Technical Journal of Engineering and Applied Sciences Available online at www.tjeas.com ©2013 TJEAS Journal-2013-3-17/2077-2082 ISSN 2051-0853 ©2013 TJEAS Evaluation of Spatial and Temporal Variation of Heavy Metals in Soil, Water and Rice Grain (Case Study: Khoramabad Plain, Iran) Hamid Reza Matinfar Assistant Professor of Lorestan University, Lorestan, Iran Corresponding author: Hamid Reza Matinfar ABSTRACT: In order to study the spatial and temporal variation of heavy elements in soils, water and rice, a research project was done in Khoramabad area and repeated with three months of May, July and September respectively. Per each test site 5 samples were selected, finally soil samples were collected. The amount of lead, nickel and cadmium was analyses. For both nickel, lead and cadmium change is not significant when the time period studied. Two-way analysis of variance test results show the spatial variation of nickel, cadmium and lead levels are a significant percentage. For both nickel and lead and cadmium change is not significant when the time period studied, significant changes in expression levels of these elements in soils was studied. The amount of Cd in paddy fields averaged 0.182 micrograms per gram of soil, which is equivalent to 663 grams per hectare. In comparison to German and Swiss standards (with respectively 33 and 75 g Cd per hectare) it is very high. The amount of Cd in grains of rice on average 0.115 micrograms per gram of dry matter is due to the amount of harmful cadmium in plants for human 0.1 microgram reported currently moderate in the tissues of rice above the limit and it is harmful for human consumption. Keywords: Spatial and temporal variation, Heavy metals, Wastewater, soil, rice INTRODUCTION 3 Heavy metals are elements with the density of over 5 gr/cm . This definition is biologically useful, since it covers many elements in the nature. But in physiological conditions only a small number of these elements can be found in the liquid form, and therefore might be available for living cells. There are elements among them which are important as micronutrients or trace elements (Iron, Zinc, Nickel, Magnesium, and Chromium) for plant metabolism, also there are some elements which are toxic for plants when their amount in the growing environment exceeds the normal limit(Adriano, 1986). There are other elements with unknown biologic role and high toxicity for plants (Mercury, Lead, Cadmium, Silver, and Arsenic). Destructive impacts of heavy metals release into nature are of great interest, presently (Ramelow, 1992). Urban traffic, household wastes, and industrial Wastewater are resources of these metals. Release of factory dust and ash from metal processing industries has led to pollution. Heavy metal pollution in farms is the result of soil treatment with contaminated wastewater and excessive application of phosphate fertilizers containing cadmium is a growing problem. Long term biological duration and remaining in the soil lead to the accumulation of these metals in the food cycle and consequently potential negative effect on human health (Lin and Schorr, 1977; Zimdahi and Skogerboo, 1997). Nickel is one of the heavy metals th which can be found abundantly in biosphere, and is the 24 element in earth crust, in terms of frequency in comparison to other elements. Besides, Nickel is one of the most common metals in surface waters. It exists in water systems in the form of absorbed soluble salts or with clay particles, organic or other materials. Nickel may be deposited or stored in sediments via settling, building complexes, and absorption on clay particles, or it might be absorbed by organisms. Little amounts of Nickel are required for creation of red blood cells in human body, but it can be relatively toxic in higher amounts. It seems that in short term Nickel will not be harmful, but in long term it can cause weight loss, damages to the heart and the leaver, and high sensitivity. Nickel can be accumulated in aquatic but it will not be magnified in food chain. Most Nickel salts, entering the body through foods, are excreted. Tech J Engin & App Sci., 3 (17): 2077-2082, 2013 Normal amount of Nickel in human body is about 7.3 grams per kilograms in average. The highest concentration of Nickel is observed in bones, lungs, kidneys, and leaver. Nickel concentration in sea water is 0.1-0.5 Nano grams per liter (Ramelow, 1992; Rohoan, 2006, and Rauret, 1998, Takijima et al., 1973). Lead is also one of the heavy metals with 1 to 200 milligrams per kilogram concentration in soils and average concentration of 15 milligrams per kilogram; its critical limit is 50 milligrams per kilogram (Lotfi, 1989, World Health Organization, 1992). Recycling and using urban Wastewater in crop product and development of green areas is one of the ways to cope with water shortage in order to maintain and protect limited water resources, protect the environment and finally agriculture development. Usually, the Wastewater of undeveloped cities with limited industry is less variety of contamination, but toxic chemical components entering into Wastewater cannot be neglected (Matin 1995).Wastewater chemical quality of different cities, are different and generally depend on economic and social condition and jobs and occupations in the city. Each member of urban society produces daily average of 150 liters of waste eater, which enters into waste eater collecting system and includes toxic elements as well as some nutrients for plants, but nutritious role of waste eaters are economically neutralized by heavy elements. Usually, urban Wastewaters contain 20 to 60 grams per liter of organic material, 5 to 13 grams per liter of nitrogen, 0.5 to 4.5 grams per liter of Potassium. Besides, harmful micro-organisms, such as pathogens and carriers of epidemic 1 diseases are in these waters as well; according to WHO data, four fifth of diseases of people in developing countries originates from contaminated water (Torabian and Baghorei, 1995 ; Matin, 1995). Research done by Mostashari showed that application of industrial waste eater in Qazvin(Iran) farms increased the concentration of Lead, Cadmium, Copper, and Zink up to several times more than standard limit in the soil and crops (Mostasharei, 2002). The results of Torabian and Mahjoori researches in 2002 showed that the Cadmium contamination range in southern Tehran farms is 0.101 to 7.54 milligrams per kilograms of soil, and in crops is 0.398 to 2.437 milligrams per kilograms of dry weight of the crop, which is higher than standard amount for human consumption. As an example the concentration of Cadmium in lettuce in Varamin region is 2.1 milligrams per kilograms of the weight of the plant, while its standard limit is 0.1 milligrams per kilograms of the weight of the plant (Torabian and Mahjoori, 2003). Not only there are diseasing microorganisms in urban Wastewater, but also toxic heavy metals can be found in abundance. It is better to determine type and concentration of heavy elements in parts of urban Wastewater and compare it with existing standards, before using it for irrigation (Table 1). Table 1. Standard Limit of Heavy Metals in Farming Soils (mg/ha) Element Zn Cu Cr Pb Ni Cd Hg Germany Standard 5000 2000 2000 2000 330 33 42 Swiss standard 7500 2500 2500 2500 500 75 25 Heavy metals in soils poison plants and also affect microorganisms and their action (Bolan et al. 2003). Cadmium has been receiving more attention among heavy metals in the soil, since it can cause chronic lung disease, osteoporosis and brittle bones, and swelling of the mucous membranes of the respiratory system, if it enters the human food cycle through contaminated water, soil or plants. Poisonous effects of this element occur in human body in the case of continuous consumption of plants with more than three milligrams per kilograms of Cadmium (Torabian and Mahjoori, 2003; Rezakhani, 2001). Generally, the concentration of Cadmium in uncontaminated soils is less than 0.1 milligrams per kilograms, while its critical concentration in contaminated soils is between 1.5 to 2.5 milligrams per kilograms of soil (Adriano, 1986). Studies about drinking water reservoirs and resources, located in downstream of mine areas in Italy, showed that there is a great amount of Cadmium, Lead, and Copper in different branches of rivers in the area due to discharge of mine drainage into them. Besides, a high amount of these metals were found in river sediments (Ramelow 1992). Studies, carried out in contaminated areas of southern Louisiana in USA, on environmental changes of Zink, Copper, Nickel, Iron, Lead, Chromium, Aluminum, Cadmium, and Silver showed that the amount of these metals in surface sediments of rivers of the area is higher than deep sediments. According to these studies, urban Wastewater mostly increased the discharged heavy metal load into environment (Morishita, 1991). Kafilzadeh et al. 1 - World Health Organization 2078 Tech J Engin & App Sci., 3 (17): 2077-2082, 2013 showed in their studies on Shiraz dry River that industrial Wastewater, urban waste, metal waste of marginal workshops and repair shops were the origin of heavy metals in this river (Kafilzade et al., 2007). Cadmium is naturally in surface and groundwater resources. This element may be found in the form of hydrate ion or complicated mineral components such as carbonate, hydroxide, chloride, sulfate, and also organic components with humic acid. Cadmium enters aquatic ecosystems through soil and bed rock erosion, contaminated atmospheric sediments from industrial factories, Wastewater from contaminated areas, and usage of sludge and fertilizer in agriculture. Sediment of rivers and lakes contain 0.2 to 0.9 milligrams per liter of Cadmium and it is less than 0.1 milligrams per liter in fresh waters. The concentration of Cadmium in phosphorous fertilizers is the function of phosphate rock, from which the fertilizer has been made. Besides, the characteristics of the soil such as pH, type and amount of clay, the amount of organic material, soil solution components, and plant residues are effective in Cadmium accumulation (Torabian et al., 2003). Usually, Cadmium is absorbed by plant’s roots and enters slowly into stem and leaves; its transport from leaves into fruit is insignificant. So, vegetables and plant organs being fed from Cadmium contaminated soils or Wastewater are very harmful. Maximum standard amount of Cadmium in crops has been reported 0.1 milligrams per kilograms (Khani et al., 2001; Barzegar et al., 2002). 2 FAO and WHO set the acceptable weekly absorption of Cadmium 420 micrograms for each adult with 60 kilograms weight (Wagner 1993). For the first time in 1963 some researchers reported contamination of chemical fertilizers with some heavy metals, especially Cadmium as a dangerous factor for human health and environment (FAO Water Reports, No.10). Researchers believe that the cause of Etai-Etai syndrome in Japan is related to irrigating rice farms with Cadmium contaminated water. There are also reports about accumulation of Cadmium in crops, especially rice and potato in Iran (Khani et al., 2001; Malakoutei et al., 2005). According to the researches of Wagner the Cadmium contamination in lettuce, spinach, celery, and potato is high, but it is lower for plants like bean, corn, and pea (USEPA, 1981). Studies of Morishtia (1991) showed that the rice, planted in soil with 0.4 to 0.5 milligrams per kilograms of Cadmium, produced the crop with Cadmium concentration of 0.08 milligrams per kilograms of dry weight, and application of water with Cadmium concentration of about 5 milligrams per liter to irrigate rice, produced crops with 1.6 milligrams per liter of dry weight (Lin and Schorr, 1977). The concentration of Cadmium in crops should not be higher than the standard limit, but crops such as fruits and vegetables which are irrigated with Wastewater or located besides roads are contaminated to Cadmium and Lead; sometimes these contaminations pollute leaves’ surfaces in the form of a cover and eating them fresh may increase the level of consumed Cadmium and Lead in human more than standard limit, consequently, control and knowledge of the concentration of these contaminations is inevitable (Matin, 1995; Mostasharei, 2002). Thus, for the purpose of studying the spatial and temporal changes of some heavy metals including Cadmium, Lead, and Nickel in Khoram Abad River farms area, and also the way these spatial and temporal changes influence on the rice, being produced in the area. Research was carried out in completely randomized blocks plan in four spatial treatments in marginal farms of Khoram Abad River, and three temporal repetition in May,July and September. METHODS AND MATERIALS The study area begins from southwest of Khoram Abad City and ends in Khoram Abad Airport. The area has warm and dry summers, and cold wet winters; the wet season begins from November and ends in May; Average annual precipitation of 516 millimeters and maximum precipitation of 78.1 millimeters in April has been reported in the area. Khoram Abad River originates from northern mountains of the city and after passing through the length of the plain, in Cham Mehr enters into Karkheh River. The river pH varies from 7.5 to 8.1. The maximum river discharge has been reported in April and May and the minimum one in September and October (Cham Anjir Station Report (1994) & Research Annual Report (1993)). Groundwater resources include Changaee Spring and deep wells with 7.4 pH and electrical conductivity of 0.57 ds/m. These soils have horizons of calcic, cambi , and ochric which declares the movement of Lime and its accumulation in lower layers of soil (Soil Studies, Lorestan Province, 1995, and Soil Studies, Khoram Abad Agricultural Co., 1996). In this research, first the soil maps and related reports were studied, and four random points were selected, by surveying the rice farms and identifying those being irrigated from river in several years. One out of these four points which was irrigated from well was chosen as the witness point (Figure 1). In order to study the spatial and 2 - Food and Agriculture Organization 2079 Tech J Engin & App Sci., 3 (17): 2077-2082, 2013 temporal heavy elements, this research was caried out in the form of completely random blocks plan in four spatial treatments in Khoram Abad City exit (treatment A), Gilvran Village (treatment B), Airport (treatment C) and town (treatment D), and three temporal iteration in May, July and September. In each iteration 5 soil samples was taken from 50 to 100 meters spaces and depth of 0 to 30 centimeters of each place, then the samples were mixed together and at the end a sample with 2 kilograms weight was produced and transferred to the lab (mixed sample). Then the extract was produced from soil and rice samples through Nitric Acid solution method (Technical Report No. 893) and the concentration of Lead, Nickel, and Cadmium in the samples was measured by Shimadzu atomic absorption instrument (Tables 2, 3, and 4). Test site Keio water resource Khoramabad River Figure 1. The location of the Area and Study Sites Table 2.Measured Concentrations of Cadmium (micrograms in grams of soil) in Different Treatments and Iterations Treatment R1 R2 R3 Mean A 0.19 0.21 0.16 0.187 B 0.18 0.18 0.16 0.173 C 0.19 0.20 0.17 0.187 D 0.11 0.10 0.10 0.103 Table 3. Measured Concentrations of Lead (micrograms in grams of soil) in Different Treatments and Iterations Treatment R1 R2 R3 Mean A 0.42 0.44 0.28 0.38 B 0.14 0.27 0.13 0.18 C 0.11 0.12 0.10 0.11 D 0 0.03 0 0.01 Table 4. Measured Concentrations of Nickel (micrograms in grams of soil) in Different Treatments and Iterations Treatment R1 R2 R3 Mean A 1.42 1.56 1.32 1.43 B 1.45 1.58 1.41 1.48 C 1.44 1.52 1.38 1.45 D 1.12 1.13 1.1 1.12 2080 Tech J Engin & App Sci., 3 (17): 2077-2082, 2013 RESULTS AND DISCUSSION Electric conductivity of the saturated extract of soils was the minimum in the witness and maximum in the rice farms, the average minimum and maximum was 0.56 and 1.97 ds/m, respectively. Saturated extract of soils’ pH in witness lands was 7.28 and 8.4 in other treatments. The minimum percentage of organic material was related to the witness lands (1.6 percent) and the maximum one to the rice farms (3 percent). In order to study the spatial and temporal changes of Nickel, Lead, and Cadmium, the two way variance analysis test was carried out; tables 5, 6, and 7 show the results. These results showed that spatial changes of Nickel (Table 5), Cadmium (Table 6), and Lead (Table 7) were meaningful in one percent level. Table 5. Variance Analysis for Nickel Source Repeat Treatment Residual Error Sum DF 2 3 6 11 SS 0.04 0.26 0.01 0.31 MS 0.021 0.086 0.002 F 10.43 41.92 P 0.0112 0.0002** **Significant level is 0.01 Table 6. Variance Analysis for Cadmium Source Repeat Treatment Residual Error Sum DF 2 3 6 11 SS 0.00 0.01 0.00 0.02 MS 0.001 0.005 0.00 F 6.30 43.08 P 0.0336 0.0002** **Significant level is 0.01 Table 7.Variance Analysis for Lead Source Repeat Treatment Residual Error Sum DF 2 3 6 11 SS 0.02 0.22 0.01 0.25 MS 0.008 0.073 0.002 F 3.58 34.27 P 0.0946 0.0004** **Significant level is 0.01 The average concentration of Cadmium was 0.1 micrograms per grams of soil in the witness treatment, irrigated by well, and from 0.187 to 0.173 micrograms per grams of soil, and near each other, for other treatments, irrigated by river water. The average concentration of Nickel was 1.12 micrograms per grams of soil in the witness treatment, and varied from 1.43 to 1.48 micrograms per grams of soil for other treatments. According to the Duncan test there was not a meaningful difference in the level of one percent between treatments which were irrigated from the river, but there was a meaningful difference between them and the witness treatment (Table 8). The average concentration of Lead was 0.01 micrograms per grams of soil in the witness treatment, and varied from 0.11 to 0.38 micrograms per grams of soil for other treatments. Table 8.The Results of Average Comparison of Different Treatments with Duncan Test in the Level of One Percent Treatment A B C D Lead a b bc c Nicle 0.38 0.18 0.11 0.01 a a a b 1.48 1.45 1.43 1.1 Common letters in each column indicate no significant differences between them The results of Duncan test in the level of one percent showed that there is a meaningful difference between the witness treatment and other ones, irrigated from the river (Table 8). Based on the Cadmium variance analysis table, with the zero test error for this test, the Duncan test was not possible. There is not a meaningful spatial change for all the three elements of Nickel, Lead, and Cadmium, on the other hand no significant changes in the concentration of these elements in the studied soils was observed during the studied time period. Average Cadmium concentration in rice farms’ soil was 0.182 micrograms per grams of soil or 663 grams per hectare, which is very high in comparison with the German and Swiss standards where the concentration of 33 and 75 grams of Cadmium is permitted respectively (Table 1). Also, the average concentration 2081 Tech J Engin & App Sci., 3 (17): 2077-2082, 2013 of Cadmium in the rice was 0.115 micrograms per grams of dry material which was not higher than the maximum limit, regarding that the natural range of concentration of this element in plant tissue which has been reported from 0.3 to 0.4 micrograms per grams of dry material, but it is worrying. Besides, the concentration of 0.1 micrograms per grams has been reported as the harmful amount of Cadmium in the plants for human beings, and the average Cadmium concentration in rice was higher than this limit. With increase of Cadmium concentration in soil, its concentration in plants increase as well, and due to its harm for human being and threat to his health, the obligation of scientific agricultural management by operational organizations to minimize the environmental impacts of Cadmium seems inevitable. The results showed that in the study area spatial changes of Cadmium, Lead, and Nickel were meaningful, but their temporal changes were not. Irrigating with water from Wastewater contaminated river led to accumulation of Cadmium in soil and rice; its concentration in rice is more than the standard limit. The results of this research were similar to those of Adriano, 1986; Kani et al., 2000; Morishtina, 1991; Cherati and Malakoti, 2004; Malakoti et al., 2000 and Takijima et al., 1973. REFERENCES Adriano DC .1986 . Trace elements in Theterres trial environment. Springer ,Verlag , New York. Barzegar A, Kochazade A. 2002. 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