Research Journal of Chemical Sciences ______________________________________________ ISSN 2231-606X Vol. 4(1), 9-16, January (2014) Res. J. Chem. Sci. International Science Congress Association 9 Assessment of Heavy Metal Distribution in Groundwater in and around Gulf of Mannar Seashore Area Using GIS TechniqueBalakrishnan A., Ramu A. and Murugesan A.Dept of Chemistry, Mohamed Sathak AJ College of Engineering, Siruseri, Chennai-603103, INDIA School of Chemistry, Madurai Kamaraj University, Madurai – 625 021, INDIA Dept of Chemistry, Sriram Engineering College, Veppampattu RS, Chennai-602024, INDIAAvailable online at: www.isca.in, www.isca.me Received 4th December 2013, revised 23rd December 2013, accepted 3rd January 2014Abstract The present study was carried out to analyze the heavy metal level of 25 bore and duck wells located at the different localities in and around Gulf of Manner seashore area during the period of pre monsoon, monsoon and post monsoon seasons. Arsenic (As), Manganese (Mn), Zinc (Zn), Cadmium (Cd), Chromium (Cr), Copper (Cu), Mercury (Hg) and Lead (Pb) concentrations in groundwater were analyzed by Atomic absorption spectrometer. The results were compared with drinking water standard prescribed by WHO, BIS, ICMR and FAO. This study shows that most of samples has high concentration of heavy metals (exceeds maximum permissible limit). A slight increment in concentration of individual metals is produced in summer season than in winter season. This study shows that all samples contains high concentrations of Hg, Pb and Mn above the maximum permissible limits as prescribed by WHO, BIS, ICMR and FAO. The spatial distributions of heavy metal in ground water were taken to Geological Information System (GIS). In Arc GIS, spatial distribution maps were prepared for the above analyzed heavy metals. Keywords: Groundwater, Gulf of Mannar, Heavy Metal, Arc GIS.Introduction Water is a vital source of life which is essential for survival of all living organisms. Water is not only the most important essential constituent of all animals, plants and other organisms but also the pivotal for the survivability of mankind in the biosphere. Ground water occurs almost everywhere beneath the earth surface not only in a single widespread aquifer, but also in thousands of local aquifer systems. Several factors such as climate, characteristics of soil, circulation of ground water through rock types, topography of the area, intrusion of saline water in coastal areas, human activities on the ground etc. posses several effects on the quality of water. Safe and good quality drinking water is the basis for good human health. Water provides some elements, but when polluted it may dangerous to human health and cause disease such as various cancers, adverse reproductive outcomes, cardiovascular disease and neurological disease4. Some heavy metals such as Cu, Fe, Mn, Ni and Zn are compulsory micronutrients for flora –fauna and microbes. Besides metal like Cd, Cr and Pb are harmful beyond a certain limit. Therefore the heavy metal concentration in drinking water should be kept in low ppb range. One of the most hazardous trace metal found in drinking water is arsenic (As) being both toxic and carcinogenic. GIS has emerged as a powerful technology for instruction, for research and for building the structure of programs. In the present study, 25 bore and duck well ground water samples have been collected from Gulf of mannar sea shore area in pre monsoon, monsoon, and post monsoon and analyzed various heavy metals like Mn, Cd, As, Hg, Cu, Cr, Pb and Zn by atomic absorption spectrometer ( Model VAIRAN AA240). The analyzed results were taken into Arc GIS environment. In GIS spatial distribution maps were prepared for the analyzed metal in three seasons like pre monsoon, monsoon, and post monsoon (figure 2, 3 and 4). Study Area: The Gulf of mannar (figure 1) which is the first marine Biosphere Reserves established in India, lies between India and Srilanka and covers an area of about 10,500sq.Km. It includes 21 coral islands located between 8 46’ and 9 14’N latitude and 78 9’ and 79 14’ longitude. The Gulf Manner (GoM) located in southeast coast of India surrounded by a chain of 21 islands starting from holy town of Rameswaram and ending at the industrial town of Tuticorin. The GoM has been declared as the “marine biosphere reserve in 1989 and consists of 3269 species of flora and fauna, including 377 species that are endemic to the region”. The Gulf of Mannar (GoM) is one of the coral reefs rich regions in India. The Gulf of Mannar is considered as “Biologists Paradise” for; it has 3600 species of flora and fauna. The mangrove habitats in the Gulf of Mannar have 9 different species of vegetation supporting a variety of marine fauna including sea birds and sea snakes. The GoM is heavily threatened by the discharge of sewage from human settlements and effluents from industries. In addition, extensive land use and urban sprawl are major environmental concerns affecting the health status of GoM. Due to suitability of these coasts for major developmental activities and the establishment of industries, ports, harbors and tourism facilities in and around, the GoM has attracted an increased human settlement along the Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 4(1), 9-16, January (2014) Res. J. Chem. Sci. International Science Congress Association 10 coast and resulted in stress on the fitness of GoM. Thus this study was aimed to assess metal distribution pattern among the 25 bore and duck well samples of GoM. Material and Methods Water samples were collected in 5L polythene container from 25 different localities (table 1) in Gulf of mannar sea shore (from Ramanathapuram to Tuticorin) area. Before collecting the sample, polythene containers cleaned by soaking it in 10% nitric acid over night washed and rinsed with distilled water on the day of sampling. At the sampling site, the bottles were rinsed twice with the water being sampled, prior to the filling. One ml of con.HNO is added to each sample. The samples are filtered immediately upon arrival at the laboratory, using a 0.45µm Millipore membrane filter10 and the water samples are stored in the laboratory at 4şC. An aliquot sample is taken into beaker, further it is digested on a hot plate and reduced to a volume less than 50ml. The digested sample is poured into a 50ml volumetric flask and made up by distilled water, which is used before to rinse the digested sample beaker11. The prepared sample is kept in the dark place and the trace elements were analyzed by using Atomic Absorption Spectrometer12,13 using air –acetylene flame. Operational conditions were adjusted in accordance with the manufacturer’s guidelines to yield optimal determination. Quantification of metals was based upon calibration curves were determined several times during the period of analysis. The detection limits for manganese, copper, chromium, lead, cadmium, zinc are 0.001, 0.001, 0.004, 0.002, 0.01, 0.005, 0.008mg/litr respectively. Results and Discussion The variation in the concentration of trace metal (Mn, Cd, As, Hg, Cu, Cr, Pb and Zn) in the groundwater during pre monsoon, monsoon and post monsoon of study area was evaluated. The obtained results of heavy metal analysis are reported in table 3, 4 and 5 respectively. A measurements and analysis shows that rocks weathering and anthropogenic inputs are found to be the main sources for heavy metals in ground water14. The concentrations of heavy metals were compared with drinking water standard prescribed by WHO, BIS, ICMR and FAO (table 2). Table-1 Sampling Area in Gulf of Mannar Seashore Area Sample No Sampling LocationsType of well GoM1 Rameshwaram Koil ( Nalatheertham) Open well GoM2 Sathya Nagar (Rameshwaram) Open well GoM3 Pamban Open well GoM4 Mandapam Open well GoM5 Seeniyappa Tharga Open well GoM6 Pirappan Valasai Open well GoM7 Uchipuli Open well GoM8 Ramanathapuram (Bharathinagar) Open well GoM9 Kilakarai Open well GoM10 Ervadi Open well GoM11 Idhambadal Pond GoM12 Sikkal Open well GoM13 Sayalkudi Tube well GoM14 Narippayur Open well GoM15 Vembar Open well GoM16 Melmanthai Tube well GoM17 Srivaigunda perumalpuram Open well GoM18 Veppalodai Tube well GoM19 Pattinamaruthur Open well GoM20 Tharuvaikulam Open well GoM21 Devispuram Open well GoM22 Therkusottan thoppu Open well GoM23 Saramani Street (Tuticorin) Tube well GoM24 Natarajapuram (Tuticorin) Tube well GoM25 Keelarathaveethi (Tuticorin) Open well Table-2 Drinking Water Standards Metals BIS(IS1050 – 91) (mg/l) BIS (IS10500 – 91) Revised 2003 (mg/l) ICMR (mg/l) WHO (mg/l) FAO (For irrigation) (mg/l) Desirable Limit Maximum Permissible limit Desirable Limit Desirable Limit Desirable Limit Desirable Limit Mn 0.1 0.3 0.1 50 0.1 0.2 Cd 0.01 0.01 0.01 - 0.005 0.1 As 0.05 0.05 0.01 - 0.05 5 Hg 0.001 0.001 0.001 - 0.001 - Cu 0.05 1.5 0.05 0.05 1 0.2 Cr 0.05 0.05 0.05 - 0.05 0.1 Pb 0.05 0.05 0.05 - 0.05 - Zn 5 15 5 0.1 5 2 Ni - - - - - 0.2 Mo - - - - - 0.01 Co - - - - - 0.05 Fe 0.3 1 0.3 0.1 0.3 5 Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 4(1), 9-16, January (2014) Res. J. Chem. Sci. International Science Congress Association 11 Figure-1 Location of Study area Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 4(1), 9-16, January (2014) Res. J. Chem. Sci. International Science Congress Association 12 Table-3 Heavy Metal contents (ppm) in groundwater during pre monsoon Sample Number Mn Cd As Hg Cu Cr Pb Zn GoM1 0.065 0.005 0.003 0.4 0.026 0.007 0.063 0.342 GoM2 0.068 0.006 0.006 0.8 0.019 0.005 0.057 0.301 GoM3 0.073 0.005 0.003 0.3 0.019 0.007 0.046 0.297 GoM4 0.061 0.004 0.003 0.041 0.018 0.007 0.312 0.287 GoM5 0.058 0.006 0.003 0.021 0.018 0.005 0.049 0.296 GoM6 0.061 0.007 0.004 0.011 0.019 0.007 0.051 0.289 GoM7 0.081 0.003 0.005 0.012 0.026 0.004 0.15 0.283 GoM8 0.15 0.003 0.006 0.015 0.026 0.006 0.234 0.487 GoM9 0.15 0.002 0.008 0.016 0.037 0.005 0.367 0.286 GoM10 1.27 0.02 0.006 0.013 0.062 0.009 0.287 0.71 GoM11 0.07 0.004 0.004 0.011 0.047 0.008 0.298 0.49 GoM12 1.34 0.006 0.004 0.014 0.038 0.007 0.274 0.59 GoM13 1.57 0.012 0.003 0.016 0.048 0.005 0.175 0.47 GoM14 1.89 0.003 0.004 BDL 0.039 0.005 0.254 0.38 GoM15 0.11 0.005 0.003 BDL 0.051 0.006 0.386 0.242 GoM16 0.097 0.05 0.004 BDL 0.062 0.006 0.345 0.332 GoM17 1.37 0.03 0.003 BDL 0.063 0.007 0.321 0.253 GoM18 2.23 0.04 0.006 BDL 0.036 0.008 0.572 0.562 GoM19 1.43 0.06 0.007 BDL 0.047 0.009 0.473 0.791 GoM20 1.49 0.07 0.007 BDL 0.031 0.004 0.431 0.782 GoM21 1.88 0.04 0.009 BDL 0.079 0.004 0.783 0.772 GoM22 0.08 0.03 0.02 0.23 0.093 0.002 0.856 1.452 GoM23 0.09 0.08 0.05 0.45 0.092 0.006 0.875 1.571 GoM24 0.06 0.12 0.007 BDL 0.091 0.005 0.853 1.281 GoM25 1.95 0.01 0.009 BDL 0.091 0.005 0.771 1.356 Table-4 Heavy Metal contents (ppm) in groundwater during monsoon Sample Number Mn Cd As Hg Cu Cr Pb Zn GoM1 0.059 0.003 0.002 0.12 0.018 0.006 0.049 0.288 GoM2 0.077 0.009 0.006 0.93 0.035 0.008 0.058 0.298 GoM3 0.069 0.004 0.003 0.21 0.019 0.007 0.047 0.292 GoM4 0.059 0.004 0.002 0.041 0.01 0.005 0.248 0.269 GoM5 0.055 0.006 0.003 0.017 0.017 0.004 0.475 0.279 GoM6 0.061 0.007 0.004 0.011 0.019 0.003 0.05 0.281 GoM7 0.073 0.003 0.005 0.012 0.03 0.005 0.14 0.269 GoM8 0.12 0.003 0.006 0.011 0.025 0.006 0.219 0.469 GoM9 0.123 0.002 0.008 0..013 0.032 0.005 0.358 0.279 GoM10 1.23 0.02 0.005 0.011 0.058 0.009 0.237 0.652 GoM11 0.08 0.004 0.003 0.011 0.045 0.006 0.246 0.456 GoM12 1.34 0.005 0.003 0.012 0.037 0.005 0.258 0.57 GoM13 1.56 0.009 0.002 0.013 0.047 0.005 0.157 0.456 GoM14 1.88 0.002 0.002 0.009 0.037 0.003 0.228 0.36 GoM15 0.1 0.005 0.002 BDL 0.051 0.005 0.269 0.237 GoM16 0.088 0.05 0.004 BDL 0.059 0.006 0.328 0.0326 GoM17 1.38 0.03 0.003 BDL 0.065 0.007 0.32 0.249 GoM18 2.28 0.04 0.005 BDL 0.039 0.007 0.569 0.555 GoM19 1.48 0.06 0.006 BDL 0.047 0.007 0.439 0.789 GoM20 1.48 0.06 0.007 BDL 0.029 0.004 0.429 0.701 GoM21 1.84 0.04 0.009 BDL 0.073 0.003 0.769 0.769 GoM22 0.08 0.03 0.02 0.23 0.083 0.002 0.828 1.349 GoM23 0.09 0.07 0.03 0.43 0.087 0.004 0.858 1.547 GoM24 0.06 0.09 0.006 BDL 0.089 0.004 0.839 1.271 GoM25 1.91 0.02 0.008 BDL 0.087 0.005 0.758 1.329 Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 4(1), 9-16, January (2014) Res. J. Chem. Sci. International Science Congress Association 13 Table-5 Heavy metal contents (ppm) in groundwater during post monsoon Sample Number Mn Cd As Hg Cu Cr Pb Zn GoM1 0.058 0.002 0.001 0.1 0.015 0.005 0.046 0.281 GoM2 0.061 0.004 0.003 0.7 0.014 0.003 0.048 0.289 GoM3 0.067 0.003 0.002 0.2 0.017 0.006 0.041 0.286 GoM4 0.056 0.003 0.001 BDL 0.013 0.005 0.245 0.265 GoM5 0.054 0.005 0.002 BDL 0.016 0.004 0.047 0.276 GoM6 0.059 0.006 0.003 BDL 0.017 0.005 0.048 0.279 GoM7 0.071 0.002 0.004 BDL 0.02 0.003 0.12 0.267 GoM8 0.1 0.002 0.005 BDL 0.022 0.005 0.216 0.465 GoM9 0.12 0.001 0.007 BDL 0.032 0.004 0.354 0.276 GoM10 1.2 0.01 0.004 BDL 0.056 0.008 0.234 0.65 GoM11 0.06 0.003 0.003 BDL 0.043 0.006 0.243 0.45 GoM12 1.3 0.005 0.003 BDL 0.036 0.005 0.253 0.56 GoM13 1.51 0.009 0.002 BDL 0.045 0.004 0.153 0.45 GoM14 1.87 0.002 0.002 BDL 0.036 0.003 0.221 0.31 GoM15 0.09 0.004 0.001 BDL 0.048 0.005 0.267 0.231 GoM16 0.087 0.04 0.003 BDL 0.058 0.005 0.321 0.321 GoM17 1.34 0.02 0.002 BDL 0.061 0.006 0.301 0.243 GoM18 2.2 0.03 0.005 BDL 0.032 0.006 0.561 0.543 GoM19 1.43 0.05 0.006 BDL 0.043 0.007 0.431 0.786 GoM20 1.45 0.06 0.006 BDL 0.025 0.003 0.421 0.768 GoM21 1.8 0.03 0.009 BDL 0.071 0.003 0.765 0.765 GoM22 0.07 0.02 0.01 0.2 0.081 0.001 0.823 1.342 GoM23 0.08 0.07 0.03 0.4 0.085 0.004 0.854 1.541 GoM24 0.05 0.09 0.005 BDL 0.087 0.003 0.834 1.265 GoM25 1.9 0.01 0.008 BDL 0.086 0.004 0.756 1.324 *BDL – Bellow the Deductable Limit Arsenic in Pre-monsoon season Cadmium in Pre-monsoon season Chromium in Pre-monsoon season Copper in Pre-monsoon season Figure-2 Spatial distribution of heavy metals during pre monsoon Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 4(1), 9-16, January (2014) Res. J. Chem. Sci. International Science Congress Association 14 Arsenic in Monsoon season Cadmium in Monsoon season Chromium in Monsoon season Copper in Monsoon season Figure-3 Spatial distribution of heavy metals during monsoon Arsenic in Post Monsoon season Cadmium in Post Monsoon season Chromium in Post Monsoon season Copper in Post Monsoon season Figure–4 Spatial distribution of heavy metals during post monsoon Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 4(1), 9-16, January (2014) Res. J. Chem. Sci. International Science Congress Association 15 Manganese: Manganese is an essential trace nutrient in all form of life. It is less toxic than those of other widespread metals such as nickel and copper15. However, exposure to manganese dusts and fumes should not exceed the ceiling value of 5mg/meven for short periods because of its toxicity level. The variation of manganese at different sites during pre monsoon, monsoon and post monsoon are shown in Table 3, 4 & 5 respectively. Cadmium: Cadmium is considered to be one among the environmentally hazardous metals, because of its high toxicity and greater capability of accumulation and retention in the body of organisms including human. In the present study, the cadmium concentration is in the range from 0.002 to 0.09ppm. The maximum acceptable limit for cadmium in drinking water is 0.005ppm16. Cd may be cause the diseases; hypertension, arteriosclerosis, cancer etc. Cd irreversibly accumulates in the human body, in particularly in kidneys and other vital organs such the lungs or the liver. In addition to its extraordinary cumulative properties,Cd is also a highly toxic metal that can disrupt a number of biological systems, usually at doses that are much lower than most toxic metal17. Arsenic: One of the most hazardous trace metal found in drinking water is arsenic (As) being both toxic and carcinogenic18. Long term intake of arsenic may give rise to skin lesionsat concentration 50mg/litr. In the present study the arsenic concentration range from 0.001 to 0.05ppm. All sample from the study area has bellow the permissible limit prescribed by WHO, BIS, ICMR and FAO. Mercury: Mercury is a toxic element and serves no physiological function in man ie., non essential element. In the present investigation, high mercury content observed in ground water is in the range from 0.011 to 0.8ppm. All samples in our study area has high content of mercury (above the maximum permissible limit prescribed by WHO,BIS, ICMR and FAO). Copper: Copper is an essential substance to human life, but chronic exposure to contaminant drinking water with copper can result in the development of anemia, liver and kidney dmage19. Copper in large doses is dangerous to infants and people with certain metabolic disorders. On the other hand, lack of copper intake causes anemia, growth inhibition and blood circulation problems20. In this present study area, the concentration of copper content range in ground water from 0.014 to 0.091ppm. This study shows all samples has bellow level of copper than permissible limit prescribed by WHO, BIS, ICMR and FAO). Chromium: Chromium is naturally occurring element which is essential to animal and human. i.e synthesis of fat from glucose and also for oxidation of fat to carbon dioxide. Chromium in excess amounts can be toxic especially the hexavalent form. In this present study area, the concentration of chromium content range in ground water from 0.001 to 0.009 ppm. This study shows all samples has bellow level of chromium than permissible limit prescribed by WHO, BIS, ICMR and FAO). Lead: Lead is a dangerous element; it is harmful even in small amount. Distribution of lead at different sites during pre monsoon and post monsoon are shown in table 2 and 3. The maximum lead content 0.875 ppm and minimum 0.041ppm have been recorded at different sites Gulf of Mannar sea shore area. This study shows most of the ground water sample has high lead content. i.e above the maximum permissible limit prescribed by WHO,BIS, ICMR and FAO). Zinc: Zinc is an essential trace element found in virtually all food and potable water in the form of salts or organic complexes. Zinc deficiency in human body may results in infantilism, impaired wound healing and several other diseases21. The values of zinc concentration obtained in this study, range from 0.231 to 1.571ppm. Zinc content in all sampling sites, are within the permissible limit. ConclusionThe concentrations of heavy metals like Mn, Cd, As, Hg, Cu, Cr, Pb and Zn have been determined by using Atomic Absorption Spectroscopy during pre monsoon, monsoon and post monsoon. Based on the experimental data, the concentration of heavy metals during pre monsoon is high compared to post monsoon. This is due to evaporation during pre monsoon. This study shows that, most of the groundwater samples have high content of Hg, Mn, Pb, Cd and Cu. The heavy metal concentration has been displayed by mapping during post monsoon, monsoon and pre monsoon. On the basis of above discussion it may conclude that the underground drinking water at almost all sites in Gulf of Mannar is highly contaminated. Therfore the use of ordinary hand pump and borewell should be discouraged. People dependants on this water are often prone to health hazards due to contaminated potable water. Therefore indigenous technologies should be adopted to make water fit for purpose. 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