Chemicals of Emerging Concern in CWA Programs.

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Chemicals of Emerging Concern in CWA Programs.

• Brian Englert, PhD.
• Engineering Analytical Support Branch
• Office of Science and Technology (OST)
• October 17-19,2007

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Disclaimer

• This presentation was developed by the author,
  and has not been subjected to the Agencys 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.

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Outline

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

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Introduction
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CWA Methods Information

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

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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

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Contaminants of Emerging Concern
PPCPs
PFOA
Prions
Endocrine Disrupting Compounds
Pesticides
Nanomaterials
PBDEs
Not an exhaustive list.
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CECs - Current Federal Activities
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PPCPs
EPAs PPCP web site http//www.epa.gov/ppcp/
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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

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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

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Other Federal Efforts Related to CECs

• USGS work
• Flush and do not flush Policy- EPA/ONDCP/DHHS
  http//www.whitehousedrugpolicy.gov/drugfact/facts
  ht/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

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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/

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Office of Water Activities
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Office of Water

• POTW Study EAD
• Health Services Industry Detailed Study - EAD
• Fish Tissue Study SHPD
• Biosolids Survey - HECD

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Office of Water
POTW Study
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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

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POTW Study

• ?Scope
• We plan to characterize the occurrence of
  various types of CECs
• flame retardants
• hormones
• pharmaceuticals
• steroids
• nonylphenols
• pesticides

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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.

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POTW Study

• POTW Study
• Brian DAmico, 202-566-1069, damico.brian_at_epa.gov
  (POTW operations)
• Brian Englert, 202.566.0754, englert.brian_at_epa.gov
  , (analytical methods)

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Office of Water
Health Services Industry Detailed Study
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Health Services Industry Detailed Study

• 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

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Health Services Industry Detailed Study

• 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

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Health Services Industry Detailed Study

• 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?

• ?Existing requirements
• Are there federal, state, or local requirements
  or guidance for disposal of spent pharmaceuticals
  and/or mercury?
• What are these requirements?
• What records, if any, do facilities keep of what
  is disposed to the sink, drain, or sewer?

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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?

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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?

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Health Services Industry Detailed Study

• 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

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Health Services Industry Detailed Study

• 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

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Health Services Industry Detailed Study

• 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

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Health Services Industry Detailed Study

• EPA Contacts
• Health Services
• Meghan Hessenauer [phone],
  hessenauer.meghan_at_epa.gov

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Office of Water
Fish Tissue Study
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SHPD

• 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

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Office of Water
Biosolids Survey
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HECD

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

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Office of Water
Analytical Method Development and Validation
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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

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PPCPs by LC/MS/MS

• 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.

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List subject to change.
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List subject to change.
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List subject to change.
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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.

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List subject to change.
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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.

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List subject to change.
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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

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Office of Water

• Analytical Methods Development and Validation
• Brian Englert, 202.566.0754, englert.brian_at_epa.gov
  , (analytical methods)

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Office of Water
Work with Partners!!!! Region 5.
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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

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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

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Region 5

• APEs and NPs
• Lawrence B. Zintek, 312-886-2925,
  Zintek.Lawrence_at_epamail.epa.gov

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Thank you!