Journal of Environmental Protection, 2013, 4, 1502-1509 Published Online December 2013 (http://www.scirp.org/journal/jep) http://dx.doi.org/10.4236/jep.2013.412172 Open Access JEP Spatial Variations of Particle-Bound Trace Metals in Ambient Air of Selected Niger Delta Communities of Rivers State, Nigeria Godson R. E. E. Ana1*, Mynepalli K. C. Sridhar1, Jerome Nriagu2 1Department of Environmental Health Sciences, Faculty of Public Health, University of Ibadan, Ibadan, Nigeria; 2Department of Environmental Health Sciences, School of Public Health, University of Michigan, Ann Arbor, USA. Email: *anagrow@yahoo.com Received August 14th, 2013; revised September 15th, 2013; accepted October 12th, 2013 Copyright © 2013 Godson R. E. E. Ana et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. In accordance of the Creative Commons Attribution License all Copyrights © 2013 are reserved for SCIRP and the owner of the intellectual property Godson R. E. E. Ana et al. All Copyright © 2013 are guarded by law and by SCIRP as a guardian. ABSTRACT The objective of this study was to determine the spatial variation of particle-bound heavy metals in two communities with different industrial status in Nigeria’s Niger Delta Area. Fourteen ambient respirable particulate matter (PM10) samples 7 each from Eleme (highly industrialized) and Ahoada East (less industrialized) communities were collected according to standard methods using Anderson High volume sampler. Samples were analyzed for trace metals including Fe, Zn, Ni, Cd, and Pb using Atomic Absorption Spectrophotometer. Data were analyzed using descriptive statistics, Man Whitney U test and Spearman Rank Correlation all at P < 0.05. PM10 levels were 1.83 times higher at Eleme than Ahoada East (P < 0.05) and all the values were higher than both the USEPA and WHO limits. At Eleme spatial varia- tion of PM10 was in the following order: APE5 > APE3 > APE7 > APE1 > APE4 > APE6 > APE2. Fe, Zn and Cd were higher at Eleme than Ahoada East and the EC/WHO values. Pb was poorly correlated with PM10 (r2 = 0.0819, P > 0.05) at Eleme. Communities with higher industrial presence in the Niger Delta are more exposed to particulate burden. Rou- tine monitoring and strict adherence to regulatory limits must be enforced. Keywords: Industrial Pollution; Particulate Matter; Trace Metals; Spatial Variation; Niger Delta Communities 1. Introduction Particulate matter (PM) one of the major contributors of air pollution remains a big threat to human health. The WHO indicates that 4% - 6% of the world population die annually due to air pollution related morbidities [1]. PM10 is particularly considered to be a reliable indicator for possible health effects [2,3]. The airborne PM is usually composed of and or ad- sorbed by organic and inorganic toxic pollutants and studies [4] have established links between high levels of PM and health effects including respiratory and cardiac diseases [5,6]. Current studies have revealed that the mor- tality and morbidity rate is directly related to concentra- tion and number of particles in the aerosol [7-12]. The nature of PM can be organic, inorganic or a mix- ture with the organic compounds contributing 10% to 40% of the mass of PM. Heavy metals are among the inorganic elements constituting the PM [13]. Some of these elements, such as As, Pb, Cd, Hg, Zn, Ni, Cu, Mn and Cr are of major concern due to their toxic nature while others, such as Fe, Ca, Ba, and Mn are mainly linked to the earth’s crust or resuspended soil. Overall, the effect of PMs depends on its shape, size, composition, mass and number concentrations and the receptor cells. The fine particles provoke lung inflamma- tion and are responsible for cardiovascular diseases [14] and are potentially toxic to human health because of their large surface areas, which are coated with different che- mical constituents and carcinogens [15]. The chemical characteristics of atmospheric PM are important for both particle toxicity and its role in climate change [16-18]. The source of toxic trace metals in ambient PM is de- *Corresponding autho .
Spatial Variations of Particle-Bound Trace Metals in Ambient Air of Selected Niger Delta Communities of Rivers State, Nigeria Open Access JEP 1503 pendent on the various anthropogenic processes in a par- ticular area. These include industrial emissions, power plants, urban traffic and combustion by-products. Com- bustion from automobiles constitutes one of the major sources of particulate emissions, especially the respirable fraction and is directly related to human health [19]. Ac- cording to Kisku et al. [20] and Sharma et al. [21] vehi- cle related emissions is the main source of particulate pollution in Lucknow. Except for storage batteries, paint and gasoline additives were the two major high-volume products containing Pb; about the same quantity of Pb, 5 to 6 million metric tons, was used to manufacture each [22]. Pb is associated with the smallest particles, the clay grain size fraction in urban soils [23], therefore the con- centration of Pb in dust originating from urban soils [24] is higher than that from simple measurements of the Pb content of the soil [25]. Several reports show that Pb induces severe neuro- logical and hematological effects on the exposed popula- tion especially children [26]. Cd and Ni are known for inducing carcinogenic effects in humans through inhala- tion. Occupational level of Cd exposure is a risk factor for chronic lung diseases [27]. Cr is known for its toxic and carcinogenic effect on the bronchial tree [28,29]. Mn exposure leads to increased neurotoxic impairments [30]. The increased level of Cu can lead to respiratory irritancy [23,31]. In Nigeria, Ana et al. [32] showed varying concentra- tions of particulate matter in selected Niger Delta com- munities. However, other researchers [33-35] reported suspended particulates and their elemental concentrations within and around industrial complexes, road side dust, and its effect on soil, vegetation and crops in other parts of the country. Efe [36] reported on spatial distribution of particulate air pollution in Nigerian cities and their im- plication for human health. The study showed that over 70% of Nigerian urban environments have mean annual ambient PM10 value of over 120 μg/m3. Okuo and Ndi- okwere [37] studied elemental concentration of Total Suspended Particles with levels as high as 1332.75 μg/m3 in Warri and elemental concentrations range (μg/m3) for metals including As (3.01 - 5.21), Cd (0.02 - 0.23), Pb (1.01 - 1.04) and Fe (1.13 - 1.38). Also Akeredolu et al., [38] and Asubiojo et al. [39] reported levels of particu- late matter 40,000 μg/m3 in industrial sites and 1033 μg/m3 in ambient air. But in all these studies there were no indications on the varying pollution levels arising from different sources. Our study therefore elucidated the spatial variations of the particle-bound trace metals between two communi- ties of different urban and industrial status in Nigeria’s Niger Delta Area. 2. Material and Methods 2.1. Description of the Study Area The study was carried out in two local government areas (LGAs): Eleme a highly industrialized LGA located about 20 km away from Port Harcourt city, the Rivers state capital and Ahoada East a less industrialized LGA located about 80 km from the state capital. The major industries at Eleme include Shell Petroleum Develop- ment Corporation (SPDC) oil wells at Ebubu, Petro- chemicals at Akpajo/Agbonjia, Refinery at Alesa/Okirika and a fertilizer complex at Onne. Both LGAs share a similar tropical climate. Their vegetation is a mixture of rainforest and mangrove/swamp forest. In addition, the aquatic resources are equally a mixture of fresh and brackish water. 2.2. Sampling Locations and Conditions Particle-bound heavy metal samples from outdoor ambi- ent air were collected systematically from 14 locations: 7 from Eleme and 7 from Ahoada East communities re- spectively (see Figure 1). Samples were collected during late dry season conditions (February-March).The average meteorological conditions recorded showed temperature range of 28˚C - 31˚C. Average windy conditions with wind speed hardly exceeding 3.5 m·s−1 at the sample locations with no cloud cover. A low relative humidity of less than 12 - 33 mm was recorded throughout the period of sampling. 2.3. Determination of Respirable Particulate Matter (PM10) The respirable particulate matter (PM10) samples were obtained using a high volume sampler Anderson model reference method No RFPS-1287-063 with 10 μm cut off inlet at a flow rate of 1 - 1.2 m3 for 4 hr. Preweighed glass fibre filter papers with dimension 20.3 × 25.4 cm (8 × 10 in) (eCat No: 1882 866) EPM 2000 were used and reweighed after sampling in order to determine the mass of the particles collected. The concentration of the par- ticulate matter (μg/m3) was computed on the basis of the net mass collected divided by the volume of air sampled. 2.4. Trace Metals Analysis The concentration of heavy metals in air was determined with slight modifications using methods described by Dorn et al. [40]. The filter papers shredded into tiny frac- tions were carefully digested with 10 ml of concentrated HNO3 inside a Teflon beaker and heated at about 120˚C until solution became clear. The content was filtered through a Whatman filter (No. 42) and final volume was
Spatial Variations of Particle-Bound Trace Metals in Ambient Air of Selected Niger Delta Communities of Rivers State, Nigeria Open Access JEP 1504 Figure 1. Air sampling locations in study communities. made up to 50 ml with Milli Q water. The concentrations of heavy metals (mg/m3) Fe, Zn, Ni, Cd, and Pb were determined using Perkin Elmer AAS model 929 with double beam background corrector. Air-acetylene flame and graphite furnace with appropriate cathode lamps were used. 2.5. Statistical Analysis Data obtained from the field and laboratory were proc- essed statistically using SPSS version 15. Data were ana- lyzed using descriptive statistics, Mann-Whitney test and Spearman correlation for quantitative variables all at 5% level of significance. 3. Results 3.1. Concentration of Respirable Particulate Matter (PM10) The PM10 and trace metals: Fe, Zn, Pb, Cd and Ni con- centration were determined in the ambient air at Eleme. Table 1 indicates that the highest PM10 levels were re- corded at Alesa (232.5 ± 23.2 µg/m3) and Ebubu (260.6 ± 47.7 µg/m3) compared to all other sampling locations and the mean PM10 levels recorded at Eleme was observed to be higher than Nigeria’s minimum (100 µg/m3) but lower than maximum (250 µg/m3) guideline limits (Figure 2) respectively. The spatial variation in the concentration of PM10 in the ambient air at Eleme is in the following or- der: APE5 > APE3 > APE7 > APE1 > APE4 > APE6 > Figure 2. PM10 levels at study locations in comparison with guideline limits. APE2. At Ahoada East Table 2 shows that the highest PM10 concentrations were recorded at Ahoada (161.4 ± 10.2 g/m3) and Ula Ehuda (141.9 ± 7.92 g/m3) as compared to other sampling locations. The mean PM10 levels were both lower than Nigeria’s Minimum guideline limit of 100 g/m3 and the maximum guideline limit of (250 µg/m3) (Figure 2).The spatial variation in the PM10 con- centration in descending order is as follows APA2 > APA3 > APA4 > APA1 > APA5 > APA7 > APA6 with the most prominent urban communities of Ahoada (APA2) and Ula Ehuda (APA3) recording the highest concentra- tions.
Spatial Variations of Particle-Bound Trace Metals in Ambient Air of Selected Niger Delta Communities of Rivers State, Nigeria Open Access JEP 1505 Table 1. PM10 and trace metal concentrations in ambient air at Eleme. Sample ID/Location/Parameter APE1 Akpajo APE2 AletoAPE3 AlesaAPE4 OgaleAPE5 Ebubu APE6 Ekporo APE7 Onne PM10 (g/m3) 75.0 ± 6.51 37.2 ± 0.35232.5 ± 23.261.0 ± 2.26260.6 ± 47.7 43.2 ± 7.49 154.4 ± 16.5 Fe (g/m3) 0.09 ± 0.02 0.09 ± 0.040.10 ± 0.07 0.10 ± 0.080.10 ± 0.09 0.10 ± 0.06 0.10 ± 0.08 Zn (g/m3) 0.04 ± 0.01 0.03 ± 0.020.05 ± 0.04 0.02 ± 0.010.05 ± 0.03 0.05 ± 0.02 0.10 ± 0.05 Pb (g/m3) 0.07 ± 0.02 0.10 ± 0.020.07 ± 0.03 0.02 ± 0.010.10 ± 0.05 0.05 0.02 0.03 ± 0.03 Cd (g/m3) 0.02 ± 0.02 0.01 ± 0.010.02 ± 0.02 0.01 ± 0.030.002 ± 0.003 0.003 ± 0.002 0.004 ± 0.001 Ni (g/m3) 0.03 ± 0.02 0.03 ± 0.010.05 ± 0.03 0.02 ± 0.020.03 ± 0.04 0.04 ± 0.02 0.03 ± 0.02 Table 2. PM10 and trace metal concentrations in ambient air at Ahoada East. Sample ID/Location/Parameter APA1 Ulapata APA2 AhoadaAPA3 Ula EhudaAPA4 IhuboguAPA5 Ihuoho APA6 Ikata APA7 Odiabidi PM10 (g/m3) 25.9 ± 3.89 161.4 ± 10.2141.9 ± 7.92 104.7 ± 8.41 20.4 ± 1.06 8.84 ± 0.50 10.4 ± 0.06 Fe (g/m3) 0.01 ± 0.01 0.03 ± 0.02 0.04 ± 0.02 0.04 ± 0.02 0.03 ± 0.01 0.03 ± 0.02 0.05 ± 0.04 Zn (g/m3) 0.08 ± 0.04 0.03 ± 0.01 0.05 ± 0.03 0.05 ± 0.03 0.04 ± 0.01 0.05 ± 0.03 0.42 ± 0.14 Pb (g/m3) 0.05 ± 0.02 0.04 ± 0.03 0.13 ± 0.08 0.03 ± 0.02 0.11 ± 0.10 0.11 ± 0.09 0.13 ± 0.07 Cd (g/m3) 0.01 ± 0.03 0.004 ± 0.0020.01 ± 0.01 0.01 ± 0.03 0.002 ± 0.001 0.004 ± 0.002 0.01 ± 0.01 Ni (g/m3) 0.01 ± 0.01 0.02 ± 0.02 0.03 ± 0.02 0.03 ± 0.02 0.05 ± 0.03 0.03 ± 0.03 0.04 ± 0.02 3.2. Concentration of Trace Metals Table 1 indicates that the highest Pb level was recorded at Ebubu (0.10 0.05 g/m3) while the highest Cd levels was recorded at Akpajo (0.02 0.02 g/m3) and Alesa (0.02 0.02 g/m3) respectively. At Ahoada East the highest Pb levels were recorded at locations in Ula Ehuda (0.13 ± 0.08 g/m3) and Odiabidi (0.13 ± 0.07 g/m3) (Table 2). Of the five heavy metals assessed three viz Fe, Zn and Cd recorded higher concentrations at Eleme. Only Pb recorded a higher concentration at Ahoada East (Figure 3). 3.3. Relationship between PM10 and Trace Metals The relationship between the PM10 and trace metals was assessed based on the level of correlations. Given the place of Pb among the most toxic heavy metals in the EPA priority list only the result of the correlation test for PM10 and Pb is reported here (Figures 4(a) and (b)). In all the cases no significant correlations were observed. 4. Discussion The concentrations of PM10 were assessed in relation to trace metals in two communities of Nigeria’s premium oil producing area with different levels of industrial ac- tivities and urbanization. The results of the respirable fraction of particulate matter and the trace metals ad- Fe Zn Pb Cd Ni 0.00 0.05 0.10 0.15 0.20 Eleme Ahoada East METALS Mean SD Figure 3. Comparison of mean values of heavy metals be- tween Eleme and Ahoada East. sorbed on the surface of the particles are given in Tables 2(a) and (b) with Figures 4(a) and (b) showing the cor- relation between these two parameters. At Eleme the spatial distribution of PM10 in the vari- ous sampling locations showed the following order: APE5 > APE3 > APE7 > APE1 > APE4 > APE6 > APE2.The first four sampling points represent locations at Ebubu where Shell Petroleum has its oil locations (APE5), refinery complex at Alesa (APE3), chemical fer- tilizer complex at Onne (APE7) and the petrochemical complex at Akpajo (APE1) recorded the highest concen- trations. The presence of these industrial facilities associated with increased human activities viz automobile emissions, burning of biomass, must have contributed to the higher PM10 concentrations in these locations than the others.
Spatial Variations of Particle-Bound Trace Metals in Ambient Air of Selected Niger Delta Communities of Rivers State, Nigeria Open Access JEP 1506 y = 1E-04x + 0.0509 R 2 = 0. 0819 0 0. 02 0. 04 0. 06 0. 08 0. 1 0. 12 050100 150 200250 300 PM10 Level s(ug/m 3) Pb Conc(mg/ m3) (a) y = -0.0003x + 0. 1028 R 2 = 0. 14 62 0 0. 02 0. 04 0. 06 0. 08 0. 1 0. 12 0. 14 050100 150 200 PM10 Leve l s(ug/m3) Pb Conc(mg/m3) (b) Figure 4. (a) Correlation between PM10 and Pb in ambient Air at Eleme; (b) Correlation between PM10 and Pb in am- bient air at Ahoada East. This observation is in concert with studies by Efe [37] where PM10 concentrations were higher in more urban- ized settings with higher industrial and traffic conditions. In the same vein at Ahoada East, the order of PM10 was: APA2 > APA3 > APA4 > APA1 > APA5 > APA7 > APA6 with the most prominent urban communities of Ahoada (APA2) and Ula Ehuda (APA3) recording the highest concentrations. The mean PM10 concentration observed at Eleme was expectedly higher (1.83 times) than that recorded at Ahoada East. This could be explained by the fact that there are more anthropogenic activities especially auto- mobile and industrial emissions at Eleme which is con- sidered to be more urbanized than Ahoada East. The presence of the refinery, petrochemical complex, chemi- cal fertilizer company and other industries have certainly contributed to the burden of particulate emissions in the ambient air environment of these localities. The mean levels of PM10 at Eleme though higher than the values from Ahoada East were comparable to that reported by Efe [37], close to that reported by Singh et al. [41], higher than that reported in most European coun- tries [42,43] and some American countries [44]. Overall, these levels were lower than Nigerian Max permissible limits [45] but higher than USEPA limits. The spatial variation in the concentration of Pb in the ambient air at Eleme is as follows: APE5 > APE2 > APAE3 = APE1 > APE6 > APE7 > APE4.Excluding APE2, the first four locations have very high industrial presence with its attendant human activities and this must have contributed to the high levels of Pb in the ambient air. Also the spatial variation at Ahoada East shows the following trend: APA7 = APA3 > APA5 = APA6 > APA1 > APA2 > APA4. In contrast to the observations at Eleme, Ahoada (APA2) the most urbanized community and the adminis- trative headquarters of the local government area re- corded the lowest Pb level. The spatial variation for other trace metals was also noted. Pb mainly from anthropo- genic sources was found to be higher at Ahoada East than Eleme and about a 1000 times higher than values reported by Lopez et al. [43], despite the higher indus- trial outlook of Eleme. These values were 60 folds (for Eleme) and 90 folds (for Ahoada East) higher than WHO limits. Fe had higher concentrations at Eleme than Ahoada East and these levels were higher than levels recorded by Sharma et al. [21], Singh et al. [41]. The Fe could have been from both natural and anthropogenic origin [46]. The concentration of Zn was higher at Eleme than Ahoada East and these levels are higher than the values reported by Singh et al. [41] as well as the WHO guide- line [2]. Nowadays, Zn has been proposed as a reliable tracer of unleaded fuel and diesel oil-powered motor ve- hicle emissions. Cd mostly from occupational origin was highest with values almost 10 times at Eleme as com- pared to Ahoada East. Ni emitted from both stationary and mobile sources had same mean concentrations for Eleme and Ahoada East suggesting similar inputs from probably automobile emissions. Several studies have shown some level of correlation and linear relationship between the PM10 concentrations and trace metals. For instance Singh et al. [41] showed a correlation of PM10 with Zn (r = 0.39, p < 0.05) and Ni (r = 0.36, p < 0.05). Also Barman et al. [45] showed a cor- relation of Ni (r = 0.71, p < 0.01), Cd (r = 0.65 < 0.01) with PM10 and similarly Sharma et al. [21] showed cor- relation of Fe (r = 0.71, p > 0.05) with PM10.This sug- gests that trace metals adsorbed on particulate matter are linearly dependent on the PM10 levels. In the present study nearly all the metals were poorly correlated with PM10 even though only the correlation between Pb and PM10 is being reported. The result was however at vari- ance with those hitherto reported. This suggests that most of the sources of PM10 were not rich in the trace metals determined. It is considered that elevated concentrations of PM10 and particle-bound trace metals have direct relation to adverse human health as well as on the environment
Spatial Variations of Particle-Bound Trace Metals in Ambient Air of Selected Niger Delta Communities of Rivers State, Nigeria Open Access JEP 1507 [47-49] Other studies have also implicated high levels of PM10 with various forms of respiratory and cardiovascu- lar disorders as well as increased hospital visitations [7]. In this study the levels of PM10 and the associated trace metals were higher in the ambient air at Eleme as com- pared with Ahoada East, implying that the populations in the former than the later would be more prone to adverse health outcomes. 5. Conclusions The study revealed that respirable particulate matter was nearly two folds higher in the ambient air at Eleme com- pared to Ahoada East and the levels even though lower than FEPA guidelines were higher than USEPA and WHO limits. Three out of the five trace metals namely Fe, Zn and Cd recorded higher concentrations at Eleme compared to Ahoada East with Pb only recording the highest concen- tration at Ahoada East. 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