ATRAZINE: CONTAMINATION IN WATER AND ASSESSMENT OF REGULATIONS Epalle Nseke, Jacob A. LeMay, and Antonio F. Machado Environmental and Occupational Health Sciences, California State University Northridge ABSTRACT LEVELS IN ENVIRONMENTAL MATRICES Atrazine is a chloro-S-triazine herbicide that is used extensively in agriculture worldwide. It is speculated to be an endocrine disruptor and has been seen to cause various birth defects in humans. Atrazine is banned in the European Union but persists as a groundwater contaminant. Water remediation for atrazine is simple carbon filtration, although many treatment plants do not use this method. The fate and transport of atrazine does not stop at application, as trace amounts makes its way to our drinking water from nearby farmland. Maximum level observed[12] Matrix Air (rainwater) 1.99 ppb Soil 5.5 to 1 ppm over 110 days Surface runoff 700 ppb Surface water (river and stream) 33 ppb Ground water INTRODUCTION Atrazine is a chloro-S-triazine herbicide that is used extensively in agriculture worldwide. Although, the European Union has placed a ban on atrazine, the U.S. still continues its use as a restricted use pesticide (RUP). Atrazine is a known endocrine disruptor and studies have been done on rats, fishes, and frogs to determine its health effects. These include: oxidative stress leading to DNA damage, alteration of the reproductive system in fishes and frogs, preterm birth, gastroschisis by maternal age, and disruption of the hypothalamic control of the pituitary ovarian function. Atrazine is degraded to other metabolites of Deisopropylatrazine (DIA), diaminochlorotriazine (DACT), deethylatrazine (DEA). These metabolites in some cases are more toxic than atrazine. Exposure to atrazine can occur in different ways. People living around active farm areas can be exposed through contaminated air or water. People living in urban areas far from the agriculture areas are exposed through drinking water. Trade Names/Synonyms: Aatrex; Actinite PK; Akticon; Argezin; Atazinax; Atranex; Atrataf; Atred; Candex; Cekuzina-T; Chromozin; Crisatrina; Cyazin; Fenamin; Fenatrol; Gesaprim; Griffex; Hungazin; Inakor; Pitezin; Primatol; Radazin; Strazine; Vectal; Weedex A; Wonuk; Zeapos; Zeazine 100 ppt Tap water 60 ppb Drinking water wells 40 ppb Atrazine possesses a high Groundwater Ubiquity Score (GUS) of approximately 3.6[13]. Atrazine is still detectable in soil and deeper layers after 22 years of environmental exposure[14]. REMEDIATION Atrazine is biodegraded by bacteria via hydrolysis Microbes metabolize melamine and the triazine herbicides such as atrazine via enzyme-catalyzed hydrolysis reactions[16]. Pseudomonas sp. ADP and several other atrazine-degrading bacteria metabolize hydroxyatrazine to cyanuric acid[16]. AtzA PHASE 1 AtzB This bacteria has also been isolated in north America Europe, Australia, and Asia[16]. Biological degradation of atrazine in water is nitrogen dependent Atrazine can serve as a nitrogen source and is degraded by certain microorganisms[18]. When nitrite is present in abundance, atrazine may not be degraded by bacteria in water[18]. PHASE 2 AtzC In some cases, atrazine is not seen to biodegrade in anaerobic water[18]. Fig. 2. Metabolic pathway for biodegradation of atrazine by bacteria[17]. REGULATIONS Country • Depending on the availability of sunlight, oxygen, microorganisms, and plants, the half-life of atrazine in water tends to be longer than 6 months. In anaerobic conditions, atrazine has been seen to not degrade aquatic systems[12]. Atrazine is a restricted use pesticide. Its use is restricted only by a certified pesticide applicator or under the direct supervision of a certified applicator[15]. DISPOSITION AND METABOLISM Atrazine metabolism in human and in mice is a cytochrome dependent (CYP) phase 1 biotransformation and a phase 2 glutathione (GSH) conjugation. • Half-life of atrazine in soil range between a few days to about 1 year, depending on application history, soil depth, soil moisture content, temperature, pH and presence of other nutrients such as nitrogen or carbon[14]. 0.410 ppb Ocean • Half-life of Atrazine in air is 14 hours[12]. Treatment for Atrazine MCL (μg/L) USA 3 Canada 5 WHO (World Health Organization) 2 China 3 European Union* 1 Cameroon** 2 Brazil 2 Australia 1 Soil[16] Air[19] Atrazine vapor and particulates in the atmosphere have been seen to dissipate with rain washout. Atrazine has a low vapor pressure so it is rarely observed in the atmosphere. 1. 2. 3. Best Available Technologies: Filter with granular activated charcoal FATE AND TRANSPORT Atrazine starts from pesticide application and is then intergraded into the environment as shown in figure. Atrazine in soil is transformed into metabolites DIA, DACT, DEA. From the environment, atrazine then makes its way to water treatment plants and, finally, to our homes. *Although atrazine has an MCL in Europe, the European union has banned the use of this pesticide. **In Cameroon as it is the case of many third world countries, the use of atrazine appears to be regulated, but a study [3] shows that these pesticides are being misused to the detriment of the farmer’s health. HEALTH EFFECTS • Endocrine disruptor in rats [4], in human [5] Atrazine affects the reproductive system and causes • Low birth weight and premature deliveries [6], increase birth defects [7] • Menstrual cycle length irregularity [8] • Infant mortality [9]. • Birth Defect associated with atrazine exposure: Gastrochisis [9], Omphalocell [9] Atrazine causes demasculinization of male gonads in fishes, amphibians, reptiles and mammals, and complete feminization in fishes, reptiles, amphibians [11] • Male genital malformation in human [12] Removal to a landfill incineration biological remediation Biological remediation is the cheapest method Water[15] During late spring and early summer significant amounts of herbicides are flushed into surface waters from agricultural fields in Midwestern states[20]. Fig. 3.Ilistration of interactions between environmental components[21] . CONCLUSION Atrazine is persistent groundwater contaminant and typically does not get filtered out of tap water[16]. Atrazine also shows signs of endocrine disruption and birth defects, but most of the data supporting human birth defects are epidemiology studies. There is also still a need for further research to understand the mechanism through which atrazine affects human health. Additionally, although exposure to city populations is minimal, small amounts of atrazine will still be ingested over a lifetime with continued the use of atrazine. We have also noticed correlative effects when atrazine is with nitrate (a fertilizer). With atrazine being so persistent in the environment and studies showing endocrine disruption, we would suggest a ban on atrazine until further studies on the effects of atrazine and atrazine with nitrate are fully understood. REFERENCES [1]Hyun Joo, Kyoungju Choi, Ernest Hodgson: \\ Human metabolism of atrazine [2] Erika L. Abel, Shaun M. Opp, Christophe L.M. J. Verlinde, Theo K. Bammler and David L. Eaton. \\Characterization of Atrazine Biotransformation by Human and Murine Glutathione S-Transferases [3] A.F. Abang, C.M. Kouame, M. Abang, R. Hannah and A.K. Fotso \\ Vegetable Growers Perception Of Pesticide Use Practices, Cost, And Health Effects In The Tropical Region Of Cameroon [4] G Giusi ; R M Facciolo ; M Canonaco ; E Alleva ; V Belloni ; F Dessi'-Fulgheri ; D Santucci \\ The Endocrine Disruptor Atrazine Accounts For Dimorphism Somatostatinergenic Neurona Expression Pattern In Mice [5] Jean-Paul Lasserre ; Fred Fack ; Dominique Revets ; Sébastien Planchon ; Jenny Renaut ; Lucien Hoffmann ; Arno C Gutleb ; Claude P Muller ; Torsten Bohn \\Effects of the Endocrine Disruptors Atrazine and PCB 153 on the Protein Expression of MCF-7 Human Cells [6] Jessica L. Rinsky, Claudia Hopenhayn, Vijay Golla,Steve Browning, andHeather M. Bush, \\ Atrazine Exposure in Public Drinking Water and Preterm Birth [7] Cécile Chevrier ; Gwendoline Limon ; Christine Monfort ; Florence Rouget ; Ronan Garlantézec ; Claire Petit ; Gaël Durand ; Sylvaine Cordier \\ Urinary Biomarkers of Prenatal Atrazine Exposure and Adverse Birth Outcomes in the PELAGIE Birth Cohort [8] Lori A. Cragin, James S. Kesner, Annette M. Bachand, Dana Boyd Barr, Juliana W. Meadows, Edward F. Krieg, John S. Reif \\ Menstrual cycle characteristics and reproductive hormone levels in women exposed to atrazine in drinking water [9] Kelly D Mattix; Paul D Wincheste; L.R. “Tres” Scherer \\ Incidence of Abdominal Wall Defects is Related to Surface Water Atrazine and Nitrate Levels [10] Tyrone B. Hayes, Lloyd L. Anderson, Val R. Beasley, Shane R. de Solla, Taisen Iguchi, Holly Ingraham, Patrick Kestemont, Jasna Kniewald, Zlatko Kniewald, Valerie S. Langlois, Enrique H. Luque, Krista A. McCoy, Mónica Muñoz-deToro, Tomohiro Oka, Cleida A. Oliveira, Frances Orton, Sylvia Ruby, Miyuki Suzawa, Luz E. Tavera-Mendoza, Vance L. Trudeau, Anna Bolivar Victor-Costa, Emily Willingham. \\ Demasculinization and feminization of male gonads by atrazine: Consistent effects across vertebrate classes [11] A J Agopian; Philip J Lupo; Mark A Canfield; Peter H Langlois \\ Case-control Study of Maternal Residential Atrazine Exposure and Male Genital Malformations [12] Agency for Toxic Substances and Disease Registry (ATSDR) \\ TOXICOLOGICAL PROFILE FOR ATRAZINE (September 2013) [13] T. Bohn, E. Cocco, L. Guignard and L. Hoffmann \\ Determination of Atrazine and degradation products in Luxembourgish drinking water: origin and fate of potential endocrine-disrupting pesticides [14] Nicolai D. Jablonowski, Stephan Koppchen, Diana Hofmann, Andreas Shaffer, Peter Burauel \\ Persistence of 14C-laveled atrazine and its residues in a field lysimeter soil after 22 years [15] USEPA \\ http://www.epa.gov/pesticides/reregistration/atrazine/index.htm [16] L.P. Wackett, M.J. Sadowsky and B. Martinez \\ Biodegradation of atrazine and related s-triazine compounds: from enzyme to field studies [17] Adapted from J3D3, Wikipedia \\ http://commons.wikimedia.org/wiki/File:Pathway_Atrazine_degradation.svg [18] William L. Hunter and Dale L. Shaner \\ Biological Remediation of Groundwater Containing Both Nitrate and Atrazine [19] S. Lazorko-Connon and G. Achari \\ Atrazine: its occurrence and treatment in water [20] Roy R. Gu 2009 \\ Prediction of the Fate and transport Process of Atrazine in a Reservoir [21] Cheuk Liua, D.H. Bennettb, W.E. Kastenbergc, T.E. McKoned, D. Brownea \\ A multimedia, multiple pathway exposure assessment of atrazine: fate, transport and uncertainty analysis