Temporal Trends of Great Lakes Legacy Contaminants: Ecological and Biological Considerations Applying the Age-Trend Model.

The USEPA Great Lakes Fish Monitoring and Surveillance Program (GLFMSP) has been monitoring top predator lake trout and walleye contaminant concentrations since the early 1970s. Our research revealed that select legacy contaminant groups (∑PCBs, ∑DDTs, ∑chlordanes, and ∑5PBDEs) have similar t1/2 and k2 values across the Great Lakes, with the exception of both Lake Erie sites and the Lake Superior─Keweenaw Point site. The slower halving times determined at both Lake Erie sites are consistent with legacy contaminant remobilization due to extreme weather climate effects and past remedial actions on the Detroit River, whereas the Lake Superior─Keweenaw Point site demonstrates contaminant halving times approaching the exponential minimum. Overall, Great Lakes select contaminant groupings have decreased between 25.8 and 97.9% since 2004. An age-normalized Great Lakes Contaminant Index (GLCI) was devised, indicating both Lake Michigan sites as the most highly impacted. The mean absolute deviation statistic was applied, documenting the need to age-correct contaminant trends due to highly variable age profiles. With the noted exceptions, the uniformity of age-corrected trend modeling suggests that a combination of the fundamental biological and physicochemical mechanisms of natural contaminant sequestration, declining dissolved water concentrations, accumulation/metabolism/depuration, and the overall reduction of legacy contaminant loading are driving the generally consistent rates of declines in the Great Lakes. Many of the biological and ecological stressors currently associated with climate change appear to be accounted for by the age-trend model.

Polychlorinated Naphthalenes across the Great Lakes: Lake Trout and Walleye Concentrations, Trends, and TEQ Assessment-2004-2018.

Polychlorinated naphthalenes (PCNs) were measured in lake trout and walleye over the period 2004-2018, utilizing isotope dilution techniques with high-resolution gas chromatography/high-resolution mass spectrometry to assess concentrations and toxic equivalence (TEQ). An age-trend model was applied to mitigate the effect of a changing lake trout age structure. Most Great Lakes Fish Monitoring and Surveillance Program sampling sites demonstrated significant half-life and percent decreases for lake trout total PCNs and total TEQ over the 2004-2018 period, the exceptions being Lake Erie lake trout and walleye which illustrated increasing concentrations. Great Lakes total PCN concentrations ranged between 5701 and 100 pg/g ww, whereas total PCN TEQ concentrations ranged between 8.89 and 0.13 pg-TEQ/g ww. Based on the average number of chlorines per naphthalene, we determined that the overall lake trout and walleye PCN congener distribution has significantly shifted to a lower-chlorinated composition in the Great Lakes (5.33 to 4.48 Cl/CN) and has resulted in a substantial 59.1% reduction of the overall total PCN TEQ burden. A prominent PCN concentration trend breakpoint was observed in Lake Ontario lake trout over the 2012-2016 period likely associated with hazardous waste cleanups, channel dredging, and spoils disposal in the Detroit River and western-basin of Lake Erie.

Concentrations, toxic equivalence, and age-corrected trends of legacy organic contaminants in Lake Champlain lake trout: 2012-2018.

Our study is the first comprehensive, multi-year assessment of polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), organochlorine pesticides (OCPs), polychlorinated naphthalenes (PCNs), polychlorinated dibenzo-p-dioxins, and polychlorinated dibenzofurans (PCDD/Fs) lake trout concentrations and trends in Lake Champlain (LC). Lake trout whole-fish, fillets, and eggs were collected over the 2012-2018 study period. Total PCB concentrations (395.7 ng/g wet weight (ww)) were the highest average concentration of any contaminant grouping reported in this study. Whole-fish lake trout modeling revealed highly significant (p < 0.05) log-linear correlations for all dioxin-like contaminants measured. Overall contaminant decreases for the 2012-2018 period ranged from 20.9% (total PCNs) to 39.3% (2378-TCDD). Contaminant decreases for total PCBs and total-5-PBDEs were 30.9% and 48.3%, respectively. Of particular significance were the measured total PBDE concentrations (74.3 ng/g ww) found in LC whole-fish lake trout. Log-linear forecasting indicates that whole-fish lake trout TEQs will be below the guidelines protective of wildlife thresholds during the periods 2035-2047 (TRGbird) and 2062-2088 (TRGmammal). Based on current USEPA guidelines, all lake trout fillets from Lake Champlain analyzed for this study exceed the human health cancer screening value of 0.15 pg-TEQ/g ww by a substantial margin (average = 8.61 pg-TEQ/g ww). Dioxin-like trend data collected for Lake Champlain indicates that the mechanisms of contaminant uptake, trends, and yearly percent decline reflect those found in the Great Lakes.

Trends of polychlorinated dioxins, polychlorinated furans, and dioxin-like polychlorinated biphenyls in Chinook and Coho salmonid eggs from a Great Lakes tributary.

Eggs from mature Chinook (Oncorhynchus tshawytscha) and Coho (Oncorhynchus kisutch) salmon were collected between 2004 and 2014 from the Salmon River fish hatchery in Altmar, New York. The egg samples were analyzed for seventeen polychlorinated dibenzodioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), as well as four dioxin-like polychlorinated biphenyls (DL-PCBs) using USEPA methods 1613 and 1668. Salmonid eggs were chosen as a tissue of interest since salmon feed at all trophic levels of the food web as they grow, and spawn in a narrow range of ages providing consistent, representative, and temporal samples of contaminant exposure. First-order decay models indicate decreasing trends for all select contaminants in both species, expressed by a toxic equivalence (TEQ) half-life (t1/2) of 11 years in Chinook and Coho eggs. No significant statistical difference in contaminant elimination rates were noted between species. TEQ elimination rates for Coho and Chinook eggs were not significantly different (p > 0.05) when compared with published Lake Ontario whole-fish lake trout elimination rates. Our research demonstrates that salmonid eggs are an effective means to assess PCDD, PCDF, and DL-PCB exposures and long-term trends in the Great Lakes.

Spatial and Temporal Trends (2004-2016) of Selected Alternative Flame Retardants in Fish of the Laurentian Great Lakes.

Following the phase-out of polybrominated diphenyl ether (PBDE) and hexabromocyclododecane (HBCDD) flame retardants (FRs) from North American markets, the use of alternative FRs has increased. In this study the occurrence and spatiotemporal distributions of 18 dechlorane analogues (collectively referred to as DECs) and 20 alternative brominated FRs (referred to as ABFRs, i.e., brominated FRs other than PBDEs and HBCDD) were investigated in top predator fish megacomposites (i.e., a composite of all 50 fish) collected yearly from each of the Great Lakes from 2004 to 2016. Frequently detected substances include dechlorane 602, 603, 604 Component B, anti- and syn-dechlorane plus, and chlordene plus, as well as several brominated benzene FRs (i.e., hexabromobenzene, pentabromotoluene, and tetrabromo- o-chlorotoluene). Concentrations of ΣDECs and ΣABFRs ranged from 0.33-31.9 ng/g lipid weight (lw) (0.01-8.3 ng/g wet weight or ww) and 0.91-54.7 ng/g lw (0.09-7.1 ng/g ww), respectively. Flame retardant contamination exhibited chemical-specific spatial variations across the five lakes. Concentrations of ΣABFRs in Lake Erie fish were generally lower than those from other lakes. By contrast, fish ΣDEC concentrations were highest in Lake Ontario and the composition of dechlorane analogues differed significantly between Lake Ontario and the other lakes, indicating likely point-source influences. Temporal analyses revealed declining trends of ΣDECs and ΣABFRs in most lakes except Lake Erie, with age corrected trend slopes of -13.5% to -8.8% and -20.1% to -7.0% per year, respectively.

Comprehensive Analysis of the Great Lakes Top Predator Fish for Novel Halogenated Organic Contaminants by GC×GC-HR-ToF Mass Spectrometry.

The U.S. Environmental Protection Agency's Great Lakes Fish Monitoring and Surveillance Program (GLFMSP) has traced the fate and transport of anthropogenic chemicals in the Great Lakes region for decades. Isolating and identifying halogenated species in fish is a major challenge due to the complexity of the biological matrix. A nontargeted screening methodology was developed and applied to lake trout using a 2-dimensional gas chromatograph coupled to a high resolution time-of-flight mass spectrometer (GC×GC-HR-ToF MS). Halogenated chemicals were identified using a combination of authentic standards and library spectral matching, with molecular formula estimations provided by exact mass spectral interpretation. In addition to the halogenated chemicals currently being targeted by the GLFMSP, more than 60 nontargeted halogenated species were identified. Most appear to be metabolites or breakdown products of larger halogenated organics. The most abundant compound class was halomethoxyphenols accounting for more than 60% of the total concentration of halogenated compounds in top predator fish from all five Great Lakes illustrating the need and utility of nontargeted halogenated screening of aquatic systems using this platform.

Age-Corrected Trends and Toxic Equivalence of PCDD/F and CP-PCBs in Lake Trout and Walleye from the Great Lakes: 2004-2014.

Our research reports polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and coplanar polychlorinated biphenyls (CP-PCBs) concentrations and age-corrected trends for lake trout and walleye in the Great Lakes over the 2004-2014 period. We determined that age-contaminant corrections are required to accurately report contaminant trends due to significant lake trout age structure changes. The age-trend model (ATM) described here uses a lake-specific age-contaminant regression to mitigate the effect of a fluctuating lake trout age structure to directly improve the log-linear regression model. ATM results indicate that half-life (t1/2) and percent decreases for PCDD/Fs, CP-PCBs, and toxic equivalence (TEQ) (average -56 to 70%) were fairly uniform and consistent across the Great Lakes over the 2004-2014 period. The vast majority of TEQ associated with all Great Lakes lake trout and walleye samples is due to the nonortho CP-PCBs (average = 79%) as compared with PCDD/Fs (average = 21%). On average, CP-PCB_126 individually accounted for over 95% of the total CP-PCB TEQ. A retrospective analysis (1977-2014) of 2378-TCDF and 2378-TCDD raw concentrations in Lake Ontario lake trout revealed decreases of 94% and 96%, respectively. Tissue residue guidelines for wildlife protection based on lake trout and walleye total TEQ were uniformly exceeded in all the Great Lakes.

Comparison of PoraPak Rxn RP and XAD-2 adsorbents for monitoring dissolved hydrophobic organic contaminants.

Accurate determination of the levels of dissolved hydrophobic organic contaminants (HOCs) is an important step in estimating the dynamics of their inputs and losses in aqueous systems. This study explores an alternative method for efficiently sampling dissolved HOCs while mitigating a number of sampling artifacts associated with traditional methods. The adsorption characteristics of a new polymeric resin, PoraPak Rxn RP (PPR), were assessed using sorption isotherm experiments and fixed bed adsorption studies. The adsorption capacities and breakthrough times for four model contaminants (phenol, p-nitrophenol, naphthalene, and 2,4,6-tribromophenol) were proportional to the contaminant's hydrophobicity. The ability of PPR to isolate dissolved polychlorinated biphenyls (PCBs) in real samples was compared with that of XAD-2, a well-known macroporous polymer that suffers from high background contamination. The results indicated that the PPR resin can be effectively used for monitoring HOCs, with low ∑PCB levels in blanks, decreasing solvent use, and reducing extraction times.

Post-1990 temporal trends of PCBs and organochlorine pesticides in the atmosphere and in fish from lakes Erie, Michigan, and Superior.

We have analyzed concentration data sets covering the period 1992-2010 from the Great Lakes Integrated Atmospheric Deposition Network and from the Great Lakes Fish Monitoring and Surveillance Program to determine and compare pollutant time trends in the atmosphere and in fish. The analytes of interest were polychlorinated biphenyls, DDTs, chlordanes, dieldrin, and α- and γ-hexachlorocyclohexane (HCHs), and the sites of interest were Lakes Erie, Michigan, and Superior. Overall, we found no significant differences between the atmospheric and fish temporal trends for any of these compounds in any of the lakes. Polychlorinated biphenyl concentrations are decreasing in both the atmosphere and in the fish with halving times of 14 ± 2 years. The halving times for DDTs, chlordanes, and dieldrin are 8.7 ± 0.4 years for both the atmosphere and the fish. The most rapid temporal trend was observed for α- and γ-HCH concentrations, which are decreasing in both the atmosphere and in fish with halving times of 3.3 ± 0.4 years. The practical implications of these results are discussed.

Atmospheric concentrations and potential sources of PCBs, PBDEs, and pesticides to Acadia National Park.

This study assessed concentrations and investigated potential source regions for PCBs, PBDEs, and organochlorine pesticides in Acadia National Park, Maine, USA. Back-trajectories and potential source contribution function (PSCF) values were used to map potential source areas for total-PCBs, BDE-47, and 10 organochlorine pesticides. The constructed PSCF maps showed that ANP receives high pollutant concentrations in air masses that travel along four main pathways: (1) from the SW along the eastern Atlantic seaboard, (2) from the WSW over St. Louis, and Columbus regions, (3) from the west over Chicago, and Toronto regions, and (4) from WNW to NNW over the Great Lakes, and Quebec regions. Transport of all studied pollutants were equally distributed between the first three pathways, with only minor contributions from the last pathway. This study concludes that the high-pollutant concentrations arriving at ANP do not exclusively originate from the major urban centers along the eastern Atlantic seaboard.

Temporal trends of polychlorinated biphenyls and organochlorine pesticides in Great Lakes fish, 1999-2009.

Temporal trend analysis of the latest Great Lake Fish Monitoring and Surveillance Program (GLFMSP) data showed statistically significant decreases in persistent bioaccumulative and toxic (PBT) contaminant (polychlorinated biphenyls (PCBs), dichloro-diphenyl-trichlorethane and its metabolites (DDTs), dieldrin, cis-chlordane, oxychlordane, cis-nonachlor) concentrations in Lakes Huron, Ontario, and Michigan lake trout over the period of 1999 to 2009. In contrast, for most contaminants, no statistically significant concentration trends were found in top predator fish in Lakes Superior and Erie during the same period. For Lakes Huron, Ontario, and Michigan 5.0 ± 2.6% average annual concentration decreases were found for PCBs, DDTs, dieldrin, and other organochlorine pesticides (OCs) decreased at a faster rate, ranging from 10 ± 4.3% to 20 ± 7.1% per year. For these three lakes, with the exception of PCBs, these current decreases are greater than were shown by an earlier trend analysis that estimated an annual contaminant decrease of about 2-5% for the period of 1980 to 2003. For Lakes Superior and Erie, the finding of no statistically significant trend is in agreement with previously reported results for these lakes.

Polybrominated diphenyl ethers (PBDEs): turning the corner in Great Lakes trout 1980-2009.

Lake trout and walleye composites were collected between 2004 and 2009 as part of the Great Lakes Fish Monitoring and Surveillance Program (GLFMSP) and analyzed for polybrominated diphenyl ethers (PBDEs). Yearly mean total PBDE concentrations (sum of congeners BDE-47, BDE-99, BDE-100, BDE-153, BDE-154) ranged from 44-192, 28-113, 50-107, 37-111, and 11-22 ng/g wet wt. for Lakes Michigan, Huron, Ontario, and Superior lake trout, and Lake Erie walleye, respectively. A 1980-2009 temporal record of PBDE concentrations in the Great Lakes' top predator fish (lake trout and walleye) was assembled by integrating previous GLFMSP data (1980-2003) with current results (2004-2009). Temporal profiles show obvious breakpoints between periods of PBDE accumulation and decline in trout for Lakes Huron, Michigan and Ontario with a significant (p < 0.0001 and r = 0.55, 0.72, and 0.51, respectively) decrease in concentration after 2000-2001. A similar transition was observed in Lake Superior for the nearshore site accompanied by a less significant decreasing trend (p = 0.016, r = 0.33), suggesting concentrations are declining very slowly or have leveled off. In contrast, Lake Erie walleye concentrations began leveling off in the late 1990s and no statistically significant trend (increasing or decreasing) has been observed in recent years. A decrease in the BDE-47/BDE-153 ratio was also recently observed, suggesting a transition to more highly brominated PBDEs is occurring in Great Lakes trout. This study provides region-wide evidence that PBDE concentrations are generally declining in Great Lakes trout, although there are clear exceptions to this trend. Results from this study reflect the positive impact of the 2004 PentaBDE ban on macro-scale aquatic freshwater ecosystems.

Total PCBs, dioxin-furan TEQs, and total mercury concentrations in mink in and out of the Rochester Embayment area of concern near and inland from the shore of Lake Ontario.

In terms of reproductive and other adverse outcomes after exposure to polychlorinated biphenyls (PCBs), dioxins, and furans, the mink (Mustela vison) is one of the most sensitive mammals. Our objective was to determine if there are differences in the concentrations of total mercury (Hg), total PCBs, and dioxin-furan toxic equivalents (TEQs) between mink living in and out of the Rochester Embayment of Lake Ontario (RELO) Area of Concern (AOC) and between mink living near the shore of Lake Ontario and inland. Concentrations of total Hg in the brain, total PCBs and dioxin-furan TEQs in adipose, and total PCBs in liver were significantly higher for mink living near the shore of Lake Ontario than inland. For mink living in and out of the AOC, differences in total PCBs and dioxin-furan TEQs in adipose and the liver were substantial but not significant. Correlations among concentrations of total Hg, total PCBs, and dioxin-furan TEQs in mink were high. Our results suggest that contamination of mink living near the southern shore of Lake Ontario primarily comes from contact with the Lake Ontario food web, not from sources in the RELO AOC.

Model estimates bioaccumulation of total PCBs, dioxin-furan TEQs, and total mercury in mink liver based on concentrations in Lake Ontario water.

We used stable isotope analysis and a bioaccumulation model to estimate concentrations of total polychlorinated biphenyls (PCBs), dioxin-furan toxic equivalents (TEQs), and total mercury (Hg) in mink and to compare predicted ranges with their chemical concentrations in mink liver (PCB, TEQ) and brain (Hg). Actual concentrations were within predicted bounds for total PCB, dioxin-furan TEQ, and Hg except in two cases (lowest PCB and highest Hg) which were very close to predicted bounds. Based on (15)N analysis, the trophic level of mink ranged from 3.4 to 3.9. Animals at the upper end of the range were exposed to Lake Ontario water and its food web, whereas those at the lower end were captured at inland locations. Because of the complexity of wetland (an important habitat for mink in this study) food webs with pelagic, littoral, and terrestrial carbon sources and overlapping (13)C signatures, whether the origins of mink diets were aquatic or terrestrial could not be determined. We have established a nondestructive biomonitoring tool to reasonably estimate concentrations of total PCBs, TEQs and total Hg in mink tissues as concentrations of these chemicals change in their water supply.

Toxaphene analysis in Great Lakes fish: a comparison of GC-EI/MS/MS and GC-ECNI-MS, individual congener standard and technical mixture for quantification of toxaphene.

Toxaphene is considered to be a problematic organochlorine pollutant because of its bioaccumulation potential and persistence in aquatic environments. In this study, whole lake trout and walleye composites were used to evaluate two analytical techniques for total toxaphene and selected congener analysis. The efficacy of using gas chromatography electron ionization tandem mass spectrometry (GC-EI/MS/MS) and electron capture negative ionization mass spectrometry (GC-ECNI-MS) were compared. Although the sensitivity using GC-ECNI-MS was approximately five times greater than GC-EI/MS/MS, the latter provided more consistent inter-Parlar relative response factors (RRF). When using technical calibration mixtures, these results suggest a more accurate total toxaphene measurement was obtained using the GC-EI/MS/MS method. Total toxaphene concentrations in lake trout composites from both methods were highly correlated (R(2) = 0.985) with the MS/MS concentrations approximately half of those determined by ECNI, suggesting systematic high bias in toxaphene concentrations when measured using GC-ECNI.

Histological lesions in mink jaws are a highly sensitive biomarker of effect after exposure to TCDD-like chemicals: field and literature-based confirmations.

The mink (Mustela vison) is one of the most sensitive mammals to 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD)-like chemicals. By literature review we established that a histological lesion of the jaw bone of mink, evidenced by squamous epithelial hyperplasia in the gingival tissue that forms nests or cords that infiltrate the periodontal ligament and alveolar bone causing osteolysis of the mandible and maxilla that could lead to squamous cell carcinoma, is the most sensitive known biomarker of effect following exposure of mink to TCDD-like chemicals. Lesions have been observed when total TCDD toxic equivalents (TEQ: dioxins, furans, coplanar polychlorinated biphenyls or PCBs) in liver exceed 40 ng/kg wet weight (ww) or when total PCB exceeds 1698 ng/g ww. This is the second report of histological evidence of this lesion in wild-caught mink, and it is the first report of the lesion being grossly detectable in naturally exposed mink. Some mink living near the south shore of Lake Ontario (exposed to the lake's food web), but not inland mink (not exposed to the lake's food web), accumulate more than 40 ng total TEQ/kg or 1698 ng total PCB/kg in liver. Because of its sensitivity, the jaw lesion biomarker is very useful for assessing the health of wildlife populations exposed to TCDD-like chemicals.

Comparison of polychlorinated biphenyl levels across studies of human neurodevelopment.

Polychlorinated biphenyls (PCBs) are persistent pollutants that are ubiquitous in the food chain, and detectable amounts are in the blood of almost every person in most populations that have been examined. Extensive evidence from animal studies shows that PCBs are neurotoxins, even at low doses. Interpretation of human data regarding low-level, early-life PCB exposure and subsequent neurodevelopment is problematic because levels of exposure were not similarly quantified across studies. We expressed the exposure levels from 10 studies of PCB and neurodevelopment in a uniform manner using a combination of data from original investigators, laboratory reanalyses, calculations based on published data, and expert opinion. The mainstay of our comparison was the median level of PCB 153 in maternal pregnancy serum. The median concentration of PCB 153 in the 10 studies ranged from 30 to 450 ng/g serum lipid, and the median of the 10 medians was 110 ng/g. We found that (a)) the distribution of PCB 153 exposure in most studies overlapped substantially, (b)) exposure levels in the Faroe Islands study were about 3-4-fold higher than in most other studies, and (c)) the exposure levels in the two recent U.S. studies were about one-third of those in the four earlier U.S. studies or recent Dutch, German, and northern Québec studies. Our results will facilitate a direct comparison of the findings on PCBs and neurodevelopment when they are published for all 10 studies.