Effects of Endocrine Disrupting Compounds on Fish What do we know and what don t we know?

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1 Effects of Endocrine Disrupting Compounds on Fish What do we know and what don t we know? MWRD Workshop on Microconstituents and Ecological Impacts of Biosolids and Effluent Reuse June 26, 28 Todd Nettesheim, Great Lakes National Program Office, USEPA, Chicago, IL Heiko L. Schoenfuss, St. Cloud State University, St. Cloud, MN

2 Outline of talk Background on emerging chemicals of concern Federal framework for addressing emerging chemicals Collaborative studies Distribution of Chemical Contaminants within a Large Wastewater Treatment Plant and in Downstream Surface Waters (Calumet) Pharmaceuticals and Personal Care Products (PPCPs), Hormones, and Alkylphenol Ethoxylates (APEs) in the North Shore Channel of the Chicago River (NSC) Conclusions and next steps

3 An AP Investigation: Pharmaceuticals found in Drinking Water - Headlines Pharmaceuticals found in drinking water, affecting wildlife and maybe humans Pharmaceuticals found in drinking water of 24 major metro areas, 34 say no testing Fish, wildlife affected by drug contamination in water No standards to handle pharmaceuticals in water Tests of Philadelphia's drinking water reveal 56 drugs And many more water_site/index.html

4 Why are PPCPs (including APEs) of concern? Produced and used in large volumes May be pseudo-persistent Chronic exposure May have biological effects Therapeutic design Non-target organisms May be endocrine disruptors alterations to sexual differentiation Boulder Creek Potomac River reproduction and growth impairments behavioral effects Little known about environmental persistence, fate

5 Federal framework - Research Interagency workgroups Pharmaceuticals in the Environment (PiE( PiE) Antimicrobial Resistance (AMR) Endocrine Disrupting Chemicals (EDCs) Screening and Testing Programs Bioassays and computational approaches Move towards interpretation and reduction of uncertainty Chemical classes / modes of action / mixtures Surveillance Effluent, drinking water, effluent, fish, etc Wastewater treatment technologies

6 Federal framework Voluntary and P2 efforts Great Lakes Binational Toxics Strategy (GLBTS) Design for the Environment (DfE) Safer Detergents Stewardship Initiative (SDSI) High Production Volume (HPV) Chemical Program Chemicals Assessment & Management Program (ChAMP) Security & Prosperity Partnership of North America Pharmaceuticals safe disposal guidance

7 Federal framework - Regulatory Clean Water Act Water quality criteria - human health and aquatic life Effluent guidelines Part 53 Biosolids Rule Safe Drinking Water Act Contaminate Candidate List (CCL) Toxics Substances Control Act

8 What do we know? Wastewater treatment plant can be effective at reducing many of these compounds However, many of these compounds are still released into the environment in measurable amounts (biosolids and effluent)

9 NPEOs are reduced through the treatment process Nonylphenol Ethoxylates in the Calumet WRP 8 7 Concentration (ng/l) Primary Influent Primary Effluent Mixed Liquor Final Effluent NP NP1EO NP2EO NP3EO NP4EO NP5EO NP6EO NP7EO NP8EO NP9EO NP1EO NP11EO NP12EO NP13EO NP14EO NP15EO NP16EO

10 However, NPECs are formed in the treatment process Nonylphenol Carboxylates in the Calumet WRP Concentration, ng/l Primary Influent Primary Effluent Mixed Liquor Final Effluent Treatment Process NP1EC NP2EC

11 14, 12, 1, 8, 6, 4, 2, Seasonality of Observed NPE Concentrations NP1EO NP2EO NP3EO NP Temperature /2/6 9/26/6 1/4/6 1/1/6 1/16/6 1/24/6 3/2/7 3/12/7 3/2/7 3/28/7 4/5/7 4/13/7 4/23/7 Date. 9/14/6 Concentration (ng/l) Effluent Temperature (C) Fall Spring Conc. as temps. NP levels below toxicity based criteria for aquatic life

12 The wastewater treatment process is also effective at removing PBDEs from effluent PBDEs in Sludge at CWRP Increasingly concentrated Conc (ug/kg dry wt) Almost 2x increase 1S 2S 3S 4S 11S 5S 1S 6S BDE-47 BDE-99 BDE-1 BDE-153 BDE-154 BDE-29

13 What do we know? (cont.) Many of these chemicals can be found in the environment Effluent Streams Great Lakes Biosolids Fish and other aquatic organisms

14 Pharmaceuticals in effluent present at High ppt to ppb levels (> 5 ng/l) lisinopril valsartan hydrochlorothiazide ibuprofen-2-hydroxy gemfibrozil Mid ppt levels (1-5 ng/l) atenolol metoprolol diltiazem furosemide ciprofloxacin carbamazepine trimethoprim ibuprofen Low ppt levels (<1 ng/l) amphetamine hydrocodone triamterene enaliprilat enalipril propanolol diltiazem-desmethyl verapamil norverapamil amlodipine sulfamethoxazole promethazine paroxetine amitriptyline benztropine norfluoxetine fluoxetine sertraline-desmethyl sertraline

15 Hormones in Effluent and Stream Concentration, ng/l Effluent Stream Levels of E1 and E2 in stream >> DHT Dihydrotestosterone levels EE2 in detected effluent above E2 17-B-estradiol Additional explanations: EE2 detected above MDL, but below RL E1 Estrone of 2ng/L TEST Testosterone AND Androstenedione 1ng/L ~ threshold EE2 17-a-ethynylestradiol Conversion of E2 to E1 in environment Stream 1ng/L redox ~ conditions threshold Sediment for endocrine resuspension Stream redox conditions Sediment E3 resuspension Estriol source Combined disruption PRO Sewer Progesterone Overflows effects (CSOs) 1 * * * * DHT E2 E1 TEST AND EE2 E3 PRO Hormone Data courtesy of: Marc A. Mills, USEPA ORD, Cincinnati, OH * - below reporting limit of 2 ng/l

16 12, Many compounds persist downstream of outfall 45, 1, Effluent Sample Stream Sample 4, Concentration (ng/l) 8, 6, 4, 35, 3, 25, 2, 2, 15, BPA NP1EO NP2EO NP3EO NP OP NP1EC NP2EC 1, Analyte

17 They can even persist well downstream of outfall Nonylphenol and its Ethoxylates in the Cal-Sag Channel 45 4 Concentration (ng/l) km downstream of outfall NP NP1EO NP2EO NP3EO NP4EO

18 Downstream Persistence in the Cal-Sag 3 outfall Concentration (ng/l outfall 28 km downstream 28 km downstream 5 Triclosan Bisphenol A

19 Pharmaceutical Chemicals Detected in EPA Pilot Study & Fillet and Liver Tissue from NSC Detected Chemicals & Method Detection Limits (MDLs) Use National Composites with Detection (N=3) Fillet Liver Detections in NSC (N=6) Fillet Liver Carbamazepine (1.86 ppb) Anti-seizure seizure Diltiazem (.26ppb) Anti-hypertension Diphenyldydramine (.26ppb) Antihistimine Fluoxetine (12.41ppb) Antidepressant 11 3 Gemfibrozil (24.82ppb) Antilipemic 8 Norfluoxetine (15.31ppb) Fluoxetine metabolite Sertaline (17.29ppb) Antidepressant *Leanne Stahl, Office of Water, USEPA, Washington DC, USA

20 APEs in NSC Large Mouth Bass 6 Fall 26 Spring 27 Concentration (ng/g) NP NP1EO NP2EO NP3EO NP4EO NP NP1EO NP2EO NP3EO NP4EO *Clifford P. Rice, Nuria Lozano, Agricultural Research Service, USDA, Beltsville, MD

21 What don t we know? Effects of the mixtures? We detected 1s to 1s of compounds (there are probably 1s of others) Presence of compounds that are not currently measured (screening studies)? No standards or criteria Significance of effects on entire population? Importance of other modes of action? Human Health impacts?

22 Conclusions Collaboration is KEY! Sampling and analytical capability are challenges Many compounds are removed significantly from treatment plants But still end of in the environment in detectable amounts Effluent (and streams) contain a wide mixture of compounds Persistent exposure to aquatic life Other possible sources Emerging concern that we ve just begun to investigate

23 Questions? Thank You! Todd Nettesheim U.S. EPA GLNPO (312)