Understanding sources, management, and impact of Endocrine Disrupting Compounds (EDCs) in the Potomac

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Understanding sources, management, and impact of Endocrine Disrupting Compounds (EDCs) in the Potomac Sudhir Murthy, PhD, PE WEF Fellow, IWA Fellow Manager, Research and Laboratory DC Water

Outline Background/ Context What are the typical estrogenic compounds in watewater? What are the treatment impacts? Where do we go from here? 2

General Information 370 mgd ADF 1,076 mgd Peak CSO Flows 2 Million Customers 725 sq mile Service Area

Evidence of Reproductive Disruption in Fish Downstream WWTP Discharges 1. Sex Ratio: skewed toward females downstream of WWTP Discharges 2. Vitellogenin (estrogen-dependent female yolk protein) elevated in males downstream of WWTP. 3. USGS have conducted research in the Potomac Fish but no causal link to Blue Plains male female 4

USGS Study The proximity to wastewater treatment plants may influence the reproductive health of bass in the Potomac watershed, but inputs from other sources likely contribute to the widespread, high incidence of testicular oocytes. Iwanowicz, L. R. et al. (2009) Reproductive Health of Bass in the Potomac, USA, Drainage: Part 1. Exploring the Effects of Proximity to Wastewater Treatment Plant Discharge. Environmental Toxicology and Chemistry. 28, 1072-1083 5

USGS Study The Potomac River in Washington, D.C. is showing multiple benefits from restoration efforts. Reduced nutrients and improved water clarity have increased the abundance and diversity of submerged aquatic vegetation (SAV) in the Potomac, according to direct measurements taken during the 18-year field study. Ruhl, H. A. and Rybicki, N. B. (2010) Long-term reductions in anthropogenic nutrients link to improvements in Chesapeake Bay habitat PNAS. 107, 16566-16570. 6

DC Council Bill Wastewater study and testing: -the Authority shall initiate a study that tests for the presence of endocrine disruptor compounds in wastewater effluent -the Authority shall present the findings of the study to an advisory Panel, the General Manager, the Mayor, and the Council within 30 days of the study s completion -this section shall be subjection to appropriation

Estrogenic Compounds Found in Wastewater Effluents Natural estrogens- estrone (E1) and estradiol (E2) Synthetic estrogen- Ethinylestradiol (EE2) Alkylphenol Ethoxylate Degradation Products (Octylphenol/Nonylphenol) 8

Major Estrogenic Compounds OH CH 3 CH 3 CH 3 CH 3 CH 3 HO Ethinyl Estradiol (Synthetic Hormone) OH CH 3 HO CH 3 Nonylphenol Isomer HO Estradiol (Natural Hormone)

Metabolites of Nonylphenol Ethoxylates (from Ahel et al., 1994; Naylor, 1992) NP ethoxylate n ~ 9-17 C 9 H 19 OCH 2 CH 2 OH n NP2EO C 9 H 19 OCH 2 CH 2 OCH 2 CH 2 OH NP1EO C 9 H 19 OCH 2 CH 2 OH NP C 9 H 19 OH

Bans and Restrictions on Use of NPE in European Union and Canada

Estrogenic Compound Yeast Estrogen Screen Plasmid her CPRG B-galactosidase Promoter Estrogen Response Element Lac-Z Plasmid Details CPRG Nucleus Cytoplasm Routledge and Sumpter, 1996

Microtiter Plates

Analyte YES Standards Data Eeq 1 Literature Ranges E2 1.0 1 EE2 1.5 0.17 1.4 E1 0.97 0.02 0.5 E3 0.011 0.002 0.3 NPs 0.00038 10-5 10-3 1 Eeq data courtesy of Dr. Benjamin Stanford, Hazen and Sawyer (Data originally published in 2007).

0% 20 40 60 80 100% % Removal Secondary Treatment ER-Yeast EEq (activity) Estrone Ethinyl-estradiol E-Screen EEq (activity) Estradiol Estriol NP 4tOP Bisphenol A Drewes et al. 2006. Removal of Endocrine Disrupting Compounds in Water Reclamation Processes. Water Environment Research Foundation (01-HHE-20T). Graphic courtesy of Hazen and Sawyer.

Blue Plains AWTP 370 mgd (AA) to 518 mgd (Max Day) TN < 7.5 mg/l & TP < 0.18 mg/l Future TN ~ 3 mg/l peak annual flows 12 C winter monthly average Potomac River Final Dual- media Filters Nitrification Denitrification Clarifiers Secondary Reactors Nitrification Secondary Denitrification Clarifiers Reactors Bar Screens and Grit Chambers Primary Clarifiers

YES Assay E2* (ng/l) Primary Effluent Secondary Effluent Nitrification Effluent Final Effluent 05/21/2004 8.2 <2.5 <2.5 <2.5 07/02/2004 10.6 37 <2.5 <2.5 12/27/2004 64.4 60 <2.5 <2.5 *expressed as 17β-estradiol equivalent

YES Assay E2-eq (ng/l) 160 120 80 40 Filtrate through 1 kd Filtrate through 30 kd Filtrate through 0.45 um Filtrate through 1.5 um Unfiltered primary effluent 0 A B D E * Primary Treatment Effluent of 4 plants 18

Water Quality EPA recommended water quality criterion for nonylphenol. Constituent (µg/l) Nonylphenol CAS number 84852153 Class-C CCC 6.6 Class C CMC 28 New constituent and criterion added. EPA recommended final aquatic life ambient water quality criterion. EPA- 822-R-05-005, December 2005. CCC- Criterion Continuous Concentration- Chronic CMC- Criterion Maximum Concentration- Acute 19

Nonylphenol Influent Nonylphenol Summer µg/l July 15.1 Aug 36.4 Winter Feb 35.2 Mar 22.5 Effluent NP Summer µg/l July 0.637 Aug 0.155 Winter Feb 1.35 Mar 1.90 Loyo- Rosales et al. (2007) Fate of Octyl- and Nonylphenol Ethoxylates and Some Carboxylated Derivatives in Three American Wastewater Treatment Plants. Environ. Sci. Technol., 41, 6815. 20

Nonylphenol Influent NPE Summer µg/l July 157 Aug 192 Winter Feb 210 Mar 134 Effluent NPE Summer µg/l July 4.74 Aug 1.62 Winter Feb 25 Mar 17 NPE= Nonylphenol Ethoxylates- 0-5 Ethoxylates Loyo- Rosales et al. (2007) Fate of Octyl- and Nonylphenol Ethoxylates and Some Carboxylated Derivatives in Three American Wastewater Treatment Plants. Environ. Sci. Technol., 41, 6815. 21

What do we know about these compounds? They like to attach to solids They can be degraded or altered to reduce estrogenic effects Mechanisms for degradation are a topic of intense scrutiny 22

Estrogen Removal at Blue Plains Preliminary work indicates; Estrogenic Activity can be removed by processes that separate solids Estrogenic activity associates with solids Estrogenic activity can be degraded in ENR process Higher SRTs and longer detention times have been linked to removal It can accumulate in the solids treatment processes 23

Ongoing Work We plan to continue our collaboration on this work and stay informed 24

The Proposal Team Erik Rosenfeldt has over 10 years of EDC/PPCP occurrence and treatment experience. He is a prinicpal engineer at Hazen and Sawyer, an Industry Leader in Emerging Contaminants Applied Research Luke Iwanowicz, USGS is a fish health scientist with expertise in the fields of virology, molecular biology, immunology, endocrine physiology, endocrine disruption and environmental health monitoring Clifford Rice, USDA is a scientist at the Animal and Natural Resources Institute, Agricultural Research Service and specializes in the detection of trace organic chemicals in the environment Sujay Kaushal, UMD focuses on understanding the interactive effects of land use on ecosystem ecology Sudhir Murthy, DC Water is Manager, Research and Laboratory and leads technology development associated with $1 billion Blue Plains CIP