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 MANY PARTNERS!!!!

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 This presentation is a summation of ongoing monitoring on both sides of the border in as many media as I could collect information on. Forgive me if I have missed something. I want to walk you through the general connection between chemicals monitoring and the CSMI process, a general status of chemical levels, some individual information on existing monitoring programs and the future direction of emerging contaminant research / monitoring in the Great Lakes. I had to consider revising this presentation once it exceeded 70 slides. I will work with Liz on fine tuning “The Beast” for a future webinar with the Chemical Workgroup.

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. Let’s talk about how chemicals fits into the CSMI process. In general, chemical monitoring is not specific to any specific lake and is typically conducted on a basin wide level. Individual Monitoring programs are unable to incorporate annual changes into sampling regimes due to hurdles with QA and cost but mostly because several years of data is ideal for assessment of chemicals. The chemical community is a relatively small one and that we are all in communication with each and try to summarize info, when possible and appropriate, over common chemicals and media. Monitoring programs are shifting toward surveillance of emerging chemicals while maintaining legacy chemical analysis and, as always, program details are subject to available funding. Key take home message – An endorsement for the continuation of long term monitoring programs, with an emphasis on emerging chemicals, from the Lake Superior group, and other groups, will be beneficial as it lends credibility to the process and allows programs to incorporate CSMI into the statements of work of grants/ cooperative agreements during competition.

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 Many of the programs have similar target analyte lists. The important take home message is that overlapping analyte lists lead to collaboration between programs, when possible and appropriate. Additionally, there are several guiding authorities that help in prioritization of chemicals for monitoring and surveillance, they are listed here.

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 Lots of research & monitoring has been done on legacy contaminants in Great Lakes media. Concentrations are generally on the decline. Not a lot of new news, but I want to emphasize that these legacy chemicals continue to be present in high enough concentrations that they are the major driver behind fish consumption advice.

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. Here is an example of the types of current use chemicals that are typically included in monitoring programs.

Emerging Contaminants in the Great Lakes Evolving list of chemicals for surveillance and monitoring: Polychlorinated napthalenes Halogenated Compounds Fluorotelomer alcohols Siloxanes Non-PBDE flame retardants Pharmaceuticals & Personal care products (PPCPs) Perfluorinated compounds Br / Cl compounds Non-halogenated compounds Degradation Products Organometallic compounds Many programs are beginning to incorporate emerging contaminant monitoring / surveillance into their base work. New contaminants proposed for surveillance and method development include: siloxanes, personal care products such as musk fragrances, polychlorinated napthalenes, pharmaceuticals, perfluorinated compounds, Fluorotelomer Alcohols, non-PBDE flame retardants Many programs are needing to upgrade analytical equipment for enhanced surveillance capabilities. Additionally identification of standards and the development of benchmark criteria continue to make this work challenging.

Great Lakes Monitoring & Surveillance Programs Air Fish Sediment + + Biota Water Tributary You can see that there is good spatial coverage of monitoring programs in the Basin and I want to emphasize the we think we are doing a pretty good job for right now. Not all chemical monitoring is represented on this slide, but this a good indication of the amount of monitoring being conducted. I want to take a min. here to identify that the media by media assessment I will be providing next has program and contact information listed whenever possible. This is provided as a way to highlight the massive amount of work that is being conducted and to provide credit where it is deserved. However, I do think that it is important to emphasize that when identifying your priorities for Lake Superior, it is most appropriate to work with the Government contact and not the principal investigator of a cooperative agreement. We will be best able to try to meet your needs and provide you with the most up to date information. I have listed a program website whenever possible and I encourage you to look at them for additional detail regarding each program and to identify the most recent publications. Also, as I mentioned before, I plan to go in to much more detail regarding chemical monitoring in the Great Lakes during a future webinar.

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 Whole fish… Differences in the program to highlight individuals vs. composites age vs. length Annual collection vs. alternating collection Both programs maintain a historical archive dating back into the 70s.

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) Declines observed until the early ~1990 Appears as though concentrations have been increasing. A 2011 Publication in Ecotoxicology by Zananski et al., using the US data set, indicate that Lake Superior fish have the highest total Hg concentrations of the 5 great lakes and that ther eis a current increasing trend at the Apostle Islands site. Source: SOLEC 2011 Draft Technical report

GLFMSP New Chemicals in Lake Trout P. H. Howard and D. C. G. Muir, Environmental Science and Technology 2010, 44, 2277 Tetraphenyl tin Triphenyl tin hydroxide Confirmed - Catalyst – non-toxic? - Observed in Blubber by E. Hoh, ES&T 2012, 46, 8001. - Biocide - Identified on the Howard/Muir 610 list as a potential PBT chemical Triphenyl phosphate Easily Oxidized Triphenyl phosphite M/H List top 50 This is a slide from the Clarkson Consortium that identifies the confirmation of new chemicals in GLFMSP fish using the Muir / Howard list as a jumping off point. Tetraphenyl tins used a starting materials or catalysts – and is considered non-toxic. However, this chemical has been confirmed in Great Lakes lake trout and Atlantic mammals suggesting a significant environmental prevalence. Triphenyl tins used as biocides and is considered toxic. The triphenyl tin hydroxide has is identified by Howard and Muir as a potential PBT. This particular compound was not detected in trout samples. However, method limitations may have excluded possible detection of this compound in the trout matrix. Triphenyl Phosphite is a candidate listed on the Howard/Muir 2010 top 50 list. The Clarkson Consortium has obtained neat standards for method development purposes and observed transformation to the triphenyl phosphate form. This form has been confirmed in fish (GLFMSP) and air (IADN).

Lake of the Year (LOY) Program 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 Top to bottom lake snapshot Hg Bioaccumulation Lake Superior I also want to emphasize that the whole fish monitoring programs are expanding their assessments of chemicals into other levels of the food chain. The Environment Canada program has been analyzing forage fish for years and the EPA program has recently incorporated bioaccumulation and trophic structure assessments into the program coordinated with the CSMI schedule. So far we have completed Superior, Huron, and Ontario. This slide displays the bioaccumulation of mercury in the 2011 Lake Superior food web. As you know trophic position increases with increasing delta N15 (trophic position marker). The current plot captures mercury concentration vs. delta N 15 enrichment from seston, zooplankton, forage fish up to lean and siscowet lake trout. Future work will supplement the isotope data with fatty acid profiles to elucidate mid-term dietary habits.

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 There are many fillet monitoring programs in the Great Lakes for assessment of chemicals as they relate to human health. In the U.S., the States / Tribes issue advice and OMOE issues advice for the Province of Ontario. Minnesota – Pat McCann Wisconsin – Candy Shrank and Henry Anderson Michigan – Korey Groetch and Michelle Bruneau OMOE – Satyendra Bhavsar Assessment of Human Health Traditionally limited to legacy chemicals States collect and analyze Great Lakes samples less frequently Information drives fish consumption advice Emerging chemical analysis supplemented by federal Programs Species selected based upon consumption and popularity for sport fishing

Chemicals Driving Fish Consumption Advice Lake State/Province PCB Dioxin Mercury Chlordane Mirex Toxaphene Superior Michigan1 x   Wisconsin Minnesota Ontario Huron Erie New York Ohio Pennsylvania Michigan Illinois  x Indiana Contaminants driving fish consumption advisories. Not all states/provinces issue advisories for all of the listed contaminants. Notice that PCBs are checked for every lake / state/ province Source: Great Lakes states and Ontario Ministry of the Environment. State of the Great Lakes 2011 Draft Technical report.

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 Liisa Jantunen Liisa.Jantunen@ec.gc.ca Mahiba Shoeib Mahiba.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/ There is a lot going on for Air Monitoring in the Great Lakes. This is the contact information for IADN, the MDN, and general research. IADN There are 5 master stations – 1 per lake – and 8 satellite stations currently in operation (2 in urban areas in the U.S.) Annex 15 of the 1987 GLWQA and the 1990 Clean Air Act Amendments called for the monitoring of airborne toxic substances and the establishment of IADN. The data are used to … Determine atmospheric loadings to the Great Lakes Analyze spatial and temporal trends in concentrations Track progress of restoration / remediation / emission reductions Identify sources – IADN key message for Lake Superior – PBEB (pentabromoethylbenzene – additive flame retardant used in thermoset polyester resins for application such as circuit boards, textiles, adhesives, and wire and cable coatings.  Unexpectedly, the concentration of PBEB was highest at the remote site of Eagle Harbor in northern Michigan. This is unusual because many compounds exhibit a strong correlation to population (highest in Chicago and Cleveland).  This suggests a local point source – possible scrap recycling or related to mining.  But, these are just hypotheses at this point. MDN - The National Atmospheric Deposition Network's Mercury Deposition Network. Stations in all 50 United States, initiated in 1995. National database of weekly concentrations of total mercury in precipitation and the seasonal and annual flux of total mercury in wet deposition.

Levels of tetrabromo esters are rapidly increasing in the air TBB and TBPH (Tetrabrominated Benzoate and Phthalate) Components of Firemaster 550 - the replacement for the penta-BDE mixtures. (off market in 2005) High production volume chemicals (greater than 1 million pounds per year) Found to double in GL air about every year Concentrations in environment are now rapidly approaching the levels of total PBDEs But actually we are starting to find their replacement – organophosphate FRs at high levels in the environment, with an indication that they are now industry’s preferred FR. It is important to track FRs collectively – from an emissions / management perspective and perhaps even a toxicity perspective. LAKE SUPERIOR example… NEED to add a talking point on the BFR found in very high concentrations at Eagle Harbor! Source: Ma et al., ES&T 2012, 46(1), 204-208

Organo-Phosphate Esters in Great Lakes Air 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 TCEP: tris(2-chloro ethyl) phosphate TCPP: tris(2-chloro propyl) phosphate TPP: tri-phenyl phosphate Triphenyl phosphate also found in fish, from a few previous slides. 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

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 GLSSP Great Lakes Restoration Initiative (GLRI) funded project to establish and implement a sediment surveillance program in the US Directed at monitoring legacy contaminants and screening for emerging chemicals Method development for screening of PPCPs, perfluorinated compounds, non-PBDE flame retardants Sampling 1 lake/year in accordance with CSMI The mission of GLSSP is to investigate the presence of persistent, bioaccumulative and toxic (PBT) chemicals, and to reveal the spatial distribution and the temporal trend of PBT pollution in the Great Lakes through retrieving the sedimentary records. The PBT contaminants of emerging concerns (CECs) are the particular focus of GLSSP. Complementary to existing surveillance programs, GLSSP will provide information to support decision making with regard to pollution control and resource management for the Great Lakes. Environment Canada Tributary and sediment monitoring for contaminates. Set stations

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 GLSSP key message addressing a Lake Superior information need – A core was collected in Duluth harbor and analyzed for hormones, BPA, NP, and OP.  BPA was below or at detection limits throughout the core (less than 1 ug/kg).  NP was also below detection limit throughout the core (less than 6 ug/kg).  Thanks to An Li and her team for collecting the sample.  And thanks to Sean Backus and EC for having the sample analyzed.  CSMI in action.

PFCA in Tributaries and Open Water Slides courtesy of Chris Marvin at Environment Canada

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 Environment Canada operates the base surveillance program for water in the Great Lakes. Recently, they have partnered with Indiana University for lower level analysis using resin column from POP Cart for lower level detection. The Great Lakes Surveillance Program is Environment Canada’s long term water quality monitoring program on the Great Lakes. They typically monitor each lake every second year, with one or two monitoring cruises conducted in that year. They have no routine monitoring on Lake Michigan but have collaborated with USEPA on organic contaminants monitoring as part of CSMI. The routine parameter list includes major ions, nutrients, some physical and biological indicators (e.g., chlorophyll a), and trace metals (including mercury). Organic contaminants are routinely monitored during the spring cruise of the CSMI year. They have also conducted some monitoring for compounds such as PFCs, BPA, in-use pesticides, pharmaceuticals and other compounds of emerging concern in recent years.

Total mercury in Great Lakes Waters This map provides an example of a typical result for contaminants in the Great Lakes, indicating higher values in the lower Great Lakes compared to the upper lakes.

Dissolved Lindane Trend Certain compounds (e.g. those with few current sources, that are subject to atmospheric transport and that do not volatilize readily from the water column back to the atmosphere) such as lindane are found at highest concentrations in Lake Superior. Note that lindane concentrations are low and trends are declining.

PBDE Passive Sampling Results (June-Oct ’11) Air Water Ruge et al. pg/m3 7.6 0.0069 pg/L 5.6 0.056 Air Water Volatilization Sum PBDE concentrations are low - < 10 pg/m3 in the atmosphere, < 10 pg/L in the water. Atmospheric PBDEs driven by population density, with very low concentrations over the open Lake. In contrast, much smaller urban-remote gradient observed for dissolved concentrations of PBDEs. So much so that there might be net volatilization of PBDEs across open Lake Superior, while there is net deposition near the coasts. Deposition Shipping Populated Rural Open Water Ruge et al.

OCP Passive Sampling Results (June-Oct ’11) Air Water α-HCH α-HCH α-Endosulfan α-Endosulfan Air results in pg/m3 dominated by HCB and alpha-HCH. Range from 51-160 pg/m3 HCB; bd-29 pg/m3 alpha-HCH. Water results in pg/L dominated by alpha-HCH and endosulfan sulfate. Range from 5.5-37 pg/L HCB; 12-440 pg/L alpha-HCH. HCB graph of flux rate in ng/m2/day representing dominant legacy exchange. Endosulfan I flux rate graph in ng/m2/day representing recently used and currently emitted OCP air-water exchange. Ruge et al.

Thermocline/Deep chlorophyll layer OM rain methylation Sedimentation Bottom waters Epilimnion Thermocline/Deep chlorophyll layer Sediments (top 20 cm) Runoff MeHg Annual Fluxes and Standing Pools – Lake Michigan Wet Dep. Sed Reflux Hypolimnion 12 kg 1-15% 2 kg 1-2% 8 kg 5-8% 3 kg 2-4% 0.4 kg 4-8% 11,000 kg 0.5% Collection locations for this work are those routinely visited during the Spring and Summer Lake Guardian cruises. Lake Michigan example Initial work by this project revealed that at most open water Great Lake sites there is a distinct accumulation of methylmercury at or just below the thermocline (THM) and deep chlorophyll (DCL) layers. The % methylmercury in these layers is maximal for the water column, which is strongly suggestive that these are sites of methylation (new MeHg production), as opposed to a site of methylmercury accumulation. Reasoning here is that you cannot preferentially accumulate methylmercury over inorganic mercury and thereby create the trends we see. Initial calculations for Lake Michigan suggest that this newly observed MeHg source is similar in magnitude to previous mass balance efforts that suggest tributaries were overwhelmingly the largest MeHg source. These observations are important because initial modeling efforts suggest the mercury source to the site of methylation in the water column is transport of recently deposited Hg from the atmosphere, thus the response time of this site of methylation to changes in mercury loading due to such regulatory actions as MATS or the recent UNEP Minamata Treaty should be very vast (one year).

Linking Mercury Sources and Invasive Species in the Near-Shore Zone Trib’s: Hg, nut’s, Waves Seiche Estuary Open Lake River mouth Quagga/Cladophora assemblages Point-sources, AOCs Hg Dep. Particle scavenging MeHg release Round goby Lake Trout methylation Oxygen supression; HABs, pathogen, & methylmercury production A collaboration between USGS and the UW-Madison This is a new focus of USGS’s work currently. Conceptual diagram of the intersection of mercury sources (air, watershed, and historical point sources) and invasive species (quaqqa, round goby) in the near-shore environment - an important location for mercury cycling and food-web interactions and related to many other GLRI projects and in many cases historical (legacy) mercury use and accumulations. Rapid spread of the quagga throughout the GLs (except Superior) has resulted in a major shift in carbon and nutrient flows (near-shore shunt) and distribution (near-shore eutrophication, off-shore oligotrophication), which has a significant impact on mercury toxicity (methylation) and food web transfer. Proliferation of Cladophora mats has resulted in widespread accumulation of organic matter accumulation and subsequent oxygen suppression in many areas of the Great Lakes that did not exist previous to 2000. We have observed (as others have) that the Cladophora is a foraging ground for the Round Goby so we suspect that transfer of this MeHg source up the food web is already happening. We are looking at mercury cycling, methylation and food web transfer in this zone, and have revealed that it is a new site of MeHg production that appears to be very meaningful on the basin scale – next slide.

Biota Monitoring Chemicals Management Plan Pam Martin Pamela.Martin@ec.gc.ca Rob Letcher Robert.Letcher@ec.gc.ca Great Lakes Herring Gull Monitoring Program (GLHGMP) Shane de Solla Shane.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 Next, I want to move into biota monitoring. I have listed gull eggs and mussel monitoring program contact info here. I will not be discussing the NOAA Mussel Watch program much as there have been few zebra mussels found in the open waters of Lake Superior so far. Gull Egg program started in 1974 by collecting herring gull eggs from 15 colonies in the Great Lakes to monitor contaminants 10-13 individual eggs (in spring) from all 15 GLHGMP sites spatial and temporal trends have been monitored in the herring gull eggs for various environmental pollutants: – recently, emerging POPs and other compounds including various legacy and current-use flame retardants 28

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

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

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

NOAA Mussel Watch Program lMussel Watch sites lMussel Watch AOC sites AOC sites ( 2009/2010) These locations have been sampled for a suite of indicators (mussels, sediment, benthos, sediment toxicity) The RED and BULE CIRCLES are “long-term” Mussel Watch sites – sites sampled before GLRI - many since 1992/93 and most with sufficient mussel data to assess temporal trends in chemical contamination. Sediment data also exists for these sites. Sites designated with STARS were newly established in (2009/2010). Mussel Watch has sites in all 30 AOCs. Have long term Mussel Watch at 5 of the AOCs. Sediment, chemicals in tissue, & bioeffects. No mussels identified in open waters of Lake Superior, YET. 32

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

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

PAHs in Water Samples for Intensive Monitoring Sites Concentration (µg/L) PAH results for 21 sites with 6-42 samples categorized by hydrologic condition. Events include rainfall and snowmelt runoff. Samples represent all seasonal periods.

OWC Results Organic Waste Contaminants for 21 sites with 6-42 samples for 15 classes of compounds. Mean values indicated by color and frequency of detection indicated by diameter of bubble.

Coordination CSMI included in RFA requests – US Binational Monitoring meetings Joint publications / reporting Peer Review Regular communication In conclusion, I want to emphasize the continued coordination and collaboration that these chemical monitoring programs employee. These connections are essential to the life of these programs, especially in the tight financial climate that they are operating in.

Future Direction Surveillance Benchmark identification Degradation products Establishing links Environment and human Food web changes and contaminant levels I also want to highlight the future direction of many of these programs…

Contributors Mahiba Shoeib – EC Tom Holsen – Clarkson U. 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 Liisa Jantunen – EC Chris Marvin – EC Kimani Kimbrough – NOAA Ed Johnson - NOAA A special thanks to the many many contributors who provided the material for this presentation.

Questions? Beth Murphy US EPA Great Lakes National Program Office Murphy.Elizabeth@epa.gov