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. –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!!!

A Brief History of “Emerging” Contaminants

Developments in Industrial Microbiology

EDC Stories Lake 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 –Ethinyl Estradiol –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 Stories Lake Apopka Alligators A “Teeny Weenie” Problem –Kyla Dunne for PBS (June 2, 1998) 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): Developmental Abnormalities of the Gonad and Abnormal Sex Hormone Concentrations in Juvenile Alligators from Contaminated and Control Lakes in Florida "Reduction in Penis Size and Plasma Testosterone Concentrations in Juvenile Alligators Living in a Contaminated Environment". General and Comparative Endocrinology 101:32-42.Reduction in Penis Size and Plasma Testosterone Concentrations in Juvenile Alligators Living in a Contaminated Environment

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 : 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: ) 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: )

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

Samples collected per time zone 17 Participating Utilities

Target Compounds Pharmaceuticals (20)Potential EDCs (26)Steroid Hormones (5) Phytoestrogens (11) AtenololAtrazine EstradiolApigenin AtorvastatinBenzophenone EstroneBiochanin A o-Hydroxy atorvastatin BHA EthinylestradiolChrysin p-Hydroxy atorvastatin BHT ProgesteroneCoumestrol Carbamazepine  -BHC TestosteroneDaidzein Diazepam  -BHCEquol Diclofenac  -BHCFormononetin Dilantin  -BHCGenistein EnalaprilBisphenol AGlycitein FluoxetineButylbenzyl phthalateMatairesinol Norfluoxetine DEETNaringenin GemfibrozilDiazinon MeprobamateDioctyl phthalate NaproxenGalaxolide RisperidoneLinuron SimvastatinMethoxychlor Simvastatin hydroxy acid Metolachlor SulfamethoxazoleMusk ketone TriclosanNonylphenol TrimethoprimOctachlorostyrene Octylphenol TCEP TCPP Tonalide Traseolide Vinclozolin

PharmaceuticalsPotential EDCsSteroid Hormones Phytoestrogens Detected in Raw Water * (24/62) AtenololAtrazine EstradiolApigenin AtorvastatinBenzophenone EstroneBiochanin A o-Hydroxy atorvastatin BHA EthinylestradiolChrysin p-Hydroxy atorvastatin BHT ProgesteroneCoumestrol Carbamazepine  -BHC TestosteroneDaidzein Diazepam  -BHCEquol Diclofenac  -BHCFormononetin Dilantin  -BHCGenistein EnalaprilBisphenol AGlycitein FluoxetineButylbenzyl phthalateMatairesinol Norfluoxetine DEETNaringenin GemfibrozilDiazinon MeprobamateDioctyl phthalate NaproxenGalaxolide RisperidoneLinuron SimvastatinMethoxychlor Simvastatin hydroxy acid Metolachlor SulfamethoxazoleMusk ketone TriclosanNonylphenol TrimethoprimOctachlorostyrene Octylphenol TCEP TCPP Tonalide Traseolide Vinclozolin Estradiol AtorvastatinBenzophenone Biochanin A o-Hydroxy atorvastatin BHA EthinylestradiolChrysin p-Hydroxy atorvastatin BHT Coumestrol  -BHC TestosteroneDaidzein Diazepam  -BHCEquol  -BHC  -BHC EnalaprilBisphenol AGlycitein FluoxetineButylbenzyl phthalateMatairesinol Norfluoxetine Naringenin Diazinon Risperidone SimvastatinMethoxychlor Simvastatin hydroxy acid Musk ketone Octachlorostyrene Octylphenol Tonalide Traseolide Vinclozolin * In at least 20% of samples

AtenololAtrazine EstradiolApigenin AtorvastatinBenzophenone EstroneBiochanin A o-Hydroxy atorvastatin BHA EthinylestradiolChrysin p-Hydroxy atorvastatin BHT ProgesteroneCoumestrol Carbamazepine  -BHC TestosteroneDaidzein Diazepam  -BHCEquol Diclofenac  -BHCFormononetin Dilantin  -BHCGenistein EnalaprilBisphenol AGlycitein FluoxetineButylbenzyl phthalateMatairesinol Norfluoxetine DEETNaringenin GemfibrozilDiazinon MeprobamateDioctyl phthalate NaproxenGalaxolide RisperidoneLinuron SimvastatinMethoxychlor Simvastatin hydroxy acid Metolachlor SulfamethoxazoleMusk ketone TriclosanNonylphenol TrimethoprimOctachlorostyrene Octylphenol TCEP TCPP Tonalide Traseolide Vinclozolin EstradiolApigenin AtorvastatinBenzophenone EstroneBiochanin A o-Hydroxy atorvastatin BHA EthinylestradiolChrysin p-Hydroxy atorvastatin BHT ProgesteroneCoumestrol  -BHC TestosteroneDaidzein Diazepam  -BHCEquol Diclofenac  -BHCFormononetin  -BHCGenistein EnalaprilBisphenol AGlycitein FluoxetineButylbenzyl phthalateMatairesinol Norfluoxetine Naringenin Diazinon Dioctyl phthalate NaproxenGalaxolide RisperidoneLinuron SimvastatinMethoxychlor Simvastatin hydroxy acid Musk ketone TriclosanNonylphenol TrimethoprimOctachlorostyrene Octylphenol Tonalide Traseolide Vinclozolin Detected in Drinking Water * (11/62) Pharmaceuticals Potential EDCs Steroid Hormones Phytoestrogens * In at least 20% of samples

Finished Water for 18 Drinking Water Treatment Facilities CompoundMax (ng/L)Median (ng/L)Frequency (%) Atrazine Meprobamate Dilantin Atenolol Carbamazepine Gemfibrozil TCEP DEET Metolachlor TCPP (Fyrol PCF) Sulfamethoxazole US Drinking Water

AP Story (March, 2008)

Relevance to Human Health

How much would you have to consume?? Phenytoin (Dilantin) Phenobarbital (Luminal) Carbamazepine (Tegretol) Primidone (Myidone) Hydrocodone Codeine Diazepam (Valium) Guaifenesin (Robitussin) Pentoxifylline (Trental) 1,200, ,000 23,000,000 5,800,000 1,500, , ,000 23,000,000 16,000,000 Compound Daily Dose (mg) Liters 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 (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 Foundation Tailored Collaboration: “Toxicological Relevance of EDCs and Pharmaceuticals in Water” Projects 3085/ 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) nd

 1 cup coffee (17 ng/L, 240 mL) EEq Comparison (“Worst” WWTP) 890 mL Secondary Wastewater (4.6 ng/L)

EEq Comparison  Teaspoon of Soy Sauce (300 ng/L, 15 mL) 1 Liter Secondary Wastewater (4.6 ng/L)

Soy Baby Formula (1700 ng/L, 4 oz Bottle)  EEq Comparison 44 Liters of Secondary Wastewater (4.6 ng/L)

Daily Intake of EEq (ng) Comparison “Typical” day for average adult, per serving Glass of milk = 0.1 ng 2 Cups coffee = 8.2 ng Glass of Juice = 0.2 ng BreakfastLunchDinner Sushi w/ soy sauce = 4.5 ng Glass of beer = 2.2 ng Cup of tea = 0.7 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

Max Concentrations, ng/L Bisphenol AAtrazineNonylphenolEstradiol Raw Finished <0.5 Bottled Water<5<0.25<80<0.5 Apple Juice<50<1026,000<100 Vegetable Juice<250<201300<5 Green Tea<50<101600<10 Beer<1000<502400<100 Cow's Milk<125<10<1250<100 Soy Milk<125<104500<20 Dairy Formula5600<50<10,000<20 Soy Formula5400<5011,000<20 Soy Sauce<2.5<0.2521,000<1 Breastmilk*1900*?? 8,000 to 19,000** *Ye, 2006**Choi, 2002 Note Atrazine MCL = 3000 ng/L in Water; RfD = 2.45 mg/day for Ave. Adult

WATERINDOOR AIR Conc. Exposure (2 L/day) Conc. Exposure (24 m 3 /day) (μg/L)(μg)(μg/m 3 )(μg) BHT TCPP (Fyrol PCF) Galaxolide Butylbenzyl phthalate Nonylphenol

“No substance is a poison by itself. It is the dose that makes a substance a poison...” Paracelsus ( ) Risk = Toxicity + Exposure

Method Reporting Limits based on 100x <DWEL Max Drinking Water Conc. (µg/L) DWEL (µg/L) Liters per day to meet DWEL Method MRL (µg/L) Recommended MRL (µg/L) Phenytoin Carbamazepine , Fluoxetine , Diazepam , Gemfibrozil , Atenolol , Meprobamate , Bisphenol A0.0251,800140, Nonylphenol0.101,80035, Sulfamethoxazole ,00012,000,

Finished Water for 18 Drinking Water Treatment Facilities CompoundMax (ng/L)Median (ng/L)Frequency (%) Atrazine* Meprobamate Dilantin Atenolol Carbamazepine Gemfibrozil TCEP DEET Metolachlor TCPP (Fyrol PCF) Sulfamethoxazole MRL > 10 ng/L MRL > 20 ng/L MRL > 50 ng/L MRL > 100 ng/L MRL > 500 ng/L MRL > 1000 ng/L US Drinking Water

Effects on Water Industry

NYC Water ~ $3.50/ 1000 gal Las Vegas ~ $1.50/ 1000 gal Bottled Water ~ $350 - $8,000/ 1000 gal

Given Enough Energy Input, Any Chemical Can Be Removed From Water… Is the Benefit Worth the Impact?

Historical and Forecast Lake Mead Elevation Top of Spillway Drought 1,000 1,040 1,080 1,120 1,160 1,200 1,240 Jan-00Jan-01 Jan-02Jan-03Jan-04Jan-05Jan-06 Jan-07 Jan-08Jan-09 Elevation Above Sea Level (feet) Historical Forecast Drinking & Hydroelectric Minimal Level

Pharm’s and EDCs in Lake Mead Benotti, Stanford, and Snyder, JEQ, in press

UV 40mJ/cm 2 <30% Removal30-70% Removal>70% Removal TestosteroneSulfamethoxazole ProgesteroneTriclosan AndrostenedioneDiclofenac EstriolAcetaminophen Ethynylestradiol Estrone Estradiol Erythromycin Trimethoprim Naproxen Hydrocodone Ibuprofen Caffeine Fluoxetine Meprobamate Diazepam Dilantin Carbamazepine DEET Atrazine Galaxolide TCEP Iopromide Pentoxifylline Metolachlor Gemfibrozil Musk Ketone

Chlorine 3.5 mg/L 24 hr

<30% Removal30-70% Removal>70% Removal Musk KetoneMeprobamateTestosterone TCEPAtrazineProgesterone IopromideAndrostenedione Estriol Ethynylestradiol Estrone Estradiol Erythromycin-H2O Sulfamethoxazole Triclosan Trimethoprim Naproxen Diclofenac Ibuprofen Hydrocodone Acetaminophen Carbamazepine Dilantin Diazepam Caffeine Fluoxetine DEET Metolachlor Galaxolide Pentoxifylline Gemfibrozil Ozone 2.5 mg/L or UV-H 2 O 2 ≈ 700 mJ + 5 mg/L

RO Membranes: Most compounds removed >>70%

Water Reuse Facility

Energy per Unit Volume for Water Treatment

Climate Change Drought Increased WW Influence On DW Novel Treatment Technologies Greenhouse Gas Emissions Population Growth Impact Cycle

What issues ARE important? What compounds should we be worried about? Microbes? CCL 1, 2, & 3? Utility Size/Pop.?

Key Messages Pharm/EDCs documented in water for >40 years If we look hard enough, we will find contaminants – No treatment process is “perfect” – Contaminant reduction vs. pollution relocation – Cleaner water vs. carbon footprint – Should DW Utilities be proactive???

Key Messages Method reporting limits and treatment goals must be health-based If MRLs were 1 μ g/L, we would have detected no contaminants If MRLs were 0.1 μ g/L, we would have detected only two target compounds - NO pharmaceuticals If MRLs were 0.01 μ g/L, only ½ of the compounds detected would have been reported Detection does not = risk, just as ND does not = safe!

Key Messages Ecological concerns must be addressed We should strive for cleaner & safer water – the public will bear the costs The world will depend on water reuse Trace contaminants WILL be detected If treatment needed, wastewater makes the most sense More efficient treatment = more greenhouse gases and costs to the public