U.S. and Canadian Lakewide Contaminant Monitoring

1. U.S. and Canadian Lakewide Contaminant Monitoring Beth Murphy U.S. EPA, Great Lakes National Program Office Clarkson University Research Consortium Environment Canada U.S. EPA Great Lakes National Program Office Ontario Ministry of the Environment U.S. Geological Survey NOAA

2. Overview of Presentation • Connection between CSMI and Monitoring Programs • Status of contaminants monitoring in the Great Lakes • Legacy contaminants • Emerging contaminants • Overview of U.S.EPA and Environment Canada Great Lakes monitoring and surveillance programs • Future Directions in Emerging Contaminant Research

3. Chemical Monitoring Programs & CSMI • In general, chemical monitoring is not specific to any one lake. Programs collect and analyze data on a basin wide level. • Programs are typically unable to incorporate annual changes into sampling regime. • Results are compared and summarized through peer reviewed journal articles, governmental reporting (indicators), presentations, and collaborations between programs. • Programs incorporating Legacy and “Emerging” chemicals into routine analysis. • Funding dependant.

4. Chemical Prioritization • CSMI • Great Lakes Water Quality Agreement • Annex 3 Chemicals of Mutual Concern • “New” list of chemicals is in development • In previous agreement – included legacy contaminants • PCBs, organochlorine pesticides, mercury • Chemical Management Plan • Monitoring and Surveillance Working Group • Priorities integrated with Risk Assessment and Management • Includes new, emerged and emerging contaminants • PBDEs and other flame retardants, PFCs, Siloxanes, other metals • Historical Program trends • Surveillance • Collaboration potential

5. Legacy Contaminants in the Great Lakes • Routine monitoring of: organochlorine pesticides, polycyclic aromatic hydrocarbons, PCBs, etc. • Concentrations of legacy contaminants have generally declined in Great Lakes media • PCBs & mercury are still driving fish consumption advisories

6. Current Use Chemicals • Routine monitoring of: Flame Retardants, Hg, PCDD/Fs, Musks, PFOS/A, etc. • Many of these chemicals concentrations are at steady state or are declining . • Method development and benchmark criteria continue to make the analysis and interpretation of some of these chemicals difficult.

7. Emerging Contaminants in the Great Lakes • Polychlorinated napthalenes • Fluorotelomer alcohols • Non-PBDE flame retardants • Perfluorinated compounds • Br / Cl compounds • Non-halogenated compounds • Organometallic compounds • Halogenated Compounds • Siloxanes • Pharmaceuticals & Personal care products (PPCPs) • Degradation Products Evolving list of chemicals for surveillance and monitoring:

8. Great Lakes Monitoring & Surveillance Programs • Air • Fish • Sediment + + • Biota • Water • Tributary

9. Whole Fish Monitoring National Fish Contaminants Monitoring and Surveillance Program – Environment Canada • Daryl McGoldrick • http://www.ec.gc.ca/scitech/default.asp?lang=en&n=828EB4D2-1 Great Lakes Fish Monitoring and Surveillance Program – US EPA • Elizabeth Murphy • Clarkson University - tholsen@clarkson.edu • http://www.epa.gov/grtlakes/monitoring/fish/index.html

10. Mercury in Lake Superior Lake Trout • Declines observed until the early ~1990 • Appears as though concentrations have been increasing. • Consistent with observations in other studies in the Great Lakes Region - see Ecotoxicology 20(7) Source: SOLEC 2011 Draft Technical report

11. GLFMSP New Chemicals in Lake Trout P. H. Howard and D. C. G. Muir, Environmental Science and Technology 2010, 44, 2277 Confirmed - Catalyst – non-toxic? - Observed in Blubber by E. Hoh, ES&T 2012, 46, 8001. Tetraphenyl tin - Biocide - Identified on the Howard/Muir 610 list as a potential PBT chemical Triphenyl tin hydroxide Easily Oxidized Triphenyl phosphate Confirmed Triphenylphosphite M/H List top 50

12. Joint CSMI GLFMSP Lake of the Year (LOY) Program • Detailed Bioaccumulation Study • Water (dissolved and particulate) • Phytoplankton • Zooplankton • Mussels • Benthic macro invertebrates • Forage fish • Lake trout Hg Bioaccumulation Lake Superior Top to bottom lake snapshot

13. Sport Fish Monitoring Fillet Monitoring Programs • U.S. States Minnesota http://www.health.state.mn.us/divs/eh/fish/ Wisconsin http://dnr.wi.gov/topic/fishing/consumption/ Michigan http://www.michigan.gov/eatsafefish • OMOE www.ontario.ca/fishguide • Tribes / First Nations GLIFWC http://www.glifwc.org/ Mn Chippewa http://www.mnchippewatribe.org/wqd.htm

14. Chemicals Driving Fish Consumption Advice

15. Air Monitoring Integrated Atmospheric Deposition Network Environment Canada • Hayley Hung Hayley.Hung@ec.gc.ca • http://www.ec.gc.ca/natchem//default.asp?lang=En&n=1590DD07-1 U.S. EPA • Todd Nettesheim Nettesheim.Todd@epa.gov • Indiana University hitesr@indiana.edu • http://www.epa.gov/grtlakes/monitoring/air2/index.html Great Lakes Atmospheric Research • LiisaJantunen Liisa.Jantunen@ec.gc.ca • MahibaShoeibMahiba.Shoeib@ec.gc.ca Mercury Deposition Network Illinois State Water Survey • David Gay, Program Coordinator dgay@illinois.edu • http://mercnet.briloon.org/projects/NADP_-_Mercury_Deposition_Network_National_Atmospheric_Deposition_Program/141/

16. Levels of tetrabromo esters are rapidly increasing in the air Source: Ma et al., ES&T 2012, 46(1), 204-208

17. Atmospheric Research Organo-Phosphate Esters in Great Lakes Air • Used mostly as flame retardants and plasticizers but have many other uses • Canadian Chemical Management Plan Priority compounds • High volume production compounds • Levels are very high for indoor air (100s ng/m3) and dust (1000s ng/g). • TCEP is being phased out in North America and has been banned in EU TCPP: tris(2-chloro propyl) phosphate TPP: tri-phenyl phosphate TCEP: tris(2-chloro ethyl) phosphate • OPEs were analysed in air samples from Lake Superior 2011 and in archived air samples from 2005. • Levels of S-OPEs averaged ~500pg/m3 which is 20-30 times higher than S-PBDEs. • Levels were about the same in 2005 and 2011

18. Sediment Monitoring Great Lakes Sediment Surviellance Program (GLSSP) • U.S. EPA (Cooperative Agreement) • Todd Nettesheim: Nettesheim.Todd@epa.gov • University of Illinois at Chicago An Li anli@uic.edu • Environment Canada • Chris Marvin- Chris.Marvin@ec.gc.ca • Debbie Burniston, WQMSD -  Debbie.Burniston@ec.gc.ca

19. Preliminary GLSSP summary for Superior • Spatial distribution based on surface sediment samples: • Sites S022 (near Duluth) and S106 (east of Keweenaw Peninsula) stand out to have much higher concentrations than other sites for target legacy pollutants (PCDD/Fs, PCBs, PCNs, DDE). • PBDEs are also higher at S022. • PFCs may exhibit a different trend – lower concentrations at S022 • Other emerging pollutants have low concentrations in general. • Time trend based on core samples • Chronological resolution is limited by low sedimentation rates • Research questions • Higher-than-expected concentrations of heavy (8-10 chlorines) PCBs were found and are yet to be confirmed. • Site S008 may deserve further investigation • Elevated levels of soot carbon were found • Previous work suggested PCB contamination at site

20. PFCA in Tributaries and Open Water

21. Water Monitoring Great Lakes Surveillance Program • Alice Dove www.ec.gc.ca/scitech • Indiana University • Ron Hites hitesr@indiana.edu • Marta Venier mvenier@indiana.edu Passive Sampling • Rainer Lohmann - University of Rhode Island • rlohmann@mail.uri.edu • http://www.gso.uri.edu/users/lohmann • Derek Muir - Environment Canada • Derek.Muir@ec.gc.ca Mercury Cycling and Bioaccumulation in the Great Lakes • David P. Krabbenhoft – USGS • dkrabbe@usgs.gov • http://cida.usgs.gov/glri/projects/toxic_substances/mercury_cycling.html

22. Total mercury in Great Lakes Waters

23. Dissolved Lindane Trend

24. PBDE Passive Sampling Results (June-Oct ’11) pg/L pg/m3 Air 7.6 5.6 0.056 0.0069 Water Volatilization Deposition Open Water Shipping Populated Rural Ruge et al.

25. OCP Passive Sampling Results (June-Oct ’11) Water Air α-HCH α-HCH α-Endosulfan α-Endosulfan Ruge et al.

26. Sedimentation Sed Reflux Wet Dep. OM rain MeHg Annual Fluxes and Standing Pools – Lake Michigan 2 kg Runoff Epilimnion 1-2% 12 kg 1-15% Thermocline/Deep chlorophyll layer 8 kg 5-8% methylation methylation Hypolimnion 3 kg 2-4% 4-8% Bottom waters 0.4 kg Sediments (top 20 cm) 11,000 kg 0.5%

27. Hg Dep. Linking Mercury Sources and Invasive Species in the Near-Shore Zone River mouth Estuary Open Lake Trib’s: Hg, nut’s, Seiche Waves MeHg release Lake Trout Point-sources, AOCs Round goby Oxygen supression; HABs, pathogen, & methylmercury production methylation Quagga/Cladophora assemblages A collaboration between USGS and the UW-Madison

28. Biota Monitoring Chemicals Management Plan • Pam MartinPamela.Martin@ec.gc.ca • Rob Letcher Robert.Letcher@ec.gc.ca Great Lakes Herring Gull Monitoring Program (GLHGMP) • Shane de SollaShane.deSolla@ec.gc.ca NOAA Mussel Watch • Kimani Kimbrough Kimani.Kimbrough@noaa.gov • Ed Johnson Ed. Johnson @noaa.gov • http://ccma.nos.noaa.gov/about/coast/nsandt/download.aspx

29. Spatiotemporal (1990-2010) Trends of OPFRs in Herring Gull Egg Pools CMP 3 Photo: R. Letcher

30. Twenty Years of Temporal Changes in PFOS and PFCAs in Herring Gull Eggs CMP PFOS Agawa Rocks ∑PFCA x ∑PFCA Chantry Is Gull Is x Toronto Hbr PFOS x ∑PFCA x ∑PFCA x Channel-Shelter Is x Niagara River x L. Superior Detroit River PFOS ∑PFCA ∑PFCA L. Huron L. Michigan L. Ontario ∑PFCA L. Erie PFOS ∑PFCA 80 400 Fighting Is Agawa Rocks 120 300 60 300 PFOS 200 80 200 40 40 100 100 20 0 0 0 0 100 900 400 Niagara R PFOS 60 80 300 600 60 40 PFOS (ng/g ww) ∑PFCA (ng/g ww) 200 40 300 20 20 Gull Is 100 0 0 0 0 ∑PFCA (ng/g ww) PFOS (ng/g ww) Toronto Hbr 1200 120 PFOS 400 80 800 80 300 60 200 40 400 40 Channel-Shelter Is 100 20 0 0 0 0 1990 1995 2000 2005 2010 60 300 Chantry Is PFOS 200 40 100 20 0 0 1990 1995 2000 2005 2010

31. GLHGMP Temporal of PCBs and 2,3,7,8 TCDD in Herring Gull Egg Pools

32. NOAA Mussel Watch Program lMussel Watch sites lMusselWatch AOC sites AOC sites ( 2009/2010)

33. Tributary Monitoring USGS • GLRI Toxic Contaminant Monitoring in Tributaries • Steve Corsisrcorsi@usgs.gov • http://cida.usgs.gov/glri/projects/toxic_substances/contaminant_loadings.html

34. Multi-tiered approach • 59 total tributaries • Passive samplers at all sites • SPMD, POCIS • 30 day exposures • PAHs • Organic Waste Contaminants • Organochlorine Pesticides • Total PCBs • PBDEs • Estrogenicity (yeast estrogen screen) • Water samples at 54 sites • Organic Waste Contaminants, DOC, optical properties • Hydrologic and seasonal variability for 20 sites over two years • 1-6 samples for 34 sites • Sediment samples at 15 sites • AOC focus • Sediment deposition: long-term exposure • PCBs and Organochlorine pesticides

35. PAHs in Water Samples for Intensive Monitoring Sites Concentration (µg/L)

36. OWC Results

37. Coordination • CSMI included in RFA requests – US • Binational Monitoring meetings • Joint publications / reporting • Peer Review • Regular communication

38. Future Direction • Surveillance • Benchmark identification • Degradation products • Establishing links • Environment and human • Food web changes and contaminant levels

39. Contributors • MahibaShoeib – EC • Alice Dove – EC • Vi Richardson – EC • Rainer Lohmann – URI • Derek Muir – EC • Hayley Hung – EC • Rob Letcher - EC • Pam Martain - EC • Shane DeSolla – EC • David Krabbenhoft – USGS • Steve Corsi – USGS • David Gay – ISWS Tom Holsen – Clarkson U. Bernard Crimmins – Clarkson U. Philip Hopke – Clarkson U. James Pagano – SUNY Oswego Michael Milligan – SUNY Fredonia Sean Backus - EC Daryl McGoldrick – EC Satyendra Bhavsar – OMOE Todd Nettesheim – EPA LiisaJantunen – EC Chris Marvin – EC Kimani Kimbrough – NOAA Ed Johnson - NOAA

40. Questions?Beth MurphyUS EPA Great Lakes National Program OfficeMurphy.Elizabeth@epa.gov