International Conference on: “New Role for the World Sugar Economy in a Changed Political and Economic Environment ” Environmental Impact Assessment of Heavy Metal Pollution in Soil from Assiut Fertilizer Plant, Egypt Thabet A. Mohameda, Ragab ElS. Rabeiyb, Mohamed Abuel – Kassem Mohamedb,Mahmoud A. Gandourc a National Institute of Occupational Safety and Health (NIOSH), Assiut. b Mining and Metallurgical Engineering Dept. Faculty of Engineering, Assiut University. c Chemistry Dept., Faculty of Science, Assiut University. Abstract: The Phosphate fertilizer industry is considered as one of the main sources of pollution to air, water, soil and vegetations. A phosphate fertilizer plant is located near Assiut city, Egypt, has strong negative environmental impacts on the adjacent area. A soil sampling network was developed around the plant to assess these harmful effects. 72 Soil samples were taken and analyzed to represent the spatial distribution of 5 trace elements. The soil samples have been analyzed using SEM- EDS method to evaluate the heavy metal elements of Cd, Pb, Zn, Hg, and As in the soil. The obtained results gave evidence of soil pollution on the study area caused by the emissions which released from the phosphate fertilizer plant. The average values of heavy metals concentrations (%) in the soil is 18.96%, 6.06%, 7.89%, 29.77% and 5.92% for Hg, Zn, As, Pb and Cd respectively. These values exceed much more than the permissible levels. Five control soil samples were taken upwind the fertilizer plant to compare them with the polluted area. The average values of the control samples were 1.31% for Hg, 0.08% for Zn, and 0.05% for Pb. While the elements As and Cd are not detected in the soil located upwind the plant. This comparison refers that the soil contaminations by heavy metals are caused only by the pollutants emitted from Assiut fertilizer plant. Key words: Soil Pollution, SEM- EDS Analysis, Heavy Metal Contaminations, Phosphate Fertilizer Industry. 1. Introduction: Heavy metals are important trace elements in nutrition of plants, animals, and human (e.g. Zn, Cu, Mn, Cr, Ni), while others are not known to have positive nutritional effects (e.g. Cd, Pb, Hg, As). However, all of these elements may cause toxic effects (some of them at a very low content level), if they occur excessively. Previous studies revealed that heavy metals have negative effects on 10-13 November 2012, Aswan, Egypt Thabet A. Mhoamed et al TL3.6/ 1 International Conference on: “New Role for the World Sugar Economy in a Changed Political and Economic Environment ” the microbial activity, composition of soil, inhibition of the germination of seeds and growth of plants [3]. Other effects of pollutants can be described as inhibitory effects by blocking the uptake of other elements and hence depriving the plant from absorbing essential elements from the soil [4]. The bioaccumulation of heavy metals over large territories and long time periods may result in the gradual damage of living organisms, and the functionality of the soil [1]. Assiut phosphate fertilizer plant, under consideration is located 9 km south of Assiut city, is processing phosphate rock for the production of Single Superphosphate SSP and Granulated Superphosphate GSP fertilizers. The production of the plant was 960,000 tons on 2009 [1.1]. Huge amounts of dust and gases are liberating from industrial units, bearing heavy metals that atmospherically dispersed and deposited in the nearby area producing a high degree of pollution in the air, soil, and aquatic system [2]. 72 soil samples were collected from the study area to determine the extent of heavy metal pollutants in contaminated soils. SEM-EDS technique was used for the quantitative estimation of elements Cd, Pb, Zn, Hg, and As in soil samples. Also micro quantitative analysis helps in technological measures to prevent heavy metals transfer to food chain. The objective of this study is to: (1) analyze the effect of atmospheric deposition of heavy metals from Assiut fertilizer plant in its surrounded soil, (2) determine to what extent the pollutants dispersed on the study area, and (3) study the effects of heavy metals on the growing vegetations. 2. Materials and Methods 2.1 Study Area The superphosphate fertilizer plant is located at 9 km north of Assiut city (27 N and 31○ E). The Plant lies between Nile river (East) and Ibraheemia canal (West). The area around the factory is cultivated with some main crops such as wheat, faba bean and clover in winter and sorghum, maize and cotton in summer. In addition, some fruit orchards like grapes, banana, jawava and figs are found in the area. The area under investigation is an agricultural land of 25 km2 and inhabited with 5000 individuals in three scattering villages. ○ 2.2 Sample Collection and Preparation 72 Soil samples were obtained using a stainless steel auger; disposable trowel at each location to a depth of 6 inches below the soil surface; any grass or other vegetative materials were removed and excluded from the collected soil sample. Each soil sample is composed of five subsamples which taken from a 10-13 November 2012, Aswan, Egypt Thabet A. Mhoamed et al TL3.6/ 2 International Conference on: “New Role for the World Sugar Economy in a Changed Political and Economic Environment ” circle of 5 meters diameter. One subsample was taken from the center and rests were taken from the circumference of the circle. Sample locations are illustrated in Figure 1. The collected soil samples were placed in provided containers, stored in coolers which containing ice, and shipped to the Electron Microscope Unit in Assiut University [5]. The soil samples were collected from the investigated area in both Winter (W) and Summer (S) seasons of the year 2010. Also, five control soil samples were taken from an unpolluted area; 3km up wind the fertilizer processing units. The reference samples were specified according to the specifications of the National Institute of Standards and Technology (NIST) [6 & 7]. All soil samples were dried in oven at 60 ºC for four hours to remove moisture content. Dried samples were grinded into fine powder using agate mortar [8]. These samples are analyzed be the Scanning Electron Microscope-Energy Dispersive Spectrometer (SEM-EDS). Figure 1: Location of the study area and soil samples 2.3 SEM-EDS Technique The micrographs were recorded using SEM JEOL model, JSE-5610LV with an accelerating voltage of 20 kv, at High Vacuum (HV) mode and secondary Electron Image (SEI). The maximum magnification possible in this equipment is 300000 times with resolution of X500 for all samples. The semi quantification elemental analysis to identify the weight percentage of major and minor elements present in the samples was done using the OXFORD INA Energy Dispersive xray spectrometer (SEM-EDS). This technique is used in numerous applications for environmental science and technology [6, 8]. 10-13 November 2012, Aswan, Egypt Thabet A. Mhoamed et al TL3.6/ 3 International Conference on: “New Role for the World Sugar Economy in a Changed Political and Economic Environment ” Energy dispersive x-ray spectrometer is a popular method for the determination of trace elements in geological and environmental samples. With the morphological characters obtained from SEM, supported by Energy Dispersive x-ray EDS micro analysis device, it is possible to identify the elements Cd, Pb, Zn, Hg and As that present in soil samples. 3. Results and Discussion 3.1 Morphology of Soil Samples The SEM microstructure and corresponding EDS spectrum were obtained for all soil samples and one typical micrographs and spectrum of soil samples are given in Figure 2 (a, b). The weight percentages of elements in typical five sample locations with control sample for soil obtained from EDS are given in Table 1. For quantitative electronic microscopic investigation preparations of samples becomes very important and, besides, such a procedure combines two particular actions: selection of very low concentration fine dispersive fraction to maximum separate particles into monomineral aggregates on the surface, and coating of conductive layer in order to reduce charge effect. The morphology of fine-dispersive fraction of sample soil appears as a selection of scaly aggregates with wide dispersion of dimensions from 0.5 to 5-7 μm. Apparently, electrolytic properties, when the sample was being formed, caused aggregation of illite and vermiculite in flakes of asymmetric shape [8]. The fact that particles are composed of plane aggregates (scales), may be explained by no uniformity of optical plane particles- there are darker and lighter portions. Figure 2 (a) Example of SEM spectrum of a soil sample 10-13 November 2012, Aswan, Egypt Thabet A. Mhoamed et al TL3.6/ 4 International Conference on: “New Role for the World Sugar Economy in a Changed Political and Economic Environment ” Figure 2 (b) Example of SEM microstructure of the sample The results of x-ray phase analysis and study of soils fine-dispersive fractions by SEM makes possible to identify separate minerals and to assess their sizes and shapes. Nevertheless, unambiguous visual identification and confirmation of the presence of the all minerals in a sample was quite probabilistic. Most likely, without separation of fine dispersive fraction for sufficiently narrow in sizes fraction, cover of larger particles upon the fine ones and total adherence into aggregates will shade the identification of morphologic characters of mineral particles. Morphological analysis by SEM of fine dispersive fraction has shown that there does not occur any evident division of particles into separate identifiable minerals. Only quartz particles may be identified unambiguously, Illite, smectite and vermiculite from asymmetric flake like aggregates of various sizes. 3.2 Statistical Analysis Table (1) Statistical Analysis of the soil samples in the investigated area Minimum Average Maximum Permissible Limit Element Control Control Control Soil Soil Soil % Samples Samples Samples Sample Samples Sample References Cd 0.510 N.D 3.990 0.002 9.01 0.006 0.00002 Adriano.,1986 Pb 6.270 0.480 20.745 0.786 57.65 1.02 0.02 " Zn 0.080 0.050 7.044 0.552 72.58 1.49 0.03 " Hg 7.570 1.020 16.593 1.390 26.92 2.28 - As 0.540 N,D 5.360 0.002 18.98 0.007 0.004 10-13 November 2012, Aswan, Egypt " Adriano.,1986 Thabet A. Mhoamed et al TL3.6/ 5 International Conference on: “New Role for the World Sugar Economy in a Changed Political and Economic Environment ” From Table 1 the data obtained from SEM-EDS microanalysis for soil samples showed that the percentages of heavy metal contents are different, especially Cd and Pb. Metal contents are ranged from 9.01% - 0.510%, 57.65% – 6.27%, 72.58% – 0.08%, 26.92% - 7.57%, and 18.98% - 0.540% for Cd, Pb, Zn, Hg As respectively. Figure 3: Concentration of heavy metals compared with control and guideline values Comparing the average values of heavy metal contents with that of both the control sample and the permissible levels it was found from Fig. 3 that the average value of Pb content equals 13 times that of the control sample, where it reached 313.5 times to Pb present in permissible level. But for Cd average value equals 25500 times to that of the permissible level and Cd in control sample is not detected. For Zn, the average value reached 1.6 times of that of the control sample and 2.6 of the permissible levels. For Hg, the average value is 7.4 times to that of the control sample. At last for As average value equals 135 times to that of the permissible level where As and Cd are not detected in control sample. As samples have been taken in the two seasons, winter and summer, it revealed that the average concentration values of heavy metal pollutants increase than that of summer. The temperature degree in this region is relatively high in summer and this enhances dispersion of pollutants, so the deposited atmospheric matter is decreased. But in winter where temperature degree is moderately low, the average concentration of pollutants is localized and is precipitated in the area under investigation. Also it was found that the average concentrations of heavy metal pollutants decrease faraway the plant location. 10-13 November 2012, Aswan, Egypt Thabet A. Mhoamed et al TL3.6/ 6 International Conference on: “New Role for the World Sugar Economy in a Changed Political and Economic Environment ” 4. Conclusion and Recommendations 4.1 Conclusion The phosphate fertilizer plant brings about serious heavy metal pollution problem. The soil is seriously polluted by heavy metals. The contents of Cd, Pb, Zn, Hg and As in soil reached a dangerous level where their concentration values surpassed those of the reference sample by significant values [10]. Cd and As are not detected in control sample and this refers that almost concentrations of the two elements do harm to the environment. As the estimation of pollutants in soil samples are highly affected by heavy metals, these metals can be absorbed by plant and in turn transfer to the food chain causing environmental risk. It is noticed that the leaves of the plant have covered with fine dust that hinders photosynthesis processes which refer that the area is affected by air pollution by the atmospheric emission from industries. The plants seem to have no exclusion mechanism in leaf structure [7], and hence, they seem to absorb Pb and Cd from atmosphere during the photosynthesis process. This phenomenon has support from visual evidence that the plants in the study area suffer due to small leaves, lesser number of leaves and deformed growth of plants. Hence, it may be concluded that the area which we studied suffer more from air pollution than from the soil pollution. If the atmospheric emissions from chimneys are governed by the standard pollution norms, the area may be saved from future pollution problems. 4.2 Environmental Recommendations Analysis of soil sampling data indicates that all obtained samples taken around the phosphate fertilizer plant contained toxic heavy metals in concentration which exceed the soil screening levels [9]. So the unacceptable concentration levels of these heavy metals can cause a human health risk to the people living in the concerned area. Based on what has been mentioned above, the following may be recommended: The concerned agency should delineate further surface and subsurface extent of soil contamination in the area surrounding the fertilizer plant. Egyptian Environmental Affairs Agency (EEAA) should develop and implement a soil and other contaminated media remedial plan to address the community exposure situation . Phosphate Fertilizer Plant should apply the control measures to reduce the fugitive and stack emissions of heavy metals in order to reduce community exposure. 10-13 November 2012, Aswan, Egypt Thabet A. Mhoamed et al TL3.6/ 7 International Conference on: “New Role for the World Sugar Economy in a Changed Political and Economic Environment ” Acknowledgment The authors would like to acknowledge Dr. Atif Abu El Wafa, dean of Sugar Technology Research Institute (STRI), for his support in the analysis of the soil samples. Also, the acknowledgement is extended to the team of Electron Microscopy Unit (EMU), Assiut University for their efforts in SEM-EDS microanalysis. References 1- Zanders, J. et al.: The accumulation and leaching of fertilizer- derived cadmium in Newland Podzol soil. In: 5th Conf. on the biogeochemistry of trace Element. Proc. Of Ext.(Ed: Wenczel W.W.et al.) , 1999 ,(1) 566 – 567. 2- Ruhling, A., Steinnes, E., Atmospheric heavy metal deposition in Europe 1995- 1996 Nord, 1998, 15,(1). 3- Johansson, S.A., Campbell, J.L., PIXE: A novel technique for elements analysis; Campbell's first book on PIXE, John Wiley & Sons, Inc. 1998. 4- Liao, G., Chao, W. Assessment of heavy metallic ions pollution for a river near a metal mine. J. Mining and Metallurgy, 2004, 13(1): 86-90 (in Chinese). 5- Liao, G., Liao, Da., Quan-ming, Li. Heavy metals contamination characteristics in soil of different mining activity zones. Trans. Nonferrous Met. Soc. 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