Chemicals of Emerging Concern in CWA Programs.

1. Chemicals of Emerging Concern in CWA Programs. Brian Englert, PhD. Engineering & Analytical Support Branch Office of Science and Technology (OST) October 17-19,2007

2. This presentation was developed by the author, and has not been subjected to the Agency�s peer and administrative review. Therefore, the conclusions and opinions drawn are solely those of the authors and may not reflect the views of the Agency.

3. Outline: Introduction CECs - Current Federal Activities OW Activities Methods Development for Pesticides, Pharmaceuticals, Steroids and Hormones.

5.  CWA Methods Information WWW.EPA.GOV/WATERSCIENCE/METHODS/ Facts Sheets, FAQs, Rule Text, EPA Methods Send an email to us at OSTCWAMETHODS @ EPA.GOV CWA Methods Team Ms. Meghan Hessenauer Dr. Brian Englert Mr. Lemuel Walker Dr. Robin Oshiro Ms. Marion Kelly

6. CECs? Why are we concerned? Environmental concern due to known and unknown concentrations and effects As analytical methods overcome current limitations detection of these chemicals will increase as will public awareness Some of these chemicals may impact the human hormone system others are designed to. Previous reports of intersex fish have generated public interest

10. Interagency Workgroups related to CECs Pharmaceuticals in the Environment Workgroup Co-leads are EPA/FDA with CDC, NIEHS, NOAA, USDA, USGS Goals Develop two strategies by December 2007 Research strategy for human and veterinary pharmaceuticals in the environment Research strategy for antibiotics in the environment; focusing on the question of antibiotic resistance Established from the White House OSTP Toxics and Risks Subcommittee

11. Interagency Workgroups related to CECs Endocrine Disruption in the Environment Workgroup Lead is EPA with NIEHS, DOI, NOAA, FDA, CDC, NSF, ATSDR, NCI, DOE, DOD, USDA, The Smithsonian Institution Goals Develop a planning framework for Federal research related to human health and ecological effects of endocrine disrupting compounds Identify research gaps and develop a coordinated plan to address priority research needs Established from the White House OSTP Toxics and Risks Subcommittee

12. Other Federal Efforts Related to CECs USGS work Flush and do not flush Policy- EPA/ONDCP/DHHS http://www.whitehousedrugpolicy.gov/drugfact/factsht/proper_disposal.html Drug Take-Back Pilot Studies - Endocrine Disruption in the Environment Workgroup Lead is EPA with NIEHS, DOI, NOAA, FDA, CDC, NSF, ATSDR, NCI, DOE, DOD, USDA, The Smithsonian Institution Universal Waste Rule-EPA/OSW

13. Office of Research and Development. Science to Achieve Results (STAR) Grants http://es.epa.gov/ncer/grants/ Various research to develop new chemical analysis methods, understand aquatic and health effects and new approaches for prioritizing chemicals for monitoring Endocrine Disruptors Research Program http://www.epa.gov/endocrine/

15. Office of Water POTW Study � EAD Health Services Industry Detailed Study - EAD Fish Tissue Study � SHPD Biosolids Survey - HECD

17. POTW Study y ?Objectives -Develop analytical methods to identify and measure contaminants of emerging concern (CECs) in wastewater and sludge -characterize occurrence of CECs in POTW influent, effluent, and sludge -Evaluate CEC removal effectiveness by POTW unit operations

18. POTW Study ?Scope We plan to characterize the occurrence of various types of CECs: flame retardants hormones pharmaceuticals steroids nonylphenols pesticides

19. POTW Study  Characterization and Treatment Effectiveness Over the next few years, we plan one-day screener sampling at POTWs to characterize the presence/absence of CECs. We have completed screeners at four POTWs Based on those findings and available resources, we will select POTWs for treatment effectiveness performance sampling. These more extensive multi-day samplings will help us identify design and operational practices that could optimize removal of emerging contaminants.

20. POTW Study POTW Study: Brian D�Amico, 202-566-1069, damico.brian@epa.gov (POTW operations) Brian Englert, 202.566.0754, englert.brian@epa.gov, (analytical methods)

22. Rationale and Background for Detailed Study The Health Services Industry includes establishments engaged in various aspects of human health (e.g. hospitals, dentists, medical/dental laboratories) and animal health (e.g. veterinarians). According to the 2002 Census, there are over 475,000 facilities in the health services industry. The vast majority of establishments in the health services industries are not subject to categorical limitations and standards (ELGs). EPA received comments urging it to consider studying this industry. In particular, commenters raised concern about endocrine disruptor compounds (EDCs) and mercury discharges from dentists

23. Scope of Detailed Study Mercury discharges from dentists NACWA found that dental facilities discharge more mercury to POTWs than any other sector Based on a NAQWA study, dental offices account for 35 to 80% of mercury entering POTWs Un-used or expired pharmaceutical discharges to POTWs from hospitals, long-term care facilities, and veterinarians Recent studies indicate the presence of phamaceuticals in waters of the U.S. Need for obtaining quantitative information about the amount entering POTWs from the Health Care Sector

24. What Information Are We Collecting? ?Current Industry Practices and Discharges What are the current industry practices and discharges? To what extent are each of these practices applied? What factors drive current practices? Health Services Industry Detailed Study

25. Health Services Industry Detailed Study What Information Are We Collecting? ?Control Technologies and Best Management Practices What technologies and BMPs are available for health care facilities to implement: (1) as alternatives to wastewater disposal; and (2) to control discharges. Is there any qualitative or quantitative information on the efficiency of these technologies and BMPs? Is there any quantitative or qualitative information on the costs associated with identified technologies and/or BMPs?

26. Health Services Industry Detailed Study What Information Are We Collecting? ?Impacts on POTWs Do POTWs experience interference problems related to spent pharmaceuticals or mercury discharges? Are mercury or pharmaceuticals �passing through� the POTW?

27. Dental Mercury Current practices Most dental offices currently use some type of basic filtration system to reduce the amount of mercury solids passing into the sewer system. Existing requirements No federal requirements Some states, localities and regions have enacted requirements or provided guidance NAQWA and ADA guidance Control Technologies Amalgam separators (99% removal) BMPs

28. Pharmaceuticals Current practices Based on information collected to date, long term health care facilities primarily dispose of spent pharmaceuticals via sewering Hospitals have more alternatives (e.g. returns program) Existing requirements Many existing disposal practices are driven by Federal requirements. Control Technologies Best management practices and alternatives to flushing

29. Schedule CY2007: Complete data collection for identifying current industry practices, existing guidance/requirements, and possible control practices and technologies CY2008: Estimate pollutant loadings, identify best practices and technologies for controlling pollutant discharges and associated costs, and final report

30. EPA Contacts: Health Services: Meghan Hessenauer (202) 566-1040, hessenauer.meghan@epa.gov

32. National Pilot Study of PPCPs in Fish Tissue Sampling for 37 PPCPs in fish tissue from effluent-dominated streams at five locations in various parts of the U.S. Analysis expected to be completed by December 2007

34. National Targeted Biosolids Survey Sampling for presence and concentration of metals, priority pollutants, PPCPs and flame retardants Draft report expected December 2007

36. Development, Validation & Use of EPA Methods Develop Publish, Post and Peer Review Multi-lab Study � several matrices Revise, WebPost and Peer Review Propose and Take Comment Promulgate � Available for Compliance

37. Method Overview Method currently under peer review Technology-High Precision Liquid Chromatography/Tandem Mass Spectrometry (HPLC/MS-MS) positive and negative ESI. Chemistry-Acidic and basic extraction using using a Hydrophilic-Lipophilic-Balance (HLB) cartridge. Optional sonication step for high solids content matrices. Number and types of analytes-75 analytes, combination of antibiotics, OTC and prescription drugs. PPCPs by LC/MS/MS

41. Steroids & Hormones � GC/HRMS Method Overview Method currently under peer review Technology-Gas Chromatography/High Resolution Mass Spectrometry (GC/HRMS). Chemistry Used-Separatory funnel or CLLE extraction with dichloromethane. ASE or Soxhlet extraction for high solids content. Number and types of analytes-27 steroids and hormones found in prescription drugs and CAFOs.

43. Pesticides & Metabolites � GC/HRMS Method Overview Method currently under peer review Technology-Gas Chromatography/High Resolution Mass Spectrometry (HRGC/HRMS). Chemistry-separatory extraction at neutral pH or continuous LE, Soxhlet extraction for high solids content. Number and types of analytes-60 Organochlorine Pesticides, Organophosphate Pesticides, Triazine Pesticides and Pyrethroid Pesticides or pesticide metabolites.

45. Development and Validation of EPA 1614 Method 1614: GC/Hi Res MS for PBDEs - brominated flame retardants � published August 2003. Not yet promulgated. Developed at Axys Analytical 8 PBDEs of primary concern � measured by isotope dilution 36 other PBDE congeners � measured by internal standard with recovery correction Multiple laboratory validation of Method 1614 completed in 2005 Showed that a temperature-programmed injector and short (15-m) column would be required to prevent decomposition of BDE 209 in the injector

46. Analytical Methods Development and Validation: Brian Englert, 202.566.0754, englert.brian@epa.gov, (analytical methods)

48. D7065-06 ASTM Method for NP and APEs Nonylphenol (NP) and alkylphenol ethoxylates (APEs) are surfactants Developed by EPA Region 5 laboratory in collaboration with ASTM International Status Holding time study by EPA Region 5 showed sample holding time can be 28 days when samples are preserved with acid Interlab validation study started June 2006 ASTM published D7065-06 in 2007 Vol. 11.02 Available for monitoring

49. LC/MS/MS Standard for APEs and NPs Nonylphenol, Nonylphenol Monoethoxylate, Nonylphenol Diethoxylate and Octylphenol in Environmental Waters Robust LC/MS/MS Method with SPE Extraction Save Money Save Solvents Environmentally Greener Solid Phase Extraction Meet Saltwater Criteria MDL Study on Reagent Water (100 ppt) Monitor Levels Relative to Endocrine Disruptor Effects Surrogates ESI Negative - 2-Bromo-4(tert-octyl)phenol (Br-OP) ESI Positive - n-NP2EO

50. APEs and NPs: Lawrence B. Zintek, 312-886-2925, Zintek.Lawrence@epamail.epa.gov