GREAT LAKES FISH MONITORING AND SURVEILLANCE PROGRAM TECHNICAL REPORT Status and Trends of Contaminants in Whole Fish through 2016 - _ ».<*¦ \, ¦ United States Environmental Protection Agency February 2021 EPA 905-R-20-002 Great Lakes RESTORATION, Prepared By: United States Environmental Protection Agency Great Lakes National Program Office ------- GREAT LAKES FISH MONITORING AND SURVEILLANCE PROGRAM TECHNICAL REPORT ACKNOWLEDGMENTS The U.S. Environmental Protection Agency (EPA) Great Lakes National Program Office (GLNPO) supported this work through agreements and contracts with several state, provincial, tribal, academic, private laboratory, and contractor collaborators including: 1) award agreement GL00E01505 "The Great Lakes Fish Monitoring and Surveillance Program: Expanding the Boundaries" with Clarkson University, State University of New York (SUNY) Oswego, and SUNY Fredonia; 2) EPA Contract No. EP-C-15- 012, Water Security Division Mission Support, with CSRA LLC, a General Dynamics Information Technology company (herein after referred to CSRA) under the direction of Louis Blume, Contracting Officer's Representative; 3) a CSRA purchase order (under EPA Contract No. EP-C-15-012) with Aquatec Biological Sciences, Inc., (Aquatec); and 4) agreements with several field sampling teams which are identified annually. Field sampling teams for this monitoring program include Michigan Department of Natural Resources Alpena Fisheries Research Station and Charlevoix Fisheries Research Station, U.S. Geological Survey (USGS) Lake Superior and Lake Ontario Biological Stations, U.S. Fish & Wildlife Service (USFWS) Green Bay Fish and Wildlife Conservation Office, Great Lakes Indian Fish and Wildlife Commission, Wisconsin Department of Natural Resources, and Ohio Department of Natural Resources Sandusky Fisheries Research Unit. GLNPO would like to acknowledge the Michigan DNR Alpena Fisheries Research Station and Aquatec for their participation in an inter-laboratory comparison study of fish age enumeration structures that concluded in 2016 and USFWS Green Bay Fish and Wildlife Conservation Office for reading coded wire tags removed from Lake Trout collected for the GLFMSP. GLNPO gratefully acknowledges the support of the following team members in the preparation of this Technical Report: Affiliation Team Members EPA GLNPO Brian Lenell, Elizabeth Murphy, Louis Blume Clarkson University Thomas Holsen, Bernard Crimmins CSRA Marian Smith, Kenneth Miller Cover Photo Credit: Greg Kennedy, USGS Great Lakes Science Center. Citation: U.S. Environmental Protection Agency, 2021. Great Lakes Fish Monitoring and Surveillance Program Technical Report: Status and Trends of Contaminants in Whole Fish through 2016. EPA 905-R- 20-002. CONTACT INFORMATION For additional information, questions, or comments about this document, please contact Brian Lenell (EPA GLNPO) using the contact information provided below. Brian Lenell U.S. EPA 77 West Jackson Boulevard, G-9J Chicago, IL 60604-3507 Tel: 312-353-4891 lenell .brian@epa.gov FEBRUARY 2021 PAGE | ii ------- GREAT LAKES FISH MONITORING AND SURVEILLANCE PROGRAM TECHNICAL REPORT Acknowledgments ii List of Figures iv List of Tables iv 1 Executive Summary 1 2 Introduction 2 3 Description of Methods 3 3.1 Sample Collection 3 3.1.1 Base Monitoring Program 3 3.1.2 Cooperative Science and Monitoring Initiative (CSMI)/Special Studies 3 3.2 Biological Data Collection and Homogenization 5 3.3 Analysis 5 4 Quality Assurance and Quality Control 6 5 Results 7 5.1 Sample Collection 7 5.1.1 Base Monitoring Program 7 5.1.2 Cooperative Science and Monitoring Initiative (CSMI)/Special Studies 7 5.2 Biological Data Collection and Homogenization 8 5.3 Analysis 10 5.3.1 PCBs 10 5.3.2 PBDEs 13 5.3.3 Mercury 15 5.3.4 HBCDD 17 5.3.5 PFAS 17 5.3.6 Contaminants of Emerging Concern (CECs) 19 6 Future Reporting 20 7 Summary 20 References 20 Appendix A - List of Recent GLFMSP Publications A-l FEBRUARY 2021 PAGE | iii ------- GREAT LAKES FISH MONITORING AND SURVEILLANCE PROGRAM TECHNICAL REPORT LIST OF FIGURES Figure 1: GLFMSP Collection Sites 4 Figure 2. Mean Total PCB Concentration (ppb) in Lake Trout/Walleye 1992-2016 12 Figure 3. Mean Total PBDE (5 Congeners) Concentration (ppb) in Lake Trout/Walleye 2002-2016 14 Figure 4. Mean Total Mercury Concentration (ppb) in Lake Trout/Walleye 2000-2016 16 Figure 5. Concentrations of Halogenated Compound Classes in GLFMSP Mega-composite Samples from 2016 19 Table 1: 2016 Base Monitoring Program Analytical Data Sets 6 Table 2: 2016 Base Monitoring Program Field Data 7 Table 3: 2016 CSMI Lake Trout Field Data 7 Table 4: 2016 CSMI Forage Fish Field Data 8 Table 5: 2016 CSMI R/V Lake Guardian Collected Field Data 8 Table 6: 2016 Base Monitoring Program Biological Data 9 Table 7: 2016 CSMI/Special Studies Lake Trout Biological Data 9 Table 8: 2016 Age Data (Base Monitoring Program and CSMI/Special Studies Lake Trout) 10 Table 9: Summary of 2016 Total PCB Site Means and Temporal Trends 11 Table 10: Summary of 2016 Total PBDE (5 congeners) Site Means and Temporal Trends 13 Table 11: Summary of 2016 Total Mercury Site Means and Temporal Trends 15 Table 12: Summary of 2016 Total HBCDD Mega-composite Means 17 Table 13: Summary of 2016 Total PFAS and PFOS Composite Means 18 FEBRUARY 2021 PAGE | iv ------- GREAT LAKES FISH MONITORING AND SURVEILLANCE PROGRAM TECHNICAL REPORT 1 EXECUTIVE SUMMARY The U.S. Environmental Protection Agency (EPA) Great Lakes National Program Office (GLNPO) Great Lakes Fish Monitoring and Surveillance Program (GLFMSP) is a long-term monitoring program designed to: 1) collect, analyze and report contaminant concentrations in Great Lakes fish , 2) improve understanding of contaminant cycling throughout food webs in the Great Lakes, and 3) screen for emerging chemicals in fish tissue to identify priority chemicals warranting future trend analysis and study. Samples collected for the GLFMSP are screened for emerging chemicals and analyzed for several different classes of contaminants including polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), mercury, hexabromocyclododecane (HBCDD), per- and polyfluoroalkyl substances (PFAS), toxaphene, chlordanes, and other organochlorine pesticides (OCPs). An assessment of data through 2016 shows that concentrations of several contaminants are decreasing in Great Lakes top predator fish. These trends may be attributed to pollution reduction and clean-up efforts within the Great Lakes watershed. Key highlights from the 1992-2016 monitoring show that the: Mean total PCB concentrations in fish declined at all sites since 1992; Mean total PBDE concentrations in fish declined at all sites since 2002; and Mercury concentrations in fish declined at the Rockport, Lake Huron and Apostle Islands, Lake Superior sites since 2006. The GLFMSP collects fish at one of two long-term monitoring stations in each of the Great Lakes, in the late summer to fall of each year, with stations alternating within each lake annually. In support of the 2016 Lake Superior Cooperative Science and Monitoring Initiative (CSMI), fish and other samples (e.g., benthic invertebrates, water samples) were also collected at both GLFMSP collection sites in Lake Superior. Analytical results are made publicly available approximately 18 to 22 months after field collection, following biological data collection, homogenization, chemical analysis, and data quality review. In 2016, samples were collected between June and November at GLFMSP even-year sites within each lake. This report summarizes the field sample and biological data collection results (e.g., species, number of fish, length, weight, gender, age) from all 2016 GLFMSP collection efforts and presents the analytical results from five classes of contaminants (PCBs, PBDEs, mercury, HBCDD, and PFAS) in Lake Trout (Salvelimis namaycash) and Walleye (Sander vitrens) collected for the GLFMSP Base Monitoring Program. The analytical results from 2016 are placed into the context of long-term trends beginning when each contaminant was first subjected to routine monitoring. PCBs: Trend data show that mean total PCB concentrations at each site continue to show a statistically significant decline over the short term (2006-2016) and the long term (1992-2016). PBDEs: Mean total PBDE concentrations showed a statistically significant decline at all Lake Trout sites in Lakes Superior, Michigan, Huron, and Ontario in the short term (2006-2016) and in the long term (2002-2016). The decline in mean total PBDE concentrations in Walleye at the Middle Bass Island, Lake Erie site was significant in the long term, but not in the short term. Mercury: Mean mercury concentrations continue to show a statistically significant decline over the past decade(2006-2016) at the Rockport, Lake Huron site and the Apostle Islands, Lake Superior site; however, concentrations show a statistically significant increase at the Saugatuck, Lake Michigan site, and no long-term change was observed at the Middle Bass Island, Lake Erie site or the Oswego, Lake Ontario site. The overall increase in mercury concentration observed at Saugatuck was small, and the analysis does not include age-corrected fish data. When evaluated across a longer time period beginning FEBRUARY 2021 PAGE | 1 ------- GREAT LAKES FISH MONITORING AND SURVEILLANCE PROGRAM TECHNICAL REPORT when mercury was first subjected to monitoring at these sites (2000-2016), only the Apostle Islands, Lake Superior site had a statistically significant decline; no statistically significant change was observed for Saugatuck, Rockport, Middle Bass Island, or Oswego sites. HBCDD and PFAS: There are currently not enough years of data to evaluate temporal trends for HBCDD or PFAS. In 2016, mean total HBCDD was highest at the Rockport, Lake Huron site and lowest at the Middle Bass Island, Lake Erie site. In 2016, mean total PFAS and mean perfluorooctanesulfonic acid (PFOS) (a PFAS compound) concentrations tended to be highest at the Middle Bass Island, Lake Erie site and the Oswego, Lake Ontario site and lowest at the Apostle Islands, Lake Superior site. CECs: This report also presents the results of Contaminants of Emerging Concern (CEC) screening analyses performed on Base Monitoring Program samples. The most abundant CEC compound class found in this screening was halomethoxyphenols. 2 INTRODUCTION The U.S. Environmental Protection Agency (EPA) Great Lakes National Program Office (GLNPO) Great Lakes Fish Monitoring and Surveillance Program (GLFMSP) is a long-term monitoring program that was initiated in 1977 and designed to: 1) collect, analyze and report contaminant concentrations in Great Lakes fish , 2) improve understanding of contaminant cycling throughout food webs in the Great Lakes, and 3) screen for emerging chemicals in fish tissue to identify priority chemicals warranting future trend analysis and study. Lake Trout and Walleye are targeted by the GLFMSP for biomonitoring because these top predator fish occupy the highest trophic levels in the Great Lakes aquatic food web and as such tend to accumulate higher levels of persistent and bioaccumulative contaminants (McGoldrick and Murphy. 2016). The present design of the GLFMSP includes two components: 1) Base Monitoring Program and 2) Cooperative Science and Monitoring Initiative (CSMI)/Special Studies. The GLFMSP helps EPA satisfy its statutory requirements under Section 118 of the Clean Water Act to establish a Great Lakes system-wide surveillance network to monitor the water quality of the Great Lakes (33 U.S.C. § 1268 et sea.) with a specific emphasis on the monitoring of toxic pollutants. It also helps satisfy the Agency's obligations under the Great Lakes Water Quality Agreement (GLWQA) to "monitor environmental conditions so that the Parties may determine the extent to which General Objectives, Lake Ecosystem Objectives, and Substance Objectives are being achieved," and "undertake monitoring and surveillance to anticipate the need for further science activities and to address emerging environmental concerns" (GLWQA 2012). Further, this program allows EPA to meet commitments in the Great Lakes Restoration Initiative (GLRI) Action Plan III to "assess the overall health of the Great Lakes ecosystem and identify the most significant remaining problems" (GLRI 2019). This report summarizes sample and biological data collection results for the 2016 Base Monitoring Program and C SMI/Special Studies collection efforts and presents the 2016 Base Monitoring Program analytical results in context with long-term trends. This report focuses on analytical results from five classes of contaminants (polychlorinated biphenyls [PCBs], polybrominated diphenyl ethers [PBDEs], mercury, hexabromocyclododecane [HBCDD], and per- and polyfluoroalkyl substances [PFAS]) which have been designated as binational chemicals of mutual concern through the GLWQA Chemicals of Mutual Concern Annex (Annex 3) (GLWQA 2012) and also includes results from Contaminants of Emerging Concern (CEC) screening analyses. FEBRUARY 2021 PAGE | 2 ------- GREAT LAKES FISH MONITORING AND SURVEILLANCE PROGRAM TECHNICAL REPORT 3 DESCRIPTION OF METHODS This section summarizes methods for sample collection, biological data collection, homogenization, and analysis. 3.1 SAMPLE COLLECTION Field sampling teams perform sample collections every year in the late summer to fall according to sample collection standard operating procedures (SOPs) (EPA 2012a) and deliver fish to a homogenization laboratory after collection. A total of seven sampling teams collected fish for the Base Monitoring Program and C SMI/Special Studies components in 2016 between June and November: Great Lakes Indian Fish & Wildlife Commission Michigan Department of Natural Resources, Alpena Fisheries Research Station Michigan Department of Natural Resources, Charlevoix Fisheries Research Station Ohio Department of Natural Resources, Division of Wildlife Sandusky Fisheries Research Station U.S. Geological Survey Lake Ontario Biological Station U.S. Geological Survey Lake Superior Biological Station Wisconsin Department of Natural Resources Detailed information on collection methods can be found in the subsections below. 3.1.1 Base Monitoring Program Top predator fish are collected at two sites in each of the Great Lakes with sites alternating within each lake annually (Figure 1) for the Base Monitoring Program. Collection sites are intended to be representative of offshore conditions in each Lake. Lake Trout (Salvelinus namaycash) are collected in all lakes and Walleye (Sander vitreus) are collected at one site located in the western basin of Lake Erie which is too shallow to support lake trout. Lake trout in the size range of 600-700 mm are targeted and Walleye in the size range of 400-500 mm are targeted for collection (target number of fish per site = 50). Fish size ranges were determined with the assumption that they represented specific age ranges, 6-8 years for Lake Trout and 4-5 years for Walleye. Detailed collection and site information for the GLFMSP Base Monitoring Program is located in the GLFMSP Quality Assurance Project Plan (QAPP) (EPA 2012a). 3.1.2 Cooperative Science and Monitoring Initiative (CSMI)/Special Studies The Cooperative Science and Monitoring Initiative (CSMI) is a binational effort instituted under the 2012 GLWQA to coordinate science and monitoring activities in one of the five Great Lakes each year to generate data and information for environmental management agencies. The GLFMSP supports the CSMI via additional sample collection efforts and analyses to gather information regarding contaminant cycling throughout food webs in the Great Lakes. During the CSMI field year, fish are collected at both GLFMSP sites within the CSMI lake; in 2016, the CSMI lake was Lake Superior. Lake Trout in the size and age range collected as part of the Base Monitoring Program are targeted (target number of fish per site = 10). The top five most abundant species of forage fish in the CSMI lake are also collected at both sites when available (total target number of fish per site = 110). The GLFMSP cooperators collect sediment, benthic invertebrates, phytoplankton, zooplankton/seston, and water samples in the CSMI lake aboard the R/V Lake Guardian. Detailed collection and site information for the GLFMSP CSMI/Special Studies component is provided in the GLFMSP QAPP (EPA 2012a). FEBRUARY 2021 PAGE | 3 ------- GREAT LAKES FISH MONITORING AND SURVEILLANCE PROGRAM TECHNICAL REPORT Stations Odd Year Depth (m) Keweenaw Point-"*! Apostle Islands Map Projection: Albers Equal Area Rockport Sturgeon Bay Lake Huron Port Austin Oswego Lake Ontario Lake hchigan North Hamlin Saugatuck Dunkirk Middle Bass Island Figure 1: GLFMSP Collection Sites. FEBRUARY 2021 PAGE j 4 ------- GREAT LAKES FISH MONITORING AND SURVEILLANCE PROGRAM TECHNICAL REPORT 3.2 BIOLOGICAL DATA COLLECTION AND HOMOGENIZATION The homogenization laboratory receives fish from the field sampling teams and processes these fish in the winter to spring time period. In 2016, the homogenization laboratory was Aquatec Biological Sciences, Inc. (Aquatec). Aquatec follows approved GLFMSP specific SOPs (Aquatec 2016) when processing samples. The homogenization laboratory recorded biological data (e.g. length, width, weight) and any abnormalities (e.g., tumors, fins missing, wounds), collected samples for aging purposes (e.g., scales, otoliths, maxillae, coded wire tags [CWTs]), and aged the fish. In 2016, lake trout age was determined based on annuli enumeration of maxillae and otoliths1. Fish age is an important variable when assessing contaminant trends and as such, the GLFMSP compositing scheme was revised in 2013 to group fish according to age (rather than by length) prior to homogenization and chemical analysis. CWTs were also used to age lake trout when available. Walleye age was determined based on annuli enumerations of otoliths. EPA reviewed the ages and assigned fish into five fish per composites (target number of composites per site = 10) based on age for sites where the target 50 fish were collected. At the Apostle Islands site, a total of 46 lake trout were collected, so nine composites of five fish and one composite of one fish were created. At the Oswego site, a total of 19 fish were collected. Low sample numbers could result in more variable site means because they are based on less data owing to: 1) decreased sample sizes as a smaller number of composites are created for the site; and/or 2) fewer than the target of five fish comprised the composites. Because of this, composites including fewer fish were created for Oswego to minimize within-composite age variability among fish. After grouping fish into composites based on EPA's criteria noted above, the homogenization laboratory processed the whole fish and prepared composites of these samples. In addition, a mega-composite was prepared (i.e., tissue from all composites from a single site) where applicable for screening of contaminants of emerging concern. The single fish composite from Apostle Islands was not included in the mega-composite for this site in 2016. The homogenization laboratory created tissue aliquots and delivered them to the analytical laboratory cooperator and to EPA's archival facility. 3.3 ANALYSIS The analytical laboratory cooperator receives fish tissue aliquots from the homogenization laboratory in the spring of the year following collection year. The analytical laboratory cooperators that analyzed the 2016 collected fish tissue were Clarkson University, State University of New York (SUNY) Oswego, and SUNY Fredonia. The 2016 Base Monitoring Program analytical data sets are presented in Table 1. All analytical data generated to support the GLFMSP are prepared in accordance with an approved QAPP and SOPs (Clarkson University 2016). Upon sample receipt, the analytical laboratory cooperator analyzed the homogenate tissue for different classes of contaminants including PCBs, PBDEs, mercury, HBCDD, PFAS, toxaphene, chlordanes, and other organochlorine pesticides (OCPs). The analytical laboratory cooperator also utilized mega- composite samples collected for the Base Monitoring Program to determine the presence of CECs. Following data review by EPA, the data are used for reporting and made available to the public in the Great Lakes Environmental Database (GLENDA), and can also be requested from EPA (contact information is provided on page ii of this report). 1 After the 2016 field season, the GLFMSP concluded a four-year, inter-laboratory comparison study of multiple age enumeration structures to allow for a more rapid, accurate, and precise measurement of age prior to homogenization (Murphv et al. 2018 V Refer to Section 6 Future Reporting for more information. FEBRUARY 2021 PAGE | 5 ------- GREAT LAKES FISH MONITORING AND SURVEILLANCE PROGRAM TECHNICAL REPORT Table 1: 2016 Base Monitoring Program Analytical Data Sets Collection Effort Analytes Composites and mega-composites Percent Moisture Mercury PCBs/OCPs/PBDEs/Lipids/Mirex Composites only PFAS Mega-composites only Dioxins / Furans & Co planar PCB congeners HBCDD CECs Results generated by all analytical methods were reported on a wet weight basis in accordance with SOPs (Clarkson University 2016). No mathematical adjustments based on lipid content or fish age were performed on the 2016 results or as part of the trend analyses presented in this report. Long-term analytical data in the GLFMSP presented in this report have not been corrected to adjust for fish age ~ the reason being that fish have only been aged since 2003 as part of the sampling process and historically were grouped into estimated age composites according to length measurements. To ensure consistency in how data are reported, publicly available data for GLFMSP are reported as contaminant concentrations for each composite for a given sampling year at each collection site. Age-corrected data from the GLFMSP are presented in Pagano et al. (2018) and Zhou et al. (2018). 4 QUALITY ASSURANCE AND QUALITY CONTROL The GLFMSP operates under a quality management plan (QMP), a QAPP, and numerous SOPs. The GLFMSP quality management system is defined in the GLFMSP QMP (EPA 2012b). Quality assurance/quality control (QA/QC) activities and procedures associated with the sample collection, biological data collection, homogenization, and analysis of fish samples are described in the QAPPs and SOPs identified in Section 3. Several types of laboratory QC measures including equipment blanks, standard reference materials, blind duplicates, method blanks, replicate samples, and surrogate spikes, are implemented at both the homogenization laboratory and the analytical laboratory to monitor data quality. These measures assist in identifying and correcting problems as they occur. They also define the quality of data generated by the program. QC metrics are tailored to specific sample and analytical processes. The analytical laboratory cooperator's QAPP provides specific QC requirements to identify background contamination and extraction efficiency and ensure accurate identification and quantification of targeted analytes. If any QC criteria are not met, the data are reviewed carefully to identify the cause of the problem and determine the appropriate corrective action. If reanalysis is not warranted, the data are submitted with QC flags to indicate the nature of the failure. To date, no major QA/QC issues have been identified through 2016. FEBRUARY 2021 PAGE | 6 ------- GREAT LAKES FISH MONITORING AND SURVEILLANCE PROGRAM TECHNICAL REPORT 5 RESULTS This section summarizes results from 2016 sample collection, biological data collection, and analysis and presents the 2016 Base Monitoring Program analytical results in context with long-term trends. 5.1 SAMPLE COLLECTION 5.1.1 Base Monitoring Program A total of 165 lake trout were collected in Lakes Superior, Huron, Michigan, and Ontario and a total of 50 Walleye were collected in Lake Erie in 2016 (Table 2). Due to low availability of lake trout in the target size range at two collection sites, a total of 19 lake trout were collected at Oswego and a total of 46 lake trout were collected at Apostle Islands instead of the target 50. Low fish availability at the Oswego site may have been caused by strong winds at the site during the collection, which can shift the thermocline and tend to scatter fish. Table 2: 2016 Base Monitoring Program Field Data Lake Site Species Date Depth (m) Collection Method Field Length Range (mm) Field Weight Range (g) Erie (n=50) Middle Bass Island Walleye November 2016 3.5-4 Gillnet 382-516 494-1501 Huron (n=50) Rockport Lake Trout October, November 2016 2.7-5.6 Gillnet 598-855 2052-6995 Michigan (n=50) Saugatuck Lake Trout September 2016 30 Gillnet 574-743 1490-5085 Ontario (n=19) Oswego Lake Trout September, November 2016 15-37 Gillnet 569-767 1940-5356 Superior (n=46) Apostle Islands Lake Trout October 2016 6-15 Gillnet 577-714 1558-3258 5.1.2 Cooperative Science and Monitoring Initiative (CSMI)/Special Studies In 2016, 10 additional lake trout were collected in Lake Superior, from Keweenaw Point (Table 3). Additional lake trout were not collected from Apostle Islands due to low availability of samples in the target size range. A total of 356 forage fish were collected from Keweenaw Point and Apostle Islands (Table 4). Sediment, benthic invertebrates, phytoplankton, zoop 1 ankton/seston. Mysis and water samples were also collected from both Lake Superior sites during a dedicated Research Vessel (R/V) Lake Guardian CSMI survey (Table 5). Table 3: 2016 CSMI Lake Trout Field Data Lake Site Date Depth (m) Collection Method Field Length Range (mm) Field Weight Range (g) Superior Keweenaw October, ^,,11 ,,, / im n 4. \t u onc 8 Gillnet 551-683 (n=10) Point November 2016 1400-2850 FEBRUARY 2021 PAGE | 7 ------- GREAT LAKES FISH MONITORING AND SURVEILLANCE PROGRAM TECHNICAL REPORT Table 4: 2016 CSMI Forage Fish Field Data Lake Site Species Collected Date Depth (m) Collection Method Superior Apostle Islands Rainbow Smelt (n=78) Bloater (n=60) Ninespine Stickleback (n=52) Cisco (n=30) Deepwater Sculpin (n=30) Lake Whitefish (n=30) Slimy Sculpin (n=12) Spoonhead Sculpin (n=5) June 2016 35-135 Bottom Trawl Superior Keweenaw Point Round Whitefish (n=23) Bloater (n=13) Kiyi (n=12) Longnose Sucker (n=10) Burbot (n=l) June 2016 15-146 Gillnet Table 5: 2016 CSMI R/V Lake Guardian Collected Field Data Lake Site Sample Type and Sampling Depth (m) Date Collection Method Water (3 m) June 2016 Pump Superior Apostle Islands Zo o p 1 a nk to n/ S c s t o n/. \ / vsis (whole water tow from 68 m) June 2016 Nested net (153 |im for zooplankton/seston and 500 |im for \ lysis) Sediment (69 m) June 2016 Ponar Benthic invertebrates (69 m) June 2016 Benthic sled (500 |im net) & Ponar grab (separated through 253 |im sieve) Water (3 m) June 2016 Pump Superior Keweenaw Point Zo o p 1 a nk to n/ S c s t o n/. \ /vsis (whole water tow from 53 m) June 2016 Nested net (153 |im for zooplankton/seston and 500 |im for \ lysis) Sediment (54 m) June 2016 Ponar Benthic invertebrates (~50 m) June 2016 Benthic sled (500 |im net) & Ponar grab (separated through 253 |im sieve) 5.2 BIOLOGICAL DATA COLLECTION AND HOMOGENIZATION Tables 6 and 7 provide a summary of biological data measurements (excluding age results which are included in Table 8) as recorded by the homogenization laboratory for the 2016 Base Monitoring Program and CSMI/Special Studies samples. FEBRUARY 2021 PAGE | 8 ------- GREAT LAKES FISH MONITORING AND SURVEILLANCE PROGRAM TECHNICAL REPORT Table 6: 2016 Base Monitoring Program Biological Data Lake Site Species Lab Length Range (mm) Lab Weight Range (g) Gender Count (M,F) Dominant Maturity Stagea'b Erie (n=50) Middle Bass Island Walleye 381-519 489-1490 31, 19 Mature (62%) Huron (n=50) Rockport Lake Trout 552-846 2017-6892 23,27 Mature (46%), Ripe (52%) Michigan (n=50) Saugatuck Lake Trout 558-738 1466-5027 30, 20 Mature (62%) Ontario (n=19) Oswego Lake Trout 533-742 1902-5327 9, 10 Gravid (42.1%), Mature (47.4%) Superior (n=46) Apostle Islands Lake Trout 423-702 1528-3220 40,6 Mature (87%) aMature = fish is sexually mature (egg deposition status is either unknown, unimportant, or nonapplicable); Ripe = ovary is full of eggs that are ready for deposition and fertilization (ovary wall structure weakened or broken, eggs escape upon external palpation); Gravid = ovary is full of eggs that are not yet ready for deposition or fertilization (eggs still contained within ovary wall structure) h % = percent of total number offish collected at each site Table 7: 2016 CSMI/Special Studies Lake Trout Biological Data Lake Site Species Lab Length Range (mm) Lab Weight Range (g) Gender Count (M, F) Dominant Maturity Stage Superior . Lake , , Keweenaw Point (n=10) Trout 560-669 1308-2716 10,0 Mature (100%) a-b aMature = fish is sexually mature (egg deposition status is either unknown, unimportant, or nonapplicable) b % = percent of total number offish collected at each site Table 8 provides a summary of age data for 2016 Base Monitoring Program and CSMI/Special Studies lake trout samples. Age results included in the table were determined based on annuli enumeration of otoliths and on CWTs. The dominant aging method used to obtain the final age for each fish is listed. Final age was determined based on CWT where available and then based on annuli enumeration of otolith if no CWT was present. No Walleye from Middle Bass Island exceeded the target age range of 4-5 years. The majority of Lake Trout exceeded the target age range of 6-8 years in Rockport (70%) and Apostle Islands (60%), while 40% exceeded the age range in Keweenaw Point, 22% exceeded the age range in Saugatuck, and 11% exceeded the age range in Oswego. It would be expected that fish exceeding the age range may have higher contaminant concentrations due to longer exposure times (i.e., bioaccumulation) of the environmental contaminants. FEBRUARY 2021 PAGE | 9 ------- GREAT LAKES FISH MONITORING AND SURVEILLANCE PROGRAM TECHNICAL REPORT Table 8: 2016 Age Data (Base Monitoring Program and CSMI/Special Studies Lake Trout) Lake Site Species Age Range (years) Dominant Aging Method Percent of Fish Exceeding Target Age Range Erie (n=50) Middle Bass Island Walleye 2-4 Otolith 0% Huron (n=50) Rockport Lake Trout 5-18 Otolith 70% Michigan (n=50) Saugatuck Lake Trout 4-16 Otolith, CWT 22% Ontario (n=19) Oswego Lake Trout 4-11 CWT 11% Superior (n=46) Apostle Islands Lake Trout 6-22 Otolith 60% Superior (n=10) Keweenaw Point Lake Trout 8-11 Otolith 40% Lake Trout age was also determined based on annuli enumeration of maxillae as part of the four-year, inter-laboratory comparison study of multiple age enumeration structures described in Section 3.2 (Murphy et al. 2018). Information on maxilla age results for 2016 samples as well as 2013-2015 samples is presented in the Journal of Great Lakes Research publication "Revised fish aging techniques improve fish contaminant trend analyses in the face of changing Great Lakes food webs" (Murphy et al. 2018). 5.3 ANALYSIS The sections below summarize results for five contaminants (PCBs, PBDEs, mercury, HBCDD, and PFAS) in fish collected for the Base Monitoring Program in 2016, places these results in context with long-term trends, and present results from the CEC screening analyses performed on these samples. The 2016 CSMI/Special Studies Program analytical results will be presented in future GLFMSP reports. Due to low sample numbers at Oswego, as stated in Section 3.2. the number of fish assigned to composites varied to minimize age variability. The calculation of abundance weighted means (i.e., weighted based on the number of fish per composite) and standard errors for the 2016 Oswego data mitigates the impact of the varying number of fish per composite; however, there could still be some comparability concerns when evaluating composite results across years at this site. As stated in Section 3.2. one composite from Apostle Islands contained only one fish instead of the target five. This composite was analyzed for all contaminants but was not included in site means presented in this report. 5.3.1 PCBs The GLFMSP provides long-term data trends for PCBs in Lake Trout and Walleye from the 1970s - present. Prior to 1991, methods and target congeners varied. In this report, PCB trends for even year sites from 1992- 2016 are presented as these are the date ranges for which the current sampling design (i.e., 10 composites of five fish with sites alternating within each lake annually) has been implemented. Site mean total PCB concentrations ranged from 136 to 628 ng/g across the five sites (Table 9) in 2016. Mean total PCB concentrations were calculated based on 142 out of 209 individual PCB congeners. Measured results were not censored based on reporting or detection limits and all reported results were FEBRUARY 2021 PAGE | 10 ------- GREAT LAKES FISH MONITORING AND SURVEILLANCE PROGRAM TECHNICAL REPORT included in the totals. In general, mean total PCB concentrations have exhibited a decreasing trend at all sites over both the 2006 - 2016 (Table 9) and 1992-2016 (Table 9 and Figure 2) time frames. Estimated declines since 2006 are statistically significant at all sites and range from 30% at Saugatuck to 76% at Apostle Islands. Estimated PCB declines since 1992 are statistically significant and range from 65% at Middle Bass Island to 81% at Rockport. Table 9: Summary of 2016 Total PCB Site Means and Temporal Trends Lake Site # Composites Species 2016 Site Means Total PCB Concentration (standard error) (ng/g) Estimated % Decline 1992-2016 (95% CI LL- UL)d Estimated % Decline 2006-2016 (95% CI LL-UL) Erie Middle Bass Island 10 Walleye 488 (40.0) 65 (57 - 72) 33 (17 -45) Huron Rockport 10 Lake Trout 355 (70.4) 81 (77 -84) 57 (38 -70) Michigan Saugatuck 10 Lake Trout 610 (118) 80 (75 - 83) 30 (6 - 49) Ontario Oswego 6 a Lake Trout 628 (101)° 81 (78 -83) 46 (30 - 58) Superior Apostle Islands 9 b Lake Trout 136 (24.7) 77 (68 - 84) 76 (65 - 83) a Composites included 2-4 fish each to minimize age variability within a composite b Based on 9 composites of 5 fish (single fish composite not included) c Site mean is weighted based on number of fish per composite dCILL-UL indicates confidence inten'al lower level-upper level FEBRUARY 2021 PAGE | 11 ------- GREAT LAKES FISH MONITORING AND SURVEILLANCE PROGRAM TECHNICAL REPORT Figure 2. Mean Total PCB Concentration (ppb) in Lake Trout/Walleye 1992-2016. Notes: 1) Stations are not representative of the entire lake. 2)A missing bar = samples not collected for that site/year. 3) An asterisk (*) indicates less than 5 composites are included in the sampling period. 4) Lake Trout were collected in all lakes except Lake Erie. 5) The last two digits of collection years are displayed above corresponding bars as 'XX. FEBRUARY 2021 PAGE j 12 ------- GREAT LAKES FISH MONITORING AND SURVEILLANCE PROGRAM TECHNICAL REPORT 5.3.2 PBDEs The GLFMSP began monitoring for PBDEs using congener-specific analyses in 2000, with a complete set of analyses for most lakes available beginning in 2002. Site mean total PBDE concentrations ranged from 9.75 to 45.1 ng/g across the five sites (Table 10) in 2016. Mean total PBDE concentrations were calculated based on five congeners (47, 99, 100, 153, and 154) that have been analyzed consistently across all years. These are the only PBDE congeners that have been consistently measured by GLFMSP and are the PBDE congeners found in the highest concentrations in Great Lakes fish (Zhou et al. 2017). Measured results were not censored based on reporting or detection limits and all reported results were included in the totals. Mean total PBDE concentrations showed a statistically significant decline at all sites over the 2006-2016 time series (Table 10) and range from 20% at Middle Bass Island to 58% at Apostle Islands. Estimated total PBDE concentration declines over the 2002-2016 time series (Table 10 and Figure 3) are statistically significant at all Lake Trout sites and range from 48% at Apostle Islands to 66% at Saugatuck. The 16% decline in PBDE concentration in Walleye at Middle Bass Island since 2002 is not statistically significant. Table 10: Summary of 2016 Total PBDE (5 congeners) Site Means and Temporal Trends Lake Site # Composites Species 2016 Total PBDE Site Mean Concentration (standard error) (ng/g) Estimated % Decline d 2002-2016 (95% CI LL- UL)* Estimated % Decline 2006-2016 (95% CI LL- UL) Erie Middle Bass Island 10 Walleye 9.75 (0.931) 16 (-4-31) 20 (2 - 34) Huron Rockport 10 Lake Trout 32.0 (6.20) 59 (41 - 72) 40 (6-61) Michigan Saugatuck 10 Lake Trout 41.9(8.51) 66 (52 - 76) 41 (19-58) Ontario Oswego 6a Lake Trout 45.1 (12.4)° 51 (33 -64) 40 (18 - 56) Superior Apostle Islands 9 b Lake Trout 37.7 (8.70) 48 (24 - 64) 58 (38 - 72) a Composites included 2-4 fish each to minimize age variability within a composite h Based on 9 composites of 5 fish (single fish composite not included) c Site mean is weighted based on number of fish per composite dA negative percent decline ofX% corresponds to a percent increase ofX% e CILL-UL indicates confidence inten'al lower level-upper level FEBRUARY 2021 PAGE | 13 ------- GREAT LAKES FISH MONITORING AND SURVEILLANCE PROGRAM TECHNICAL REPORT Figure 3. Mean Total PBDE (5 Congeners) Concentration (ppb) in Lake Trout/Walleye 2002-2016. Notes: 1) Stations are not representative of the entire lake. 2) »l: missing bar = samples not collected for that site/year. 3) An asterisk (*) indicates less than 5 composites are included in the sampling period. 4) Lake Trout were collected in all lakes except Lake Erie. 5) The last two digits of collection years are displayed above corresponding bars as 6) Total PBDE = sum of congeners 47, 99, 100, 153, and 154. FEBRUARY 2021 PAGE j 14 ------- GREAT LAKES FISH MONITORING AND SURVEILLANCE PROGRAM TECHNICAL REPORT 5.3.3 Mercury The GLFMSP began monitoring for total mercury in 1999. Mean total mercury concentrations are shown at all even-year sampling sites from 2000-2016 in Figure 4. Site mean mercury concentrations ranged from 93 to 170 ng/g across the five sites (Table 11) in 2016. In general, mean mercury concentrations showed a statistically significant decline over the 2006-2016 time series (Table 11) at Rockport and Apostle Islands. At Saugatuck, a statistically significant increase of 24% was exhibited from 2006 - 2016. Mercury concentrations in 2006 at Saugatuck were the lowest reported for the time series, which could explain the increasing trend observed from 2006-2016. Since 2000, only Apostle Islands had a statistically significant decline in mercury concentrations (56%). No statistically significant changes in the concentrations of mercury have been detected for Middle Bass Island or Oswego since 2006. While the other four sites, i.e., Middle Bass Island, Rockport, Saugatuck, and Oswego, exhibited an increase in mercury concentrations for the 2000-2016 time frame (ranging from 1% at Middle Bass Island to 6% at Rockport), none were statistically significant (Table 11). Increasing age of Lake Trout collected at Saugatuck and Rockport may explain the lack of trends over the entire time period (Zhou et al. 2017). Refer to section 5.2 for discussion of correlation between fish age and contaminant concentrations. Table 11: Summary of 2016 Total Mercury Site Means and Temporal Trends Lake Site # Composites Species 2016 Total Mercury Site Mean Concentration (standard error) (ng/g) Estimated % Decline d 2000-2016 (95% CI LL- UL)e Estimated % Decline d 2006-2016 (95% CI LL- UL) Erie Middle Bass Island 10 Walleye 93 (5.0) -1 (-15 to 11) 5 (-9 to 17) Huron Rockport 10 Lake Trout 170(14) -6 (-32 to 15) 35 (17 to 49) Michigan Saugatuck 10 Lake Trout 170(11) -5 (-25 to 11) -24 (-44 to -6) Ontario Oswego 6a Lake Trout 150 (23)° -4 (-22 to 11) -12 (-37 to 8) Superior Apostle Islands 9 b Lake Trout 130 (6.4) 56 (46 to 65) 51 (39 to 61) a Composites included 2-4 fish each to minimize age variability within a composite h Based on 9 composites of 5 fish (single fish composite not included) c Site mean is weighted based on number of fish per composite dA negative percent decline ofX% corresponds to a percent increase ofX% e CILL-UL indicates confidence inten'al lower level-upper level FEBRUARY 2021 PAGE | 15 ------- GREAT LAKES FISH MONITORING AND SURVEILLANCE PROGRAM TECHNICAL REPORT Saugatuck ^ Middle Bass Island (walleye GLFMSP Collection Site Apostle Islands 500 300 200 100 100 500 400 - 300 - 200 100 500 - 400 300 200- 100 0 - Rockport Oswego "I 300 km Figure 4. Mean Total Mercury Concentration (ppb) in Lake Trout/Walleye 2000-2016. Notes; 1) Stations are not representative of the entire lake. 2) A missing bar = samples not collected for that site/year. 3) An asterisk (*) indicates less than 5 composites are included in the sampling period. 4) Lake Trout were collected in all takes except Lake Erie. 5) The last two digits of collection years are displayed above corresponding bars as 'XX. FEBRUARY 2021 PAGE j 16 ------- GREAT LAKES FISH MONITORING AND SURVEILLANCE PROGRAM TECHNICAL REPORT 5.3.4 HBCDD The GLFMSP added analysis of three HBCDD isomers in mega-composite samples to the program in 2012, beginning with analysis of samples that were originally collected in 2010. Four years of data (2010, 2012, 2014, and 2016) are available for even-year sites. Because the six-year time period is not sufficient to allow for a meaningful evaluation of trends, temporal trends for total HBCDD concentration are not evaluated in this report. However, each mega-composite sample was analyzed for three HBCDD isomers in triplicate, such that site means and associated analytical variability could be calculated. Total HBCDD mega-composite means range from 3.34 ng/g at Middle Bass Island to 7.15 ng/g at Saugatuck (Table 12) in 2016. Mean total HBCDD concentrations were calculated based on the three analyzed HBCDD isomers. Measured results were not censored based on reporting or detection limits and all reported results were included in the totals. Mean total HBCDD concentration was highest at Rockport and lowest at Middle Bass Island. Table 12: Summary of 2016 Total HBCDD Mega-composite Means Lake Site # Replicatesa Species 2016 Total HBCDD Mega-composite Concentration (standard error) (ng/g) Erie Middle Bass Island 3 Walleye 3.34 (0.05) Huron Rockport 3 Lake Trout 10.3 (0.08) Michigan Saugatuck 3 Lake Trout 7.15 (0.04) Ontario Oswego 3 Lake Trout 6.11 (0.44) Superior Apostle Islands 3 Lake Trout 6.50 (0.10) a Single mega-composite samples were analyzed in triplicate (so variability estimates include analytical variability but not sampling variability, which is included in the calculated standard errors for other analyte classes presented in this report) 5.3.5 PFAS The GLFMSP began monitoring PFAS compounds in 2011. The list of analyzed PFAS compounds has varied since 2011. In 2016, monitored PFAS compounds included 26 perfluorinated carboxylic acids and sulfonates with 4 to 13 carbons, including 10 branched isomers. In recent years, including 2016, the method used to quantify PFAS was modified to improve reproducibility in complex biological tissues (Point et al. 2019). Due to the evolving analytical methodology and smaller number of composites analyzed, it is not appropriate at this time to assess temporal trends for PFAS compounds. Table 13 shows total PFAS and Perfluorooctanesulfonic acid (PFOS) site mean concentrations and their associated standard errors for the composites that were analyzed at each site. Because the PFAS analysis scheme was generally consistent across sites, the mean concentrations can be compared to each other, even if each one is a low-biased estimate. As seen in Table 13. total PFAS and PFOS concentrations are generally highest at Middle Bass Island and Oswego, and lowest at Apostle Islands. Mean total PFAS concentrations were calculated based on the 16 PFAS compounds that were analyzed, excluding branched isomers. Measured results were not censored based on reporting or detection limits and all reported results were included in the totals. FEBRUARY 2021 PAGE | 17 ------- GREAT LAKES FISH MONITORING AND SURVEILLANCE PROGRAM TECHNICAL REPORT Table 13: Summary of 2016 Total PFAS and PFOS Composite Means Lake Site # Composites Species 2016 Total PFAS Mega-composite Concentration (standard error) (ng/g) 2016 PFOS Composite Mean (standard error) (ng/g) Erie Middle Bass Island 3 Walleye 69.5 (12.7) 61.0(11.9) Huron Rockport 3 Lake Trout 30.5 (4.9) 18.8 (2.8) Michigan Saugatuck 3 Lake Trout 32.0 (2.1) 27.5 (1.7) Ontario Oswego 3 Lake Trout 69.7 (2.0) 63.4 (1.9) Superior Apostle Islands 3 Lake Trout 11.4(0.77) 5.5 (0.39) FEBRUARY 2021 PAGE | 18 ------- GREAT LAKES FISH MONITORING AND SURVEILLANCE PROGRAM TECHNICAL REPORT 5.3.6 Contaminants of Emerging Concern (CECs) Since 2014, Base Monitoring Program mega-composites samples have been screened for CECs. Initial screening studies have been focused on detecting organic compounds that contain one or more chlorine or bromine atom. Historically, organic chemicals containing carbon bonded to chlorine or bromine have been found to be bioaccumulative and to potentially exhibit adverse effects on lake biota (e.g., PCBs, OCPs, PBDEs) (Howard and Muir 2010). The most abundant compound class identified in the CEC screenings performed on the 2016 samples is the halomethoxyphenols. This class of compounds accounts for more than 60% of the total halogenated compound concentration in top predator fish from all five Great Lakes. The halomethoxyphenols represent a greater contribution to the total body burden of halogenated species than legacy PCBs (Figure 6). Methoxyphenols are also known as guaiacols. As a compound class, halomethoxyphenols include chlorinated guaiacols, as well as methoxyphenols containing other halogens such as bromine and iodine. Little is known about the effects of this class of compounds in fish. 7000 6000 5000 ~ 4000 3000 2000 1000 PCBs (monitored) Other Halo-organics (monitored)* Halomethoxyphenols (not monitored)*1 Halo-organics (not monitored)** Figure 5. Concentrations of Halogenated Compound Classes in GLFMSP Mega-composite Samples from 2016. * Includes PBDEs and OCPs. ** Compound classes not currently on the Base Monitoring Program analyte list but discovered via screening for CECs. Concentrations were determined using reference standards where available or structurally similar compounds. FEBRUARY 2021 PAGE | 19 ------- GREAT LAKES FISH MONITORING AND SURVEILLANCE PROGRAM TECHNICAL REPORT 6 FUTURE REPORTING A decreasing rate of decline for total PCB concentrations in Lake Huron Lake Trout was observed beginning in 2000. Upon further assessment, the slowing decline was found to be related to fish age. In 2013, the GLFMSP revised its compositing scheme to ensure fish were group according to age, rather than by length, prior to homogenization and chemical analysis. The revised age assignment procedure was warranted in the face of observed changes in Great Lakes food web structure. These changes can drive declines in fish growth rates and thus impact bioaccumulation potential of contaminants in top predator species such as Lake Trout and Walleye (Zhou et al. 2018). A four-year, inter-laboratory comparison of multiple age enumeration structures was completed in 2017 to select the best measurement of fish age (Murphy et al. 2018). The maxilla bone was determined to be the most precise, accurate, and rapidly assessed structure for fish age determinations for the GLFMSP, based on comparisons between age enumeration structures and the known fish age from the CWT. Use of Lake Trout and Walleye maxilla for GLFMSP aging commenced in 2017, and fish ages presented in subsequent GLFMSP technical reports will be based on this aging estimation method. Additional CSMI/Special Studies analytical results will also be presented in future GLFMSP technical reports. 7 SUMMARY The 2016 GLFMSP Technical Report details sampling information from the 2016 Base Monitoring Program and 2016 CSMI, assesses data and trends through 2016, and shows that concentrations of several contaminants are decreasing in Great Lakes top predator fish. Key highlights include: Mean total PCB concentrations in fish declined at all sites since 1992; Mean total PBDE concentrations in fish declined at all sites since 2002; and Mercury concentrations in fish declined at the Rockport, Lake Huron and Apostle Islands, Lake Superior sites since 2006, but increased at the Saugatuck, Lake Michigan site. Declines in mean total PCB concentrations are shown to be statistically significant in both short-term (2006-2016) and long-term (1992-2016) timeframes. Declines in mean total PBDE concentrations are shown to be statistically significant in both short-term (2006-2016) and long-term (2002-2016). However, the short-term decline in mean total PBDE concentrations at Middle Bass Island, Lake Erie was not statistically significant. Declines in mean total mercury concentrations are shown to be statistically significant over the past ten years (2000-2016) at the Rockport, Lake Huron site, and the Apostle Islands, Lake Superior site. Increases in mean total mercury concentrations are shown to be statistically significant at the Saugatuck, Lake Michigan site, and no statistically significant changes were observed at the Middle Bass Island, Lake Erie site or the Oswego, Lake Ontario site. Currently, there are not enough years of data to evaluate trends for HBCDD or PFAS. REFERENCES Aquatec Biological Sciences, Inc., 2016. Great Lakes Fish Monitoring and Surveillance Program Standard Operating Procedure. Clarkson University, 2016. Quality Assurance Project Plan for the Great Lakes Fish Monitoring and Surveillance Program (GLFMSP): Expanding the Boundaries. Great Lakes Restoration Initiative (GLRI) Action Plan III, 2019. https ://www.epa. gov/sites/production/files/2019-10/documents/glri-action-plan-3 -201910- 30pp.pdf. FEBRUARY 2021 PAGE | 20 ------- GREAT LAKES FISH MONITORING AND SURVEILLANCE PROGRAM TECHNICAL REPORT Great Lakes Water Quality Agreement (GLWQA), 2012. Canada-United States. https://binational.net//wp-content/uploads/2014/05/1094 Canada-USA-GLWOA- e.pdf. 1-56. Howard, P.H., Muir, D.C.G., 2010. Identifying new persistent and bioaccumulative organics among chemicals in commerce. Environmental Science and Technology. 44 (7), 2277-2285. McGoldrick, D.J., Murphy, E.W., 2016. Concentration and distribution of contaminants in lake trout and walleye from the Laurentian Great Lakes (2008-2012). Environmental Pollution. 217, 85-96. Murphy, E.W., Smith, M.L., He, J.X., Wellenkamp, W., Barr, E., Downey, P.C., Miller, K.M., Meyer, K.A., 2018. Revised fish aging techniques improve fish contaminant trend analyses in the face of changing Great Lakes food webs. Journal of Great Lakes Research. 44, 725-734. Pagano, J.J, Garner, A.J., McGoldrick, D.J., Crimmins, B.S., Hopke, P.K., Milligan, M.S. Milligan, Holsen, T., 2018. Age corrected trends and toxic equivalence of PCDD/F and CP-PCBs in Lake Trout from the Great Lakes: 2004-2014. Environmental Science and Technology. 52, 712-721. Point, A., Holsen, T., Fernando, S., Hopke, P., Crimmins, B., 2019. Towards the development of a standardized method for extraction and analysis of PFAS in biological tissues. Environmental Science: Water Research and Technology. 5, 1876-1886. U.S. Environmental Protection Agency (EPA), 2012a. Great Lakes Fish Monitoring and Surveillance Program (GLFMSP): Quality Assurance Project Plan for Sample Collection Activities. https ://www.epa.gov/sites/production/files/2016- 02/documents/glfmsp qapp version 2 111312 merged 508 O.pdf U.S. Environmental Protection Agency (EPA), 2012b. Great Lakes Fish Monitoring and Surveillance Program (GLFMSP): Quality Management Plan. https ://www.epa.gov/sites/production/files/2016- 02/documents/glfmsp qmp version 2 final 111312 508.pdf. Zhou, C., Pagano, J., Crimmins, B.A., Hopke, P.K., Milligan, M.S., Murphy, E.W., Holsen, T.M., 2018. Polychlorinated biphenyls and organochlorine pesticides concentration patterns and trends in top predator fish of Laurentian Great Lakes from 1999-2014. Journal of Great Lakes Research. 44, 716-724. FEBRUARY 2021 PAGE | 21 ------- GREAT LAKES FISH MONITORING AND SURVEILLANCE PROGRAM TECHNICAL REPORT APPENDIX A - LIST OF RECENT GLFMSP PUBLICATIONS The following is a list of GLFMSP publications produced between 2016 and 2019. Crimmins, B.S., Holsen, T.M., 2019. Non-targeted Screening in Environmental Monitoring Programs. Advances in Experimental Medicine and Biology: Advancements of Mass Spectrometry in Biomedical Research. 1140, 731-741. Crimmins, B.S., McCarty, H.B., Fernando, S., Milligan, M.S., Pagano, J.J., Holsen, T.M., Hopke, P.K., 2018. Commentary: Integrating Non-targeted and Targeted Screening in Great Lakes Fish Monitoring Programs. Journal of Great Lakes Research. 44, 1127-1135. Dupree, E.J., Crimmins, B.S., Holsen, T.M., Darie, C.C., 2019. Developing Well-Annotated Species- Specific Protein Databases Using Comparative Proteogenomics. Advances in Experimental Medicine and Biology: Advancements of Mass Spectrometry in Biomedical Research. 1140, 389- 400. Dupree, E.J., Crimmins, B.S., Holsen, T.M., Darie, C.C., 2019. Proteomic analysis of the lake trout (Salvelinus namaycush) liver identifies proteins from evolutionarily close and -distant fish relatives. Proteomics. 19(24), el800429. DOI: 10.1002/pmic.201800429 Fakouri Baygi, S., Crimmins, B.S., Hopke, P.K., Holsen, T.M., 2016. Comprehensive Emerging Chemical Discovery: Perfluorinated and Polyfluorinated Compounds in Lake Michigan Trout. Environmental Science and Technology. 50, 9460-9468. Fernando, S., Renaguli, A., Milligan, M., Pagano, J., Hopke, P., Holsen, T., Crimmins, B., 2018. Comprehensive Analysis of the Great Lakes Top Predator Fish for Novel Halogenated Organic Contaminants by GCxGC-HR-ToF. Environmental Science and Technology. 52, 2909-2917. Garner, A.J., Pagano, J.J., 2019. Trends of polychlorinated dioxins, polychlorinated furans, and dioxin- like polychlorinated biphenyls in Chinook and Coho salmonid eggs from a Great Lakes tributary. Environmental Pollution. 247, 1039-1045. Hites, R.A., Holsen, T.M., 2019. Temporal trends of PCBs and DDTs in Great Lakes fish compared to those in air. Science of the Total Environment. 646, 1413-1418. Lepak, R.F., Hoffman, J.C., Janssen, S.E., Krabbenhoft, D.P., Ogorek, J.M., DeWild J.F., Tate, M.T., Babiarz, C.L., Yin, R., Murphy, E.W., Engstrom, D.R., Hurley, J.P., 2019. Mercury source changes and food web shifts alter contamination signatures of predatory fish from Lake Michigan. Proceedings of the National Academy of Sciences. 116(47), 23600-23608. McGoldrick, D.J., Murphy, E.W., 2016. Concentration and distribution of contaminants in lake trout and walleye from the Laurentian Great Lakes (2008-2012). Environmental Pollution. 217, 85-96. Murphy, E.W., Smith, M.L., He, J.X., Wellenkamp, W., Barr, E., Downey, P.C., Miller, K.M., Meyer, K.A., 2018. Revised fish aging techniques improve fish contaminant trend analyses in the face of changing Great Lakes food webs. Journal of Great Lakes Research. 44, 725-734. Pagano, J.J, Garner, A.J., McGoldrick, D.J., Crimmins, B.S., Hopke, P.K., Milligan, M.S. Milligan, Holsen, T., 2018. Age Corrected Trends and Toxic Equivalence of PCDD/F and CP-PCBs in Lake Trout from the Great Lakes: 2004-2014. Environmental Science and Technology. 52, 712- 721. FEBRUARY 2021 PAGE | A-l ------- GREAT LAKES FISH MONITORING AND SURVEILLANCE PROGRAM TECHNICAL REPORT Point, A., Holsen, T., Fernando, S., Hopke, P., Crimmins, B., 2019. Towards the development of a standardized method for extraction and analysis of PFAS in biological tissues. Environmental Science: Water Research and Technology. 5, 1876-1886. Williams, M., Murphy, E., McCarty, H., Snyder, B., Schrank, McCann, P., Crimmins, B., 2017. Variation in essential fatty acids EPA and DHA in fish fillets of fish from the Great Lakes region. Journal of Great Lakes Research. 43, 150-160. Wu, Y., Tan, H., Zhou, C., Crimmins, B.S., Holsen, T.M., Chen, D., 2018. Bioaccumulation and Spatiotemporal Trends of Polyhalogenated Carbazoles in Great Lakes Fish from 2004 to 2016. Environmental Science and Technology. 52, 4536-4545. Wu, Y., Tan, H., Zhou, C., Crimmins, B.S., Holsen, T.M., Chen, D., 2019. Spatial and Temporal Trends (2004 - 2016) of Alternative Flame Retardants in Great Lakes Fish - A Story After the Discontinuation of PBDEs for More Than A Decade. Environmental Science and Technology. 53, 1786-1796. Zhou, C., Cohen, M., Crimmins, B., Zhou, H., Johnson, T., Hopke, P., Holsen, T., 2017. Mercury Temporal Trends in Top Predator Fish of the Laurentian Great Lakes from 2004 to 2015: Are Concentrations Still Decreasing? Environmental Science and Technology. DOI: 10.1021/acs.est.7b00982 Zhou, C., Pagano, J., Crimmins, B.A., Hopke, P.K., Milligan, M.S., Murphy, E.W., Holsen, T.M., 2018. Polychlorinated biphenyls and organochlorine pesticides concentration patterns and trends in top predator fish of Laurentian Great Lakes from 1999-2014. Journal of Great Lakes Research. 44, 716-724. Zhou, C., Pagano, J. McGoldrick, D., Chen, D., Crimmins, B., Hopke, P., Milligan, M., Murphy, E., Holsen, T., 2019. Legacy Polybrominated Diphenyl Ethers (PBDEs) Trends in Top Predator Fish of the Laurentian Great Lakes (GL) from 1979 to 2016: Will Concentrations Continue to Decrease? Environmental Science and Technology. 53, 6650-6659. FEBRUARY 2021 PAGE | A-2 ------- |