DIRECT DETERMINATION OF PERCHLORATE IN DRINKING WATER BY ION CHROMATOGRAPHY Mehmet Fatih CENGIZ, Ayşe Kevser BİLGİN Akdeniz University, Faculty of Engineering, Food Engineering Department, Antalya/TURKEY ABSTRACT : Perchlorates, which are commonly used in fertilizers and fireworks, rockets and other explosives as solid oxidizer; reduce the synthesis of thyroid hormones by preventing the transportation of iodine through the thyroid gland and thus cause to permanent health problems especially in woman and infants. The main exposure to the perchlorates takes place due to pollution of ground and surface water via to contamination from the agricultural areas and industrial wastes.In this work, a sensitive Ion Chromatography(IC) method was proposed for the determination of perchlorate in drinking water samples. The method entails measurement of conductivity, filtration through 0,45 ìm syringe filter and injection. No sample pretreatment and concentration steps were required prior to the injection. Perchloratewas separated by anion-exchange chromatography and detected by conductivity detector. The calibration curve was linear in the concentration range comprised between in the range of 10 ìg/Land 200 ìg/Lperchlorate(R2 = 0,998). The limit of detection (LOD) and limit of quantification (LOQ) were estimated to be 2,41 µg/L and 8,04 µg/L , respectively. The recovery values of drinking water was 97,74 % ± 0,72. Six different tap water samples were analyzed with the improved technique. No perchlorateresidues (>LOD) were found to be in the analyzed water samples. Compared to other reported methods for perchlorate, the developed IC method is sensitive and simple as well as does not require any chemical derivatization and sample pre-concentration. Therefore this method could be suggested as an alternative analytical metod for routine laboratory testing. Analytical conditions System Dionex ICS-5000 Ion chromatography system Column IonPac™ AS19 (250 mm × 2 mm i.d.) Guard column IonPac™ AG19 (50 mm × 2 mm i.d.) Flow rate 1 mL/min Mobil Phase 10 mM NaOH Detection Conductivity detector Column Temperature 30 ºC Detector Temperature Injection Volume 125 μL, full loop injection System back pressure ~1800 psi Total run time 30 min INTRODUCTION: Perchlorate is a well-known environmental contaminant. Pregnant and nursing women, fetus, infant and young children, individuals with hypothyroidism are sensitive groups for the exposure of trace level of perchlorate. Perchlorate is a compound containing one chlorine atom and four oxygen atoms (Kirk vd.,2003) . Although there has been various technique such as spectrophotometric, chromatographic and colorimetric for the determination of perchlorate, it has commonly been determined using ion chromatography (IC) with suppressed conductivity detection Anthropogenic Sources of Perchlorate Rocket Fuel Fireworks High explosives Flares Herbicides Automobile airbags Tracer munitions Detergents (Soldin vd.,2001). Method performance Linearite 10 µg/L - 200 µg/L (R2 = 0,998). Calibration equation y = 1174 x – 0.647 Limit of detection (LOD) 2,41 µg/L Limit of quantification (LOQ) 8,04 µg/L, Recovery 97,74 % ± 0,72. Repeatability (RSD) 4,24 Table 1. Perchlorate Concentration Of Water in Different Regions Area Sample Perchlorate level References California tap water <4-29 μg/l Anonymous,2011 India ground-water 0,02-0,74 µg/l Anonymous,2012 China drinking water ˂ 0.02-54,4 µg/l Wu vd.,2010 Califonia well water 18-280 µg/l Motzer vd. , 2001 Middle Rio Grande Basin 0,12-1,8 µg/l Plummer vd.,2006 California ve ABD (Southwest) > 0,1 µg/l Fram vd.,2011 California(Northeast coast) ˂1 µg/l Fram vd. ,2011 Turkey (Hatay region) irrigation water 0,59 µg/l Sungur vd.,2010 0,44 µg/l REFERENCES : ANONYMOUS 2013A, www.bilgiustam.com,(2013) ANONYMOUS, 2013B, http://Mass.Gov/dep Anonymous, 2011, U.S. Department Of Health And Human Services Public Health Service., Toxicological profile for perchlorates. Agency For Toxic Substances and Disease Registry, Atlanta, Goergia,(2011). Anonymous, 2012, California Department Of Public Health, Perchlorate in California drinking water: monitoring update for active and standby sources. http://www.dhs.ca.gov/ps/ddwem/chemicals/ perchl/monitoringupdate.htm,(2012). BOLDYREV, V.V., Thermal decomposition of ammonium perchlorate. Thermochimica Acta 443(1), 1-36 ,(2006). EPA 2009. Basic Information about P in Drinking Water, http://water.epa.gov/drink/contaminant,(2009). FRAM, M. S., Belitz, K., Probability of detecting perchlorate under natural conditions in deep groundwater in California and the Southwestern United States. Environmental Science Technology 45 , Pp:1271–1277,(2011). GREER, M. A., Goodman, G., Pleus, R. C., and Greer, S. E., Health effects assessment for environmental perchlorate contamination: the dose response for inhibition of thyroidal radioiodine uptake in humans. Environ Health Perspect 110. Pp:927-37,(2002). KIRK, A.B., Smith, E.E., Tian, K., Anderson, T., Dasgupta, P.K., Perchlorate in milk. Enviromental Science Technology 37, Pp: 4979–4981,(2003). MOTZER, W. E., Perchlorate: problems, detection, and solutions. Environmental Forensics 2, Pp: 301–311,(2001). PARKER, D.R., Seyfferth, A. L., Reese, B. K., Perchlorate in groundwater: a synoptic survey of “Pristine” sites in the coterminous United States. Environmental Science Technology 42, Pp: 1465–1471,(2008) . PLUMMER, L.N., Bohlke, J.K, Doughten, M.W., Perchlorate in pleistocene and holocene groundwater in North-Central New Mexico. Environmental Science and Technology 40, Pp: 1757–1763,(2006) . SOLDIN, O.P., Braverman, L.E., Lamm, S.H., Perchlorate clinical pharmacology and human health: a review. Therapeutic Drug Monitoring 23(4), Pp:316-331,(2001) . SUNGUR, Ş., Sangün, M.K., Ion chromatographic determination of perchlorate in foods consumed in Hatay region. Food Chemistry 126(1), Pp:326-331, (2010) . UNITED STATES GOVERNMENT ACCOUNTABILITY Office (GAO), Perchlorate: a system to track sampling and cleanup results is needed. Report to the chairman, subcommittee, on environment and hazardous materials. Committee on Energy and Commerce, House of Representatives, Washington, DC,(2005). WU, Q., Zhang, T., Sun, H.W., Kannan, K., Perchlorate in tap water, groundwater, surface waters, and bottled water from China and its association with other inorganic anions and with disinfection byproducts. Archives of Environmental Contamination and Toxicologyl 58, Pp: 543–550,(2010) . Real samples: In order to evaluate the effectiveness of this method for the determination of glyphosate, the collected tap water (n=6) samples were analysed. There were no glyphosate residues in the tested water samples.