Distinctive biotransformation and biodefluorination of 6:2 versus 5:3 fluorotelomer carboxylic acids by municipal activated sludge.

Fluorotelomer carboxylic acids (FTCAs) represent an important group of per- and polyfluoroalkyl substances (PFAS) given their high toxicity, bioaccumulation potential, and frequent detection in landfill leachates and PFAS-impacted sites. In this study, we assessed the biodegradability of 6:2 FTCA and 5:3 FTCA by activated sludges from four municipal wastewater treatment plants (WWTPs) in the New York Metropolitan area. Coupling with 6:2 FTCA removal, significant fluoride release (0.56∼1.83 F-/molecule) was evident in sludge treatments during 7 days of incubation. Less-fluorinated transformation products (TPs) were formed, including 6:2 fluorotelomer unsaturated carboxylic acid (6:2 FTUCA), perfluorohexanoic acid (PFHxA), perfluoropentanoic acid (PFPeA), and perfluorobutanoic acid (PFBA). In contrast, little fluoride (0.01∼0.09 F-/molecule) was detected in 5:3 FTCA-dosed microcosms, though 25∼68% of initially dosed 5:3 FTCA was biologically removed. This implies the dominance of "non-fluoride-releasing pathways" that may contribute to the formation of CoA adducts or other conjugates over 5:3 FTCA biotransformation. The discovery of defluorinated 5:3 FTUCA revealed the possibility of microbial attacks of the C-F bond at the γ carbon to initiate the transformation. Microbial community analysis revealed the possible involvement of 9 genera, such as Hyphomicrobium and Dechloromonas, in aerobic FTCA biotransformation. This study unraveled that biotransformation pathways of 6:2 and 5:3 FTCAs can be divergent, resulting in biodefluorination at distinctive degrees. Further research is underscored to uncover the nontarget TPs and investigate the involved biotransformation and biodefluorination mechanisms and molecular basis.

Environmental Fate of Cl-PFPECAs: Accumulation of Novel and Legacy Perfluoroalkyl Compounds in Real-World Vegetation and Subsoils.

Per- and polyfluoroalkyl substances (PFAS) are globally distributed and potentially toxic compounds. We report accumulation of chloroperfluoropolyethercarboxylates (Cl-PFPECAs) and perfluorocarboxylates (PFCAs) in vegetation and subsoils in New Jersey. Lower molecular weight Cl-PFPECAs, containing 7-10 fluorinated carbons, and PFCAs containing 3-6 fluorinated carbons were enriched in vegetation relative to surface soils. Subsoils were dominated by lower molecular weight Cl-PFPECAs, a divergence from surface soils. Contrastingly, PFCA homologue profiles in subsoils were similar to surface soils, likely reflecting temporal-use patterns. Accumulation factors (AFs) for vegetation and subsoils decreased with increasing CF2, 6-13 for vegetation and 8-13 in subsoils. In vegetation, for PFCAs having CF2 = 3-6, AFs diminished with increasing CF2 as a more sensitive function than for longer chains. Considering that PFAS manufacturing has transitioned from long-chain chemistry to short-chain, this elevated vegetative accumulation of short-chain PFAS suggests the potential for unanticipated PFAS exposure levels globally in human and/or wildlife populations. This inverse relationship between AFs and CF2-count in terrestrial vegetation is opposite the positive relationship reported in aquatic vegetation suggesting aquatic food webs may be preferentially enriched in long-chain PFAS. AFs normalized to soil-water concentrations increased with chain length for CF2 = 6-13 in vegetation but remained inversely related to chain length for CF2 = 3-6, reflecting a fundamental change in vegetation affinity for short chains compared to long.

Environmental Fate of Cl-PFPECAs: Predicting the Formation of PFAS Transformation Products in New Jersey Soils.

Although next-generation per- and polyfluorinated substances (PFAS) were designed and implemented as safer and environmentally degradable alternatives to "forever" legacy PFAS, there is little evidence to support the actual transformation of these compounds and less evidence of the safety of transformed products in the environment. Multiple congeners of one such PFAS alternative, the chloro-perfluoropolyether carboxylates (Cl-PFPECAs), have been found in New Jersey soils surrounding a manufacturing facility. These compounds are ideal candidates for investigating environmental transformation due to the existence of potential reaction centers including a chlorinated carbon and ether linkages. Transformation products of the chemical structures of this class of compounds were predicted based on analogous PFAS transformation pathways documented in peer-reviewed literature. Potential reaction products were used as the basis for high-resolution mass-spectrometric suspect screening of the soils. Suspected transformation products of multiple congeners, the Cl-PFPECAs, including H-PFPECAs, epox-PFPECAs, and diOH-PFPECAs, were tentatively observed in these screenings. Although ether linkages have been hypothesized as potential reaction centers under environmental conditions, to date, no documentation of ether scission has been identified. Despite exhaustive scrutiny of the high-resolution data for our Cl-PFPECA-laden soils, we found no evidence of ether scission.

Limitations of Current Approaches for Predicting Groundwater Vulnerability from PFAS Contamination in the Vadose Zone.

Published literature for reported sorption coefficients (Kd) of eight anionic per- and polyfluoroalkyl substances (PFAS) in soil was reviewed. Kd values spanned three to five log units indicating that no single value would be appropriate for use in estimating PFAS impacts to groundwater using existing soil-water partition equations. Regression analysis was used to determine if the soil or solution parameters might be used to predict Kd values. None of the 15 experimental parameters collected could individually explain variability in reported Kd values. Significant associations between Kd and soil calcium and sodium content were found for many of the selected PFAS, suggesting that soil cation content may be critical to PFAS sorption, as previously noted in sources like Higgins and Luthy (2006), while organic carbon content was significant only at elevated levels (>5%). Unexplained discrepancies between the results from studies where PFAS were introduced to soil and desorbed in the laboratory and those that used material from PFAS-impacted sites suggest that laboratory experiments may be overlooking some aspects critical to PFAS sorption. Future studies would benefit from the development and use of standardized analytical methods to improve data quality and the establishment of soil parameters appropriate for collection to produce more complete data sets for predictive analysis.

Nontargeted mass-spectral detection of chloroperfluoropolyether carboxylates in New Jersey soils.

The toxicity and environmental persistence of anthropogenic per- and poly-fluoroalkyl substances (PFAS) are of global concern. To address legacy PFAS concerns in the United States, industry developed numerous replacement PFAS that commonly are treated as confidential information. To investigate the distribution of PFAS in New Jersey, soils collected from across the state were subjected to nontargeted mass-spectral analyses. Ten chloroperfluoropolyether carboxylates were tentatively identified, with at least three congeners in all samples. Nine congeners are ≥(CF2)7 Distinct chemical formulas and structures, as well as geographic distribution, suggest airborne transport from an industrial source. Lighter congeners dispersed more widely than heavier congeners, with the most widely dispersed detected in an in-stock New Hampshire sample. Additional data were used to develop a legacy-PFAS fingerprint for historical PFAS sources in New Jersey.

Investigation of levels of perfluoroalkyl substances in surface water, sediment and fish tissue in New Jersey, USA.

Per- and polyfluoroalkyl substances (PFAS) are persistent, bioaccumulative, and toxic substances found in New Jersey (NJ) due to historic and current industrial activities and the use of aqueous film forming foams. This research documents PFAS occurrence in surface water, sediments, and fish tissue at 11 targeted waterbodies in NJ suspected to be impacted by PFAS. Thirteen PFAS compounds were quantified from each media. The profile of detected PFAS differed among media from the same site, with shorter chain PFAS tending to predominate in surface water while longer chain PFAS predominated in fish and sediments. All water samples contained detectable levels of at least four perfluoroalkyl substances. PFOA, PFHpA and PFPeA were detected at every site. ΣPFAS concentrations in water samples ranged from 22.9 to 279.5 ng/L. At least one, and up to eight, PFAS were detected in sediment samples at 10 sites, while there were no detections of PFAS in sediments at the reference site. ΣPFAS concentrations in sediment samples ranged from below detection to 30.9 ng/g. At least one fish of each species at every site had detectable levels of PFAS compounds. ΣPFAS concentrations in fish were highest at sites downstream from a military facility, and lowest at the reference site. PFOS, PFDA, PFUnA and PFDoA were the predominant PFAS detected in fish tissue. PFOS was generally found in fish tissue at higher concentrations than other PFAS, with higher PFOS concentrations found in the tissue of yellow perch, American eel, pumpkinseed, and largemouth bass collected at sites with higher detections of PFOS in surface waters. PFOS levels in nearly all fish species were, on average, high enough to trigger fish consumption advisories. Additional studies are needed to further evaluate the sources and occurrence of PFAS in NJ and to better understand their movement through the environment and potential risks.

Reconnaissance of Surface Water Estrogenicity and the Prevalence of Intersex in Smallmouth Bass (Micropterus Dolomieu) Inhabiting New Jersey.

The observation of testicular oocytes in male fishes has been utilized as a biomarker of estrogenic endocrine disruption. A reconnaissance project led in the Northeastern United States (US) during the period of 2008-2010 identified a high prevalence of intersex smallmouth bass on or near US Fish & Wildlife Service National Wildlife Refuges that included the observation of 100% prevalence in smallmouth bass males collected from the Wallkill River, NJ, USA. To better assess the prevalence of intersex smallmouth bass across the state of New Jersey, a tiered reconnaissance approach was initiated during the fall of 2016. Surface water samples were collected from 101 (85 river, 16 lake/reservoir) sites across the state at base-flow conditions for estrogenicity bioassay screening. Detectable estrogenicity was observed at 90% of the sites and 64% were above the US Environmental Protection Agency trigger level of 1 ng/L. Median surface water estrogenicity was 1.8 ng/L and a maximum of 6.9 ng/L E2EqBLYES was observed. Adult smallmouth bass were collected from nine sites, pre-spawn during the spring of 2017. Intersex was identified in fish at all sites, and the composite intersex prevalence was 93.8%. Prevalence across sites ranged from 70.6% to 100%. In addition to intersex, there was detectable plasma vitellogenin in males at all sites. Total estrogenicity in surface water was determined at these fish collection sites, and notable change over time was observed. Correlation analysis indicated significant positive correlations between land use (altered land; urban + agriculture) and surface water estrogenicity. There were no clear associations between land use and organismal metrics of estrogenic endocrine disruption (intersex or vitellogenin). This work establishes a baseline prevalence of intersex in male smallmouth bass in the state of New Jersey at a limited number of locations and identifies a number of waterbodies with estrogenic activity above an effects-based threshold.

Emerging Chlorinated Polyfluorinated Polyether Compounds Impacting the Waters of Southwestern New Jersey Identified by Use of Nontargeted Analysis.

Per- and polyfluoroalkyl substances (PFAS) are a widespread, environmentally persistent class of anthropogenic chemicals that are widely used in industrial and consumer products and frequently detected in environmental media. Potential human health impacts from long-term exposure to legacy PFAS resulted in the industrial development and use of numerous replacement species in recent decades. Environmental investigative activities have been crucial in identifying the existence and environmental transport of emerging PFAS in environmental media. Previous investigations in an industrially impacted region of southwestern New Jersey has shown consistently elevated levels of legacy PFAS, motivating additional examination by non-targeted mass spectrometry to identify emerging PFAS contamination. This study applied non-targeted analysis to water samples collected in Gloucester and Salem Counties in southwestern New Jersey, revealing the existence of a series of novel chloro-perfluoro-polyether carboxylates and related PFAS species originating from an industrial PFAS user in the region. There is sparse publicly available toxicity information for the emerging chemical species, but estimated concentrations exceeded the state drinking water standards for perfluorooctanoic acid (PFOA) and perfluorononanoic acid (PFNA). Non-targeted analysis was used to estimate the effectiveness of point-of-entry water treatment systems for removal of the emerging species and reduced the abundance of PFAS by >90%.

Occurrence and source identification of perfluoroalkyl acids (PFAAs) in the Metedeconk River Watershed, New Jersey.

The Brick Township Municipal Utilities Authority (BTMUA), which relies on the Metedeconk River as its primary source of water supply, initiated a perfluoroalkyl acid (PFAA) source trackdown study in collaboration with the New Jersey Department of Environmental Protection (NJDEP) after discovering that the concentration of one PFAA, perfluorooctanoic acid (PFOA), was elevated at their raw surface water intake. Water samples were collected over eight sampling events between September 2011 and July 2014. Samples included surface water, groundwater, stormwater, sanitary sewer water, and commercial/industrial process water. Each sample was analyzed for ten PFAAs. Results from a set of samples collected from the 80 km2 South Branch Metedeconk River watershed directed the focus of this study to a 7.5-km2 area of interest. Within this area, a high concentration of PFAA contamination was documented in a localized zone. Subsequent groundwater sampling led to the identification of a plume of groundwater contamination emanating from an industrial/business park. The suspected source of PFAA detected in the river and drinking water intake was identified to a small industrial facility that used materials containing PFOA. Groundwater PFOA concentrations as high as 70,000 ng/L were found in samples taken within 200 m of the parcel and surface water concentrations as high as 130 ng/L were observed in the river. While various PFAAs were detected in the samples, particularly in groundwater samples, PFOA was identified as the primary contaminant of concern with respect to the river and the BTMUA water supply.

The Likelihood of Coliform Bacteria in NJ Domestic Wells Based on Precipitation and Other Factors.

The influence of precipitation on coliform bacteria detection rates in domestic wells was investigated using data collected through the New Jersey Private Well Testing Act. Measured precipitation data from the National Weather Service (NWS) monitoring stations was compared to estimated data from the Multisensor Precipitation Estimate (MPE) in order to determine which source of data to include in the analyses. A strong concordance existed between these two precipitations datasets; therefore, MPE data was utilized as it is geographically more specific to individual wells. Statewide, 10 days of cumulative precipitation prior to testing was found to be an optimal period influencing the likelihood of coliform detections in wells. A logistic regression model was developed to predict the likelihood of coliform occurrence in wells from 10 days of cumulative precipitation data and other predictive variables including geology, season, coliform bacteria analysis method, pH, and nitrate concentration. Total coliform (TC) and fecal coliform or Escherichia coli (FC/EC) were detected more frequently when the preceding 10 days of cumulative precipitation exceeded 34.5 and 54 mm, respectively. Furthermore, the likelihood of coliform detection was highest in wells located in the bedrock region, during summer and autumn, analyzed with the enzyme substrate method, with pH between 5 and 6.99, and (for FC/EC but not TC) nitrate greater than 10 mg/L. Thus, the likelihood of coliform presence in domestic wells can be predicted from readily available environmental factors including timing and magnitude of precipitation, offering outreach opportunities and potential changes to coliform testing recommendations.

Seasonality of Coliform Bacteria Detection Rates in New Jersey Domestic Wells.

It is important that indicators of fecal pollution are reliable. Coliform bacteria are a commonly used indicator of fecal pollution. As other investigators have reported elsewhere, we observed a seasonal pattern of coliform bacteria detections in domestic wells in New Jersey. Examination of a statewide database of 10 years of water quality data from 93,447 samples, from 78,207 wells, generated during real estate transactions, revealed that coliform bacteria were detected in a higher proportion of wells during warm weather months. Further examination of the seasonal pattern of other data, including well water pH, precipitation, ground and surface water temperatures, surface water coliform bacteria concentrations, and vegetation, resulted in the hypothesis that these bacteria may be derived from nonfecal (or environmentally adapted) as well as fecal sources. We provide evidence that the coliform seasonality may be the result of seasonal changes in groundwater extraction volumes (and to a lesser extent precipitation), and temperature-driven changes in the concentration of surface or near-surface coliform sources. Nonfecal coliform sources may not indicate the presence of fecal wastes and hence the potential presence of pathogens, or do so in an inconsistent fashion. Additional research is needed to identify the sources of the coliforms detected in groundwater.

Mercury emissions from cement-stabilized dredged material.

Upland placement of dredged materials from navigation channels in the New York/New Jersey Harbor is currently being used to manage sediments deemed inappropriate for open water disposal. Although upland placement sites are equipped with engineering controls (leachate collection and/or barrier walls), little is known of the potential impacts of this approach to air quality. The aim of this study was to estimate the flux of mercury to the atmosphere from New York/New Jersey Harbor stabilized dredged material (SDM) that was used for land reclamation at a site in northeastern New Jersey. Total gaseous mercury (TGM) was measured at a site receiving SDM in August and October 2001 and May and November 2002. TGM was also monitored at an urban reference site 3.5 km west of the SDM site in September 2001 and from February 2002 to July 2002 and from October 2002 to February 2003. The concentration of TGM at the urban reference site averaged 2.2 +/- 1.1 ng m(-3), indicating some local contribution to the Northern Hemisphere background. TGM concentrations exhibited seasonality with the highest values in summer (3.3 +/- 2.1 ng m(-3) in June 2002) and the lowest in winter (1.7 +/- 0.6 ng m(-3) in January 2003). TGM concentrations at the SDM placement site ranged from 2 to 7 ng m(-3) and were significantly higher (p < 0.001) than those at the urban reference site. Sediment-air fluxes of Hg at the SDM placement site estimated by the micrometeorological technique ranged from -13 to 1040 ng m(-2) h(-1) (sediment to air fluxes being positive) and were significantly correlated to solar radiation (r2 = 0.81). The estimated contribution of Hg emissions from land-applied SDM to local TGM concentrations was found to be negligible (<4%). However, the estimated annual volatilization rate of TGM atthe SDM site (130 kg y(-1))was comparable to those of other industrial sources in New Jersey (140-450 kg y(-1)).