Source Apportionment of Polychlorinated Biphenyls in Atmospheric Deposition in the Seattle, WA, USA Area Measured with Method 1668.

Atmospheric deposition can be an important pathway for the delivery of toxic polychlorinated biphenyls (PCBs) to ecosystems, especially in remote areas. Determining the sources of atmospheric PCBs can be difficult, because PCBs may travel long distances to reach the monitoring location, allowing for a variety of weathering processes that may alter PCB fingerprints. Previous efforts to determine the sources of atmospheric PCBs have been hampered by the electron capture detection methods used to measure PCBs. In this work, EPA method 1668, which is capable of measuring all 209 congeners, was used to measure PCBs in bulk atmospheric deposition at seven locations in the Green-Duwamish River watershed in and near Seattle, WA. Analysis of this data set via Positive Matrix Factorization allowed the identification of six factors that represent PCB sources. Four factors, representing approximately 88% of all PCB mass, are strikingly similar to unweathered Aroclors, suggesting minimal weathering during transport and/or local PCB sources at some sites. A fifth factor contained virtually all of the PCB 11 mass and represents PCBs from pigments. It explained approximately 39% of the Toxic Equivalency Quotient in the atmospheric deposition samples. The remaining factor contained non-Aroclor PCBs and may be related to silicone.

Sewer Sediment Bacterial Communities Suggest Potential to Transform Persistent Organic Pollutants.

Sediments of combined sewers are seeded with microbes from a variety of sources, and experience varying biogeochemical conditions. A variety of redox processes have been demonstrated to occur within sewer systems, as well as transformation of several recalcitrant xenobiotic contaminants. Illumina sequencing of the 16S ribosomal RNA gene from sediments of three combined sewer systems in the northeastern United States resulted in 10 000 to 47 000 operational taxonomic units per sample. Whereas orders Clostridiales and Bacteroidales, considered human fecal indicators, were dominant in one city's sediments; other cities had communities suggestive of diverse redox processes, including reductive dechlorination of chlorinated organic compounds. Collection systems previously associated with polychlorinated biphenyl (PCB) biotransformation, and those with elevated in situ PCB concentrations, had high abundances of Dehalococcoidetes. The results suggest that wastewater collection systems have intrinsic passive treatment capacity, reducing contaminant loads on water resource recovery facilities and, ultimately, on receiving waters.

Source Apportionment of Atmospheric Polychlorinated Biphenyls in New Jersey 1997-2011.

Concentrations of polychlorinated biphenyls (PCBs) in the Delaware River currently exceed the Water Quality Criteria of 16 pg/L for the sum of PCBs due in part to atmospheric deposition. The purpose of this work was to use a source apportionment tool called Positive Matrix Factorization (PMF) to identify the sources of PCBs to the atmosphere in this area and determine whether their concentrations are declining over time. The data set was compiled by the Delaware Atmospheric Deposition Network (DADN) from samples taken in Camden, NJ from 1999 to 2011 and New Brunswick, NJ from 1997 to 2011. The PMF analysis revealed four resolved factors at each site. The factors that dominate the PCB burden in the atmosphere at both Camden and New Brunswick resemble Aroclor 1242. These factors declined in concentration during some portions of the monitoring period, but this decline slowed or stopped during 2003-2011. None of the factors displayed consistent declines in concentration throughout the monitoring periods, and some factors actually increased in concentration during some periods. This suggests natural attenuation alone will not control atmospheric PCB concentrations, and additional efforts are needed to control PCB atmospheric emissions as well as the numerous other sources of PCBs to the estuary.

Forensic Analysis of Polychlorinated Dibenzo-p-Dioxin and Furan Fingerprints to Elucidate Dechlorination Pathways.

Polychlorinated dibenzo-p-dioxins and -furans (PCDD/Fs) are persistent organic pollutants whose main removal process in the environment is due to biodegradation, and particularly anaerobic reductive dechlorination. Since PCDD/F congeners that are substituted in the lateral 2, 3, 7, and 8 positions are the most toxic, removal of these chlorines is advantageous, but previous studies have only demonstrated their removal under laboratory conditions. We evaluated a concentration data set of PCDD/F congeners with four or more chlorines along with all 209 polychlorinated biphenyl (PCB) congeners in surface water, treated and untreated wastewater, landfill leachate, and biosolids (NY CARP data set) to determine whether peri and peri/lateral dechlorination of PCDD/Fs occurs in these environments. Positive Matrix Factorization (PMF) applied to the data set revealed a factor indicative of the microbial dechlorination of PCBs, and this factor also contained a variety of non-2,3,7,8 substituted PCDD/F congeners. These results suggest that dechlorination of PCDD/Fs at the lateral positions is facile if not preferred in these environments. The relative lack of tetra- and penta-chlorinated PCDD/Fs suggested that dechlorination proceeds to PCDD/F congeners with less than four chlorines. The PMF results were confirmed by examining three samples that contained >90% PCB dechlorination products from the Fresh Kills Landfill and the Hudson River. Even without factor analysis, these samples demonstrated almost identical PCDD/F congener patterns. This study suggests that PCDD/Fs are reductively dechlorinated to nontoxic non-2,3,7,8 PCDD/F congeners in sewers and landfills as well as in the sediment of the Upper Hudson River.

Polychlorinated biphenyl congener patterns in fish near the Hanford Site (Washington State, USA).

It is well-known that absorption, distribution, metabolism, and excretion (ADME) processes in fish can alter polychlorinated biphenyl (PCB) congener patterns in fish, but these patterns have never been investigated using an advanced source-apportionment tool. In this work, PCB congener patterns in freshwater fish were examined with positive matrix factorization (PMF). PCB congeners were quantified via EPA Method 1668 in fillet and carcass of six species in four study areas in the Columbia River near the Hanford Site. Six factors were resolved with PMF2 software. Depletion and enhancement of PCB congeners in factors, relative to Aroclor 1254, suggested biotransformation (via cytochrome P450) and bioaccumulation in fish, respectively. Notable differences were observed among species and across study locations. For example, sturgeon and whitefish exhibited congener patterns consistent with Aroclor weathering, suggesting potential PCB metabolism in these species. In terms of location, average concentration of total PCBs for all species combined was significantly higher (P < 0.05) at Hanford 100 and 300 areas, relative to upriver and downriver study sites. Furthermore, a distinct PCB signature in sturgeon and whitefish, collected at Hanford study areas, suggests that Hanford is a unique PCB source.

Microbial dechlorination of polychlorinated biphenyls, dibenzo-p-dioxins, and -furans at the Portland Harbor Superfund site, Oregon, USA.

The Portland Harbor (Oregon, USA) has been declared a "Superfund" site because it is impacted by a variety of contaminants, including polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins and -furans (PCDD/Fs). Using data collected in the remedial investigation, concentrations of PCBs and PCDD/Fs in sediment and water were examined using positive matrix factorization to look for evidence that PCBs and PCDD/Fs are dechlorinated by anaerobic bacteria. This process has long been known to occur in sediments. Recently, it has been recognized that PCB and PCDD/F dechlorination may also occur in other anaerobic environments, such as in landfills, sewers, and groundwater. The results indicate that a factor related to the dechlorination of PCBs and PCDD/Fs was present in the water but not in the sediment. Spatial patterns in dechlorination products suggest that they come primarily from groundwater. Dechlorination products comprise 22% of the PCBs in the water. The Portland Harbor therefore represents the third major US watershed in which PCBs appear to undergo dechlorination in an environment other than sediment, suggesting that the microbial dechlorination of PCBs and PCDD/Fs is more common than previously assumed. In addition, the Portland Harbor is impacted by PCBs generated inadvertently during the production of pigments, such as PCB 11, which alone exceeded the 64 pg/L federal water quality standard for the sum of PCBs in two of 120 whole water samples.

Indoor air quality in green buildings: A case-study in a residential high-rise building in the northeastern United States.

Improved indoor air quality (IAQ) is one of the critical components of green building design. Green building tax credit (e.g., New York State Green Building Tax Credit (GBTC)) and certification programs (e.g., Leadership in Energy & Environmental Design (LEED)) require indoor air quality measures and compliance with allowable maximum concentrations of common indoor air pollutants. It is not yet entirely clear whether compliance with these programs results in improved IAQ and ultimately human health. As a case in point, annual indoor air quality measurements were conducted in a residential green high-rise building for five consecutive years by an industrial hygiene contractor to comply with the building's GBTC requirements. The implementation of green design measures resulted in better IAQ compared to data in references of conventional homes for some parameters, but could not be confirmed for others. Relative humidity and carbon dioxide were satisfactory according to existing standards. Formaldehyde levels during four out of five years were below the most recent proposed exposure limits found in the literature. To some degree, particulate matter (PM) levels were lower than that in studies from conventional residential buildings. Concentrations of Volatile Organic Compounds (VOCs) with known permissible exposure limits were below levels known to cause chronic health effects, but their concentrations were inconclusive regarding cancer health effects due to relatively high detection limits. Although measured indoor air parameters met all IAQ maximum allowable concentrations in GBTC and applicable LEED requirements at the time of sampling, we argue that these measurements were not sufficient to assess IAQ comprehensively because more sensitive sampling/analytical methods for PM and VOCs are needed; in addition, there is a need for a formal process to ensure rigor and adequacy of sampling and analysis methods. Also, we suggest that a comprehensive IAQ assessment should include mixed mode thermal comfort models, semi-volatile organic compounds, assessment of new chemicals, and permissible exposure levels of many known indoor VOCs and bioaerosols. Plus, the relationship between energy consumption and IAQ, and tenant education on health effects of indoor pollutants and their sources may need more attention in IAQ investigations in green buildings.

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.

Source apportionment of polychlorinated biphenyls in the sediment of the Newtown Creek superfund site.

Polychlorinated biphenyls (PCBs) are a primary contaminant of potential concern at the Newtown Creek superfund site. Measurements of PCBs in hundreds of samples of sediment (surface and cores) within Newtown Creek and at nearby reference locations were obtained from the Remedial Investigation (RI) databases. This data set was analyzed using Positive Matrix Factorization (PMF). A weight-of-evidence approach was used to attribute the PMF-generated fingerprints to sources. The PMF analysis generated eight factors (fingerprints or sources) that represent primary sources, such as Aroclors, as well as secondary sources, including the East River and Combined Sewer Outfalls (CSOs). In addition to the high-production volume Aroclors (1016/1242, 1248, 1254, and 1260), some less-widely used Aroclors (1232 and 1268) were found in Newtown Creek sediment. Aroclor 1268 is disproportionately abundant in the deepest sediments, while PCBs likely from CSOs are relatively more abundant in surface sediment.

Source apportionment of polychlorinated biphenyls in Chicago air from 1996 to 2007.

While the overall atmospheric polychlorinated biphenyl (PCB) levels in many urban areas are declining, it is not clear whether this decline is due to control strategies or merely due to natural attenuation. To investigate this issue, Positive Matrix Factorization (PMF) was used to identify the dominant sources of gas-phase PCBs in the atmosphere of Chicago, IL using a data set collected from 1996 to 2007 by the Integrated Atmospheric Deposition Network (IADN). Both the older PMF2 software and the newer EPA-sponsored PMF 3.0 software were employed. Both models resolved 5 factors, but they yielded somewhat different results in terms of the congener patterns of the factors and their temporal variation. The PMF2 software resolved factors that better resembled the original Aroclor formulations. While it is possible to apply an exponential decay model to this data set and derive statistically significant rate constants that indicate that ΣPCBs and some of the resolved factors are declining in Chicago air, examining plots of the 365-day moving average concentrations shows that they do not decrease in a fashion consistent with exponential decay. Instead, they display periods of decline as well as periods of increase. Thus an exponential decay model is not appropriate, and long-term time trends identified from this 12-year data set cannot be used to predict the future trends in PCB concentrations in the air of Chicago. Two of the five resolved factors resemble low MW Aroclors, and declined from 1996 to 2007. The other three factors, which represent the majority of the mass in the data set, are either not declining or actually increasing over time. Thus past efforts to eliminate PCBs from the Great Lakes ecosystem have been only marginally effective, if at all. Additional effort is needed to identify and eliminate atmospheric PCB sources in Chicago.

Source apportionment of polychlorinated biphenyls in the sediments of the Delaware River.

Polychlorinated biphenyls (PCBs) are toxic, persistent, bioaccumulative compounds that threaten water quality in many areas, including the Delaware River. In 2003, total maximum daily loads for PCBs were promulgated for the tidal portion of the river, requiring the collection of a massive and unprecedented data set on PCBs in an urban estuary using state of the art, high-resolution high mass spectrometry (EPA method 1668 revision A). In previous publications, this data set has been examined using positive matrix factorization (PMF) to apportion PCB sources in the air, water, and permitted discharges to the river. Here, the same technique is used to apportion PCB sources in the sediment. This holistic approach allows the comparison of source types and magnitudes to the air, water, and sediment, and allows conclusions to be drawn about the cycling of PCBs in a typical urbanized estuary. A data set containing 87 chromatographic peaks representing 132 PCB congeners in 81 samples and 6 duplicated samples was analyzed. Seven factors were resolved. Three represent relatively unweathered Aroclors. Two were related to the non-Aroclor sources of diarylide yellow pigments and titanium tetrachloride production. The two remaining factors were probably originally related to Aroclors, but they are so highly weathered as to be unrecognizable as Aroclors, and thus have probably resided in the river for a long time. Comparing the abundance of the resolved PCB factors in the air, water, discharges, and sediment demonstrates that high molecular weight formulations, such as Aroclor 1260 and PCBs 206, 208, and 209 produced during titanium tetrachloride synthesis accumulate preferentially in the sediment, in keeping with their greater hydrophobicity. In contrast, lower molecular weight formulations, including the products of PCB dechlorination occurring in sewers, do not accumulate appreciably. PCB 11 from pigment use does accumulate in sediments and also seems to be distributed throughout the estuary via the 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 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.

Fluxes of polychlorinated biphenyls volatilizing from the Hudson River, New York measured using micrometeorological approaches.

This study represents the first time that a micrometeorological technique, using turbulent transport measurements, has been used to determine the direction and magnitude of air-water exchange of polychlorinated biphenyls (PCBs). The study was conducted during July 2008 on the Hudson River estuary near the Tappan Zee Bridge, which is the site of some of the most serious PCB contamination in the world. Gas-phase ΣPCB concentrations measured at two heights above the water column averaged 1.1 ng m(-3), and concentrations were usually lower in the upper air sample, indicating net transport of PCBs from the water column to the air. Volatilization PCB fluxes were calculated using the modified Thornthwaite-Holzman equation. Values of friction velocity and atmospheric stability were calculated using the Aerodynamic Gradient and Eddy Correlation techniques. The PCB fluxes were corrected for changes in atmospheric stability using the atmospheric stability factor of water vapor (ϕ(w)) calculated from empirical formulations which ranged from 1.0 to 3.2 (neutral to stable atmospheric boundary layer conditions). Vertical ΣPCB fluxes ranged from +0.5 µg m(-2) d (-1) to +13 µg m(-2) d (-1). Mono- through tri-homologues accounted for about half of ΣPCB fluxes, with tetra- through hexa-homologue accounting for the other half. This work demonstrates the utility of a micrometeorological approach to measuring the air-water exchange of organic contaminants.

Evidence for dechlorination of polychlorinated biphenyls and polychlorinated dibenzo-p-dioxins and -furans in wastewater collection systems in the New York metropolitan area.

Polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) are persistent organic pollutants targeted by the Stockholm Convention. Both contain aromatic chlorines and are subject to microbial dechlorination. Dechlorination of PCBs in sewers in the Delaware River basin was recently reported. In this work, two data sets on concentrations of PCBs and PCBs+PCDD/Fs in wastewater treatment plant influents and effluents were analyzed to look for evidence that these compounds undergo dechlorination in the sewers of the New York/New Jersey Harbor area. The two data sets come from the Contamination Assessment and Reduction Project (CARP) and were analyzed via Positive Matrix Factorization (PMF). Analysis of the data set containing only PCB concentrations suggests that PCBs are dechlorinated in the sewers of the NY/NJ Harbor via the same pathways observed in the sewers of the Delaware River basin and that advanced dechlorination of PCB mixtures is more likely to occur in combined sewers vs separate sanitary sewers. When the combined data set of PCBs+PCDD/Fs was analyzed, the factor containing PCB dechlorination products also contained high proportions of 1,2,3,4,6,7,8-heptachlorodibenzo-p-dioxin (HpCDD), a known product of the dechlorination of octachlorodibenzo-p-dioxin (OCDD), and other known dechlorination products of PCDD/Fs. Despite being the most abundant PCDD/F congener in all of the samples in the database, OCDD was a minor component in the dechlorination factor. This provides the first evidence that PCDD/Fs may be dechlorinated in sewers.

Effect of membrane filtration on the fate of polychlorinated biphenyls in wastewater treatment.

The Spokane River is impacted by levels of polychlorinated biphenyls (PCBs) that have triggered fish consumption advisories and exceed water quality standards. Select wastewater treatment plants (WWTPs) on the river have been upgraded from secondary (biological) treatment to tertiary treatment in the form of membrane filtration to address phosphorus contamination. Because membrane filtration is effective at removing particles, it is likely to reduce PCB concentrations in the effluent as well. In this work, PCBs measured in the influents and effluent of several WWTPs discharging to the river were examined. Implementation of membrane filtration reduced PCB concentrations in the effluent (and therefore PCB loads to the river) by 33% at a facility that produces recycled and virgin paper and by ∼55% at municipal WWTPs, compared to secondary (activated sludge) treatment. Largest reductions in concentrations in effluent and loads were achieved for higher molecular weight (MW) PCB congeners (i.e. those with six or more chlorines), homologs, and formulations. The more modest reductions in effluent concentrations achieved at the paper WWTP may be due to the mix of PCBs in the wastewater there: it contained primarily the low MW Aroclor 1242 (presumably from carbonless copy paper) and PCB 11 (3,3'-dichlorobiphenyl) possibly from pigments. PCBs that appear to be associated with silicone products such as caulk, tubing, and o-rings are relatively more abundant in the effluent of some plants compared to the influent, suggesting that these congeners arise from contamination during sampling or from within the plant itself. At some WWTPs, this contamination accounts for nearly a third of PCBs measured in the effluent.

The effect of co-substrate activation on indigenous and bioaugmented PCB dechlorinating bacterial communities in sediment microcosms.

Microbial reductive dechlorination by members of the phylum Chloroflexi, including the genus Dehalococcoides, may play an important role in natural detoxification of highly chlorinated environmental pollutants, such as polychlorinated biphenyls (PCBs). Previously, we showed the increase of an indigenous bacterial population belonging to the Pinellas subgroup of Dehalococcoides spp. in Anacostia River sediment (Washington DC, USA) microcosms treated with halogenated co-substrates ("haloprimers"), tetrachlorobenzene (TeCB), or pentachloronitrobenzene (PCNB). The PCNB-amended microcosms exhibited enhanced dechlorination of weathered PCBs, while TeCB-amended microcosms did not. We therefore developed and used different phylogenetic approaches to discriminate the effect of the two different haloprimers. We also developed complementary approaches to monitor the effects of haloprimer treatments on 12 putative reductive dehalogenase (rdh) genes common to Dehalococcoides ethenogenes strain 195 and Dehalococcoides sp. strain CBDB1. Our results indicate that 16S rRNA gene-based phylogenetic analyses have a limit in their ability to distinguish the effects of two haloprimer treatments and that two of rdh genes were present in high abundance when microcosms were amended with PCNB, but not TeCB. rdh gene-based phylogenetic analysis supports that these two rdh genes originated from the Pinellas subgroup of Dehalococcoides spp., which corresponds to the 16S rRNA gene-based phylogenetic analysis.

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.

Evidence for widespread dechlorination of polychlorinated biphenyls in groundwater, landfills, and wastewater collection systems.

One of the few pathways for environmental transformation of polychlorinated biphenyls (PCBs) is microbial dechlorination under anaerobic conditions, which is reported to occur in contaminated sediments of rivers, lakes and harbors. The goal of this work was to determine whether PCB dechlorination occurs in built waste treatment environments. We analyzed a large database on PCB congener concentrations in effluents and some influents of facilities in the Delaware River Basin. Positive matrix factorization was used to identify the sources of PCBs and to look for evidence of dechlorination. Seven factors were resolved from the data set of 89 congeners in 645 samples. Two of the resolved factors represented dechlorination signals. One of these was dominated by PCBs 4 and 19 and represents an advanced stage of dechlorination of Aroclors to di- and trichlorinated congeners. This dechlorination signal was most prevalent in effluents from sites with contaminated groundwater and from wastewater treatment plants (WWTPs) that serve combined sewers or treat landfill leachate. The other dechlorination signal appeared to represent an intermediate stage of dechlorination, because it was dominated by two coeluting groups of tetrachlorinated congeners: PCBs 44 + 47 + 65 and 45 + 51. This partial dechlorination signal was most prevalent in the 40 WWTPs with separate (sanitary) sewer systems, where it often comprised more than 20% of the PCBs in the effluents. Both dechlorination signals were present in WWTP influents, but were not observed in stormwater runoff, suggesting that dechlorination occurs in sewers. This work represents the first convincing evidence of PCB dechlorination occurring outside of contaminated aquatic sediments or anaerobic digesters. The results suggest that PCBs are dechlorinated by anaerobic bacteria in sewers, landfills, and contaminated groundwater. These two dechlorination signals comprise about 19% of the total loads of PCBs to the Delaware River from the sampled dischargers.

Reactivity of alkyl polyhalides toward granular iron: development of QSARs and reactivity cross correlations for reductive dehalogenation.

Attempts to develop quantitative structure-activity relationships (QSARs) for reductive dehalogenation by granular iron have been hindered by the unavailability of high quality predictor variables, have included relatively few compounds, and on occasion have relied on data lacking internal consistency. We herein investigate the reduction of 24 alkyl polyhalides by granular iron and the better-defined, homogeneous reductants Cr(H(2)O)(6)(2+) and an Fe(II) porphyrin. QSARs were constructed with a new set of computationally derived gas phase homolytic carbon-halogen bond dissociation energies and solvated one-electron reduction potentials determined using a quantum chemistry composite method (G3MP2). Reactivity cross correlations between reductant systems were also developed. Reactivity trends were generally consistent among all reductants and revealed pronounced structural influences. Compounds reduced at C-Br were orders of magnitude more reactive than analogues reduced at C-Cl; the number and identity of α- (Br ∼ Cl > CH(3) > F > H) and ß-substituents (Br > Cl) also influenced reactivity. Nonlinearities encountered during QSAR and cross correlation development suggest that reactions of highly halogenated alkyl polyhalides with granular iron are limited by mass transfer, as supported by estimates of mass transfer coefficients. For species not suspected to exhibit mass transfer limitations, reasonably strong cross correlations and comparable substituent effects are consistent with dissociative electron transfer as the rate-determining step.