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DETERMINATION OF ELEMENTAL COMPOSITION OF SOIL SAMPLES FROM SOME SELECTED DUMPSITES IN ABEOKUTA, OGUN STATE, NIGERIA, USING ATOMIC ABSORPTION SPECTROPHOTOMETER
OKEYODE I.C AND RUFAI A. A
DEPARTMENT OF PHYSICS, COLLEGE OF NATURAL SCIENCES, UNIVERSITY OF AGRICULTURE, ABEOKUTA, NIGERIA

ABSTRACT
The elemental composition of copper, manganese, iron, zinc, lead, nickel magnesium and sodium in the soil samples from some selected dumpsites and 20m away from the dumpsites within Abeokuta metropolis in Ogun state, Nigeria, have been measured and determined using Atomic Absorption Spectrophotometer. At dumpsites, the concentrations of iron, manganese, zinc, lead, nickel magnesium, sodium and copper ranged from 86.89 277.33 mg/l, 1.9731 5.6644 mg/l, 0.3299 4.847 mg/l, 0.4132 2.8137 mg/l, 0.0896 0.1376 mg/l, 1.9731 5.6644 mg/l, 0.9203 29.00 mg/l and 0.1645 5.4191 mg/l respectively, while at control sites (20m away from dumpsite), the concentrations ranged from 37.64 -109.94 mg/l, 0.5342 1.7910 mg/l, 0.1015 0.3692 mg/l, 0.2150 - 0.7595 mg/l, 0.0590 - 0.0881 mg/l, 0.0927 - 0.3976 mg/l, 0.4385 and 0.9876 mg/l and 0.004 and 0.416 mg/l respectively. The concentrations of metals in soils at the decomposed biodegradable wastes dumpsites and 20m away from dumpsites showed that there is an evidence of relative increase in concentrations of metals in soils at dumpsites compared to those 20m away from dumpsites. The results compared well with the values obtained from some parts of the country. Keywords: Dumpsites, Abeokuta, Heavy Metal, Elemental Composition

INTRODUCTION
Waste disposal whether domestic, commercial or industrial in the world, is a problem that continues to grow with human civilization and no method so far is completely safe. Experience has shown that all forms of waste disposal have negative effects on the environment, public health and local economics [1]. [12], pointed out that Pollution in soil systems is strictly related to human activities such as industry, agriculture, burning of fossil fuels, mining and metallurgical processes and their waste disposal. Toxic elements, such as heavy metals and metalloids, can be retained by soils and/or mobilised to soil solution by biological and chemical mechanisms with a potential impact on human health (contamination of drinking water supplies, uptake by vegetation and input into the food chain; [8], [10]. Metals are natural components of the environment including soil but they are of great concern when they are being added continuously. Refuse dumping is one of the ways in which elements are being added into soil. Leachate from dumpsites is of particular interest when it contains potentially toxic heavy metals. These metals are known to bio-accumulate in soil and have long persistence time through interaction with soil component and consequently enter food chain through plants or animals [5];[9];[14]. [3], from the analysis made from his studies in Uyo, noted that metals such as Fe, Pb and Cu may also contaminate soil water which constitute the major sources of drinking water. Lead is a very toxic element, apart from the contamination of soil and agricultural land by other elements, its toxicity may lead to encephalopathy, renal effect and hematological effects as pointed out by [3] and [6]. Degradation of land is generally caused by solid wastes of different types. In order to solve the problem posed in our environment by waste disposal, there must be proper management of solid waste. Solid waste as defined by United States Environmental Protection Agency is any useless unwanted or discarded material with insufficient liquid content to be free flowing. The non-free flowing or sticky nature of the solid waste gives rise to the accumulation of solid wastes on some habitable parts of the earth.
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Solid is an asset when properly managed and Nigeria government has been and is being invested much on municipal solid waste management in cities one of which is Abeokuta, a case study, nevertheless the goal has not been met. This work is aimed at determining the elemental composition of the soil samples obtained from some of the major dumpsites in Abeokuta, in a way to quantify this information, to analysis the result to see if the values are within the acceptable limits and to serve as a baseline data for future monitoring.

DESCRIPTION OF ABEOKUTA (THE STUDY AREA)

Abeokuta town, capital of Ogun state, southwestern Nigeria. It is situated between latitude 3 20and 3 54 and longitude 7 9 and 7 39 on the east bank of the Ogun River, around a group of rocky outcroppings that rise above the surrounding wooded savanna. It lies on the main railway (1899) from Lagos, 48 miles (78 km) south, and on the older trunk road from Lagos to Ibadan; it also has road connections to Ilaro, Shagamu, Iseyin, and Ktou (Benin). Abeokuta (Refuge Among Rocks) was founded about 1830 by Shodeke), a hunter and leader of the Egba refugees who fled from the disintegrating Oyo empire. As of 2005, Abeokuta and the surrounding area had a population of 593,140 but there has been dramatic population increase as shown by recently released figure of voters by INEC. Being an ancient city, many of the dumpsites are illegal and are situated very close to living areas.

Figure 1:

Map showing the area of study

SAMPLE COLLECTION
Six densely populated areas within Abeokuta metropolis were covered. Table 1 shows the locations of the dumpsites using Global Positioning System.

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Table1: Areas covered with their positions using Global Positioning System (GPS)

Sites

Locations

Longitude (OE)

Latitude (ON) 003.34818 003.36512 003.35312

1 2 3

Sapon Market LantoroOkeyidi

07.15348 07.15975

Kuto market behind St. John Anglican 07.13541 Pry. Sch.

4 5 6

Panseke Opp. First Bank Plc

07.13316

003.33265 003.32550 003.35516

Adigbe Opposite Navy Secondary School 07.12600 Saje Opposite Ebenezer Baptist Church 07.17556 Road

Due to the fact that soil vary intrinsically, soil samples were obtained through random sampling in five different spots per dumpsite. The years of existence of the dumpsites ranged from 2 years and above. To serve as control, soil samples were obtained 20m from the dumpsites, The samples were collected into non-reacting polyethylene bags, at depth of about 10 15cm below the earth surface and thoroughly mixed to form a composite and were taken to the laboratory.

MATERIALS AND METHODS

The main material used in the determination of the elemental composition of these samples is the Flame Atomic Absorption Spectrophotometer model S4 series, which can only analyze solutions. Soil samples being solid samples needed to be digested so as to be in solutions. 2 gram of fine particles of dried soil samples from dumpsites were weighed into a 100ml digestion tube. Each of the tubes was labeled to avoid mix-up. 10ml each of nitric acid and hydrogen peroxide were added while SO4 was added in small amount and the mixture was thoroughly stirred. The nitric acid destroys the bulk of the organic matter, it is boiled off during the digestion process until only the SO4 acid remains. White fumes are evolved and beyond to reflux in the flask. At this point the solution gets very hot and the SO4 acts in the remaining organic matter. The process was continued until the solutions were cleared. The solution was decanted and diluted with deonised water up to 100ml before being filtered. The same procedure were repeated for all the samples and for the control samples as well. Before metal concentrations were determined, standard solutions were prepared in each case and were used to eliminate sample standard matrix indifferences. The instrument was calibrated for all the measurement carried out using de-ionized and standard solutions, these standard solutions are different for different elements. Since AAS measure absorption of optical radiation by atoms in the gaseous state, the standard solutions as prepared for each element.

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RESULTS
The concentration of iron, manganese, copper, zinc, lead, nickel, magnesium, sodium in soil samples in each dumpsite and 20m away from the dumpsites i.e. control site are shown in tables 2 to 7.

Table 2: Elemental Composition of the Soil sample at Sapon Market

Elements (mg/l) Fe Mn Cu Zn Pb Ni Mg Na

Dumpsite 108.03 1.9731 0.8454 4.8470 2.81370 0.0945 7.392 29.00

Control site 42.471 1.7910 0.22070 0.3692 0.7595 0.0621 0.3687 0.8444

Table 3: Elemental Composition of the Soil sample at Lantoro Okeyidi

Elements (mg/l) Fe Mn Cu Zn Pb Ni Mg Na

Dumpsite 107.67 5.6644 1.3705 1.2283 0.7788 0.1376 25.340 2.2110

Control site 47.81 1.1900 0.0252 0.1330 0.4140 0.0860 0.3218 0.6604

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Table 4: Elemental Composition of the Soil sample at Kuto Market

Elements (mg/l) Fe Mn Cu Zn Pb Ni Mg Na

Dumpsite 127.99 2.6204 0.1645 0.3299 0.4169 0.1283 1.8862 1.6598

Control site 67.31 1.6312 0.0040 0.1220 0.2893 0.0763 0.0927 0.4385

Table 5: Elemental Composition of the Soil sample at Panseke

Elements (mg/l) Fe Mn Cu Zn Pb Ni Mg Na

Dumpsite 277.33 3.2125 0.3343 0.5026 1.0197 0.1125 2.0356 0.9203

Control site 109.94 0.7527 0.0400 0.1034 0.3848 0.0590 0.3499 0.6774

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Table 6: Elemental Composition of the Soil sample at Adigbe

Elements (mg/l) Fe Mn Cu Zn Pb Ni Mg Na

Dumpsite 86.89 5.6567 5.4191 1.5337 0.7976 0.0956 2.6503 1.4820

Control site 37.64 0.5342 0.4160 0.1015 0.3520 0.0881 0.2134 0.7088

Table 7: Elemental Composition of the Soil sample at Saje

Elements (mg/l) Fe Mn Cu Zn Pb Ni Mg Na

Dumpsite 100.32 2.7889 0.4455 0.9947 0.4132 0.0896 42.57 1.0778

Control site 80.27 1.3062 0.0133 0.2150 0.2150 0.0810 0.3976 0.9876

DISCUSSION
The metals considered in this study include copper, manganese, iron, zinc, lead, nickel magnesium and sodium. The first four metals are refer to as micronutrients (Fe, Mn, Zn, and Cu), The next two sets of metals are refer to as heavy metals i.e (Pb and Ni) when their concentrations are above the tolerance level. Then the last two are highly needed by plants for their normal growth. The concentrations of metals in the samples from dumpsites
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studied and in the samples from distance 20m away from the dumpsites showed that there was relatively an increase in concentrations of metals in soils obtained from dumpsites compared to those 20m away from dumpsites. The natural range of the concentration of Fe in the soil is 15 250 mg/l. At dumpsites, (fig 2), the concentration of iron ranged from 86.89 277.33 mg/l while at the control sites, the concentration was between 37.64 and 109.94 mg/l. From the results obtained, it was noticed that the highest concentration of Fe was recorded at Panseke dumpsite which is a commercial area and the least value was found at Adigbe. The concentrations of Fe were higher than the concentrations of other elements in all the sites visited. This is due to the fact that Fe contents in minerals of the soil is high. [3] reported the result of a study on Elelewo dumpsites Uyo in Nigeria with the concentrations of iron between 51.5 155 mg/l. This result is within the natural range of soil, the concentration of Fe is higher in this present study than the concentrations obtained by [3]. The permissible range for the concentration of manganese in soils is in the range of 1.00 45.0 mg/l. At dumpsites, the concentration of manganese ranged from 1.9731 5.6644 mg/l while at control site (20m away from dumpsite) the concentration ranged from 0.5342 1.7910 mg/l, (see fig 3). The result shows that concentration of manganese in Panseke and Adigbe control sites fall below the natural range. The highest concentration was recorded at Lantoro Okeyidi dumpsite situated very close to the main road where vulcanizing processes are done. Reports from the study of Elelewo dumpsite by [3] and [15] showed that the concentration of manganese were relatively low compared to the result obtained from this study. [6] reported the concentration of Mn located within Akwa Ibom State, Nigeria. The value fell within the range of 2,313.5 and 3,175.0 ppm at dumpsite and at 10m away from dumpsite, the concentration ranged from 2,004.5 to 2,348.0ppm. The natural range for the concentration of copper in soils is 0.035 0.400 mg/l. At dumpsites the concentration ranged from 0.1645 5.4191 mg/l and at control sites (20m away from Dumpsite) the concentration ranged between 0.004 and 0.416 mg/l (fig 4). This shows that the concentration of copper in the sample at the dumpsite was higher than the natural range. The result also showed that the concentration of copper fell below the natural range only at the Panseke control site, This may be due to the presence of large organic matter content in the sample at this location, since copper deficiency are most likely to occur in organic soil [11]; [13]; [2]. High concentration of copper in the sample at the Adigbe dumpsite might be due to the fact that wastes including domestic and agricultural were present at the site. Biodegradable waste introduces metallic copper into soil at a level slightly above natural level for soils [4];[6]. It is quite evident that the soils at the dumpsites were enriched in Cu by the refuse. The natural range for the concentration of zinc in soils is 0.05 1.5 mg/l. At dumpsites the concentration ranged from 0.3299 4.847 mg/l while at control site (20m away from Dumpsite) the concentration ranged between 0.1015 0.3692 mg/l, (fig 5). This shows that the concentration at the control sites are within natural range while at Sapon market dumpsite, zinc concentration was beyond the natural range. Excess zinc concentration may be due to motor vehicle emission sewage sludge application, smelting and scrap metal processings [7]. Low level of zinc was recorded at Kuto dumpsite, this is good for the site because zinc can be toxic to plants if present in more than very small quantity [11]. Concentration of zinc in soils at dumpsites was high compared to those in soils at 20m away from dumpsite. It was suggested that zinc might have been introduced into the soil during decomposing, [6]. It was reported by [6] that concentration of zinc in dumpsites located within Ikot Ekpene South East, Nigeria fall between 0.875 1.45 mg/l. This is relatively low compared to the result obtained from this study. The natural range for the concentration of lead in soils is 0.075 0.125 mg/l. The concentration of lead in soils at dumpsites ranged from 0.4132 2.8137 mg/l while at the control sites (20m away from Dumpsite) the concentration ranged between 0.2150 and 0.7595 mg/l (fig 6). High level of lead was obtained both at dumpsites and control sites. This may be due to differentent activities, especially industrial activities that are concentrated in these areas. The pollution of soil by lead is a very a serious problem, as lead is carcinogenic to man [16]. This means that too much of intake of Pb may lead to several effects; therefore care must be taking when lead containing wastes are being disposed. There should be proper management of lead disposal. The natural range for the concentration of nickel in soils is 0 0.5 mg/l. The concentration of nickel in soils at dumpsites ranged from 0.0896 0.1376 and at control sites (20m away from Dumpsite) the concentration ranged between 0.0590 and 0.0881 mg/l (fig 7). The result in this study reveals that the concentration of nickel falls within the natural range and there exist a marked difference between the concentration of nickel in the samples at dumpsites and 20m away from dumpsites, except at the dumpsites of Adigbe and Saje where the values were at close range. It is quite evident that the soils at the dumpsites were enriched in Ni by the refuse, since nickel may be
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added by biodegradation of nickel containing wastes into the environment [6]. This result can be compared with the result obtained in other studies. The natural range for the concentration of magnesium in the soil ranged between 5.0 175 mg/l. At dumpsites, the concentration of magnesium ranged between 1.8862 42.57 mg/l while at control site (20m away from Dumpsite) the concentration of magnesium ranged between 0.0927 and 0.3976 mg/l, (fig 8). This result is below the natural range of concentration of magnesium, therefore it can be suggested that pollution of the soil at the dumpsite is due to the decay process of tissues occuring at the study areas and some other factors which may be responsible for the observed background concentration of magnesium in the area. The natural range for the concentration of sodium in soil ranged from 2 185 mg/l. The concentration of sodium at dumpsite ranged from 0.9203 (Panseke) 29.00 mg/l (Sapon Market) and at the control sites (20m away from Dumpsites), between 0.4385 and 0.9876 mg/l, (fig 9). The concentration of sodium falls below the natural range. This may be due to the fact that Na are present in combined states and decompose under high temperature. [6], reported that the concentration of sodium in dumpsites located within Ikot-Ekpene Akwa-Ibom State ranged between 2.4 4.1 mg/l though within the natural range but relatively low when compared with the result obtained in this study. Figures 10 to 15 showed the distributions of the concentrations of each element in each location visited.

Key:
Sites
1 2 3 4 5 6

Locations
Sapon Market LantoroOkeyidi Kuto Market Panseke Adigbe Saje

Fig 2: Comparison of The Concentrations of Fe in The Samples At Dumpsites and Control Sites (20m Away From Dumpsites)
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Fig 3: Comparison of The Concentrations of Mn In The Samples At Dumpsites and Control Sites (20m Away From Dumpsites)

Fig 4: Comparison of The Concentrations of Cu In The Samples At Dumpsites and Control Sites (20m Away From Dumpsites)
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Fig 5: Comparison of The Concentrations of Zn In The Samples At Dumpsites and Control Sites (20m Away From Dumpsites)

Fig 6: Comparison of The Concentrations of Pb In The Samples At Dumpsites and Control Sites (20m Away From Dumpsites)

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Fig 7: Comparison of The Concentrations of Ni In The Samples At Dumpsites and Control Sites (20m Away From Dumpsites)

Fig 8: Comparison of The Concentrations of Mg In The Samples At Dumpsites and Control Sites (20m Away From Dumpsites)
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Fig 9: Comparison of The Concentrations of Na In The Samples At Dumpsites and Control Sites (20m Away From Dumpsites)

Fig 10: Concentrations of Elements in Sapon Market Dumpsite

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Fig 11: Concentrations of Elements in Lantoro Okeyidi Dumpsite

Fig 12: Concentrations of Elements in KutoMarket Dumpsite

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Fig 13: Concentrations of Elements in Panseke Dumpsite

Fig 14: Concentrations of Elements in Adigbe Dumpsite

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Fig 15: Concentrations of Elements in Saje Dumpsite

4.3

CONCLUSION

The concentrations of Pb and Ni in dumpsites are higher than the values in the control sites which might have being introduced from anthropogenic source. Also, essential elements for plant growth at both dumpsites and control sites are below the natural range. The concentrations of metals in soils at the decomposed biodegradable wastes dumpsites and 20m away from dumpsites showed that there is an evidence of relative increase in concentrations of metals in soils at dumpsites compared to those 20m away from dumpsites. This means that there should be a kind of measure taken in order to safely dispose off our refuse to prevent the general public from being exposed to unnecessary hazards through environmental pollution.

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