Analysis of Legacy and Novel Neutral Per- and Polyfluoroalkyl Substances in Soils from an Industrial Manufacturing Facility.

Per- and polyfluoroalkyl substances (PFASs) have been detected in an array of environmental media due to their ubiquitous use in industrial and consumer products as well as potential release from fluorochemical manufacturing facilities. During their manufacture, many fluorotelomer (FT) facilities rely on neutral intermediates in polymer production including the FT-alcohols (FTOHs). These PFAS are known to transform to the terminal acids (perfluoro carboxylic acids; PFCAs) at rates that vary with environmental conditions. In the current study on soils from a FT facility, we employed gas chromatography coupled with conventional- and high-resolution mass spectrometry (GC-MS and GC-HRMS) to investigate the profile of these precursor compounds, the intermediary secondary alcohols (sFTOHs), FT-acrylates (FTAcr), and FT-acetates (FTAce) in soils around the former FT-production facility. Of these precursors, the general trend in detection intensity was [FTOHs] > [sFTOHs] > [FTAcrs], while for the FTOHs, homologue intensities generally were [12:2 FTOH] > [14:2 FTOH] > [16:2 FTOH] > [10:2 FTOH] > [18:2 FTOH] > [20:2 FTOH] > [8:2 FTOH] ∼ [6:2 FTOH]. The corresponding terminal acids were also detected in all soil samples and positively correlated with the precursor concentrations. GC-HRMS confirmed the presence of industrial manufacturing byproducts such as FT-ethers and FT-esters and aided in the tentative identification of previously unreported dimers and other compounds. The application of GC-HRMS to the measurement and identification of precursor PFAS is in its infancy, but the methodologies described here will help refine its use in tentatively identifying these compounds in the environment.

Ecological risk based assessment used to restore riparian physical functions to a fresh water Creek.

The purpose of this study was to determine if an interdisciplinary team using a qualitative proper functioning condition (PFC) assessment protocol could identify and reverse significant detrimental ecological alterations which occurred within Gertie's Creek watershed, Ontario, Canada. At potential, Gertie's Creek supported a woody debris glacial outwash fine gravel substrate fish spawning habitat. The anthropogenic activities on Georgina Island caused a denuded anadromous fish population since the early-to mid-1990's in the Gertie's Creek watershed. The PFC assessment indicated that anthropogenic activities on Georgina Island negatively impacted stream flows in Gertie's Creek. Reduced stream flow resulted in the natural stream (lotic) riparian habitat not advancing out of an early seral silver maple and eastern hemlock vegetated swamp (forested wetland) habitat. The Gertie's Creek interdisciplinary team PFC assessment indicated that the entire watershed is not in balance with the water and sediment being supplied along with a lack of diverse riparian vegetation. Sediment was not being transported to the wetland and lake coastal areas because of chronic reduced flows. Further qualitative assessments by the authors of other smaller lentic and lotic ecosystems on Georgina Island indicate that reduced hydrologic flow is an issue for the entire island. Ecosystem function management planning works with the ecosystem to continually respond as the ecology changes in ways that enhance remarkable natural recovery.

Distribution of select per- and polyfluoroalkyl substances at a chemical manufacturing plant.

Per- and polyfluoroalkyl substances (PFAS) are used in various industrial products; however, they pose serious health risks. In this study, soil, soil gas, and groundwater samples were collected at a PFAS manufacturing facility in New Jersey, USA, to determine the presence and distribution of PFASs from the soil surface to groundwater and at various distances from the presumed source. Fluorotelomer alcohols (FTOHs) were detected in soil (< 0.26-36.15 ng/g) and soil gas (160-12,000 E µg/m3), while perfluorinated carboxylic acids (PFCAs) were found in soil (4.3-810 ng/g), soil gas (<0.10-180 µg/m3), and groundwater (37-49 µg/L). FTOH and PFCA concentrations decreased as the distance from the presumed source increased, suggesting that PFCAs are likely to migrate in groundwater, whereas FTOHs primarily move in the vapor phase. The presence of PFAS in the groundwater, soil, and soil gas samples indicate its potential for vapor intrusion; thus, some PFAS may contribute to indoor air inhalation exposure. To the best of our knowledge, this is the first report on the quantification of volatile PFAS in soil gas at a PFAS manufacturing facility.

Method development for thermal desorption-gas chromatography-tandem mass spectrometry (TD-GC-MS/MS) analysis of trace level fluorotelomer alcohols emitted from consumer products.

The scientific foundation for per- and polyfluoroalkyl substances (PFAS) measurements in water, soils, sediments, biosolids, biota, and outdoor air has rapidly expanded; however, there are limited efforts devoted to developing analytical methods to measure vapor-phase PFAS in indoor air. A gas chromatography-tandem mass spectrometry (GC-MS/MS) method coupled with thermal desorption (TD) sorbent tube analysis was developed to quantify trace levels of fluorotelomer alcohols (FTOHs) emitted from consumer products in the indoor environment. Method evaluation included determination of instrument detection limits (IDLs), quality assurance checks of target standards purchased from different vendors, sample loss during storage, and TD sorbent breakthrough with tubes coupled in-series. The IDLs for TD-GC-MS/MS analyses ranged from 0.07 - 0.09 ng/tube. No significant loss of FTOHs was observed during stability tests over 28 days with relative standard deviations (RSDs) of spiked TD tubes ranging from 3.1 - 7.7% and the RSDs of polypropylene copolymer vial storage of standard solutions ranging from 4.3 - 8.4%. TD tube breakthrough was minimal with recovered FTOHs in the second tubes <1% of the spiked concentrations in the first tubes with carrier gas volume up to 20 L. The method has been applied to determine FTOH emissions from three consumer products in micro-scale chambers. A liquid stone cleaner/sealer product contained the highest levels of 6:2, 8:2, and 10:2 FTOHs, while the mattress pad products contained lower levels of 8:2 and 10:2 FTOHs. The emission parameters, including the initial emission factors and first order decay rate constants, were obtained based on the experimental data. The developed methods are sensitive and specific for analysis of all four target FTOHs (4:2, 6:2, 8:2, 10:2 FTOHs) with chamber testing. The methods can be extended to indoor air sampling and could be applicable to ambient air sampling.