Transcriptomic and developmental effects of persistent organic pollutants in sentinel fishes collected near an arctic formerly used defense site.

Alaska contains over 600 formerly used defense (FUD) sites, many of which serve as point sources of pollution. These sites are often co-located with rural communities that depend upon traditional subsistence foods, especially lipid-rich animals that bioaccumulate and biomagnify persistent organic pollutants (POPs). Many POPs are carcinogenic and endocrine-disrupting compounds that are associated with adverse health outcomes. Therefore, elevated exposure to POPs from point sources of pollution may contribute to disproportionate incidence of disease in arctic communities. We investigated PCB concentrations and the health implications of POP exposure in sentinel fishes collected near the Northeast Cape FUD site on Sivuqaq (St. Lawrence Island), Alaska. Sivuqaq residents are almost exclusively Yupik and rely on subsistence foods. At the request of the Sivuqaq community, we examined differential gene expression and developmental pathologies associated with exposure to POPs originating at the Northeast Cape FUD site. We found significantly higher levels of PCBs in Alaska blackfish (Dallia pectoralis) collected from contaminated sites downstream of the FUD site compared to fish collected from upstream reference sites. We compared transcriptomic profiles and histopathologies of these same blackfish. Blackfish from contaminated sites overexpressed genes involved in ribosomal and FoxO signaling pathways compared to blackfish from reference sites. Contaminated blackfish also had significantly fewer thyroid follicles and smaller pigmented macrophage aggregates. Conversely, we found that ninespine stickleback (Pungitius pungitius) from contaminated sites exhibited thyroid follicle hyperplasia. Despite our previous research reporting transcriptomic and endocrine differences in stickleback from contaminated vs. reference sites, we did not find significant differences in kidney or gonadal histomorphologies. Our results demonstrate that contaminants from the Northeast Cape FUD site are associated with altered gene expression and thyroid development in native fishes. These results are consistent with our prior work demonstrating disruption of the thyroid hormone axis in Sivuqaq residents.

The Ins and Outs of Per- and Polyfluoroalkyl Substances in the Great Lakes: The Role of Atmospheric Deposition.

As part of the Integrated Atmospheric Deposition Network, precipitation (n = 207) and air (n = 60) from five sites and water samples (n = 87) from all five Great Lakes were collected in 2021-2023 and analyzed for 41 per- and polyfluoroalkyl substances (PFAS). These measurements were combined with other available data to estimate the mass budget for four representative compounds, PFBA, PFBS, PFOS, and PFOA for the basin. The median Σ41PFAS concentrations in precipitation across the five sites ranged between 2.4 and 4.5 ng/L. The median Σ41PFAS concentration in lake water was highest in Lake Ontario (11 ng/L) and lowest in Lake Superior (1.3 ng/L). The median Σ41PFAS concentration in air samples was highest in Cleveland at 410 pg/m3 and lowest at Sleeping Bear Dunes at 146 pg/m3. The net mass transfer flows were generally negative for Lakes Superior, Michigan, and Huron and positive for Lakes Erie and Ontario, indicating that the three most northern lakes are accumulating PFAS and the other two are eliminating PFAS. Atmospheric deposition is an important source of PFAS, particularly for Lake Superior.

From watersheds to dinner plates: Evaluating PFAS exposure through fish consumption in Southeast Michigan.

Muscle tissue and organ samples of six different fish species were collected from ten locations in Southeast Michigan's Huron and Rouge watersheds. Per- and polyfluoroalkyl substances (PFAS) were analyzed in 36 samples comprising filets, liver, gut, and eggs using targeted analysis and the direct total oxidizable precursor (dTOP) assay on a subset of six samples. The median concentrations of the ∑PFAS in filets from the Huron and Rouge watersheds were 13 and 6.3 ng/g wet weight (w.w.), respectively. Perfluorooctane sulfonate (PFOS) was the most detected and abundant compound in fish organs, with the liver having the largest overall burden of PFAS. The highest percent increase in targeted PFAS after the dTOP assay was observed in the Catfish filet (552%) while the smallest increase was in the Catfish liver (32%) accounting for 1.3 and 8.1 nMole F/g dry weight (d.w.), respectively. The positive matrix factorization (PMF) analysis revealed three distinct PFAS sources, of which the one attributed to PFOS explained 73% of the data. Results from this work have important implications for fish consumption in Michigan waterways. Among the filet samples analyzed, the calculated daily consumption limit of total PFOS was exceeded in approximately 82% and 91% of samples for adults and children over the age of seven years old, respectively.

PFAS in municipal landfill leachate: Occurrence, transformation, and sources.

To understand sources and processes affecting per- and polyfluoroalkyl substances (PFAS), 32 PFAS were measured in landfill leachate from 17 landfills across Washington State in both pre-and post-total oxidizable precursor (TOP) assay samples, using an analytical method that was the precursor to EPA Draft Method 1633. As in other studies, 5:3FTCA was the dominant PFAS in the leachate, suggesting that carpets, textiles, and food packaging were the main sources of PFAS. Total PFAS concentrations (Σ32PFAS) ranged from 61 to 172,976 ng/L and 580-36,122 ng/L in pre-TOP and post-TOP samples, respectively, suggesting that little or no uncharacterized precursors remained in landfill leachate. Furthermore, due to chain-shortening reactions, the TOP assay often resulted in a loss of overall PFAS mass. Positive matrix factorization (PMF) analysis of the combined pre- and post-TOP samples produced five factors that represent sources and processes. Factor 1 consisted primarily of 5:3FTCA (intermediate of 6:2 fluorotelomer degradation and characteristic of landfill leachate), while factor 2 was dominated by PFBS (degradant of C-4 sulfonamide chemistry) and, to a lesser extent, by several PFCAs and 5:3FTCA. Factor 3 consisted primarily of both short-chain PFCAs (end-products of 6:2 fluorotelomer degradation) and PFHxS (derived from C-6 sulfonamide chemistry), while the main component of factor 4 was PFOS (dominant in many environmental media but minor in landfill leachate, perhaps reflecting a production shift from longer to shorter chain PFAS). Factor 5, highly loaded with PFCAs, was dominant in post-TOP samples and therefore represented the oxidation of precursors. Overall, PMF analysis suggests that the TOP assay approximates some redox processes which occur in landfills, including chain-shortening reactions which yield biodegradable products.

Disentangling Source Profiles and Time Trends of Halogenated Flame Retardants in the Great Lakes.

Thirty-five polybrominated diphenyl ethers (PBDEs) and eight other alternative flame retardants were measured in air samples (vapor plus particles) collected at six sites near the North American Great Lakes between 2005 and 2019 as part of the Integrated Atmospheric Deposition Network (IADN). These data were analyzed using a multiple linear regression model to determine spatial and temporal trends. Overall, the levels of flame retardants remain significantly higher in urban sites compared to rural and remote sites except for pentabromoethylbenzene (PBEB), hexabromobenzene (HBB), and total Dechlorane Plus (ΣDP). Here, we report the first findings of decreasing levels of ΣDP at Sturgeon Point, New York. The atmospheric levels of total PBDEs remain unchanged over time near Lakes Michigan and Superior and declined near Lakes Erie and Ontario, with rate constants at the latter two lakes revealing halving times of approximately 7 to 14 years. This work presents results from the first investigation of PBDE source apportionment in the Great Lakes atmosphere. Source apportionment by use of positive matrix factorization (PMF) identified two legacy commercial technical mixtures (i.e., penta-BDE and deca-BDE mixes) and elucidated a factor representing ambient degradation. Our results show that weathered local sources of technical commercial mixtures, and their photolysis contribute most to the total PBDE burden in the Great Lakes atmosphere.

Sources of polychlorinated biphenyls to Upper Hudson River fish post-dredging.

Polychlorinated biphenyls (PCBs) are persistent, bioaccumulative, and toxic chemicals that are the dominant contaminant in the Upper Hudson River (UHR) in New York State where two General Electric (GE) plants historically discharged PCBs to the river. Portions of the UHR were dredged from 2009 to 2015 to address PCB contamination. In 2017, the first post-dredging survey of yearling feeder fish and sediment PCB contamination was conducted to establish a baseline for the recovery of the river. Prior analysis of the sediment data from the 2017 survey indicated that ∼2% of the PCBs in the surface sediment were higher in molecular weight than the formulation used by GE and therefore arose from non-GE sources. In this work, the fish PCB data from the 2017 survey were analyzed using Positive Matrix Factorization (PMF). Empirical Bayesian Kriging (EBK) was used to estimate PCB concentrations in the sediment at the locations where fish were collected. The results suggest that PCBs that are the products of microbial dechlorination bioaccumulate in the fish and represent 7% of the PCB mass in the fish data set. Further, the results suggest that about 13% of the PCBs in the fish may have come from non-GE sources. This is higher than the percentage of non-GE PCBs in the sediment, but can be explained by the higher molecular weight of the non-GE mixture which causes it to bioaccumulate more effectively than GE PCBs. Concentrations of the non-GE PCBs averaged about 240 ppb wet weight (whole body) in yearling feeder fish. The remedial goals range from 50 to 400 ppb ww in fillet for fish including piscivorous species that are likely to have higher PCB concentrations than feeder fish.

PFAS in drinking water and serum of the people of a southeast Alaska community: A pilot study.

Per- and polyfluoroalkyl substances (PFAS) have become a target of rigorous scientific research due to their ubiquitous nature and adverse health effects. However, there are still gaps in knowledge about their environmental fate and health implications. More attention is needed for remote locations with source exposures. This study focuses on assessing PFAS exposure in Gustavus, a small Alaska community, located near a significant PFAS source from airport operations and fire training sites. Residential water (n = 25) and serum (n = 40) samples were collected from Gustavus residents and analyzed for 39 PFAS compounds. In addition, two water samples were collected from the previously identified PFAS source near the community. Fourteen distinct PFAS were detected in Gustavus water samples, including 6 perfluorinated carboxylic acids (PFCAs), 7 perfluorosulfonic acids (PFSAs), and 1 fluorotelomer sulfonate (FTS). ΣPFAS concentrations in residential drinking water ranged from not detected to 120 ng/L. High ΣPFAS levels were detected in two source samples collected from the Gustavus Department of Transportation (14,600 ng/L) and the Gustavus Airport (228 ng/L), confirming these two locations as a nearby major source of PFAS contamination. Seventeen PFAS were detected in serum and ΣPFAS concentrations ranged from 0.0170 to 13.1 ng/mL (median 0.0823 ng/mL). Perfluorooctanesulfonic acid (PFOS) and perfluorohexanesulfonic acid (PFHxS) were the most abundant PFAS in both water and serum samples and comprised up to 70% of ΣPFAS concentrations in these samples. Spearman's correlation analysis revealed PFAS concentrations in water and sera were significantly and positively correlated (r = 0.495; p = 0.0192). Our results confirm a presence of a significant PFAS source near Gustavus, Alaska and suggest that contaminated drinking water from private wells contributes to the overall PFAS body burden in Gustavus residents.

Source apportionment of perfluoroalkyl substances in Great Lakes fish.

Due to the complex sources and fate of perfluoroalkyl substance (PFAS), their source apportionment in the environment remains a challenge. A data set of 11 straight-chain PFAS in 139 samples of fish in the Great Lakes was analyzed using positive matrix factorization (PMF) to investigate their primary sources, whose spatial variations were examined against the surrounding environmental factors. PMF analysis produced five fingerprints. Factor 1 (72% of Σ11PFAS, dominated by PFOS) probably represented emissions from primary sources (such as consumer products) and secondary sources (precursors), and increased in average abundance from west to east across the Great Lakes. Factor 2 (13% of Σ11PFAS) and factor 3 (7% of Σ11PFAS), highly loaded with long-chain PFAS and PFNA, respectively, were thought to represent PVDF manufacture or processing in metal plating. They showed higher contributions in sparsely populated Lakes Superior and Huron. Factor 4 (5% of Σ11PFAS, highly loaded with PFOS and PFHxS) presented hot spots near current and former air force bases, suggesting it was related to aqueous film-forming foams (AFFFs). Factor 5 (4% of Σ11PFAS) contained primarily PFOS and PFOSA, which may imply metabolism of precursors (PFOSA) to PFOS in vivo. Unexpectedly, the spatial trends of the five sources all showed abnormally low values near the more urbanized Chicago and Milwaukee in Lake Michigan, which may be due to their unique wastewater and stormwater infrastructure or may arise from atmospheric transport of precursors. Our study indicated that PMF was an effective tool to identify sources of PFAS in fish despite absorption, distribution, metabolism, and excretion (ADME) processes which might alter fingerprints in fish relative to their surrounding environment.

Polychlorinated biphenyls in stormwater sediments: Relationships with land use and particle characteristics.

Polychlorinated biphenyls (PCBs) are classified as persistent organic pollutants (POPs). Concentrations of 209 PCB congeners as well as profiles of the ten homologues were determined in stormwater sediments collected from various (primarily roadway) sites with different land use. The total PCB concentrations ranged from 8.3 to 57.4 ng/g dry weight (dw), with a mean value of 29.2 ng/g dw. PCB concentrations varied with nearby land use. Higher stormwater sediment PCB concentrations were found in dense urban areas (average: 39.8 ±â€¯10.5 ng/g) and residential areas (average: 35.3 ±â€¯6.2 ng/g) compared to highways passing through greenspace (average: 18.0 ±â€¯0.4 ng/g). The number of chlorines per biphenyl ranged from 3.63 to 5.39 and the toxic equivalency (TEQs) of the PCBs were between 1.5 and 18.0 pg/g at all sites. A non-Aroclor congener, PCB 11, was detected in all samples and was dominant at two sites. PCBs were sorbed to smaller stormwater particulate matter (≤75 µm) at higher concentrations compared to larger particles (>75 µm). PCB sorption tended to increase with the total organic carbon (TOC) of the particulate matter in the sediment samples. However, greater PCB mass (almost 80%) was present in the larger particles. Information on sediment PCB concentrations from different land uses, along with stormwater particulate matter data can allow the estimation of PCB loads and load reductions using stormwater control measures.

Colonization and growth of dehalorespiring biofilms on carbonaceous sorptive amendments.

Removal of polychlorinated biphenyls (PCBs) from contaminated sediments is a priority due to accumulation in the food chain. Recent success with reduction of PCB bioavailability due to adsorption onto activated carbon led to the recognition of in situ treatment as a remediation approach. In this study, reduced bioavailability and subsequent break-down of PCBs in dehalorespiring biofilms was investigated using Dehalobium chlorocoercia DF1. DF1 formed a patchy biofilm ranging in thickness from 3.9 to 6.7 µm (average 4.6 ± 0.87 µm), while the biofilm coverage varied from 5.5% (sand) to 20.2% (activated carbon), indicating a preference for sorptive materials. Quantification of DF1 biofilm bacteria showed 1.2-15.3 × 109 bacteria per gram of material. After 22 days, coal activated carbon, bone biochar, polyoxymethylene, and sand microcosms had dechlorinated 73%, 93%, 100%, and 83%, respectively. These results show that a biofilm-based inoculum for bioaugmentation of PCBs in sediment can be an efficient approach.

Positive Matrix Factorization analysis shows dechlorination of polychlorinated biphenyls during domestic wastewater collection and treatment.

Polychlorinated biphenyls (PCBs) are persistent, toxic and bioaccumulative pollutants. One of the few pathways via which they break down is microbial dechlorination, which has been shown to occur in sewers. Questions remain about where within sewers this process takes place and which conditions encourage dechlorination. These issues were examined using a large data set on PCBs in influent and effluents from a main and bypass outfall from a wastewater treatment facility in the Mid-Atlantic region of the USA. A data set containing 64 chromatographic peaks representing 103 PCB congeners measured in 74 whole water samples was analyzed by Positive Matrix Factorization (PMF). PMF resolved four factors, three of which represented Aroclors 1242, 1254, and 1260. The remaining factor represented an advanced dechlorination regime of PCBs characterized by high proportions of PCBs 4 and 19 and comprised about 35% of the PCBs in the treated effluent, among the highest levels of dechlorination observed in previous studies. Concentrations of dechlorination products were not correlated with total suspended solids, indicating they were mostly dissolved and explaining the poor removal via sedimentation during the treatment process. The factors representing Aroclors were positively correlated with total influent flow, but the dechlorination signal was not, suggesting that the dechlorination signal arises from different locations and/or processes than the Aroclors. Even though treatment and dechlorination reduced the dioxin-like toxicity of the PCB mixture, this effect might be offset by the incomplete removal of dechlorination products.

Using positive matrix factorization to investigate microbial dehalogenation of chlorinated benzenes in groundwater at a historically contaminated site.

Chlorinated benzenes are common groundwater contaminants in the United States, so demonstrating whether they undergo degradation in the subsurface is important in determining the best remedy for this contamination. The purpose of this work was to use a new data mining approach to investigate chlorinated benzene degradation pathways in the subsurface. Positive Matrix Factorization (PMF) was used to analyze long-term measurements of chlorinated benzene concentrations in groundwater at a contaminated site in New Jersey. A dataset containing 597 groundwater samples and 5 chlorinated benzenes and benzene collected from 144 wells over 20 years was investigated using PMF2 software. Despite the heterogeneity of this dataset, PMF analysis revealed patterns indicative of microbial dechlorination in the groundwater and provided insight about where dechlorination is occurring, to what extent, and under which geochemical conditions. PMF resolved a factor indicative of a source of 1,2,4-trichlorobenzene and 1,2-dichlorobenzene and two factors representing stages of dechlorination, one more advanced than the other. The PMF results indicated that virtually all of the 1,2-dichlorobenzene at the site arises from its use onsite, not from the dechlorination of trichlorobenzenes. Factors were further interpreted using ancillary data such as geochemical indicators and field parameters also measured in the samples. Analysis suggested that the partial and advanced dechlorination signals occur under different subsurface physical conditions. The results provided field validation of the current understanding of anaerobic dechlorination of chlorinated benzenes in the subsurface developed from laboratory studies. PMF is thereby shown to be a useful tool for investigating chlorinated benzene dechlorination.

Global distribution and local impacts of inadvertently generated polychlorinated biphenyls in pigments.

The non-Aroclor congener 3,3'-dichlorobiphenyl (PCB 11) has been recently detected in air, water, sediment, and biota. It has been known since at least the 1970s that this congener is produced inadvertently during the production of certain organic pigments. PCB 11 was previously measured at parts-per-billion (ppb) levels in various printed materials obtained in the US. In this work, PCB 11 was detected in samples of common consumer goods including magazines, advertisements, maps, postcards, brochures, napkins, and garments from 26 countries in five continents at concentrations ranging from 0.27 to 86 ppb. Leaching tests confirmed that PCB 11 could be released from these materials into water. We also examined whether the known sources of PCB 11 were large enough to account for the levels of PCB 11 measured in the air, water, soil and sediment of the Delaware River Basin. A mass flow analysis suggests that the outflows and sequestration of PCB 11 in the basin total between 30 and 280 kg y(-1). If PCB 11 concentrations in pigments were at the maximum average (125 ppm) allowed under the Toxic Substances Control Act (TSCA), the estimated input of PCB 11 to the Delaware River Basin would be on the order of 42 kg y(-1). Despite the large uncertainty in these numbers, the results suggest that pigments may plausibly account for the levels of PCB 11 measured in the environment.