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Issues with Emerging Contaminants in Water. What are “emerging contaminants”?. PPCPs and EDCs Pharmaceuticals Personal Care Products Endocrine Disrupting Compounds Emerging emerging contaminants?. Pharmaceuticals. Human and veterinary substances taken in response to disease/maladies.
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What are “emerging contaminants”? • PPCPs and EDCs • Pharmaceuticals • Personal Care Products • Endocrine Disrupting Compounds • Emerging emerging contaminants?
Pharmaceuticals • Human and veterinary substances taken in response to disease/maladies. • Cure disease • Alleviate disease associated symptoms • Prevent disease • “The human impulse for a cure runs quite deep, and our first instinct whenever we feel sick or heading toward sickness is to medicate.” • Jjemba, 2008
Personal Care Products • Compounds used in our daily lives • Soaps, detergents, perfumes, aftershaves • Cleaning agents, disinfectants, sprays, deodorants • Bug sprays, sunscreens • Products are typically associated with hygiene
Endocrine Disrupting Compounds • Disrupt normal function of the endocrine system • Mimic hormones; agonize or antagonize hormone activity, synthesis, or metabolism; modify hormone receptors • Active at very low levels • Concern about additive or synergistic effects caused by mixtures of EDCs • Synthetic Estrogens • Ethinyl Estradiol, bisphenol-A • Synthetic Androgens • 90% of US cattle receive growth hormone implants • Synthetic androgens remain environmentally active for months
Emerging, emerging contaminants • What’s next? • Technology will always get better • New products • New ways to find chemicals at lower concentrations • NDMA found in beer by accident • EDC activity of bisphenol-A (BPA) found by accident • Green revolution dumped millions of tons of pesticides and herbicides into the environment, but also created enough food for billions of people!!!
EDC StoriesLake Mead Feminized Carp • Found vitellogenin in male carp of Las Vegas wash and Bay in Lake Mead • Egg producing protein • Elevated levels in female fish • Found elevated levels of several potential EDCs • EthinylEstradiol • Las Vegas wastewater treatment plant outfall "Synthetic Organic Compounds and Carp Endocrinology and Histology, Las Vegas Wash and Las Vegas and Callville Bays of Lake Mead, Nevada, 1992 and 1995, " by Hugh E. Bevans, et. al
EDC StoriesLake Apopka Alligators • A “Teeny Weenie” Problem • Kyla Dunne for PBS (June 2, 1998) • http://www.pbs.org/wgbh/pages/frontline/shows/nature/gallery/alligators.html • Lou Guillette from the University of Florida • 25% smaller phallus in the adult and juvenile male alligators of lake Apopka • Low testosterone levels compared to levels in alligators from healthy lake • Penis size did not reflect amount of testosterone in blood • Causes? • 1980 DDT and dicofol spill into the lake • Chemical runoff from agriculture • Discharge from Sewage Treatment plant • Proving the link • Took alligator eggs from “Clean” lake • Grew them in p,p’ DDE and found similar results to Lake Apopka alligators • "Developmental Abnormalities of the Gonad and Abnormal Sex Hormone Concentrations in Juvenile Alligators from Contaminated and Control Lakes in Florida". Environmental Health Perspectives 102(8):680-688 • "Reduction in Penis Size and Plasma Testosterone Concentrations in Juvenile Alligators Living in a Contaminated Environment". General and Comparative Endocrinology 101:32-42.
Where have EDCs/PPCPs been found? • Surface waters throughout the world • Europe, Asia, Canada, USA • USGS report “Pharmaceuticals, hormones, and other organic wastewater contaminants in US streams 1999-2000: A national reconnaissance” • 95 compounds • 139 streams throughout US sampled • 80% tested positive • ES&T 36 (6), 1202 Koplin et al., 2002
EDC Stories (Hermaphroditic Frogs) • Tyrone Hayes • “Feminization of male frogs in the wild” (Nature, 419: 895-896) • Investigated the effects of exposure to waterborne atrazine contaminiation on Leopard Frogs • Examined different regions of US (Iowa – Utah) • Found 10-92% of males showed gonadal abnormalities • “Atrazine-induced hermaphroditism at 0.1ppb in American Leopard Frogs (Rana pipiens): Laboratory and field evidence” (EHP, 111:568-575)
Government Regulations • Compounds are not currently regulated in the United States as EDCs • Process started in 1996 • Endocrine Disrupting Screening Program (EDSP) • Assay development and validation team • Scientific and Technical validation of EDC screens • Priority setting workgroup • Develop and prioritize which compounds are tested as EDCs • Regulatory activities workgroup • Working on regulatory procedures needed to implement EDSP http://www.epa.gov/scipoly/oscpendo/
Samples collected per time zone 195 88 43 17 Participating Utilities
Target Compounds Pharmaceuticals (20) Potential EDCs (26) Steroid Hormones (5) Phytoestrogens (11) AtenololAtrazineEstradiolApigenin AtorvastatinBenzophenoneEstroneBiochanin A o-Hydroxy atorvastatinBHAEthinylestradiol Chrysin p-Hydroxy atorvastatinBHTProgesteroneCoumestrol Carbamazepinea-BHCTestosteroneDaidzein Diazepamb-BHCEquol Diclofenacg-BHCFormononetin Dilantind-BHCGenistein EnalaprilBisphenol AGlycitein FluoxetineButylbenzyl phthalateMatairesinol NorfluoxetineDEETNaringenin GemfibrozilDiazinon MeprobamateDioctyl phthalate NaproxenGalaxolide RisperidoneLinuron SimvastatinMethoxychlor Simvastatin hydroxy acidMetolachlor SulfamethoxazoleMusk ketone TriclosanNonylphenol TrimethoprimOctachlorostyrene Octylphenol TCEP TCPP Tonalide Traseolide Vinclozolin
Detected in Raw Water* (24/62) Pharmaceuticals Potential EDCs Steroid Hormones Phytoestrogens AtenololAtrazineEstradiolApigenin AtorvastatinBenzophenoneEstroneBiochanin A o-Hydroxy atorvastatinBHAEthinylestradiol Chrysin p-Hydroxy atorvastatinBHTProgesteroneCoumestrol Carbamazepinea-BHCTestosteroneDaidzein Diazepamb-BHCEquol Diclofenacg-BHCFormononetin Dilantind-BHCGenistein EnalaprilBisphenol AGlycitein FluoxetineButylbenzyl phthalateMatairesinol NorfluoxetineDEETNaringenin GemfibrozilDiazinon MeprobamateDioctyl phthalate NaproxenGalaxolide RisperidoneLinuron SimvastatinMethoxychlor Simvastatin hydroxy acidMetolachlor SulfamethoxazoleMusk ketone TriclosanNonylphenol TrimethoprimOctachlorostyrene Octylphenol TCEP TCPP Tonalide Traseolide Vinclozolin Estradiol Atorvastatin Benzophenone Biochanin A o-Hydroxy atorvastatinBHA Ethinylestradiol Chrysin p-Hydroxy atorvastatinBHTCoumestrol a-BHC Testosterone Daidzein Diazepam b-BHCEquol g-BHC -BHC Enalapril Bisphenol A Glycitein Fluoxetine Butylbenzyl phthalate Matairesinol Norfluoxetine Naringenin Diazinon Risperidone SimvastatinMethoxychlor Simvastatin hydroxy acid Musk ketone Octachlorostyrene Octylphenol Tonalide Traseolide Vinclozolin * In at least 20% of samples
Detected in Drinking Water* (11/62) Pharmaceuticals Potential EDCs Steroid Hormones Phytoestrogens AtenololAtrazineEstradiolApigenin AtorvastatinBenzophenoneEstroneBiochanin A o-Hydroxy atorvastatinBHAEthinylestradiol Chrysin p-Hydroxy atorvastatinBHTProgesteroneCoumestrol Carbamazepinea-BHCTestosteroneDaidzein Diazepamb-BHCEquol Diclofenacg-BHCFormononetin Dilantind-BHCGenistein EnalaprilBisphenol AGlycitein FluoxetineButylbenzyl phthalateMatairesinol NorfluoxetineDEETNaringenin GemfibrozilDiazinon MeprobamateDioctyl phthalate NaproxenGalaxolide RisperidoneLinuron SimvastatinMethoxychlor Simvastatin hydroxy acidMetolachlor SulfamethoxazoleMusk ketone TriclosanNonylphenol TrimethoprimOctachlorostyrene Octylphenol TCEP TCPP Tonalide Traseolide Vinclozolin EstradiolApigenin Atorvastatin Benzophenone Estrone Biochanin A o-Hydroxy atorvastatinBHAEthinylestradiol Chrysin p-Hydroxy atorvastatinBHTProgesteroneCoumestrol a-BHCTestosteroneDaidzein Diazepamb-BHCEquol Diclofenac g-BHC Formononetin d-BHCGenistein EnalaprilBisphenol AGlycitein FluoxetineButylbenzyl phthalateMatairesinol NorfluoxetineNaringenin Diazinon Dioctyl phthalate Naproxen Galaxolide RisperidoneLinuron SimvastatinMethoxychlor Simvastatin hydroxy acid Musk ketone Triclosan Nonylphenol Trimethoprim Octachlorostyrene Octylphenol Tonalide Traseolide Vinclozolin * In at least 20% of samples
How much would you have to consume?? 300 - 400 1,200,000 30 - 300 770,000 800 - 1200 23,000,000 750 - 1000 5,800,000 20 - 38 1,500,000 120 - 180 980,000 12 - 120 190,000 1200 - 2400 23,000,000 800 - 1200 16,000,000 Liters Daily Dose (mg) Compound Phenytoin ( Dilantin) Phenobarbital ( Luminal) Carbamazepine ( Tegretol) Primidone ( Myidone) Hydrocodone Codeine Diazepam (Valium) Guaifenesin ( Robitussin) Pentoxifylline ( Trental) NOTE: EPA Reference Intake = 2L/day
Human Impacts? • Nelson and Bunge, 1974: • Missouri men have lower sperm counts than men in LA, NY, and Minneapolis • No reason found • Swan et al., 2003: • Confirmed earlier study • Missouri low-sperm count men had higher levels of Atrazine, Alachlor, and Diazanon • Link between pesticides and reproductive effect • No occupational exposure • Source Identified: Drinking water contamination
More Human Cases • DES Daughters • Hypospadias doubled from 1970-1991 (Paulozzi et al, 1997) • Dioxins and endometriosis in monkeys (Rier and Foster, 2002) • Link between increases in breast, testicular and prostate cancers over past 40 years??? (Krishnan and Safe, 1993; Carlsen et al., 1995; EPA, 1997; more) • All linked to hormone mimicking or disrupting compounds
AwwaRF/WateReuse FoundationTailored Collaboration:“Toxicological Relevance of EDCs and Pharmaceuticals in Water”Projects 3085/04-003- Dr. Djanette Khiari – AwwaRF- Mr. Joshua Dickinson - WRF
E-screen Assay • MCF-7 breast cancer cells proliferate in response to estrogenic compounds • Developed by oncologists Ana Soto & Carlos Sonnenschein at Tufts University
E-screen Results(EEq ng/L) 1700 4000 300 6.0 13 2.9 2.5 4.6 nd 0.6 0.7 0.8
890 mL Secondary Wastewater (4.6 ng/L) 1 cup coffee (17 ng/L, 240 mL) EEq Comparison(“Worst” WWTP)
1 Liter Secondary Wastewater (4.6 ng/L) Teaspoon of Soy Sauce (300 ng/L, 15 mL) EEq Comparison
EEq Comparison 44 Liters of Secondary Wastewater (4.6 ng/L) Soy Baby Formula (1700 ng/L, 4 oz Bottle)
Breakfast Lunch Dinner Sushi w/ soy sauce = 4.5 ng 2 Cups coffee = 8.2 ng Glass of beer = 2.2 ng Glass of Juice = 0.2 ng Cup of tea = 0.7 ng Daily Intake of EEq (ng) Comparison • “Typical” day for average adult, per serving Glass of milk = 0.1 ng • Est. Total Daily intake of EEq = 15.9 ng
What is the Context for Risk? • Food Exposure • Air Exposure • Water Exposure • Health Endpoints • Cancer • Non-Cancer
Note Atrazine MCL = 3000 ng/L in Water; RfD = 2.45 mg/day for Ave. Adult
“No substance is a poison by itself. It is the dose that makes a substance a poison...” Paracelsus (1493-1541) Risk = Toxicity + Exposure
MRL > 1000 ng/L MRL > 50 ng/L MRL > 20 ng/L MRL > 20 ng/L MRL > 10 ng/L MRL > 20 ng/L MRL > 50 ng/L MRL > 1000 ng/L MRL > 10 ng/L US Drinking Water MRL > 500 ng/L MRL > 100 ng/L