Per- and polyfluoroalkyl substances fate and transport at a wastewater treatment plant with a collocated sewage sludge incinerator.

This study aims to understand the fate and transport of per- and polyfluoroalkyl substances (PFAS) and inorganic fluoride (IF) at an undisclosed municipal wastewater treatment plant (WWTP) operating a sewage sludge incinerator (SSI). A robust statistical analysis characterized concentrations and mass flows at all WWTP and SSI primary influents/effluents, including thermal-treatment derived airborne emissions. WWTP-level net mass flows (NMFs) of total PFAS were not statistically different from zero. SSI-level NMFs indicate that PFAS, and specifically perfluoroalkyl acids (PFAAs), are being broken down. The NMF of perfluoroalkyl sulfonic acids (PFSAs; -274 ± 34 mg/day) was statistically significant. The observed breakdown primarily occurred in the sewage sludge. However, the total PFAS destruction and removal efficiency of 51 % indicates the SSI may inadequately remove PFAS. The statistically significant IF source (NMF = 16 ± 4.2 kg/day) compared to the sink of PFAS as fluoride (NMF = -0.00036 kg/day) suggests that other fluorine-containing substances are breaking down in the SSI. WWTP PFAS mass discharges were primarily to the aquatic environment (>99 %), with <0.5 % emitted to the atmosphere/landfill. Emission rates for formerly phased-out PFOS and PFOA were compared to previously reported levels. Given the environmental persistence of these compounds, the observed decreases in PFOS and PFOA discharge rates from prior reports implies regional/local differences in emissions or possibly their accumulation elsewhere. PFAS were observed in stack gas emissions, but modestly contributed to NMFs and showed negligible contribution to ambient air concentrations observed downwind.

Sampling of freely dissolved per- and polyfluoroalkyl substances (PFAS) in surface water and groundwater using a newly developed passive sampler.

Passive sampling methods offer several advantages over traditional grab water sampling techniques, including time-integrative results which better represent long-term concentrations at the site and separation of the freely dissolved fraction of the contaminant which offers insight into the associated risk. This paper describes the performance of a newly developed equilibrium regimen passive sampler designed specifically for per- and polyfluoroalkyl substances (PFAS), called PFAS INSIGHT®. The sampler is effective in sampling ionic (sulfonates and carboxylates) and non-ionic (PFAS precursors) PFAS from aqueous solutions with detection limits similar or lower (depending on the analyte) to those achievable with conventional water sample analysis. Results include laboratory characterization of sorbent adsorption kinetics and adsorption isotherms for 15 PFAS analytes with carbon chain lengths of 4-12, the effects of the sample matrix on PFAS partitioning, and sorbent extraction efficiency. Results from PFAS INSIGHT® field deployments demonstrate good agreement between the concentrations calculated from the passive sampler data and the concentrations measured directly in conventional water samples. Approximately 35% of the passive sampling results were within 2-fold of the conventional water sample concentrations, 71% within 5-fold, and 88% within 10-fold.

Concentration profiles of per- and polyfluoroalkyl substances in major sources to the environment.

A review of published literature was conducted to present the concentrations and composition profiles of per- and polyfluoroalkyl substances (PFAS) from significant sources to the environment. The major sources of PFAS to the environment are categorized under direct and indirect sources. The characteristic compounds and concentrations are summarized as found from direct sources such as manufacturing facilities, aqueous film-forming foam (AFFF) applications, metal coating operations, and textile and paper coating operations; and from indirect sources such as landfills and wastewater treatment plants (WWTPs). The major findings are: 1) among the aqueous matrices for which data were reviewed, groundwater impacted by AFFF contamination showed the highest median concentrations for both perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), while the second-highest median concentrations were associated with landfill leachates for PFOA and metal-plating sources for PFOS; 2) many of the unknown polyfluorinated precursors present in AFFF-impacted sites could potentially convert to persistent PFAS by abiotic or biotic transformation, and therefore could act as the long-term source of contamination to the environment; 3) part per billion (ppb) concentrations of PFAS were detected in water bodies surrounding fluorochemical manufacturing plants; 4) in consumer products such as textile, paper, and personal care products, PFOA concentrations were an order of magnitude higher compared to other PFAS; 5) biotransformation products such as fluorotelomer carboxylic acids (FTCAs) and perfluoroalkyl acids (PFAAs) are detected in landfill leachates and WWTP effluents; and 6) many studies have shown increased PFAA concentrations in WWTP effluents compared to influents. This work provides a comprehensive review of the literature on the PFAS concentration and composition trends of select non-polymeric PFAS in different sources.

Investigation of an immobilization process for PFAS contaminated soils.

A two-phased bench-scale study was conducted to evaluate various sorbents for possible use as chemical stabilizing agents, along with cement solidification, for possible use in an in-situ solidification/stabilization (immobilization) treatment process for per- and polyfluoroalkyl (PFAS) contaminated soils. The first phase involved sorption experiments for six selected PFAS compounds diluted in a water solution, using five selected sorbents: granular activated carbon (GAC), activated carbon-clay blend, modified clay, biochar, iron (Fe)-amended biochar, and Ottawa sand as a control media. The second phase involved chemical stabilization treatment (via sorption), using the most effective sorbent identified in the first phase, followed by solidification of two soils from PFAS-contaminated sites. Physical solidification was achieved by adding cement as a binding agent. Results from the first phase (sorption experiments) indicated that GAC was slightly more successful than the other sorbents in sorption performance for a 3000 µg/L solution containing a mixture of the six selected PFAS analytes (500 µg/L concentration each of shorter- and longer-chain alkyl acids), and was the only sorbent used in the second phase of this study. While the GAC, activated carbon-clay blend, and modified clay sorbents showed similar sorption performance for the longer chain analytes tested, both the activated carbon-clay blend and modified clay, exhibited slightly less sorptive capacity than GAC for the shorter-chain alkyl acids. Immobilization effectiveness was evaluated by soil leachability testing using Environmental Protection Agency (EPA) Method 1312, Synthetic Precipitation Leaching Procedure (SPLP) on the samples collected from two PFAS-contaminated sites. For the majority of the PFAS soil analytes, the addition of GAC sorbent (chemical stabilization) substantially reduced the leachability of PFAS compounds from the contaminated soil samples, and the addition of cement as a physical binding agent (solidification) further decreased leachability for a few of the PFAS compounds. Overall immobilization of PFAS analytes that were detectable in the leachate from two PFAS contaminated soils ranged from 87.1% to 99.9%. Therefore, it is reasonable to consider that the laboratory testing results presented here may have application to further pilot or limited field-scale studies within a broader suite of PFAS-contaminated site treatment options that are currently available for treating PFAS contaminated soils.

Environmental Sources, Chemistry, Fate, and Transport of Per- and Polyfluoroalkyl Substances: State of the Science, Key Knowledge Gaps, and Recommendations Presented at the August 2019 SETAC Focus Topic Meeting.

A Society of Environmental Toxicology and Chemistry (SETAC) Focused Topic Meeting (FTM) on the environmental management of per- and polyfluoroalkyl substances (PFAS) convened during August 2019 in Durham, North Carolina (USA). Experts from around the globe were brought together to critically evaluate new and emerging information on PFAS including chemistry, fate, transport, exposure, and toxicity. After plenary presentations, breakout groups were established and tasked to identify and adjudicate via panel discussions overarching conclusions and relevant data gaps. The present review is one in a series and summarizes outcomes of presentations and breakout discussions related to (1) primary sources and pathways in the environment, (2) sorption and transport in porous media, (3) precursor transformation, (4) practical approaches to the assessment of source zones, (5) standard and novel analytical methods with implications for environmental forensics and site management, and (6) classification and grouping from multiple perspectives. Outcomes illustrate that PFAS classification will continue to be a challenge, and additional pressing needs include increased availability of analytical standards and methods for assessment of PFAS and fate and transport, including precursor transformation. Although the state of the science is sufficient to support a degree of site-specific and flexible risk management, effective source prioritization tools, predictive fate and transport models, and improved and standardized analytical methods are needed to guide broader policies and best management practices. Environ Toxicol Chem 2021;40:3234-3260. © 2021 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Regeneration of per- and polyfluoroalkyl substance-laden granular activated carbon using a solvent based technology.

Per- and polyfluoroalkyl substances (PFAS) are a large class of chemicals widely used for many commercial and industrial applications and have resulted in contamination at sites across globally. Pump-and-treat systems, groundwater extraction, and ex situ treatment using granular activated carbon (GAC) are being implemented, either in full or pilot scale, to treat PFAS-impacted groundwater and drinking water. The only current method of regenerating spent GAC is to reactivate it at temperatures greater than 1000 °C, which requires large amounts of energy and is quite expensive. This research focused on development and demonstration of an effective GAC regeneration technology using a solvent-based method for PFAS-laden GAC used in water treatment. Two different organic solvents (ethanol and isopropyl alcohol) with 0.5% and 1.0% ammonium hydroxide (NH4OH) as a base additive were tested to determine the most effective regenerant solution to remove PFAS from the contaminated GAC. Based on column tests using laboratory-contaminated GAC with perfluorooctanoic acid (PFOA) and perfluorooctanoic sulfonate (PFOS), the solvent-base mix (SBM) of ethanol with 0.5% NH4OH was found to be the optimum performing regenerant solution. The GAC life span assessment showed that solvent-regenerated GAC performed similar to virgin GAC without losing its optimal performance of PFAS sorption. Further, the solvent-regenerated GAC showed optimal performance even after four cycles of solvent regenerations tested using the optimum SBM. Average percent removal in laboratory-contaminated GAC using the optimum SBM was 65% and 93% for PFOS and PFOA, respectively. Four field-spent GAC samples were also regenerated using the optimum SBM. Percent removal from these samples was found to be in range of 55%-68%. The type of GAC used, level of contamination and type of PFAS present, water type and quality, and the presence of co-contaminants may have influenced the removal capacity. Distillation experiments have shown that it is feasible to concentrate the spent solvent prior to disposal, which reduces the amount of PFAS-contaminated solvent waste produced in regeneration cycles.

An ultra-sensitive method for the analysis of perfluorinated alkyl acids in drinking water using a column switching high-performance liquid chromatography tandem mass spectrometry.

In epidemiological research, it has become increasingly important to assess subjects' exposure to different classes of chemicals in multiple environmental media. It is a common practice to aliquot limited volumes of samples into smaller quantities for specific trace level chemical analyses. A novel method was developed for the determination of 14 perfluorinated alkyl acids (PFAAs) in small volumes (10mL) of drinking water using off-line solid phase extraction (SPE) pre-treatment followed by on-line pre-concentration on a WAX column before analysis on column-switching high performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS). In general, large volumes (100-1000mL) have been used for the analysis of PFAAs in drinking water. The current method requires approximately 10mL of drinking water concentrated by using an SPE cartridge and eluted with methanol. A large volume injection of the extract was introduced on to a column-switching HPLC-MS/MS using a mix-mode SPE column for the trace level analysis of PFAAs in water. The recoveries for most of the analytes in the fortified laboratory blanks ranged from 73±14% to 128±5%. The lowest concentration minimum reporting levels (LCMRL) for the 14 PFAAs ranged from 0.59 to 3.4ng/L. The optimized method was applied to a pilot-scale analysis of a subset of drinking water samples from an epidemiological study. These samples were collected directly from the taps in the households of Ohio and Northern Kentucky, United States and the sources of drinking water samples are both surface water and ground water, and supplied by different water distribution facilities. Only five PFAAs, perfluoro-1-butanesulfonic acid (PFBS), perfluoro-1- -hexanesulfonic acid (PFHxS), perfluoro-1-octanesulfonic acid (PFOS), perfluoro-n-heptanoic acid (PFHpA) and perfluoro-n-octanoic acid (PFOA) are detected above the LCMRL values. The median concentrations of these five PFAAs detected in the samples was ≤4.1ng/L with PFOS at 7.6ng/L and PFOA at 10ng/L. Concentrations of perfluoro-1-decanesulfonic acid, PFDS and other perfluoroalkyl carboxylic acids were below the LCMRL values.

Aerobic biodegradation of toluene-2,4-di(8:2 fluorotelomer urethane) and hexamethylene-1,6-di(8:2 fluorotelomer urethane) monomers in soils.

Aerobic soil biodegradation of toluene-2,4-di(8:2 fluorotelomer urethane) (FTU) and hexamethylene-1,6-di(8:2 fluorotelomer urethane) (HMU) in a forest soil and FTU in an agricultural silty clay loam soil was monitored for up to 6 months. Fluorotelomer alcohols were measured in headspace and parent monomers and all metabolites in soil extracts. Negligible degradation of FTU biodegradation occurred in the agricultural soil with 94 ± 15% recovered at day 180. However, in the forest soil, both FTU and HMU degradation was evident with significant losses of 24% (117 d) and 27% (180 day), respectively, and concomitant increases in the terminal metabolite, perfluorooctanoic acid (PFOA) concentrations were well above what could result from residual 8:2 FTOH. Kinetic modeling estimated half-lives for FTU (aromatic backbone) and HMU (aliphatic backbone) in the forest soil to be 3-5 months and 15.9-22.2 months, respectively. The addition of a structurally similar non-fluorinated FTU analog, toluene-2,4-dicarbamic acid diethyl ester (TDAEE) enhanced production of terminal end products from 8:2 FTOH degradation. However, there was no clear evidence that TDAEE enhanced cleavage of the urethane bond, thus TDAEE appeared to just serve as an additional carbon source. TDAEE's half-life was ∼ one week. A second addition of TDAEE appeared to retard subsequent degradation of FTU exemplifying the microbial dynamics and diversity impacting degradation of polyfluoroalkyl substances. Enhanced degradation of HMU was observed upon re-aeration indicating oxygen may have been limiting during some periods although degradation of intermediate metabolites to terminal metabolites was still occurring, albeit at slower rates.

Aerobic biodegradation of 8:2 fluorotelomer stearate monoester and 8:2 fluorotelomer citrate triester in forest soil.

Aerobic biodegradation of 8:2 fluorotelomer stearate (FTS) and 8:2 fluorotelomer citrate triester (TBC) was evaluated in a forest soil in closed bottle microcosms. Loss of parent, production of 8:2 fluorotelomer alcohol (8:2 FTOH), which is released along with stearic acid (SA) by microbial ester linkage, and subsequent metabolites from FTOH degradation were monitored for up to 7months. Soil microcosms were extracted with ethyl acetate followed by two heated 90/10 v/v acetonitrile/200mM NaOH extractions. Cleavage of the ester linkage in the 8:2 FTS occurred (t1/2∼28d), producing 8:2 FTOH and various levels of subsequent metabolites. Quantifying the generation of SA from ester cleavage in FTS was complicated by the natural production and degradation of SA in soil, which was probed in an additional FTS and SA study with the same soil that had been stored at 4°C for 12months. In the latter study, FTS degraded faster (t1/2∼5d) such that SA production well above soil background levels was clearly observed along with rapid subsequent SA degradation. Cold storage was hypothesized to enrich fungal enzymes, which are known to be effective at hydrolytic cleavage. 8:2 TBC biotransformation was slow, but evident with the production of PFOA well above levels expected from known FTOH residuals. Slower degradation of TBC compared to FTS is likely due to steric hindrances arising from the close proximity of three 8:2 FT chains on the citrate backbone limiting the enzyme access.

Aerobic soil biodegradation of 8:2 fluorotelomer stearate monoester.

A laboratory investigation on the biotransformation of 8:2 fluorotelomer stearate monoester (8:2 FTS) in aerobic soils was conducted by monitoring the loss of 8:2 FTS, production of 8:2 fluorotelomer alcohol (8:2 FTOH) and stearic acid, which would be released by cleavage of the ester linkage, and subsequent degradation products from FTOH for 80 d. Soil microcosms were extracted with ethyl acetate followed by two heated 90/10 v/v acetonitrile/200 mM NaOH extractions. 8:2 FTS was degraded with an observed half-life (t(1/2)) of 10.3 d. The rate of 8:2 FTS biotransformation substantially decreased after 20 d with 22% of 8:2 FTS still remaining on day 80. No biotransformation of 8:2 FTS occurred in autoclaved soil controls, which remained sterile with 102 ± 6% recovery, through day 20. 8:2 FTOH was generated with cleavage of the ester linkage of 8:2 FTS followed by a rapid decline (t(1/2) ~ 2 d) due to subsequent biodegradation. All the expected 8:2 FTOH degradation products were detected including 8:2 fluorotelomer unsaturated and saturated carboxylic acids, 7:2s FTOH, 7:3 acid, and three perfluoroalkyl carboxylic acids with the most prominent being perfluorooctanoic acid (PFOA). PFOA consistently increased over time reaching 1.7 ± 0.07 mol % by day 80. Although cleavage of the ester linkage was evidenced by 8:2 FTOH production, an associated trend in stearic acid concentrations was not clear because of complex fatty acid metabolism dynamics in soil. Further analysis of mass spectrometry fragmentation patterns and chromatography supported the conclusion that hydrolysis of the ester linkage is predominantly the first step in the degradation of 8:2 FTS with the ultimate formation of terminal products such as PFOA.

Hydrolysis of fluorotelomer compounds leading to fluorotelomer alcohol production during solvent extractions of soils.

The experimental approaches used in assessing the biodegradability of fluorotelomer-based surfactants and polymers have been under increasing scrutiny. These substances consist of an aliphatic or aromatic backbone linked to perfluoroethyl moieties by ester, ether or urethane linkages. These linkages when broken yield fluorotelomer alcohols (FTOHs), which are known to biotransform to a suite of polyfluorinated metabolites including perfluorinated carboxylic acids. Quantifying FTOH levels with minimal experimental artifacts is imperative in properly assessing the biotransformation potential and half-lives of fluorotelomer-based materials. We examined the potential for solvent-enhanced ester hydrolysis of fluorotelomer compounds with different hydrocarbon backbones including a monoester stearate (FTS), a citrate tri-ester (TBC), an acrylate (FTA), and a 2,4-toluenediamine urethane (FTU) in acetonitrile, methyl-t-butyl ether (MTBE), and ethyl acetate with live, autoclaved, 60Co-γ-irradiated, and heat-treated (400°C) soils. Substantial hydrolysis only occurred with FTS in live and γ-irradiated soils for which microbial enzymes are expected to be active, but not in autoclaved soils where enzymes are deactivated. Acetonitrile and methanol (solvents with higher dielectric constants) enhanced hydrolysis by an order of magnitude compared to less polar solvents such as MTBE and ethyl acetate. For example, in a 24-h extraction with acetonitrile of FTS-amended soil, >5wt.% FTOH was produced compared to <0.04wt.% in either ethyl acetate or MTBE. FTA hydrolysis was <0.7 wt.% after a 15-h extraction period and was not solvent dependent. No statistically significant solvent-enhanced hydrolysis was observed for TBC, FTA or FTU.

Synthesis and cytotoxic activity of novel quinazolino-beta-carboline-5-one derivatives.

A novel series of quinazolino-beta-carbolinone derivatives was synthesized and evaluated for their in vitro and in vivo anticancer activity. Many compounds have shown good in vitro activity in the range 1-8 microM concentration. Three of the compounds were further tested in nude mice bearing HT-29 colon cancer xenografts.

1,2-Diaryl-1-ethanone and pyrazolo [4,3-c] quinoline-4-one as novel selective cyclooxygenase-2 inhibitors.

Novel 1,2-diaryl-1-ethanone 1 and pyrazolo [4,3-c] quinoline-4-one 2, with pharmacophores different from the known COX inhibitors were identified as selective COX-2 inhibitors. The communication briefly describes SAR of both the series.