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Quaternary ammonium compounds (QACs), a large class of chemicals that includes high production volume substances, have been used for decades as antimicrobials, preservatives, and antistatic agents and for other functions in cleaning, disinfecting, personal care products, and durable consumer goods. QAC use has accelerated in response to the COVID-19 pandemic and the banning of 19 antimicrobials from several personal care products by the US Food and Drug Administration in 2016. Studies conducted before and after the onset of the pandemic indicate increased human exposure to QACs. Environmental releases of these chemicals have also increased. Emerging information on adverse environmental and human health impacts of QACs is motivating a reconsideration of the risks and benefits across the life cycle of their production, use, and disposal. This work presents a critical review of the literature and scientific perspective developed by a multidisciplinary, multi-institutional team of authors from academia, governmental, and nonprofit organizations. The review evaluates currently available information on the ecological and human health profile of QACs and identifies multiple areas of potential concern. Adverse ecological effects include acute and chronic toxicity to susceptible aquatic organisms, with concentrations of some QACs approaching levels of concern. Suspected or known adverse health outcomes include dermal and respiratory effects, developmental and reproductive toxicity, disruption of metabolic function such as lipid homeostasis, and impairment of mitochondrial function. QACs' role in antimicrobial resistance has also been demonstrated. In the US regulatory system, how a QAC is managed depends on how it is used, for example in pesticides or personal care products. This can result in the same QACs receiving different degrees of scrutiny depending on the use and the agency regulating it. Further, the US Environmental Protection Agency's current method of grouping QACs based on structure, first proposed in 1988, is insufficient to address the wide range of QAC chemistries, potential toxicities, and exposure scenarios. Consequently, exposures to common mixtures of QACs and from multiple sources remain largely unassessed. Some restrictions on the use of QACs have been implemented in the US and elsewhere, primarily focused on personal care products. Assessing the risks posed by QACs is hampered by their vast structural diversity and a lack of quantitative data on exposure and toxicity for the majority of these compounds. This review identifies important data gaps and provides research and policy recommendations for preserving the utility of QAC chemistries while also seeking to limit adverse environmental and human health effects.

Numerous per- and polyfluoroalkyl substances (PFASs) occur in consumer food packaging due to intentional and unintentional addition, despite increasing concern about their health and environmental hazards. We present a substance flow analysis framework to assess the flows of PFASs contained in plant fiber-based and plastic food packaging to the waste stream and environment. Each year between 2018 and 2020, an estimated 9000 (range 1100-25 000) and 940 (range 120-2600) tonnes per year of polymeric PFASs were used in 2% of food packaging in the U.S. and Canada, respectively. At least 11 tonnes per year of non-polymeric PFASs also moved through the food packaging life cycle. Approximately 6100 (range 690-13 000) and 700 (range 70-1600) tonnes per year of these PFASs were landfilled or entered composting facilities in the U.S. and Canada, respectively, with the potential to contaminate the environment. The results suggest that minimal food packaging contains intentionally added PFASs which, nonetheless, has the potential to contaminate the entire waste stream. Further, this indicates that PFASs are not needed for most food packaging. These results serve as a benchmark to judge the effectiveness of future industry and government initiatives to limit PFAS use in food packaging., Environmental Science: Processes & Impacts, 24 (11), ISSN:2050-7887, ISSN:2050-7895

Per- and polyfluoroalkyl substances (PFAS), a highly persistent and potentially toxic class of chemicals, are added to cosmetics to increase their durability and water resistance. To assess this potential health and environmental risk, 231 cosmetic products purchased in the U.S. and Canada were screened for total fluorine using particle-induced gamma-ray emission spectroscopy. Of the eight categories tested, foundations, mascaras, and lip products had the highest proportion of products with high total fluorine ≥0.384 μg F/cm2. Twenty-nine products including 20 with high total fluorine concentrations were analyzed using targeted LC-MS/MS and GC-MS. PFAS concentrations ranged from 22–10,500 ng/g product weight, with an average and a median of 264 and 1050 ng/g product weights, respectively. Here, 6:2 and 8:2 fluorotelomer compounds, including alcohols, methacrylates, and phosphate esters, were most commonly detected. These compounds are precursors to PFCAs that are known to be harmful. The ingredient lists of most products tested did not disclose the presence of fluorinated compounds exposing a gap in U.S. and Canadian labeling laws. The manufacture, use, and disposal of cosmetics containing PFAS are all potential opportunities for health and ecosystem harm. Given their direct exposure routes into people, better regulation is needed to limit the widespread use of PFAS in cosmetics., Environmental Science & Technology Letters, 8 (7), ISSN:2328-8930

This commentary presents a scientific basis for managing as one chemical class the thousands of chemicals known as PFAS (per- and polyfluoroalkyl substances). The class includes perfluoroalkyl acids, perfluoroalkylether acids, and their precursors; fluoropolymers and perfluoropolyethers; and other PFAS. The basis for the class approach is presented in relation to their physicochemical, environmental, and toxicological properties. Specifically, the high persistence, accumulation potential, and/or hazards (known and potential) of PFAS studied to date warrant treating all PFAS as a single class. Examples are provided of how some PFAS are being regulated and how some businesses are avoiding all PFAS in their products and purchasing decisions. We conclude with options for how governments and industry can apply the class-based approach, emphasizing the importance of eliminating non-essential uses of PFAS, and further developing safer alternatives and methods to remove existing PFAS from the environment., Environmental Science & Technology Letters, 7 (8), ISSN:2328-8930

Sources of exposure to per- and polyfluorinated alkyl substances (PFAS) include food, water, and given that humans spend typically 90% of our time indoors, air and dust. Quantifying PFAS prevalent indoors, such as neutral, volatile PFAS, and estimating their exposure risk to humans is thus important. To accurately measure these compounds indoors, polyethylene (PE) sheets were employed and validated as passive detection tools, and analyzed by gas chromatography-mass spectrometry. Air concentrations were compared to dust and carpet concentrations reported elsewhere. Partitioning between PE sheets of different thicknesses suggested that interactions of the PEs with the compounds are occurring by absorption. Volatile PFAS, specifically fluorotelomer alcohols (FTOHs), were ubiquitous in indoor environments. For example, in carpeted Californian kindergarten classrooms, 6:2 FTOH dominated with concentrations ranging from 9-600 ng m(−3), followed by 8:2 FTOH. Concentrations of volatile PFAS from air, carpet and dust were closely related to each other, indicating that carpets and dust are major sources of FTOHs in air. Nonetheless, air posed the largest exposure risk of FTOHs and biotransformed perfluorinated alkyl acids (PFAA) in young children. This research highlights inhalation of indoor air as an important exposure pathway and the need for further reduction of precursors to PFAA.

Carpet and rugs currently represent about half of the United States flooring market and offer many benefits as a flooring type. How carpets influence our exposure to both microorganisms and chemicals in indoor environments has important health implications but is not well understood. The goal of this manuscript is to consolidate what is known about how carpet impacts indoor chemistry and microbiology, as well as to identify the important research gaps that remain. After describing the current use of carpet indoors, questions focus on five specific areas: 1) indoor chemistry, 2) indoor microbiology, 3) resuspension and exposure, 4) current practices and future needs, and 5) sustainability. Overall, it is clear that carpet can influence our exposures to particles and volatile compounds in the indoor environment by acting as a direct source, as a reservoir of environmental contaminants, and as a surface supporting chemical and biological transformations. However, the health implications of these processes are not well known, nor how cleaning practices could be optimized to minimize potential negative impacts. Current standards and recommendations focus largely on carpets as a primary source of chemicals and on limiting moisture that would support microbial growth. Future research should consider enhancing knowledge related to the impact of carpet in the indoor environment and how we might improve the design and maintenance of this common material to reduce our exposure to harmful contaminants while retaining the benefits to consumers.

Perfluoroalkyl acids (PFAAs) are a class of organic contaminants notable for their extreme persistence. The unique chemical properties of these compounds make them difficult to remove from water using most standard water treatment techniques. To gain insight into the possibility of remediating contaminated groundwater by in situ chemical oxidation with heat-activated persulfate, PFAA removal and the generation of transformation products were evaluated under laboratory conditions. Solution pH had a strong influence on the removal of perfluorooctanoic acid (PFOA), resulting in its transformation into shorter-chain perfluorocarboxylic acids at pH values below 3. The presence of chloride and aquifer sediments decreased the efficiency of the process by less than 25% under conditions likely to be encountered in drinking water aquifers. Perfluorooctane sulfonate (PFOS) was not transformed by heat-activated persulfate under any of the conditions tested. Despite challenges related to the need to manipulate aquifer pH, the possible generation of undesirable short-chain perfluorinated carboxylic acids (PFCAs) and chlorate, and metals mobilization, heat-activated persulfate may be a useful treatment technology for sites contaminated with perfluorinated carboxylic acids and fluorotelomer-based compounds, including those used in current-generation aqueous film-forming foams.

Poly- and perfluoroalkyl substances (PFASs) have been detected in an increasing number of water supplies. In many instances, the contamination is associated with the use of PFAS-containing aqueous film-forming foams (AFFF) in firefighting activities. To investigate the potential for remediating AFFF contamination in groundwater with heat-activated persulfate, PFAS oxidation and the generation of transformation products was evaluated under well-controlled conditions. Fluorotelomer- and perfluoroalkyl sulfonamide-based polyfluorinated compounds were transformed to perfluorinated carboxylic acids, which underwent further degradation under acidic conditions produced after persulfate decomposed. The presence of aquifer sediments decreased the efficiency of the remedial process but did not alter the transformation pathways. At high concentrations, the presence of organic solvents, such as those present in AFFF formulations, inhibited transformation of a representative perfluorinated compound, perfluorooctanoic acid. Heat-activated persulfate did not transform perfluorooctanesulfonic acid or perfluorohexanesulfonic acid under any conditions. Despite challenges associated with the creation of acidic conditions in the subsurface, the potential for generation of undesirable transformation products, and the release of toxic metals, heat-activated persulfate may be a useful in situ treatment for sites contaminated with polyfluoroalkyl substances and perfluorocarboxylic acids.

In this commentary, we express our reservation about the mechanism of PFOS degradation proposed by Chang et al. (Environmental Science Water Research & Technology, 2020, 6, 3476).

Drinking water contamination with poly- and perfluoroalkyl substances (PFASs) poses risks to the developmental, immune, metabolic, and endocrine health of consumers. We present a spatial analysis of 2013–2015 national drinking water PFAS concentrations from the U.S. Environmental Protection Agency’s (US EPA) third Unregulated Contaminant Monitoring Rule (UCMR3) program. The number of industrial sites that manufacture or use these compounds, the number of military fire training areas, and the number of wastewater treatment plants are all significant predictors of PFAS detection frequencies and concentrations in public water supplies. Among samples with detectable PFAS levels, each additional military site within a watershed’s eight-digit hydrologic unit is associated with a 20% increase in PFHxS, a 10% increase in both PFHpA and PFOA, and a 35% increase in PFOS. The number of civilian airports with personnel trained in the use of aqueous film-forming foams is significantly associated with the detection of PFASs above the minimal reporting level. We find drinking water supplies for 6 million U.S. residents exceed US EPA’s lifetime health advisory (70 ng/L) for PFOS and PFOA. Lower analytical reporting limits and additional sampling of smaller utilities serving

The groundwater remediation industry continues to progress towards less expensive, more sustainable in situ remedies. However, in situ treatment requires site-specific performance data that can be difficult or impossible to obtain using conventional laboratory microcosm studies. To improve the representativeness of laboratory scale treatability studies, and aid in remedial technology implementation, we developed the In Situ Microcosm Array (ISMA). This autonomous diagnostic device enables the deployment of 10 flow-through sediment columns within a standard 10-cm groundwater-monitoring well. Suspended at the desired aquifer depth, the fully encapsulated ISMA meters groundwater directly from the aquifer to microcosms containing competing remedial technologies. Field demonstrations of the instrument were performed in two aquifers contaminated, respectively, with trichloroethylene and hexavalent chromium, and with perchlorate. A cost assessment positions ISMA deployment costs within the range of conventional laboratory treatability studies. Results demonstrate the ISMA’s utility to perform cost-effective, high-throughput, screenings of multiple intervention strategies in the field, without impacting the subsurface environment examined.

Bio-refineries produce large volumes of waste streams with high organic content, which are potentially interesting for further processing. Anaerobic digestion (AD) can be a key technology for treatment of these sidestreams, such as molasses. However, the high concentration of salts in molasses can cause inhibition of methanogenesis. In this research, concentrated and diluted molasses were subjected to biomethanation in two types of submerged anaerobic membrane bioreactors (AnMBRs): one with biogas recirculation and one with a vibrating membrane. Both reactors were compared in terms of methane production and membrane fouling. Biogas recirculation seemed to be a good way to avoid membrane fouling, while the trans membrane pressures in the vibrating MBR increased over time, due to cake layer formation and the absence of a mixing system. Stable methane production, up to 2.05 L L−1 d−1 and a concomitant COD removal of 94.4%, was obtained only when diluted molasses were used, since concentrated molasses caused a decrease in methane production and an increase in volatile fatty acids (VFA), indicating an inhibiting effect of concentrated molasses on AD. Real-time PCR results revealed a clear dominance of Methanosaetaceae over Methanosarcinaceae as the main acetoclastic methanogens in both AnMBRs.

Nanoscale zero-valent iron (nZVI) is a strong nonspecific reducing agent that is used for in situ degradation of chlorinated solvents and other oxidized pollutants. However, there are significant concerns regarding the risks posed by the deliberate release of engineered nanomaterials into the environment, which have triggered moratoria, for example, in the United Kingdom. This critical review focuses on the effect of nZVI injection on subsurface microbial communities, which are of interest due to their important role in contaminant attenuation processes. Corrosion of ZVI stimulates dehalorespiring bacteria, due to the production of H2 that can serve as an electron donor for reduction of chlorinated contaminants. Conversely, laboratory studies show that nZVI can be inhibitory to pure bacterial cultures, although toxicity is reduced when nZVI is coated with polyelectrolytes or natural organic matter. The emerging toolkit of molecular biological analyses should enable a more sophisticated assessment of combi...

© 2015 American Chemical Society. Sulfate radical (SO4•-) is a strong, short-lived oxidant that is produced when persulfate (S2O82-) reacts with transition metal oxides during in situ chemical oxidation (ISCO) of contaminated groundwater. Although engineers are aware of the ability of transition metal oxides to activate persulfate, the operation of ISCO remediation systems is hampered by an inadequate understanding of the factors that control SO4•-production and the overall efficiency of the process. To address these shortcomings, we assessed the stoichiometric efficiency and products of transition metal-catalyzed persulfate oxidation of benzene with pure iron- and manganese-containing minerals, clays, and aquifer solids. For most metal-containing solids, the stoichiometric efficiency, as determined by the loss of benzene relative to the loss of persulfate, approached the theoretical maximum. Rates of production of SO4•-or hydroxyl radical (HO•) generated from radical chain reactions were affected by the concentration of benzene, with rates of S2O82-decomposition increasing as the benzene concentration increased. Under conditions selected to minimize the loss of initial transformation products through reaction with radicals, the production of phenol only accounted for 30%-60% of the benzene lost in the presence of O2. The remaining products included a ring-cleavage product that appeared to contain an α,β-unsaturated aldehyde functional group. In the absence of O2, the concentration of the ring-cleavage product increased relative to phenol. The formation of the ring-cleavage product warrants further studies of its toxicity and persistence in the subsurface.

Persulfate (S2O8(2-)) is being used increasingly for in situ chemical oxidation (ISCO) of organic contaminants in groundwater, despite an incomplete understanding of the mechanism through which it is converted into reactive species. In particular, the decomposition of persulfate by naturally occurring mineral surfaces has not been studied in detail. To gain insight into the reaction rates and mechanism of persulfate decomposition in the subsurface, and to identify possible approaches for improving its efficacy, the decomposition of persulfate was investigated in the presence of pure metal oxides, clays, and representative aquifer solids collected from field sites in the presence and absence of benzene. Under conditions typical of groundwater, Fe(III)- and Mn(IV)-oxides catalytically converted persulfate into sulfate radical (SO4(•-)) and hydroxyl radical (HO(•)) over time scales of several weeks at rates that were 2-20 times faster than those observed in metal-free systems. Amorphous ferrihydrite was the most reactive iron mineral with respect to persulfate decomposition, with reaction rates proportional to solid mass and surface area. As a result of radical chain reactions, the rate of persulfate decomposition increased by as much as 100 times when benzene concentrations exceeded 0.1 mM. Due to its relatively slow rate of decomposition in the subsurface, it can be advantageous to inject persulfate into groundwater, allowing it to migrate to zones of low hydraulic conductivity where clays, metal oxides, and contaminants will accelerate its conversion into reactive oxidants.

Robust methods to detect and characterize engineered nanoparticles (ENPs) in environmental samples are an urgent need, particularly given the increasing use of ENPs in consumer products. To be successful, methods should enable differentiation of ENPs from background nanoparticulates and other system components. The element specificity of inductively coupled plasma mass spectrometry (ICP-MS) can, to some degree, satisfy this requirement. Given the polydisperse nature of particles in natural systems, combining ICP-MS with a size separation method holds particular promise. This paper compares hydrodynamic chromatography (HDC) and asymmetrical flow field flow fractionation (AF4), both coupled with ICP-MS, in their capacity to detect, quantify, and characterize nanoparticles. The detection limits, resolution, and recoveries for both techniques were determined using gold nanoparticle standards. AF4 is capable of separating mixtures of 5, 20, 50 and 100 nm gold ENPs with significantly greater resolution than HDC, with these resolution differences being most pronounced in the smaller size range. However, HDC recoveries ranged from 77 to 96%, while recovery during AF4 ranged from 4 to 89%. The low AF4 recoveries generally occurred for the largest ENPs at the lowest concentrations examined. The limits of detection for both techniques were found to be approximately 5 μg L−1, however different experimental conditions could lower this value. HDC provides an additional benefit over AF4 by proving capable of separating a dissolved signal from a NP sample.