeria cities is scarce, such cities include Ibadan. The city is characterized by lack of proper sewage and waste disposal systems which have drastically reduced available quantity of water to the populace, thereby threatening human welfare. The study area lies within latitude 7015N 7030N and longitude 3045E 4000E, ~78 Km inland of Lagos; 128 km inland northeast of Lagos and 530 km southwest of Abuja (Figure 1), the city is a prominent transit point between the coastal region and the areas to the north. The population of the study area (central Ibadan) is approximately one million three hundred and thirty-eight thousand six hundred and fifty-nine (1,338,659) (NPC 2006) over an area of ~128 km2 landmass. This work is aimed at evaluating the arsenic contents of different rocks and various water sources in Oluyole and its environs.

Figure 1: Location map of the Study area showing sampling location.

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Methods
Rock samples (Banded gneiss, Augen gneiss, and Quartzite) were picked in all the areas where water samples were taken to access the effect of weathering on the various water sources. Six (6) Rock samples (3 fresh and 3 weathered) were chosen on the basis of physical similarities, analyzed, and the observed Arsenic concentration provided the need to analyse other media. Fifty water samples were collected from spring (5), stream (10), swamp (4), industrial effluent/drain (14) and groundwater (12), (Figure 2) during the dry season to remove any form of dilution. Samples were collected and acidified with concentrated hydrochloric acid into a two liter polythene bottle while measurements of pH, Electrical conductivity (EC) and Total dissolved solutes (TDS) were taken in-situ. Inductively Coupled PlasmaOptical Emission Spectrometry (ICP-OES) method was used for water analysis at Activation Laboratory Canada; while whole rock Inductively Coupled Plasma-Mass Spectrometry (ICP-MS Code (4A-4B)) was used for the rock analysis, at Acme Analytical Laboratories Canada.

Figure 2: Various water sources in the study area

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International Journal of Advances in Science and Technology, Vol. 4, No.2, 2012 Table 1: Geochemical results of the rock Elements (Wt%) SiO2 Al2 O3 Fe2 O3 Mg O Ca O Na2 O K2 O Ti2 O P2 O 5 Mn O Ba ppm Cu ppm As ppm LOI Total CIA standard 75-100 PIA standard 75-100 CIW standard 75-100 RR standard >30 >30 >30 R1 76.83 11.28 2.22 0.06 1.23 2.31 5.03 0.12 0.01 0.04 445 0.3 0.8 0.6 99.72 56.8262 31.49 56.83 6.811 R2 72.13 14.59 1.67 0.53 2.00 3.59 4.42 0.20 0.07 0.02 1188 6.4 0.01 0.5 99.75 59.3089 4 41.34 59.31 4.944 R3 74.13 14.17 0.64 0.25 1.26 3.55 5.22 0.05 0.03 0.01 688 0.7 0.01 0.5 99.84 58.5537 2 36.98 58.55 5.231 R4 75.10 12.37 2.12 0.12 1.17 2.86 4.93 0.18 0.02 0.02 573 0.7 0.01 0.9 99.78 57.99344 34.88 57.99 6.071 R5 72.50 14.90 1.64 0.54 2.26 3.93 3.54 0.19 0.05 0.02 921 2.6 0.01 0.2 99.79 60.49533 46.12 60.5 4.866 R6 73.49 14.46 0.61 0.20 0.76 2.71 7.59 0.04 0.05 < .01 1021 0.5 0.01 -0.1 99.81 56.66144 26.92 56.66 5.082

Result and Discussion

Geochemical results of the three rock types (banded, augen gneiss and quartzite) done for both fresh (R1 R3) and equivalent weathered samples (R4 R6) are summarized in Table 1. High and low arsenic concentration was observed in the fresh and weathered quartzite respectively, which implies that Arsenic has been weathered and leached via the soil to the various water media especially groundwater of the study area, especially in area underlain by quartzite. Barium was also found to be high in the fresh and weathered rocks. A precise evaluation of degree of chemical weathering (Table 1) in the rock sampled was obtained by calculating the chemical Index of Alteration (CIA) (Nesbitt and Young, 1982), and Plagioclase Index of Alteration (PIA), (Fedo, et al 1995); high CIA and PIA values reveals high/intensive weathering of the rock in the source area (Osae, et al 2006). Chemical index of weathering (CIW) (Harnois, 1988), and Ruxton Ratio (RR) (Ruxton, 1968), were used to determine the extent of weathering in the rocks sampled.

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Figure 3: (a) As with W.H.O standard, (b) Pb with W.H.O standard, (c) Fe with W.H.O standard, (d) Column chart showing the various water sources with the pollution index

The water quality parameters are summarized in Table 2. The pH values of different water sources (spring, swamp, stream, effluent and groundwater) range from 5.89 to 7.23 with the highest value (5.89) observed in effluents. High pH values for the effluent reveal an elevated level of toxic metals which could be linked to the various discharges of metal ions into the drains. Electrical conductivity (EC) (s/cm) which estimates the amount of total dissolved solids (TDS) (mg/l) is found to be within the permissible WHO,2006 standard (1400 s/cm) for all the water sources with values ranging from 0.17-112.4, this implies that the TDS (mg/l) for all the water sources (0.169-73.06) are also within the W. H. O (2006) standard (1000 mg/l). Concentrations and summary of metals in the water sources with the W.H.O (2006), EPA (2009), and SON (2007) standards respectively, plus Mean Composition of World Rivers (MCWR: Hem, 1985; Brownlow, 1979; Subramanian, 1983; and Sarin and Subramanian, 1984), revealed the mean concentration values of Pb, Cu, Zn, As, Ba to be generally less than 1.5mg/l for all the water types, with a maximum concentration of 0.68mg/l for Pb (in Swamp), 0.22mg/l for Cu (in Swamp), 1.25mg/l for Zn (in Groundwater), 0.007mg/l for As (in Effluent), 0.36mg/l for Ba (in Stream), while the mean concentrations of the other metals including Fe are generally less than 150mg/l with a maximum concentration of 44.64mg/l for Fe (in Swamp), the other metals has a maximum mean concentration to be less than 350mg/l; these are K (146.70mg/l), Ca (341.40mg/l) and Na (464.30mg/l) which are found in swamp.

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2.0

1.5

1.0

0.5

0.0

Spring

Stream

Figure 4a: Box plot showing pollution index of spring and stream

10

8 4

Effluents

Swamp

Groundwater

Figure 4b: Box plot showing pollution index of effluents, swamp and groundwater

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International Journal of Advances in Science and Technology, Vol. 4, No.2, 2012 Since the important factors in determining water chemistry are rainfall quantity and quality, evaporation, mineral weathering, topographic relief, vegetative cover, and biological activity; the metals were then compared with mean concentrations of world rivers (MCWR: Hem, 1985; Brownlow, 1979; Subramanian, 1983; and Sarin and Subramanian, 1984) the mean concentration for spring and groundwater in all the metals analysed for are at a close range to the MCWR (Hem, 1985; Brownlow, 1979; Subramanian, 1983; and Sarin and Subramanian, 1984), while the mean concentrations of Ca, Pb, Ba and K are about double that of MCWR (Hem, 1985; Brownlow, 1979; Subramanian, 1983; and Sarin and Subramanian, 1984). Mean concentrations of Cu, Zn, and Fe, in swamp and effluent is in the order of one thousand (1000)times more than MCWR (Hem, 1985; Brownlow, 1979; Subramanian, 1983; and Sarin and Subramanian, 1984), this is an indication of contamination of the water types to the MCWR (Hem, 1985; Brownlow, 1979; Subramanian, 1983; and Sarin and Subramanian, 1984), As is however noticed to be about 10times lower than MCWR (Hem, 1985; Brownlow, 1979; Subramanian, 1983; and Sarin and Subramanian, 1984), this reveals no contamination of the metal in all the water types. From the comparison with MCWR (Hem, 1985; Brownlow, 1979; Subramanian, 1983; and Sarin and Subramanian, 1984) the order of contamination of the water sources are swamp>effluent>stream>groundwater>spring: while the order of concentration of the micro-nutrients are Cu>Fe>Zn>K>Na>Ca>Ba>As.

Comparing the mean value for various water sources with the WHO 2006 standard in Table 3, all the metals are found within the permissible limits except the following: arsenic (As) was above the permissible limits in effluents (0.1mg/l), high As observed maybe through the leaching of quartzite that has high As content and it may also come from waterrun-off (effluent) of glass and electronic production wastes found around Lebanon street and Agbokojo areas. This shows that human activity is more responsible than the volcanic release which occurs in Bangladesh. Arsenic exposure can cause various health effects, such as irritation of the stomach, skin changes and lung irritation, skin and lung cancer, infertility problems, miscarriages, and damage of the DNA. (Water Treatment Solutions Lenntech, Netherlands; Drinking Water Contaminants, U.S E.P.A 2009). Lead (Pb) was found above the permissible limits in effluent (0.03mg/l), groundwater (0.04mg/l) and swamp (0.07mg/l). Environmental pathways for Pb transportation may be via air, water and soil (Beverland and Agius 2002). The atmospheric path includes Pb particles emitted from vehicles as halides (e.g. PbBrCl, PbBrCl, NH4Cl), which are Pb salt that enters water easily through the exhausts of cars; it also comes through incessant burning of petroleum products and tubes from mechanic workshops around; corrosion of household water system (pipes) also contribute to leaching of Pb into the waters (Win et al., 2003). The effect of high Pb in water could be enormous, it can cause rise in blood pressure, miscarriages and subtle abortions, declined fertility of men through sperm damage, behavioral disruption in children, such as aggression and serious damage of the brain of an unborn child. Iron (Fe) was found to be high in effluent (2.6mg/l) and swamp (4.9mg/l), while high value of potassium was noticed in all the water sources with concentration above 13.48mg/l. High Fe concentration is due to its use as a commercial product in the making of containers, cars, laundry machines, building materials, photography all of which gets rusted in the soil and then pollutes the waters, some of these products are also thrown directly into the drainage system, Local smelters are seen around Agbokojo, Lebanon street, and Agbeni recycling battery cases from used discarded batteries which also enhances high concentration of the metal. Studies have shown that incessant pouring of smelt particle, may lead into enrichment of Fe in topsoil; dissolution of organic materials due to improper drainage and toilet system may also cause the enrichment of Fe into waters. (Plumlee 2002, Jorgensen et al 2005, & Shomar 2006). Excessive accumulation of Fe may lead to conjunctivitis, lung cancer, and ultimately death. (Figure 3a, b, c) Risk evaluation: Pollution index (Pi) of Li et al., 2003 was used to quantify the pollution risk in various water sources using the empirical relationship in eq. 1

Pi =

Ci Si

eq (1)

Pi is the environmental quality index for heavy metal;

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International Journal of Advances in Science and Technology, Vol. 4, No.2, 2012 Ci is the heavy metal content in water sample (mg/l), Si is the permitted sample of the same metal (mg/l). Where Pi >1 indicates a polluted water and Pi < 1 suggests an unpolluted water. The pollution distribution was graded based on the W.H.O 2006 standard. Pollution Index (Pi): The pollution index showed that spring, stream and groundwater of the area are safe while the effluents and swamp are polluted. Pi (Table 4; Figure 3d) reveals Pb and K to have polluted the various water sources, while Fe is found to pollute the effluents, swamps and groundwater of the study area. Arsenic was observed in the effluents while the other metals are found not to have polluted the waters. A box plot (Figure 4a,b) was plotted to reveal the polluted waters, since any value greater than one shows pollution of the area. Inter-elemental Analysis: A strong and positive correlation (Tables a,b) was observed in most of the metals for spring, stream, swamp, and effluents, which implied that the metals were derived from the same anthropogenic source, while a weak correlation was noticed in all the metals for groundwater except Fe-Cu (0.54), same trend was observed for K in all the water sources, this implies that K is derived from a different source mostly natural (Geogenic).

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Table 5a: Inter-elemental analysis for spring and stream

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International Journal of Advances in Science and Technology, Vol. 4, No.2, 2012 Table 5b: Inter-elemental analysis for stream, effluents and groundwater

Conclusion
A detailed Physico-chemical study of the various water sources in the study area revealed the following: An evidence of As in the quartzite, which was evident in the effluent thus, the metal can become a major hazard in the groundwater in future through the weathered bedrock and human activity. Pb and Fe are found above the permissible limits in effluent, swamp and groundwater. Pollution index indicated the most polluted water to be effluent and then swamp. K was noticed in all the water sources and it correlated negatively with all the other suggesting that it was derived from a geogenic source.

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Authors Profile
(Mrs)Laniyan, T.T. B.Sc (UI), M.Sc(UI) PhD (University of Ibadan-In View). She is a Lecturer in the department of Earth Sciences, Olabisi Onabanjo University. Area of Specialisation: Applied Geochemistry Research interests: Applied Geochemistry, Environmental and Economic Geology. Current (Research) Projects/Activities Geochemical analysis of environmental Contaminant in Ibadan, SW Nigeria Dr. Abimbola. A.F. B.Sc.(Hons), M.Sc.(Ilorin), Ph.D.(Ibadan), MNAH, MNMGS, COMEG. Regd He is a Reader in the department of Geology, University of Ibadan. Nigeria Area of Specialisation: Applied Geochemistry Current (Research) Projects/Activities Chemostratigraphy (Sequence Geochemistry) and palyno-geochemical studies of the Cretaceous Tertiary shales of the Dahomey and Chad basins.(Commencement date: June 2002). Systematic Geochemical Baseline Mapping (Commencement date: June 2001). Mr. Omosanya, K.O. B.Sc.(Hons) (OOU),DCS(Mapoly), M.Sc.(Leeds), Ph.D.(Cardiff University-In view) He is a Lecturer in the department of Earth Sciences, Olabisi Onabanjo University. Area of Specialisation: Basin Analysis/Structural Geology, Applied Geophysics, and Environmental Geochemistry. Current (Research) Projects/Activities Structures, Petrography, and Petrogenesis of rocks in Ago-Iwoye NE, SW, Nigeria & Modelling of Gravity Anomalies in Ago-iwoye, NE, SW.(Started May, 2011) Slope structures in some part of Dahomey basin (Started August, 2011) Submarine Landslides and Salt Structures on continental margins (Espiritos Santos and Niger delta) (Started October, 2011). Future Research Area: 3D geochemical and geophysical mapping of Leechate in Groundwater of Ijedu-ode and Ago-Iwoye, SW Nigeria.

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Table 2: Chemical analyses of the Water types in Ibadan Metropolis

LOCATION Spring Range Mean Median Swamp Range Mean Median Stream Range Mean Median Effluent Range Mean Median Grd. water Range Mean Median WHO 2006 E.P.A 2005 S.O.N 2007 Pb (mg/l) 0.01-0.02 0.01 0.01 0.01-0.08 0.68 0.01 0.01-0.02 0.01 0.01 0.01-0.10 0.03 0.01 0.01-0.01 0.01 0.005 0.01 0.015 0.01 Cu (mg/l) 0.00-0.01 0.01 0.00 0.00-0.02 0.22 0.01 0.00-0.01 0.01 0.00 0.00-0.04 0.01 0.00 0.031-0.041 0.041 0.0255 2.00 1 1 0.01-1.18 0.28 0.00 0.941-1.2505 1.2505 0.78 3.00 5 3 0.01-1.34 0.15 0.01 0.01-0.12 1.09 0.01 Zn (mg/l) 0.01-0.04 0.02 0.01 Fe (mg/l) 0.01-0.84 0.30 0.01 0.01-4.96 44.64 0.02 0.09-1.35 0.41 0.05 0.17-12.10 2.64 0.09 0.02-0.02 0.02 0.01 0.50 0.3 0.3 K (mg/l) 2.20-23.50 14.50 2.20 3.60-16.30 146.70 63.20 5.30-86.90 22.94 2.65 2.10-320 60.57 1.05 16.8-16.85 16.85 8.45 13.48 Ca (mg/l) 35.00-85.70 54.22 35.00 4.30-37.93 341.40 81.00 25.50-60.10 36.53 12.75 13.50-220 63.28 6.75 15.8-15.9 15.9 8.0 200.00 75 200 200 8.1-9.55 9.55 5.5 200.00 Na (mg/l) 25.60-59.40 48.10 25.60 6.90-51.59 464.30 189.00 15.40-196 55.84 7.70 13.30-235 108.59 6.65 Ba (mg/l) 0.02-0.02 0.02 0.02 0.02-0.02 0.18 0.02 0.09-2.52 0.36 0.05 0.04-2.41 0.47 0.02 0.4-0.405 0.405 0.205 0.70 2 0.7 As (mg/l) 0.01-0.01 0.01 0.01 0.01-0.01 0.01 0.01 0.01-0.01 0.01 0.01 0.01-0.20 0.07 0.01 0.01-0.01 0.01 0.005 0.01 0.05 0.01 7.2 6.5-8.5 6.5-8.5 6.5-8.5 1000.00 500 500 1400.00 1400 1000 7.0 7.50 0.85 1.31 pH 7.0 7.1 7.0 7.0 7.2 7.0 6.06-7.23 6.71 6.81 5.89-6.98 6.50 6.49 TDS(mg/l) 19.24-73.06 49.36 57.46 1.05-99.3 36.26 39.91 0.26-1.90 0.37 0.23 0.26-1.91 0.62 0.59 EC (s/cm). 29.6-112.4 75.94 88.40 .68-64.55 55.79 61.40 0.17-1.24 0.58 0.36 0.17-1.24 0.95 0.90

NOTES: W.H.O World Health Organization; E.P.A Environmental Protection Agency; S.O.N Standards Organization of Nigeria; EC - Electrical Conductivity.

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