Mercury source changes and food web shifts alter contamination signatures of predatory fish from Lake Michigan.

To understand the impact reduced mercury (Hg) loading and invasive species have had on methylmercury bioaccumulation in predator fish of Lake Michigan, we reconstructed bioaccumulation trends from a fish archive (1978 to 2012). By measuring fish Hg stable isotope ratios, we related temporal changes in Hg concentrations to varying Hg sources. Additionally, dietary tracers were necessary to identify food web influences. Through combined Hg, C, and N stable isotopic analyses, we were able to differentiate between a shift in Hg sources to fish and periods when energetic transitions (from dreissenid mussels) led to the assimilation of contrasting Hg pools (2000 to present). In the late 1980s, lake trout δ202Hg increased (0.4‰) from regulatory reductions in regional Hg emissions. After 2000, C and N isotopes ratios revealed altered food web pathways, resulting in a benthic energetic shift and changes to Hg bioaccumulation. Continued increases in δ202Hg indicate fish are responding to several United States mercury emission mitigation strategies that were initiated circa 1990 and continued through the 2011 promulgation of the Mercury and Air Toxics Standards rule. Unlike archives of sediments, this fish archive tracks Hg sources susceptible to bioaccumulation in Great Lakes fisheries. Analysis reveals that trends in fish Hg concentrations can be substantially affected by shifts in trophic structure and dietary preferences initiated by invasive species in the Great Lakes. This does not diminish the benefits of declining emissions over this period, as fish Hg concentrations would have been higher without these actions.

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?

Polybrominated diphenyl ethers (PBDEs) were widely used as fire retardants and have been detected throughout the Great Lakes (GL) ecosystem. The concentration trends (after fish age normalization) of PBDEs in top predator fish (lake trout and walleye) of the GLs were determined from 1979 to 2016, which includes most of the period when PBDEs were manufactured and used in this region. The fish samples were collected by two national (U.S. and Canada) long-term monitoring and surveillance programs. Trends in total concentrations (age-normalized) of the five major PBDE congeners (BDE-47, 99, 100, 153, and 154) found in fish across all five lakes have varied over time. Significant increases were observed from 1990 to 2000 (16.3% per year). Rapidly decreasing concentrations (-19.5% per year) were found from 2000 to 2007. Since 2007, the decreasing trend has become smaller (less than -5.5% per year) and relatively unchanged from 2011 to 2015. BDE-47, the congener with the highest concentrations in lake trout, has decreased continuously (ranging from -6.7% to -16.2% per year) in all lakes except Lake Erie. This decrease can be associated with the voluntary and regulatory phase out of production and/or usage of PBDEs since 2000. However, it has been offset by recent (since 2007) increasing trends of the other four higher brominated BDE congeners, especially BDE-100 and 154. Production and usage of commercial penta- and octa- BDE mixtures containing primarily the five major PBDE congeners was discontinued in 2004 in the U.S.A. and 2008 in Canada. These results indicate increasing fish uptake and bioaccumulation of higher brominated BDE congeners may be related to the transformation of BDE-209 to lower brominated BDE compounds in the GL environment or food web. Considering the abundance of BDE-209 in existing products and sediment in GL region, the duration of the unchanging total PBDE concentration trend in GL fish could be longer than expected.

Polychlorinated biphenyls and organochlorine pesticides concentration patterns and trends in top predator fish of Laurentian Great Lakes from 1999 to 2014.

Concentration patterns and temporal trends of legacy persistent, bioaccumulative and toxic (PBT) contaminants were determined using the Great Lake Fish Monitoring and Surveillance Program (GLFMSP) top predator fish data from 1999 to 2014 and applying Kendall-Theil robust regression after cluster-based age normalization. For most Great Lakes sites, significant decreasing concentration trends ranging from -4.1% to -21.6% per year (with the only exception being mirex in Lake Erie walleye) were found for PBTs including polychlorinated biphenyls (PCBs), dichloro-diphenyl-trichlorethane (DDTs), dieldrin, endrin, chlordane, oxychlordane, nonachlor, mirex, and hexachlorobenzene (HCB) reflecting the successful historical and ongoing reduction of fugitive releases and remediation efforts in the U.S. and Canada including physical removal (dredging) coupled with sediment sequestration. Generally, lower concentrations and faster decreasing trends are observed in western/northern sampling sites compared to eastern/southern sites as the former sites are generally more remote from population centers and industrial activities. PCBs, which can be released from ongoing sources, have the highest concentration, the second slowest decreasing trend, and increasing mass fractions of the contaminants studied suggesting that they will continue to be the legacy contaminant of greatest concern into the future.

Revised fish aging techniques improve fish contaminant trend analyses in the face of changing Great Lakes food webs.

Incorporation of fish age into the assessment of status and trends for persistent, bioaccumulative and toxic chemicals in the Great Lakes has become an important step for the U.S. EPA's Great Lakes Fish Monitoring and Surveillance Program (GLFMSP). A slowing in the rate of decline for total PCBs in Lake Huron beginning in 2000, led the Program to complete a retrospective analysis to assess how chemical contamination may be influenced by fish age. Analytical results suggest that fish age is an important variable when assessing contaminant trends and that the Program needed to revise its compositing scheme to group fish according to age, rather than by length, prior to homogenization and chemical analysis. An Interlaboratory comparison study of multiple age structures was performed to identify the most appropriate age estimation structure for the Program. The lake trout (Salvelinus namaycush) maxillae was selected, over the otolith, as the most precise, accurate, and rapidly assessed structure for the Program when compared between laboratories and against the known age from the coded wire tag (CWT). Age-normalization practices can now be implemented when assessing contaminant concentrations and trends for the GLFMSP.

Concentration and distribution of contaminants in lake trout and walleye from the Laurentian Great Lakes (2008-2012).

Biomonitoring programs for persistent, bioaccumulative, and/or toxic chemicals of concern in fish tissues have been operated by the governments of Canada and the United States in the Great Lakes since the 1970's. The objectives of these programs are to assess concentrations of harmful chemicals in whole body top predator fish as an indicator of ecosystem health and to infer potential harm to fish and fish consuming wildlife in the Great Lakes Basin. Chemicals of interest are selected based upon national and binational commitments, risk assessment, and regulation, and include a wide range of compounds. This review summarizes all available data generated by Environment Canada and the United States Environmental Protection Agency for chemicals measured in whole body homogenates of Lake Trout (Salvelinus namaycush) and Walleye (Sander vitreus) for the time period spanning 2008 to 2012 from each of the five Great Lakes. The summary shows that concentrations of legacy compounds, such as, POPs listed in the Stockholm Convention and mercury continue to dominate the chemical burden of Great Lakes fish. This assessment, and others like it, can guide the creation of environmental quality targets where they are lacking, optimize chemical lists for monitoring, and prioritize chemicals of concern under agreements such as the Great Lakes Water Quality Agreement and the Stockholm Convention.

Concentration of organic contaminants in fish and their biological effects in a wastewater-dominated urban stream.

Data are presented on the concentrations of alkylphenol and alkylphenol ethoxylates (APEs) and persistent organic compounds in largemouth bass collected from a waste-water dominated stream in downtown Chicago. The fish residue concentrations of APEs are compared to concentrations of the APEs in the water that were collected at weekly intervals over two months bracketing the fall (2006) and a spring (2007) fish collection. The concentrations of APEs were significantly higher in the spring-collected fish (5.42µg/g) versus the fall (0.99µg/g) tand these differences were shared by differences in the water concentrations (spring - 11.47 versus fall - 3.44µg/L). The differences in water concentration were negatively correlated with water temperatures observed over the two sampling times. Fish residue concentrations of persistent organic compounds (PCBs, PBDEs, toxaphene, and many legacy pesticides including the DDT family) did not vary from fall to spring. Some of these residue concentrations were comparable to the highest NPE (nonylphenol ethoxylate) homologue concentrations, e.g. NP1EO was 3.5µg/g in the bass for the spring, the PBDE-congener 47 and p,p'-DDE averaged 1.0µg/g and 0.5µg/g, respectively, over both seasons. All the other persistent single-analyte concentrations were lower. Biological endpoints for endocrine effects measured in the same fish showed that there was an apparent positive correlation for physiological effects based on increased vitellogenin levels in males versus concentration of NPEs; however there were no observable histological differences in fall versus spring fish samples.

Effects of biologically-active chemical mixtures on fish in a wastewater-impacted urban stream.

Stream flow in urban aquatic ecosystems often is maintained by water-reclamation plant (WRP) effluents that contain mixtures of natural and anthropogenic chemicals that persist through the treatment processes. In effluent-impacted streams, aquatic organisms such as fish are continuously exposed to biologically-active chemicals throughout their life cycles. The North Shore Channel of the Chicago River (Chicago, Illinois) is part of an urban ecosystem in which >80% of the annual flow consists of effluent from the North Side WRP. In this study, multiple samplings of the effluent and stream water were conducted and fish (largemouth bass and carp) were collected on 2 occasions from the North Shore Channel. Fish also were collected once from the Outer Chicago Harbor in Lake Michigan, a reference site not impacted by WRP discharges. Over 100 organic chemicals with differing behaviors and biological effects were measured, and 23 compounds were detected in all of the water samples analyzed. The most frequently detected and highest concentration (>100µg/L) compounds were ethylenediaminetetraacetic acid and 4-nonylphenolmono-to-tetraethoxycarboxylic acids. Other biologically-active chemicals including bisphenol A, 4-nonylphenol, 4-nonylphenolmono-to-tetraethoxylates, 4-tert-octylphenol, and 4-tert-octylphenolmono-to-tetraethoxylates were detected at lower concentrations (<5µg/L). The biogenic steroidal hormones 17ß-estradiol, estrone, testosterone, 4-androstene-3,17-dione, and cis-androsterone were detected at even lower concentrations (<0.005µg/L). There were slight differences in concentrations between the North Side WRP effluent and the North Shore Channel, indicating minimal in-stream attenuation. Fish populations are continuously exposed to mixtures of biologically-active chemicals because of the relative persistency of the chemicals with respect to stream hydraulic residence time, and the lack of a fresh water source for dilution. The majority of male fish exhibited vitellogenin induction, a physiological response consistent with exposure to estrogenic compounds. Tissue-level signs of reproductive disruption, such as ovatestis, were not observed.