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      Confined water–encapsulated activated carbon for capturing short-chain perfluoroalkyl and polyfluoroalkyl substances from drinking water

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          Significance

          Adsorption is the most established method used to block human exposure through drinking water to the notorious perfluoroalkyl and polyfluoroalkyl substances (PFASs), yet is challenged by the increasing short-chain PFAS crisis due to the inherent defects of solid–liquid mass transfer. Herein, by assembling the confined water structure in situ in hydrophobic nanopores, we introduce a dual-drive mode in the activated carbon to completely eliminate the mass transfer barrier and dramatically enhance its adsorption performance for various short-chain PFASs. Significantly, the methodology demonstrated is a potential in situ upgrade of existing adsorption devices. This work will thus revolutionize the understanding of the role of confined water in mass transfer and enable an in situ solution for the short-chain PFAS crisis.

          Abstract

          The global ecological crisis of perfluoroalkyl and polyfluoroalkyl substances (PFASs) in drinking water has gradually shifted from long-chain to short-chain PFASs; however, the widespread established PFAS adsorption technology cannot cope with the impact of such hydrophilic pollutants given the inherent defects of solid–liquid mass transfer. Herein, we describe a reagent-free and low-cost strategy to reduce the energy state of short-chain PFASs in hydrophobic nanopores by employing an in situ constructed confined water structure in activated carbon (AC). Through direct (driving force) and indirect (assisted slip) effects, the confined water introduced a dual-drive mode in the confined water–encapsulated activated carbon (CW-AC) and completely eliminated the mass transfer barrier (3.27 to 5.66 kcal/mol), which caused the CW-AC to exhibit the highest adsorption capacity for various short-chain PFASs (C-F number: 3-6) among parent AC and other adsorbents reported. Meanwhile, benefiting from the chain length– and functional group–dependent confined water–binding pattern, the affinity of the CW-AC surpassed the traditional hydrophobicity dominance and shifted toward hydrophilic short-chain PFASs that easily escaped treatment. Importantly, the ability of CW-AC functionality to directly transfer to existing adsorption devices was verified, which could treat 21,000 bed volumes of environment-related high-load (~350 ng/L short-chain PFAS each) real drinking water to below the World Health Organization’s standard. Overall, our results provide a green and cost-effective in situ upgrade scheme for existing adsorption devices to address the short-chain PFAS crisis.

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          Most cited references53

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          Multiwfn: a multifunctional wavefunction analyzer.

          Multiwfn is a multifunctional program for wavefunction analysis. Its main functions are: (1) Calculating and visualizing real space function, such as electrostatic potential and electron localization function at point, in a line, in a plane or in a spatial scope. (2) Population analysis. (3) Bond order analysis. (4) Orbital composition analysis. (5) Plot density-of-states and spectrum. (6) Topology analysis for electron density. Some other useful utilities involved in quantum chemistry studies are also provided. The built-in graph module enables the results of wavefunction analysis to be plotted directly or exported to high-quality graphic file. The program interface is very user-friendly and suitable for both research and teaching purpose. The code of Multiwfn is substantially optimized and parallelized. Its efficiency is demonstrated to be significantly higher than related programs with the same functions. Five practical examples involving a wide variety of systems and analysis methods are given to illustrate the usefulness of Multiwfn. The program is free of charge and open-source. Its precompiled file and source codes are available from http://multiwfn.codeplex.com. Copyright © 2011 Wiley Periodicals, Inc.
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            Revealing noncovalent interactions.

            Molecular structure does not easily identify the intricate noncovalent interactions that govern many areas of biology and chemistry, including design of new materials and drugs. We develop an approach to detect noncovalent interactions in real space, based on the electron density and its derivatives. Our approach reveals the underlying chemistry that compliments the covalent structure. It provides a rich representation of van der Waals interactions, hydrogen bonds, and steric repulsion in small molecules, molecular complexes, and solids. Most importantly, the method, requiring only knowledge of the atomic coordinates, is efficient and applicable to large systems, such as proteins or DNA. Across these applications, a view of nonbonded interactions emerges as continuous surfaces rather than close contacts between atom pairs, offering rich insight into the design of new and improved ligands.
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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.

                Author and article information

                Contributors
                Journal
                Proc Natl Acad Sci U S A
                Proc Natl Acad Sci U S A
                PNAS
                Proceedings of the National Academy of Sciences of the United States of America
                National Academy of Sciences
                0027-8424
                1091-6490
                26 June 2023
                4 July 2023
                26 December 2023
                : 120
                : 27
                : e2219179120
                Affiliations
                [1] aState Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University , Nanjing 210023, Jiangsu, PR China
                Author notes
                1To whom correspondence may be addressed. Email: hdhu@ 123456nju.edu.cn or hqren@ 123456nju.edu.cn .

                Edited by Alexis Bell, University of California, Berkeley, CA; received November 10, 2022; accepted April 18, 2023

                Author information
                https://orcid.org/0009-0006-9338-3291
                https://orcid.org/0000-0003-0193-0333
                Article
                202219179
                10.1073/pnas.2219179120
                10318985
                37364117
                43c9df03-d1d6-4493-9ae4-49cba9f7ad00
                Copyright © 2023 the Author(s). Published by PNAS.

                This article is distributed under Creative Commons Attribution-NonCommercial-NoDerivatives License 4.0 (CC BY-NC-ND).

                History
                : 10 November 2022
                : 18 April 2023
                Page count
                Pages: 10, Words: 6811
                Categories
                research-article, Research Article
                eng, Engineering
                416
                Physical Sciences
                Engineering

                adsorption,molecular dynamics,water purification,pfas,dual-drive

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