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      PFAS River Export Analysis Highlights the Urgent Need for Catchment-Scale Mass Loading Data

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          Concentration-discharge relationships reflect chemostatic characteristics of US catchments

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            Per- and polyfluoroalkyl substances in the environment

            Over the past several years, the term PFAS (per- and polyfluoroalkyl substances) has grown to be emblematic of environmental contamination, garnering public, scientific, and regulatory concern. PFAS are synthesized by two processes, direct fluorination (e.g., electrochemical fluorination) and oligomerization (e.g., fluorotelomerization). More than a megatonne of PFAS is produced yearly, and thousands of PFAS wind up in end-use products. Atmospheric and aqueous fugitive releases during manufacturing, use, and disposal have resulted in the global distribution of these compounds. Volatile PFAS facilitate long-range transport, commonly followed by complex transformation schemes to recalcitrant terminal PFAS, which do not degrade under environmental conditions and thus migrate through the environment and accumulate in biota through multiple pathways. Efforts to remediate PFAS-contaminated matrices still are in their infancy, with much current research targeting drinking water. Per- and polyfluoroalkyl substances (PFAS) are products of the modern chemical industry that have been enthusiastically incorporated into both essential and convenience products. Such molecules, containing fully fluorine-substituted methyl or methylene groups, will persist on geologic time scales and can bioaccumulate to toxic levels. Evich et al . review the sources, transport, degradation, and toxicological implications of environmental PFAS. Despite their grouping together, these compounds are heterogeneous in chemical structure, properties, transformation pathways, and biological effects. Remediation is possible but expensive and is complicated by dispersion in soil, water, and air. It is important that we thoroughly investigate the properties of potential replacements, many of which are merely different kinds of PFAS, and work to mitigate the harms of the most toxic forms already released. —MAF A review explains that per- and polyfluoroalkyl substances in the environment are a persistent hazard that we must understand and mitigate. BACKGROUND Dubbed “forever chemicals” because of their innate chemical stability, per- and polyfluoroalkyl substances (PFAS) have been found to be ubiquitous environmental contaminants, present from the far Arctic reaches of the planet to urban rainwater. Although public awareness of these compounds is still relatively new, PFAS have been manufactured for more than seven decades. Over that time, industrial uses of PFAS have extended to >200 diverse applications of >1400 individual PFAS, including fast-food containers, anti-staining fabrics, and fire-suppressing foams. These numerous applications are possible and continue to expand because the rapidly broadening development and manufacture of PFAS is creating a physiochemically diverse class of thousands of unique synthetic chemicals that are related by their use of highly stable perfluorinated carbon chains. As these products flow through their life cycle from production to disposal, PFAS can be released into the environment at each step and potentially be taken up by biota, but largely migrating to the oceans and marine sediments in the long term. Bioaccumulation in both aquatic and terrestrial species has been widely observed, and while large-scale monitoring studies have been implemented, the adverse outcomes to ecological and human health, particularly of replacement PFAS, remain largely unknown. Critically, because of the sheer number of PFAS, environmental discovery and characterization studies struggle to keep pace with the development and release of next-generation compounds. The rapid expansion of PFAS, combined with their complex environmental interactions, results in a patchwork of data. Whereas the oldest legacy compounds such as perfluoroalkylcarboxylic (PFCAs) and perfluoroalkanesulfonic (PFSAs) have known health impacts, more recently developed PFAS are poorly characterized, and many PFAS even lack defined chemical structures, much less known toxicological end points. ADVANCES Continued measurement of legacy and next-generation PFAS is critical to assessing their behavior in environmental matrices and improving our understanding of their fate and transport. Studies of well-characterized legacy compounds, such as PFCAs and PFSAs, aid in the elucidation of interactions between PFAS chemistries and realistic environmental heterogeneities (e.g., pH, temperature, mineral assemblages, and co-contaminants). However, the reliability of resulting predictions depends on the degree of similarity between the legacy and new compounds. Atmospheric transport has been shown to play an important role in global PFAS distribution and, after deposition, mobility within terrestrial settings decreases with increasing molecular weight, whereas bioaccumulation increases. PFAS degradation rates within anaerobic settings and within marine sediments sharply contrast those within aerobic soils, resulting in considerable variation in biotransformation potential and major terminal products in settings such as landfills, oceans, or soils. However, regardless of the degradation pathway, natural transformation of labile PFAS includes PFAS reaction products, resulting in deposition sites such as landfills serving as time-delayed sources. Thus, PFAS require more drastic, destructive remediation processes for contaminated matrices, including treatment of residuals such as granular activated carbon from drinking water remediation. Destructive thermal and nonthermal processes for PFAS are being piloted, but there is always a risk of forming yet more PFAS products by incomplete destruction. OUTLOOK Although great strides have been taken in recent decades in understanding the fate, mobility, toxicity, and remediation of PFAS, there are still considerable management concerns across the life cycle of these persistent chemicals. The study of emerging compounds is complicated by the confidential nature of many PFAS chemistries, manufacturing processes, industrial by-products, and applications. Furthermore, the diversity and complexity of affected media are difficult to capture in laboratory studies. Unquestionably, it remains a priority for environmental scientists to understand behavior trends of PFAS and to work collaboratively with global regulatory agencies and industry toward effective environmental exposure mitigation strategies.
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              Short-chain perfluoroalkyl acids: environmental concerns and a regulatory strategy under REACH

              Background Short-chain PFASs (per- and polyfluoroalkyl substances) are widely used as alternatives to long-chain PFASs. Long-chain PFASs become gradually regulated under REACH (EC No. 1907/2006) and other international regulations, due to having persistent, bioaccumulative and toxic properties and/or being toxic for reproduction. The increasingly used short-chain PFASs are assumed to have a lower bioaccumulation potential. Nonetheless, they have other properties of concern and are already widely distributed in the environment, also in remote regions. The REACH Regulation does not directly address these emerging properties of concern, complicating the implementation of regulatory measures. Therefore, this study illustrates these environmental concerns and provides a strategy for a regulation of short-chain PFASs within REACH. Results Short-chain PFASs have a high mobility in soil and water, and final degradation products are extremely persistent. This results in a fast distribution to water resources, and consequently, also to a contamination of drinking water resources. Once emitted, short-chain PFASs remain in the environment. A lack of appropriate water treatment technologies results in everlasting background concentrations in the environment, and thus, organisms are permanently and poorly reversibly exposed. Considering such permanent exposure, it is very difficult to estimate long-term adverse effects in organisms. Short-chain PFASs enrich in edible parts of plants and the accumulation in food chains is unknown. Regarding these concerns and uncertainties, especially with respect to the precautionary principle, short-chain PFASs are of equivalent concern to PBT substances. Therefore, they should be identified as substances of very high concern (SVHC) under REACH. The SVHC identification should be followed by a restriction under REACH, which is the most efficient way to minimize the environmental and human exposure of short-chain PFASs in the European Union. Conclusion Due to an increasing use of short-chain PFASs, an effective regulation is urgently needed. The concerns of short-chain PFASs do not match the “classical” concerns as defined under REACH, but are not of minor concern. Therefore, it is of advantage to clearly define the concerns of short-chain PFASs. This might facilitate the following restriction process under REACH.
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                Author and article information

                Contributors
                Journal
                Environmental Science & Technology Letters
                Environ. Sci. Technol. Lett.
                American Chemical Society (ACS)
                2328-8930
                2328-8930
                March 12 2024
                February 19 2024
                March 12 2024
                : 11
                : 3
                : 266-272
                Affiliations
                [1 ]School of Biological and Environmental Sciences, Liverpool John Moores University, Liverpool L3 3AF, United Kingdom
                [2 ]School of Environmental Sciences, University of Hull, Hull HU6 7RX, United Kingdom
                [3 ]Environment Agency, Bristol BS1 5AH, United Kingdom
                [4 ]School of Geography, Earth and Environmental Sciences, University of Plymouth, Drakes Circus, Plymouth PL4 8AA, United Kingdom
                [5 ]U.S. Geological Survey, Denver Federal Center, P.O. Box 25046, Mail Stop 415, Denver, Colorado 80225, United States
                Article
                10.1021/acs.estlett.4c00017
                336b5222-11e8-4de7-bea6-9b1d45060aef
                © 2024

                https://creativecommons.org/licenses/by/4.0/

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