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Endosulfan Contamination in Water : a Review on to an Efficient Method for Its Removal

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Endosulfan Contamination in Water : a Review on to an Efficient Method for Its Removal Journal of Chemistry and Chemical Sciences, Vol.6(2), 182-191, February 2016 ISSN 2229-760X (Print) (An International Research Journal), www.chemistry-journal.org ISSN 2319-7625 (Online) Endosulfan Contamination in Water : A Review on to an Efficient Method for its Removal Jayaprabha K.N.1 and Suresh K.K.2* 1Kizhakkeveettil (H), Thrikkalathoor P.O., Muvattupuzha, Kerala – 683541 2Assistant Professor, Department of Zoology, NSS College, Pandalam, Kerala - 689501 [email protected] (Received on: February 25, 2016) ABSTRACT Endosulfan is one of the known highly toxic organochlorine pesticides. The global ban on the manufacture and use of endosulfan was recommended by The Stockholm Convention held in April 2011 because of its adverse effects on human health and the environment. This report discusses about the pollution caused by endosulfan in rural areas of Kasargod district in Kerala where Plantation Corporation of Kerala started aerial spraying of the pesticide in the 1970s. Until the year 2000, more than 50,000 villagers of this district have been exposed to endosulfan, and over 3000 were affected by rare diseases like mental retardation, cerebral palsy, cancer etc. The reports from various government authorities and non-government organizations confirm the presence of endosulfan in water and soil in the exposed areas. The exposure and use of endosulfan contaminated food and water is said to cause endocrine disruptions, reproductive system disorders, central nervous system disorders, liver and kidney dysfunctions in animals and human beings. There are literature reports on the removal of endosulfan from water and soil using suitable adsorbents which mainly uses carbon derived from various sources. Here we discuss about the use of different nanocomposite for endosulfan adsorption and removal. Keywords: Endosulfan, Method for its Removal. 1. Introduction Persistent organic pollutants (POPs) are a class of chemicals that are toxic, stay in the environment for long time period and biomagnify as they move up in the food chain. Organochlorines represent one of the important classes of POPs which is hazardous to both environment as well as human beings. Endosulfan (6, 7, 8, 9, 10-hexachlor-1, 5, 5a, 6, 9, 9a hexahydro- 6, 9-methano-2, 3, 4-benzo dioxathiepin-3- oxide) (Fig.1) is an organochlorine insecticide currently used throughout the world on a variety of vegetables, fruits, cereals and cotton.1 February, 2016 |Journal of Chemistry and Chemical Sciences|www.chemistry-journal.org Jayaprabha K.N, et al., J. Chem. & Cheml. Sci. Vol.6(2), 182-191 (2016) 183 Fig.1 Endosulfan: Chemical structure Endosulfan has two stereoisomers, α and β, form in the ratio 7:3, being highly toxic to fish and aquatic systems due to its low water solubility.2 Endosulfan enters the air, water and soil during its manufacture and use. It has different environmental fate depending on the medium it gets exposed to. Both the isomers of endosulfan undergo photolysis upon exposure to light to give endosulfan diol with a half life of about 7 years. In water, the hydrolysis product is the same but the rate depends on pH. In soil, it undergoes biodegradation forming endosulfan sulfate which is equally toxic and more persistent in the environment than the parent compound. The half life varies from 60 days for alpha form to 800 days for beta form. In water, endosulfan has a half life of about 35 to 150 days. It does not easily dissolve in water and may accumulate in bodies of fish and other aquatic organisms.3 It is readily absorbed by stomach, by lungs and through skin. Endosulfan is widely found in both surface water and groundwater throughout the world, including in India.4 World Health Organization drinking water quality standards permits a maximum 20 μg/L for endosulfan. According to the Bureau of Indian Standards, 2012, the permissible limit of endosulfan in drinking water is 0.4μg/l. According to the United States Environmental Protection Agency (EPA), the maximum permissible limit for endosulfan in lakes, rivers and streams is 74μg/L.5 EPA classifies endosulfan as Category Ib – Highly Hazardous. The European Union also rates it as Highly Hazardous. World Health Organisation (WHO) classifies endosulfan in Category II – Moderately Hazardous. The Industrial Toxicological Research Centre (ITRC) in India, the nodal centre for the Regional Based Assessment of Persistent Toxic Substances (PTS) for the Indian Ocean region by the United Nations Environment Programme-Global Environment Facility (UNEP-GEF), classifies endosulfan as Extremely Hazardous.6 India is the fourth largest producer of pesticides in the world and the world’s largest producer and user of endosulfan, the major companies being Excel industries, Hindustan Insecticides Limited (HIL) and EID Parry.7 II. A few examples of Endosulfan poisoning around the world A report by Environmental Justice Foundation describes different incidents of endosulfan poisoning around the world.8 Approximately 3,38,000 tonnes of endosulfan has February, 2016 |Journal of Chemistry and Chemical Sciences|www.chemistry-journal.org 184 Jayaprabha K.N, et al., J. Chem. & Cheml. Sci. Vol.6(2), 182-191 (2016) been used globally in 2005. In Sudan in1988, endosulfan barrels washed in irrigation canals caused fish kills and three people died after drinking water from the canal. In the Philippines, endosulfan accounted for the largest number of deaths due to pesticide poisoning reported in 1991. In Sulawesi, Indonesia, 32 cases of poisoning due to endosulfan have been reported from 1990 to 1993. In Columbia, around 200 cases of poisoning due to endosulfan were reported. In 2004, 36 persons of all age groups in a rural area of Jabalpur, India were poisoned after consuming wheat-grains or flour contaminated with endosulfan.8 III. Endosulfan poisoning in Kasargod, Kerala (India) Kasaragod, the northern most district in Kerala (India) has about 5600 acres of cashew plantations, owned by the Plantation Corporation of Kerala (PCK), spreading through about 11 village panchayats. These villages are Enmakaje, Belur, Kumbadaje, Badiadka, Muliyar, Karadukka, Periya, Pullur, Ajanur, Kallar, Panathady, Kayyur, Cheemeni. The plantations were aerially sprayed with the chemical pesticide endosulfan since 1976, till 2001, regularly three times a year. As a result of public outcry, intervention from some courts and the government, spraying was stopped from 2003.9 Figure 2 is a map showing the cashew plantation area under PCK. Fig.2: Map showing the PCK plantation area (Kasargod district, Kerala) and the surrounding affected areas.10 In the 1970s, stunted growth and deformed limbs were observed among new born calves in the Kasargod area. By 1990s, serious disorders started appearing among the human population. Dr. Mohankumar, a doctor practising in the Enmakaje panchayath has found from his observations that there were 51 cancer deaths in just 126 houses near the Kodenkeri stream at Enmakaje Panchayath.11 The confirmed cases of various diseases till January 5, 2001, as reported by Dr. Y S Mohankumar, are shown in the table below. February, 2016 |Journal of Chemistry and Chemical Sciences|www.chemistry-journal.org Jayaprabha K.N, et al., J. Chem. & Cheml. Sci. Vol.6(2), 182-191 (2016) 185 Table 1: Confirmed cases of various diseases in Kasargod district due to endosulfan spraying. Diseases Number of cases Cancer 49 Mental retardation 23 Congenital anomalies 9 Psychiatric cases 43 Epilepsy 23 Suicide 9 Total 156 After the Bhopal gas tragedy, Endosulfan spraying in Kasargod was the biggest chemical tragedy. Government of Kerala appointed 11 commissions to study the issue. Apart from this, various Non-government Organizations (NGOs) have put their efforts in analyzing the role of endosulfan in causing the abnormalities.12 The results obtained by various committees are discussed below. The concentration of endosulfan residues in water in the affected villages of Kasargod were analysed by Centre for Science and Environment (CSE), New Delhi, on 17th February 2001, one and half month after the last aerial spray carried out on 26th December 2000. The amount of endosulfan was found to be about 7 to 51 times higher than the Maximum Residual Limit (MRL). The amount in one of the soil sample studied was 391 times larger than the MRL.11 The CSE study also revealed that about 189 parts per million (ppm) of endosulfan is present in blood samples. National institute of occupational health (NIOH) submitted a report on “The Investigation of Unusual Illnesses Allegedly Produced by Endosulfan Exposure in Padre Village of Kasargod District (N. Kerala)” to the National Human Rights Commission, in July 2002, wherein they have analysed endosulfan levels in water, soil and blood samples.13 The NIOH report suggested that the main cause for a number of diseases in children is endosulfan spraying. The Frederick Institute of Plant Protection and Toxicology, Chennai (FIPPAT), commissioned by PCK did not find even traces of endosulfan in any of the samples two months after spraying, whereas NIOH found endosulfan in the samples after nine months.14 Tables 2 and 3 show the level of endosulfan in water samples and blood samples, respectively, collected by NIOH from different affected villages of Kasargod after nine months of aerial spraying of endosulfan. The amount of endosulfan in water (Table 2) was much less compared to that in blood (Table 3). February, 2016 |Journal of Chemistry and Chemical Sciences|www.chemistry-journal.org 186 Jayaprabha K.N, et al., J. Chem. & Cheml. Sci. Vol.6(2), 182-191 (2016) Table 2: The level of endosulfan in water samples collected in the month of September/October 2001. (NIOH report)14 Sample α-endosulfan β-endosulfan Endosulfan sulfate Total endosulfan source (ppb) (ppb) (ppb) (ppb) Well 0.0086 0.0088 0.0035 0.0209 Suranga 0.0065 0.0022 Not detected 0.0087 Stream 0.0081 0.0123 Not detected 0.0204 Pond 0.0138 0.0416 0.0113 0.0667 Table 3: Endosulfan residue found in blood samples of school children.
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