An Overview of Potential Alternatives for the Multiple Uses of Per- and Polyfluoroalkyl SubstancesClick to copy article linkArticle link copied!
- Romain Figuière*Romain Figuière*Email: [email protected]Department of Environmental Science, Stockholm University, Stockholm SE-10691, SwedenMore by Romain Figuière
- Luc T. MiazLuc T. MiazDepartment of Environmental Science, Stockholm University, Stockholm SE-10691, SwedenMore by Luc T. Miaz
- Eleni SavvidouEleni SavvidouDepartment of Environmental Science, Stockholm University, Stockholm SE-10691, SwedenMore by Eleni Savvidou
- Ian T. CousinsIan T. CousinsDepartment of Environmental Science, Stockholm University, Stockholm SE-10691, SwedenMore by Ian T. Cousins
Abstract
Per- and polyfluoroalkyl substances (PFAS) are used in a wide range of different industrial and consumer applications. However, due to their extreme environmental persistence and their impacts on human and ecosystem health, PFAS have been subject to many regulatory activities, including initiatives to incentivize industry to transition toward PFAS-free alternatives. Although efforts have been made to map all uses of PFAS, work is still needed to provide an overview of their potential alternatives. Based on the functional substitution approach, this study develops an online database that documents all known uses of PFAS, describes the functions provided by PFAS in these uses, lists potential alternatives that can deliver equivalent or similar functions to PFAS, and evaluates the suitability of the identified alternatives to replace PFAS. Overall, the database lists 325 different applications of PFAS across 18 use categories. In total, 530 PFAS-free alternatives are identified. Based on a screening of potential concerns of the identified alternatives, their performance compared to PFAS, and their availability on the market, it is concluded that potentially suitable alternatives to PFAS are available for 40 different applications. For 83 applications, no alternatives could be identified at the time of the study and should be the focus of further research activities.
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License Summary*
You are free to share(copy and redistribute) this article in any medium or format and to adapt(remix, transform, and build upon) the material for any purpose, even commercially within the parameters below:
Creative Commons (CC): This is a Creative Commons license.
Attribution (BY): Credit must be given to the creator.
*Disclaimer
This summary highlights only some of the key features and terms of the actual license. It is not a license and has no legal value. Carefully review the actual license before using these materials.
License Summary*
You are free to share(copy and redistribute) this article in any medium or format and to adapt(remix, transform, and build upon) the material for any purpose, even commercially within the parameters below:
Creative Commons (CC): This is a Creative Commons license.
Attribution (BY): Credit must be given to the creator.
*Disclaimer
This summary highlights only some of the key features and terms of the actual license. It is not a license and has no legal value. Carefully review the actual license before using these materials.
Synopsis
This study provides an overview of the availability of suitable alternatives to PFAS across their multiple uses.
1. Introduction
2. Methods
2.1. Definitions
2.1.1. Definition of PFAS
2.1.2. Definition of Uses
Figure 1
Figure 1. General structure of the database. Note: this figure illustrates the structure of the database by using specific examples of PFAS used as fluorinated gases and in food contact materials. As it is not possible to represent all functions for all applications in all sub-uses and use categories of PFAS, “···” was used to indicate that more uses, sub-uses, applications, and functions are covered in the database than those listed in the figure.
2.1.3. Definition of Functions
2.1.4. Definition of Alternatives
2.2. Overview of the Database
List of PFAS used | Functions provided by PFAS | Potential alternatives to PFAS |
---|---|---|
Substance name | Chemical function | Name of the alternative |
CAS number (if available) | End-use function | CAS number (if relevant and available) |
Elemental composition (if available) | Function as a service | Type of alternative |
If the substance is a polymer | Performance requirements for alternatives (if relevant) | General chemistry description of alternative |
Source of information | Source of information | If the alternative has been assessed for PBT (if relevant) |
If the alternative has been classified under CLP (if relevant) | ||
If the alternative is listed in the Substitution Support Portal (if relevant) | ||
Description of potential loss in performance | ||
Description of market availability | ||
Source of information |
2.3. Literature Search Strategy
2.3.1. Information on Uses of PFAS and Substance Identities
2.3.2. Search for Functions of PFAS
2.3.3. Identification and Evaluation of Alternatives
2.3.3.1. Identification of Potential Alternatives
2.3.3.2. Identification of the Composition of Alternative Products
2.3.3.3. Hazard Characterization of Alternatives
2.3.3.4. Evaluation for Potential Performance Loss
2.3.3.5. Evaluation of the Market Availability
2.4. Analysis of the Data
2.4.1. Overview of the Data Included in the Database
2.4.2. Analysis of Alternatives to PFAS
2.4.2.1. Safety Considerations
2.4.2.2. Performance Loss Considerations
2.4.2.3. Market Availability
2.4.2.4. Evaluation of Substitution Potential
Figure 2
Figure 2. Substitution potential according to changes in performance and market availability of the alternatives.
2.5. Illustrative Case Study
3. Results and Discussion
3.1. Number of Substances and Uses of PFAS Included in the Database
Use categories | Sub-uses | Applications | Chemical functions | End-use functions | Services |
---|---|---|---|---|---|
Active pharmaceutical ingredients (API) | 2 | 14 | 1 | 24 | 21 |
Biocides (BP) | 1 | 4 | 1 | 4 | 4 |
Building and construction products (Build.) | 9 | 17 | 14 | 18 | 30 |
Consumer mixtures (Consu.) | 7 | 15 | 7 | 15 | 12 |
Cosmetic products (Cosm.) | 5 | 32 | 9 | 12 | 6 |
Electronics and semiconductors sector (Elec.) | 3 | 29 | 17 | 22 | 37 |
Energy sector (Energy) | 9 | 19 | 17 | 19 | 24 |
Firefighting foams (FFF) | 1 | 5 | 1 | 1 | 3 |
Fluorinated gases (F-gases) | 7 | 29 | 8 | 14 | 27 |
Food contact materials (FCM) | 2 | 4 | 4 | 4 | 9 |
Industrial production (Indust.) | 8 | 28 | 12 | 18 | 11 |
Lubricants (Lubr.) | 3 | 42 | 11 | 13 | 19 |
Medical products (Med.) | 6 | 21 | 14 | 18 | 29 |
Metal plating and metal products manufacture (Metal) | 2 | 4 | 8 | 10 | 14 |
Petroleum and mining (Mining) | 2 | 9 | 10 | 13 | 15 |
Plant protection products (PPP) | 1 | 6 | 3 | 7 | 5 |
Textile, upholstery, leather, apparel, and carpets (TULAC) | 7 | 20 | 11 | 15 | 21 |
Transport sector (Transp.) | 10 | 27 | 16 | 24 | 45 |
Total | 85 | 325 | 39 | 131 | 201 |
3.1.1. PFAS Used in Fluorinated Gases
3.2. Functions of PFAS
3.2.1. PFAS Used in Fluorinated Gases
3.3. Alternatives to PFAS
3.3.1. PFAS Used in Fluorinated Gases
3.4. Assessment of Alternatives to PFAS
3.4.1. Safety Considerations
3.4.2. Substitution Potential of PFAS
Figure 3
Figure 3. Substitution Potential of PFAS.
3.5. Potential Applications and Limitations of the Database
Data Availability
The database of alternatives to PFAS that has been built in this article is freely available as a data set on the Zenodo platform via the following link: https://zenodo.org/doi/10.5281/zenodo.8434809.
Supporting Information
The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.est.4c09088.
Additional details on the methods followed to build up the database and additional analysis of the data on alternatives to PFAS, including extracts of the database (PDF)
Applications of PFAS listed in the database; links between applications of PFAS listed in the database and the uses identified by Glüge et al.; composition of alternative products to uses of PFAS; list of applications of PFAS without identified alternatives; list of PFAS used as fluorinated gases; list of functions delivered by PFAS used as fluorinated gases; and list of alternatives to PFAS used as fluorinated gases (XLSX)
Terms & Conditions
Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.
References
This article references 63 other publications.
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- 2Glüge, J.; Scheringer, M.; Cousins, I. T.; DeWitt, J. C.; Goldenman, G.; Herzke, D.; Lohmann, R.; Ng, C. A.; Trier, X.; Wang, Z. An Overview of the Uses of Per- and Polyfluoroalkyl Substances (PFAS). Environ. Sci. Process. Impacts 2020, 22 (12), 2345– 2373, DOI: 10.1039/D0EM00291GGoogle ScholarThere is no corresponding record for this reference.
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- 4Guelfo, J. L.; Korzeniowski, S.; Mills, M. A.; Anderson, J.; Anderson, R. H.; Arblaster, J. A.; Conder, J. M.; Cousins, I. T.; Dasu, K.; Henry, B. J.; Lee, L. S.; Liu, J.; McKenzie, E. R.; Willey, J. 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. Environ. Toxicol. Chem. 2021, 40 (12), 3234– 3260, DOI: 10.1002/etc.5182Google Scholar4https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXitlCntLrI&md5=902964202add770c857d6e4906171c23Environmental 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 MeetingGuelfo, Jennifer L.; Korzeniowski, Stephen; Mills, Marc A.; Anderson, Janet; Anderson, Richard H.; Arblaster, Jennifer A.; Conder, Jason M.; Cousins, Ian T.; Dasu, Kavitha; Henry, Barbara J.; Lee, Linda S.; Liu, Jinxia; McKenzie, Erica R.; Willey, JaniceEnvironmental Toxicology and Chemistry (2021), 40 (12), 3234-3260CODEN: ETOCDK; ISSN:0730-7268. (Wiley-Blackwell)A Society of Environmental Toxicol. and Chem. (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 chem., 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) std. and novel anal. 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 addnl. pressing needs include increased availability of anal. stds. 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 anal. methods are needed to guide broader policies and best management practices. Environ Toxicol Chem 2021;00:1-27. 2021 The Authors. Environmental Toxicol. and Chem. published by Wiley Periodicals LLC on behalf of SETAC.
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- 8Cousins, I. T.; DeWitt, J. C.; Glüge, J.; Goldenman, G.; Herzke, D.; Lohmann, R.; Ng, C. A.; Scheringer, M.; Wang, Z. The High Persistence of PFAS Is Sufficient for Their Management as a Chemical Class. Environ. Sci. Process. Impacts 2020, 22 (12), 2307– 2312, DOI: 10.1039/D0EM00355GGoogle Scholar8https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXit1aks7jL&md5=f36013e904880abdaaa6f2753f9371a9The high persistence of PFAS is sufficient for their management as a chemical classCousins, Ian T.; DeWitt, Jamie C.; Gluge, Juliane; Goldenman, Gretta; Herzke, Dorte; Lohmann, Rainer; Ng, Carla A.; Scheringer, Martin; Wang, ZhanyunEnvironmental Science: Processes & Impacts (2020), 22 (12), 2307-2312CODEN: ESPICZ; ISSN:2050-7895. (Royal Society of Chemistry)Per- and polyfluoroalkyl substances (PFAS) are a class of synthetic org. substances with diverse structures, properties, uses, bioaccumulation potentials and toxicities. Despite this high diversity, all PFAS are alike in that they contain perfluoroalkyl moieties that are extremely resistant to environmental and metabolic degrdn. The vast majority of PFAS are therefore either non-degradable or transform ultimately into stable terminal transformation products (which are still PFAS). Under the European chems. regulation this classifies PFAS as very persistent substances (vP). We argue that this high persistence is sufficient concern for their management as a chem. class, and for all "non-essential" uses of PFAS to be phased out. The continual release of highly persistent PFAS will result in increasing concns. and increasing probabilities of the occurrence of known and unknown effects. Once adverse effects are identified, the exposure and assocd. effects will not be easily reversible. Reversing PFAS contamination will be tech. challenging, energy intensive, and costly for society, as is evident in the efforts to remove PFAS from contaminated land and drinking water sources.
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- 19Hopkins, Z. R.; Sun, M.; DeWitt, J. C.; Knappe, D. R. U. Recently Detected Drinking Water Contaminants: GenX and Other Per- and Polyfluoroalkyl Ether Acids. J. AWWA 2018, 110 (7), 13– 28, DOI: 10.1002/awwa.1073Google Scholar19https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXht1ahtb%252FK&md5=a9cb4b60041abff45c4d7c2fce74a5f7Recently Detected Drinking Water Contaminants: GenX and Other Per- and Polyfluoroalkyl Ether AcidsHopkins, Zachary R.; Sun, Mei; De Witt, Jamie C.; Knappe, Detlef R. U.Journal - American Water Works Association (2018), 110 (7), 13-28CODEN: JAWWA5; ISSN:1551-8833. (John Wiley & Sons, Inc.)For several decades, a common processing aid in the prodn. of fluoropolymers was the ammonium salt of perfluorooctanoic acid (PFOA). Because PFOA is persistent, bioaccumulative, and toxic, its prodn. and use are being phased out in the United States. In 2009, the US Environmental Protection Agency stipulated conditions for the manuf. and com. use of GenX, a PFOA replacement. While GenX is produced for com. purposes, the acid form of GenX is also generated as a byproduct during the prodn. of fluoromonomers. The discovery of high concns. of GenX and related perfluoroalkyl ether acids (PFEAs) in the Cape Fear River and in finished drinking water of more than 200,000 North Carolina residents required quick action by researchers, regulators, public health officials, com. labs., drinking water providers, and consulting engineers. Information about sources and toxicity of GenX as well as an anal. method for the detection of GenX and eight related PFEAs is presented. GenX/PFEA occurrence in water and GenX/PFEA removal by different drinking water treatment processes are also discussed.
- 20Sun, M.; Arevalo, E.; Strynar, M.; Lindstrom, A.; Richardson, M.; Kearns, B.; Pickett, A.; Smith, C.; Knappe, D. R. U. Legacy and Emerging Perfluoroalkyl Substances Are Important Drinking Water Contaminants in the Cape Fear River Watershed of North Carolina. Environ. Sci. Technol. Lett. 2016, 3 (12), 415– 419, DOI: 10.1021/acs.estlett.6b00398Google Scholar20https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhvVaksL3M&md5=b070b9d1270efb9317f0548d28b85fd9Legacy and Emerging Perfluoroalkyl Substances Are Important Drinking Water Contaminants in the Cape Fear River Watershed of North CarolinaSun, Mei; Arevalo, Elisa; Strynar, Mark; Lindstrom, Andrew; Richardson, Michael; Kearns, Ben; Pickett, Adam; Smith, Chris; Knappe, Detlef R. U.Environmental Science & Technology Letters (2016), 3 (12), 415-419CODEN: ESTLCU; ISSN:2328-8930. (American Chemical Society)Long-chain per- and polyfluoroalkyl substances (PFASs) are being replaced by short-chain PFASs and fluorinated alternatives. For ten legacy PFASs and seven recently discovered perfluoroalkyl ether carboxylic acids (PFECAs), we report (1) their occurrence in the Cape Fear River (CFR) watershed, (2) their fate in water treatment processes, and (3) their adsorbability on powd. activated carbon (PAC). In the headwater region of the CFR basin, PFECAs were not detected in raw water of a drinking water treatment plant (DWTP), but concns. of legacy PFASs were high. The U.S. Environmental Protection Agency's lifetime health advisory level (70 ng/L) for perfluorooctanesulfonic acid and perfluorooctanoic acid (PFOA) was exceeded on 57 of 127 sampling days. In raw water of a DWTP downstream of a PFAS manufacturer, the mean concn. of perfluoro-2-propoxypropanoic acid (PFPrOPrA), a replacement for PFOA, was 631 ng/L (n = 37). Six other PFECAs were detected, with three exhibiting chromatog. peak areas up to 15 times that of PFPrOPrA. At this DWTP, PFECA removal by coagulation, ozonization, biofiltration, and disinfection was negligible. The adsorbability of PFASs on PAC increased with increasing chain length. Replacing one CF2 group with an ether oxygen decreased the affinity of PFASs for PAC, while replacing addnl. CF2 groups did not lead to further affinity changes.
- 21Gebreab, K. Y.; Eeza, M. N. H.; Bai, T.; Zuberi, Z.; Matysik, J.; O’Shea, K. E.; Alia, A.; Berry, J. P. Comparative Toxicometabolomics of Perfluorooctanoic Acid (PFOA) and next-Generation Perfluoroalkyl Substances. Environ. Pollut. 2020, 265, 114928 DOI: 10.1016/j.envpol.2020.114928Google Scholar21https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXht1OgsLzI&md5=aaa6d52e57cf1a4220389fa652e548b2Comparative toxicometabolomics of perfluorooctanoic acid (PFOA) and next-generation perfluoroalkyl substancesGebreab, Kiflom Y.; Eeza, Muhamed N. H.; Bai, Tianyu; Zuberi, Zain; Matysik, Jorg; O'Shea, Kevin E.; Alia, A.; Berry, John P.Environmental Pollution (Oxford, United Kingdom) (2020), 265 (Part_A), 114928CODEN: ENPOEK; ISSN:0269-7491. (Elsevier Ltd.)Owing to environmental health concerns, a no. of per- and polyfluoroalkyl substances (PFAS) have been phased-out, and increasingly replaced by various chem. analogs. Most prominent among these replacements are numerous perfluoroether carboxylic acids (PFECA). Toxicity, and environmental health concerns assocd. with these next-generation PFAS, however, remains largely unstudied. The zebrafish embryo was employed, in the present study, as a toxicol. model system to investigate toxicity of a representative sample of PFECA, alongside perfluorooctanoic acid (PFOA) as one of the most widely used, and best studied, of the "legacy" PFAS. Acute embryotoxicity (i.e., lethality), along with impaired development, and variable effects on locomotory behavior, were obsd. for all PFAS in the zebrafish model. Alterations of metabolic profiles suggested targeting of hepatocytes (i.e., hepatotoxicity), as well as apparent modulation of neural metabolites, and moreover, were consistent with a previously proposed role of mitochondrial disruption and peroxisome proliferator-activated receptor (PPAR) activation as reflected by dysfunctions of carbohydrate, lipid and amino acid metab. and consistent with a previously proposed contribution of PFAS to metabolic syndrome. Taken together, it was generally concluded that toxicity of PFECA is quant. and qual. similar to PFOA, and these analogs, likewise, represent potential concerns as environmental toxicants.
- 22Yang, L.-H.; Yang, W.-J.; Lv, S.-H.; Zhu, T.-T.; Adeel Sharif, H. M.; Yang, C.; Du, J.; Lin, H. Is HFPO-DA (GenX) a Suitable Substitute for PFOA? A Comprehensive Degradation Comparison of PFOA and GenX via Electrooxidation. Environ. Res. 2022, 204, 111995 DOI: 10.1016/j.envres.2021.111995Google Scholar22https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXitVSjt77E&md5=ca6530659de32131c0d87280add38798Is HFPO-DA (GenX) a suitable substitute for PFOA? A comprehensive degradation comparison of PFOA and GenX via electrooxidationYang, Li-Hui; Yang, Wen-Jian; Lv, Si-Hao; Zhu, Ting-Ting; Adeel Sharif, Hafiz Muhammad; Yang, Cao; Du, Juan; Lin, HuiEnvironmental Research (2022), 204 (Part_A), 111995CODEN: ENVRAL; ISSN:0013-9351. (Elsevier Inc.)Due to the potential hazard of perfluorooctanoic acid (PFOA), hexafluoropropylene oxide dimer acid (HFPO-DA, GenX) has become a typical alternative since 2009. However, GenX has recently been reported to have equal or even greater toxicity and bioaccumulation than PFOA. Considering the suitability of alternatives, it is quite essential to study and compare the degrdn. degree between PFOA and GenX in water. Therefore, in the present study, a comprehensive degrdn. comparison between them via electrooxidn. with a titanium suboxide membrane anode was conducted. The degrdn. rate decreased throughout for PFOA, while it first increased and then decreased for GenX when the permeate flux increased from 17.3 L to 100.3 L m-2·h-1. The different responses of PFOA and GenX to flux might be attributed to their different solubilities. In addn., the higher kobs of PFOA demonstrated that it had a better degradability than GenX by 2.4-fold in a mixed soln. The fluorinated byproduct perfluoropropanoic acid (PFPrA) was detected as a GenX intermediate, suggesting that ether bridge splitting was needed for GenX electrooxidn. This study provides a ref. for assessing the degradability of GenX and PFOA and indicates that it is worth reconsidering whether GenX is a suitable alternative for PFOA from the point of view of environmental protection.
- 23Jacobs, M. M.; Malloy, T. F.; Tickner, J. A.; Edwards, S. Alternatives Assessment Frameworks: Research Needs for the Informed Substitution of Hazardous Chemicals. Environ. Health Perspect. 2016, 124 (3), 265– 280, DOI: 10.1289/ehp.1409581Google Scholar23https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BC287ptFOmsw%253D%253D&md5=7968028e1435b705c2f6a6853b050075Alternatives Assessment Frameworks: Research Needs for the Informed Substitution of Hazardous ChemicalsJacobs Molly M; Malloy Timothy F; Tickner Joel A; Edwards SallyEnvironmental health perspectives (2016), 124 (3), 265-80 ISSN:.BACKGROUND: Given increasing pressures for hazardous chemical replacement, there is growing interest in alternatives assessment to avoid substituting a toxic chemical with another of equal or greater concern. Alternatives assessment is a process for identifying, comparing, and selecting safer alternatives to chemicals of concern (including those used in materials, processes, or technologies) on the basis of their hazards, performance, and economic viability. OBJECTIVES: The purposes of this substantive review of alternatives assessment frameworks are to identify consistencies and differences in methods and to outline needs for research and collaboration to advance science policy practice. METHODS: This review compares methods used in six core components of these frameworks: hazard assessment, exposure characterization, life-cycle impacts, technical feasibility evaluation, economic feasibility assessment, and decision making. Alternatives assessment frameworks published from 1990 to 2014 were included. RESULTS: Twenty frameworks were reviewed. The frameworks were consistent in terms of general process steps, but some differences were identified in the end points addressed. Methodological gaps were identified in the exposure characterization, life-cycle assessment, and decision-analysis components. Methods for addressing data gaps remain an issue. DISCUSSION: Greater consistency in methods and evaluation metrics is needed but with sufficient flexibility to allow the process to be adapted to different decision contexts. CONCLUSION: Although alternatives assessment is becoming an important science policy field, there is a need for increased cross-disciplinary collaboration to refine methodologies in support of the informed substitution and design of safer chemicals, materials, and products. Case studies can provide concrete lessons to improve alternatives assessment.
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Abstract
Figure 1
Figure 1. General structure of the database. Note: this figure illustrates the structure of the database by using specific examples of PFAS used as fluorinated gases and in food contact materials. As it is not possible to represent all functions for all applications in all sub-uses and use categories of PFAS, “···” was used to indicate that more uses, sub-uses, applications, and functions are covered in the database than those listed in the figure.
Figure 2
Figure 2. Substitution potential according to changes in performance and market availability of the alternatives.
Figure 3
Figure 3. Substitution Potential of PFAS.
References
This article references 63 other publications.
- 1Buck, R. C.; Franklin, J.; Berger, U.; Conder, J. M.; Cousins, I. T.; de Voogt, P.; Jensen, A. A.; Kannan, K.; Mabury, S. A.; van Leeuwen, S. P. J. Perfluoroalkyl and Polyfluoroalkyl Substances in the Environment: Terminology, Classification, and Origins. Integr. Environ. Assess. Manag. 2011, 7 (4), 513– 541, DOI: 10.1002/ieam.2581https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXhtF2jtrnM&md5=b3bbf89fd9b71a0a30c5e8c390ccfddaPerfluoroalkyl and polyfluoroalkyl substances in the environment: Terminology, classification, and originsBuck, Robert C.; Franklin, James; Berger, Urs; Conder, Jason M.; Cousins, Ian T.; de Voogt, Pim; Jensen, Allan Astrup; Kannan, Kurunthachalam; Mabury, Scott A.; van Leeuwen, Stefan P. J.Integrated Environmental Assessment and Management (2011), 7 (4), 513-541CODEN: IEAMCK; ISSN:1551-3777. (John Wiley & Sons Inc.)A review. The primary aim of this article is to provide an overview of perfluoroalkyl and polyfluoroalkyl substances (PFASs) detected in the environment, wildlife, and humans, and recommend clear, specific, and descriptive terminol., names, and acronyms for PFASs. The overarching objective is to unify and harmonize communication on PFASs by offering terminol. for use by the global scientific, regulatory, and industrial communities. A particular emphasis is placed on long-chain perfluoroalkyl acids, substances related to the long-chain perfluoroalkyl acids, and substances intended as alternatives to the use of the long-chain perfluoroalkyl acids or their precursors. First, we define PFASs, classify them into various families, and recommend a pragmatic set of common names and acronyms for both the families and their individual members. Terminol. related to fluorinated polymers is an important aspect of our classification. Second, we provide a brief description of the 2 main prodn. processes, electrochem. fluorination and telomerization, used for introducing perfluoroalkyl moieties into org. compds., and we specify the types of byproducts (isomers and homologues) likely to arise in these processes. Third, we show how the principal families of PFASs are interrelated as industrial, environmental, or metabolic precursors or transformation products of one another. We pay particular attention to those PFASs that have the potential to be converted, by abiotic or biotic environmental processes or by human metab., into long-chain perfluoroalkyl carboxylic or sulfonic acids, which are currently the focus of regulatory action. The Supplemental Data lists 42 families and subfamilies of PFASs and 268 selected individual compds., providing recommended names and acronyms, and structural formulas, as well as Chem. Abstrs. Service registry nos. Integr Environ Assess Manag 2011;7:513-541. © 2011 SETAC.
- 2Glüge, J.; Scheringer, M.; Cousins, I. T.; DeWitt, J. C.; Goldenman, G.; Herzke, D.; Lohmann, R.; Ng, C. A.; Trier, X.; Wang, Z. An Overview of the Uses of Per- and Polyfluoroalkyl Substances (PFAS). Environ. Sci. Process. Impacts 2020, 22 (12), 2345– 2373, DOI: 10.1039/D0EM00291GThere is no corresponding record for this reference.
- 3Wang, Z.; MacLeod, M.; Cousins, I. T.; Scheringer, M.; Hungerbühler, K. Using COSMOtherm to Predict Physicochemical Properties of Poly- and Perfluorinated Alkyl Substances (PFASs). Environ. Chem. 2011, 8 (4), 389– 398, DOI: 10.1071/EN101433https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXhtFaqsL3F&md5=2d12daa17a91c85a40bd265f807f0650Using COSMOtherm to predict physicochemical properties of poly- and perfluorinated alkyl substances (PFASs)Wang, Zhanyun; MacLeod, Matthew; Cousins, Ian T.; Scheringer, Martin; Hungerbuhler, KonradEnvironmental Chemistry (2011), 8 (4), 389-398CODEN: ECNHAA; ISSN:1449-8979. (CSIRO Publishing)Recently, there has been concern about the presence of poly- and perfluorinated alkyl substances (PFASs) in the environment, biota and humans. However, lack of physicochem. data has limited the application of environmental fate models to understand the environmental distribution and ultimate fate of PFASs. We employ the COSMOtherm model to est. physicochem. properties for 130 individual PFASs, namely perfluoroalkyl acids (including branched isomers for C4-C8 perfluorocarboxylic acids), their precursors and some important intermediates. The estd. physicochem. properties are interpreted using structure-property relationships and rationalized with insight into mol. interactions. Within a homologous series of linear PFASs with the same functional group, both air-water and octanol-water partition coeff. increase with increasing perfluorinated chain length, likely due to increasing mol. vol. For PFASs with the same perfluorinated chain length but different functional groups, the ability of the functional group to form hydrogen bonds strongly influences the chems.' partitioning behavior. The partitioning behavior of all theor. possible branched isomers can vary considerably; however, the predominant iso-Pr and monomethyl branched isomers in tech. mixts. have similar properties as their linear counterparts (differences below 0.5 log units). Our property ests. provide a basis for further environmental modeling, but with some caveats and limitations.
- 4Guelfo, J. L.; Korzeniowski, S.; Mills, M. A.; Anderson, J.; Anderson, R. H.; Arblaster, J. A.; Conder, J. M.; Cousins, I. T.; Dasu, K.; Henry, B. J.; Lee, L. S.; Liu, J.; McKenzie, E. R.; Willey, J. 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. Environ. Toxicol. Chem. 2021, 40 (12), 3234– 3260, DOI: 10.1002/etc.51824https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXitlCntLrI&md5=902964202add770c857d6e4906171c23Environmental 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 MeetingGuelfo, Jennifer L.; Korzeniowski, Stephen; Mills, Marc A.; Anderson, Janet; Anderson, Richard H.; Arblaster, Jennifer A.; Conder, Jason M.; Cousins, Ian T.; Dasu, Kavitha; Henry, Barbara J.; Lee, Linda S.; Liu, Jinxia; McKenzie, Erica R.; Willey, JaniceEnvironmental Toxicology and Chemistry (2021), 40 (12), 3234-3260CODEN: ETOCDK; ISSN:0730-7268. (Wiley-Blackwell)A Society of Environmental Toxicol. and Chem. (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 chem., 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) std. and novel anal. 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 addnl. pressing needs include increased availability of anal. stds. 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 anal. methods are needed to guide broader policies and best management practices. Environ Toxicol Chem 2021;00:1-27. 2021 The Authors. Environmental Toxicol. and Chem. published by Wiley Periodicals LLC on behalf of SETAC.
- 5Ankley, G. T.; Cureton, P.; Hoke, R. A.; Houde, M.; Kumar, A.; Kurias, J.; Lanno, R.; McCarthy, C.; Newsted, J.; Salice, C. J.; Sample, B. E.; Sepúlveda, M. S.; Steevens, J.; Valsecchi, S. Assessing the Ecological Risks of Per- and Polyfluoroalkyl Substances: Current State-of-the Science and a Proposed Path Forward. Environ. Toxicol. Chem. 2020, 40 (3), 564– 605, DOI: 10.1002/etc.4869There is no corresponding record for this reference.
- 6Fenton, S. E.; Ducatman, A.; Boobis, A.; DeWitt, J. C.; Lau, C.; Ng, C.; Smith, J. S.; Roberts, S. M. Per- and Polyfluoroalkyl Substance Toxicity and Human Health Review: Current State of Knowledge and Strategies for Informing Future Research. Environ. Toxicol. Chem. 2020, 40 (3), 606– 630, DOI: 10.1002/etc.4890There is no corresponding record for this reference.
- 7European Chemicals Agency Restriction on the manufacture, placing on the market and use of PFASs. https://echa.europa.eu/registry-of-restriction-intentions/-/dislist/details/0b0236e18663449b (accessed 2024–03–27).There is no corresponding record for this reference.
- 8Cousins, I. T.; DeWitt, J. C.; Glüge, J.; Goldenman, G.; Herzke, D.; Lohmann, R.; Ng, C. A.; Scheringer, M.; Wang, Z. The High Persistence of PFAS Is Sufficient for Their Management as a Chemical Class. Environ. Sci. Process. Impacts 2020, 22 (12), 2307– 2312, DOI: 10.1039/D0EM00355G8https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXit1aks7jL&md5=f36013e904880abdaaa6f2753f9371a9The high persistence of PFAS is sufficient for their management as a chemical classCousins, Ian T.; DeWitt, Jamie C.; Gluge, Juliane; Goldenman, Gretta; Herzke, Dorte; Lohmann, Rainer; Ng, Carla A.; Scheringer, Martin; Wang, ZhanyunEnvironmental Science: Processes & Impacts (2020), 22 (12), 2307-2312CODEN: ESPICZ; ISSN:2050-7895. (Royal Society of Chemistry)Per- and polyfluoroalkyl substances (PFAS) are a class of synthetic org. substances with diverse structures, properties, uses, bioaccumulation potentials and toxicities. Despite this high diversity, all PFAS are alike in that they contain perfluoroalkyl moieties that are extremely resistant to environmental and metabolic degrdn. The vast majority of PFAS are therefore either non-degradable or transform ultimately into stable terminal transformation products (which are still PFAS). Under the European chems. regulation this classifies PFAS as very persistent substances (vP). We argue that this high persistence is sufficient concern for their management as a chem. class, and for all "non-essential" uses of PFAS to be phased out. The continual release of highly persistent PFAS will result in increasing concns. and increasing probabilities of the occurrence of known and unknown effects. Once adverse effects are identified, the exposure and assocd. effects will not be easily reversible. Reversing PFAS contamination will be tech. challenging, energy intensive, and costly for society, as is evident in the efforts to remove PFAS from contaminated land and drinking water sources.
- 9European Commission OLD Chemicals strategy for sustainability. European Commission website. https://environment.ec.europa.eu/strategy/chemicals-strategy_en (accessed 2023–11–16).There is no corresponding record for this reference.
- 10Cousins, I. T.; Goldenman, G.; Herzke, D.; Lohmann, R.; Miller, M.; Ng, C. A.; Patton, S.; Scheringer, M.; Trier, X.; Vierke, L.; Wang, Z.; DeWitt, J. C. The Concept of Essential Use for Determining When Uses of PFASs Can Be Phased Out. Environ. Sci. Process. Impacts 2019, 21 (11), 1803– 1815, DOI: 10.1039/C9EM00163H10https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhtVGgs7jK&md5=c5ab87c71bbe9cd2843731d85f9ac75bThe concept of essential use for determining when uses of PFASs can be phased outCousins, Ian T.; Goldenman, Gretta; Herzke, Dorte; Lohmann, Rainer; Miller, Mark; Ng, Carla A.; Patton, Sharyle; Scheringer, Martin; Trier, Xenia; Vierke, Lena; Wang, Zhanyun; DeWitt, Jamie C.Environmental Science: Processes & Impacts (2019), 21 (11), 1803-1815CODEN: ESPICZ; ISSN:2050-7895. (Royal Society of Chemistry)Because of the extreme persistence of per- and polyfluoroalkyl substances (PFASs) and their assocd. risks, the Madrid Statement argues for stopping their use where they are deemed not essential or when safer alternatives exist. To det. when uses of PFASs have an essential function in modern society, and when they do not, is not an easy task. Here, we: (1) develop the concept of "essential use" based on an existing approach described in the Montreal Protocol, (2) apply the concept to various uses of PFASs to det. the feasibility of elimination or substitution of PFASs in each use category, and (3) outline the challenges for phasing out uses of PFASs in society. In brief, we developed three distinct categories to describe the different levels of essentiality of individual uses. A phase-out of many uses of PFASs can be implemented because they are not necessary for the betterment of society in terms of health and safety, or because functional alternatives are currently available that can be substituted into these products or applications. Some specific uses of PFASs would be considered essential because they provide for vital functions and are currently without established alternatives. However, this essentiality should not be considered as permanent; rather, const. efforts are needed to search for alternatives. We provide a description of several ongoing uses of PFASs and discuss whether these uses are essential or non-essential according to the three essentiality categories. It is not possible to describe each use case of PFASs in detail in this single article. For follow-up work, we suggest further refining the assessment of the use cases of PFASs covered here, where necessary, and expanding the application of this concept to all other uses of PFASs. The concept of essential use can also be applied in the management of other chems., or groups of chems., of concern.
- 11Cousins, I. T.; De Witt, J. C.; Glüge, J.; Goldenman, G.; Herzke, D.; Lohmann, R.; Miller, M.; Ng, C. A.; Patton, S.; Scheringer, M.; Trier, X.; Wang, Z. Finding Essentiality Feasible: Common Questions and Misinterpretations Concerning the “Essential-Use. Concept. Environ. Sci. Process. Impacts 2021, 23 (8), 1079– 1087, DOI: 10.1039/D1EM00180AThere is no corresponding record for this reference.
- 12European Commission Questions and Answers on essential use chemicals. European Commission - European Commission. https://ec.europa.eu/commission/presscorner/detail/en/qanda_24_2152 (accessed 2024–10–23).There is no corresponding record for this reference.
- 13State of Maine Legislation LD 1503: An Act to Stop Perfluoroalkyl and Polyfluoroalkyl Substances Pollution ; 2021. https://www.mainelegislature.org/legis/bills/getPDF.asp?paper=HP1113&item=5&snum=130 (accessed 2024–08–18).There is no corresponding record for this reference.
- 14Environmental Working Group California lawmaker introduces bill to end non-essential uses of toxic ‘forever chemicals.’ https://www.ewg.org/news-insights/news-release/2024/02/california-lawmaker-introduces-bill-end-non-essential-uses-toxic (accessed 2024–12–14).There is no corresponding record for this reference.
- 15Minnesota Pollution Control Agency PFAS in products. https://www.pca.state.mn.us/get-engaged/pfas-in-products (accessed 2024–08–18).There is no corresponding record for this reference.
- 16Governing Legislative Efforts Against ‘Forever Chemicals’ Grow Across Nation. Governing. https://www.governing.com/policy/legislative-efforts-against-forever-chemicals-grow-across-nation (accessed 2024–11–04).There is no corresponding record for this reference.
- 17United Nations Environment Programme New POPs under the Stockholm Convention. Stockholm Convention website. https://chm.pops.int/?tabid=2511 (accessed 2024–11–04).There is no corresponding record for this reference.
- 18Occupational Safety and Health Administration Transitioning to Safer Chemicals - Why Transition to Safer Alternatives? https://www.osha.gov/safer-chemicals/why-transition (accessed 2024–07–30).There is no corresponding record for this reference.
- 19Hopkins, Z. R.; Sun, M.; DeWitt, J. C.; Knappe, D. R. U. Recently Detected Drinking Water Contaminants: GenX and Other Per- and Polyfluoroalkyl Ether Acids. J. AWWA 2018, 110 (7), 13– 28, DOI: 10.1002/awwa.107319https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXht1ahtb%252FK&md5=a9cb4b60041abff45c4d7c2fce74a5f7Recently Detected Drinking Water Contaminants: GenX and Other Per- and Polyfluoroalkyl Ether AcidsHopkins, Zachary R.; Sun, Mei; De Witt, Jamie C.; Knappe, Detlef R. U.Journal - American Water Works Association (2018), 110 (7), 13-28CODEN: JAWWA5; ISSN:1551-8833. (John Wiley & Sons, Inc.)For several decades, a common processing aid in the prodn. of fluoropolymers was the ammonium salt of perfluorooctanoic acid (PFOA). Because PFOA is persistent, bioaccumulative, and toxic, its prodn. and use are being phased out in the United States. In 2009, the US Environmental Protection Agency stipulated conditions for the manuf. and com. use of GenX, a PFOA replacement. While GenX is produced for com. purposes, the acid form of GenX is also generated as a byproduct during the prodn. of fluoromonomers. The discovery of high concns. of GenX and related perfluoroalkyl ether acids (PFEAs) in the Cape Fear River and in finished drinking water of more than 200,000 North Carolina residents required quick action by researchers, regulators, public health officials, com. labs., drinking water providers, and consulting engineers. Information about sources and toxicity of GenX as well as an anal. method for the detection of GenX and eight related PFEAs is presented. GenX/PFEA occurrence in water and GenX/PFEA removal by different drinking water treatment processes are also discussed.
- 20Sun, M.; Arevalo, E.; Strynar, M.; Lindstrom, A.; Richardson, M.; Kearns, B.; Pickett, A.; Smith, C.; Knappe, D. R. U. Legacy and Emerging Perfluoroalkyl Substances Are Important Drinking Water Contaminants in the Cape Fear River Watershed of North Carolina. Environ. Sci. Technol. Lett. 2016, 3 (12), 415– 419, DOI: 10.1021/acs.estlett.6b0039820https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhvVaksL3M&md5=b070b9d1270efb9317f0548d28b85fd9Legacy and Emerging Perfluoroalkyl Substances Are Important Drinking Water Contaminants in the Cape Fear River Watershed of North CarolinaSun, Mei; Arevalo, Elisa; Strynar, Mark; Lindstrom, Andrew; Richardson, Michael; Kearns, Ben; Pickett, Adam; Smith, Chris; Knappe, Detlef R. U.Environmental Science & Technology Letters (2016), 3 (12), 415-419CODEN: ESTLCU; ISSN:2328-8930. (American Chemical Society)Long-chain per- and polyfluoroalkyl substances (PFASs) are being replaced by short-chain PFASs and fluorinated alternatives. For ten legacy PFASs and seven recently discovered perfluoroalkyl ether carboxylic acids (PFECAs), we report (1) their occurrence in the Cape Fear River (CFR) watershed, (2) their fate in water treatment processes, and (3) their adsorbability on powd. activated carbon (PAC). In the headwater region of the CFR basin, PFECAs were not detected in raw water of a drinking water treatment plant (DWTP), but concns. of legacy PFASs were high. The U.S. Environmental Protection Agency's lifetime health advisory level (70 ng/L) for perfluorooctanesulfonic acid and perfluorooctanoic acid (PFOA) was exceeded on 57 of 127 sampling days. In raw water of a DWTP downstream of a PFAS manufacturer, the mean concn. of perfluoro-2-propoxypropanoic acid (PFPrOPrA), a replacement for PFOA, was 631 ng/L (n = 37). Six other PFECAs were detected, with three exhibiting chromatog. peak areas up to 15 times that of PFPrOPrA. At this DWTP, PFECA removal by coagulation, ozonization, biofiltration, and disinfection was negligible. The adsorbability of PFASs on PAC increased with increasing chain length. Replacing one CF2 group with an ether oxygen decreased the affinity of PFASs for PAC, while replacing addnl. CF2 groups did not lead to further affinity changes.
- 21Gebreab, K. Y.; Eeza, M. N. H.; Bai, T.; Zuberi, Z.; Matysik, J.; O’Shea, K. E.; Alia, A.; Berry, J. P. Comparative Toxicometabolomics of Perfluorooctanoic Acid (PFOA) and next-Generation Perfluoroalkyl Substances. Environ. Pollut. 2020, 265, 114928 DOI: 10.1016/j.envpol.2020.11492821https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXht1OgsLzI&md5=aaa6d52e57cf1a4220389fa652e548b2Comparative toxicometabolomics of perfluorooctanoic acid (PFOA) and next-generation perfluoroalkyl substancesGebreab, Kiflom Y.; Eeza, Muhamed N. H.; Bai, Tianyu; Zuberi, Zain; Matysik, Jorg; O'Shea, Kevin E.; Alia, A.; Berry, John P.Environmental Pollution (Oxford, United Kingdom) (2020), 265 (Part_A), 114928CODEN: ENPOEK; ISSN:0269-7491. (Elsevier Ltd.)Owing to environmental health concerns, a no. of per- and polyfluoroalkyl substances (PFAS) have been phased-out, and increasingly replaced by various chem. analogs. Most prominent among these replacements are numerous perfluoroether carboxylic acids (PFECA). Toxicity, and environmental health concerns assocd. with these next-generation PFAS, however, remains largely unstudied. The zebrafish embryo was employed, in the present study, as a toxicol. model system to investigate toxicity of a representative sample of PFECA, alongside perfluorooctanoic acid (PFOA) as one of the most widely used, and best studied, of the "legacy" PFAS. Acute embryotoxicity (i.e., lethality), along with impaired development, and variable effects on locomotory behavior, were obsd. for all PFAS in the zebrafish model. Alterations of metabolic profiles suggested targeting of hepatocytes (i.e., hepatotoxicity), as well as apparent modulation of neural metabolites, and moreover, were consistent with a previously proposed role of mitochondrial disruption and peroxisome proliferator-activated receptor (PPAR) activation as reflected by dysfunctions of carbohydrate, lipid and amino acid metab. and consistent with a previously proposed contribution of PFAS to metabolic syndrome. Taken together, it was generally concluded that toxicity of PFECA is quant. and qual. similar to PFOA, and these analogs, likewise, represent potential concerns as environmental toxicants.
- 22Yang, L.-H.; Yang, W.-J.; Lv, S.-H.; Zhu, T.-T.; Adeel Sharif, H. M.; Yang, C.; Du, J.; Lin, H. Is HFPO-DA (GenX) a Suitable Substitute for PFOA? A Comprehensive Degradation Comparison of PFOA and GenX via Electrooxidation. Environ. Res. 2022, 204, 111995 DOI: 10.1016/j.envres.2021.11199522https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXitVSjt77E&md5=ca6530659de32131c0d87280add38798Is HFPO-DA (GenX) a suitable substitute for PFOA? A comprehensive degradation comparison of PFOA and GenX via electrooxidationYang, Li-Hui; Yang, Wen-Jian; Lv, Si-Hao; Zhu, Ting-Ting; Adeel Sharif, Hafiz Muhammad; Yang, Cao; Du, Juan; Lin, HuiEnvironmental Research (2022), 204 (Part_A), 111995CODEN: ENVRAL; ISSN:0013-9351. (Elsevier Inc.)Due to the potential hazard of perfluorooctanoic acid (PFOA), hexafluoropropylene oxide dimer acid (HFPO-DA, GenX) has become a typical alternative since 2009. However, GenX has recently been reported to have equal or even greater toxicity and bioaccumulation than PFOA. Considering the suitability of alternatives, it is quite essential to study and compare the degrdn. degree between PFOA and GenX in water. Therefore, in the present study, a comprehensive degrdn. comparison between them via electrooxidn. with a titanium suboxide membrane anode was conducted. The degrdn. rate decreased throughout for PFOA, while it first increased and then decreased for GenX when the permeate flux increased from 17.3 L to 100.3 L m-2·h-1. The different responses of PFOA and GenX to flux might be attributed to their different solubilities. In addn., the higher kobs of PFOA demonstrated that it had a better degradability than GenX by 2.4-fold in a mixed soln. The fluorinated byproduct perfluoropropanoic acid (PFPrA) was detected as a GenX intermediate, suggesting that ether bridge splitting was needed for GenX electrooxidn. This study provides a ref. for assessing the degradability of GenX and PFOA and indicates that it is worth reconsidering whether GenX is a suitable alternative for PFOA from the point of view of environmental protection.
- 23Jacobs, M. M.; Malloy, T. F.; Tickner, J. A.; Edwards, S. Alternatives Assessment Frameworks: Research Needs for the Informed Substitution of Hazardous Chemicals. Environ. Health Perspect. 2016, 124 (3), 265– 280, DOI: 10.1289/ehp.140958123https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BC287ptFOmsw%253D%253D&md5=7968028e1435b705c2f6a6853b050075Alternatives Assessment Frameworks: Research Needs for the Informed Substitution of Hazardous ChemicalsJacobs Molly M; Malloy Timothy F; Tickner Joel A; Edwards SallyEnvironmental health perspectives (2016), 124 (3), 265-80 ISSN:.BACKGROUND: Given increasing pressures for hazardous chemical replacement, there is growing interest in alternatives assessment to avoid substituting a toxic chemical with another of equal or greater concern. Alternatives assessment is a process for identifying, comparing, and selecting safer alternatives to chemicals of concern (including those used in materials, processes, or technologies) on the basis of their hazards, performance, and economic viability. OBJECTIVES: The purposes of this substantive review of alternatives assessment frameworks are to identify consistencies and differences in methods and to outline needs for research and collaboration to advance science policy practice. METHODS: This review compares methods used in six core components of these frameworks: hazard assessment, exposure characterization, life-cycle impacts, technical feasibility evaluation, economic feasibility assessment, and decision making. Alternatives assessment frameworks published from 1990 to 2014 were included. RESULTS: Twenty frameworks were reviewed. The frameworks were consistent in terms of general process steps, but some differences were identified in the end points addressed. Methodological gaps were identified in the exposure characterization, life-cycle assessment, and decision-analysis components. Methods for addressing data gaps remain an issue. DISCUSSION: Greater consistency in methods and evaluation metrics is needed but with sufficient flexibility to allow the process to be adapted to different decision contexts. CONCLUSION: Although alternatives assessment is becoming an important science policy field, there is a need for increased cross-disciplinary collaboration to refine methodologies in support of the informed substitution and design of safer chemicals, materials, and products. Case studies can provide concrete lessons to improve alternatives assessment.
- 24BizNGO Principles for Alternatives Assessment. BizNGO. https://www.bizngo.org/alternatives-assessment/commons-principles-alt-assessment (accessed 2024–07–30).There is no corresponding record for this reference.
- 25Tickner, J. A.; Schifano, J. N.; Blake, A.; Rudisill, C.; Mulvihill, M. J. Advancing Safer Alternatives Through Functional Substitution. Environ. Sci. Technol. 2015, 49 (2), 742– 749, DOI: 10.1021/es503328m25https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXitFaqsbfO&md5=f8bf55b8005a2a995fc139fd376fb8a0Advancing Safer Alternatives Through Functional SubstitutionTickner, Joel A.; Schifano, Jessica N.; Blake, Ann; Rudisill, Catherine; Mulvihill, Martin J.Environmental Science & Technology (2015), 49 (2), 742-749CODEN: ESTHAG; ISSN:0013-936X. (American Chemical Society)A review is presented. To achieve the ultimate goal of sustainable chems. management policy-the transition to safer chems., materials, products, and processes-current chems. management approaches could benefit from a broader perspective. Starting with considerations of function, rather than characterizing and managing risks assocd. with a particular chem., may provide a different, solns.-oriented lens to reduce risk assocd. with the uses of chems. It may also offer an efficient means, complementing existing tools, to reorient chems. management approaches from time-intensive risk assessment and risk management based on single chems. to comparative evaluation of the best options to fulfill a specific function. This article describes a functional approach to chems. management we call "functional substitution" that encourages decision-makers to look beyond chem. by chem. substitution to find a range of alternatives to meet product performance. We define functional substitution, outline a rationale for greater use of this concept when considering risks posed by uses of chems., and provide examples of how functional approaches have been applied toward the identification of alternatives. We also discuss next steps for implementing functional substitution in chem. assessment and policy development.
- 26Roy, M. A.; Cousins, I.; Harriman, E.; Scheringer, M.; Tickner, J. A.; Wang, Z. Combined Application of the Essential-Use and Functional Substitution Concepts: Accelerating Safer Alternatives. Environ. Sci. Technol. 2022, 56 (14), 9842– 9846, DOI: 10.1021/acs.est.2c0381926https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38Xhs1WhurbO&md5=364d39990edd78844f17849257db1c69Combined Application of the Essential-Use and Functional Substitution Concepts: Accelerating Safer AlternativesRoy, Monika A.; Cousins, Ian; Harriman, Elizabeth; Scheringer, Martin; Tickner, Joel A.; Wang, ZhanyunEnvironmental Science & Technology (2022), 56 (14), 9842-9846CODEN: ESTHAG; ISSN:1520-5851. (American Chemical Society)There is no expanded citation for this reference.
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- 33European Chemicals Agency Annex E to the Annex XV Restriction Report for the Restriction on the Manufacture, Placing on the Market and Use of PFASs; ECHA: Helsinki, 2023. https://echa.europa.eu/registry-of-restriction-intentions/-/dislist/details/0b0236e18663449b (accessed 2023–07–10).There is no corresponding record for this reference.
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- 35OECD Per- and Polyfluoroalkyl Substances and Alternatives in Coatings, Paints and Varnishes (CPVs), Report on the Commercial Availability and Current Uses; OECD Series on Risk Management; 70; OECD Publishing: Paris, 2022. DOI: 10.1787/6745457d-en (accessed 2023–09–01).There is no corresponding record for this reference.
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- 57Glüge, J.; London, R.; Cousins, I. T.; DeWitt, J.; Goldenman, G.; Herzke, D.; Lohmann, R.; Miller, M.; Ng, C. A.; Patton, S.; Trier, X.; Wang, Z.; Scheringer, M. Information Requirements under the Essential-Use Concept: PFAS Case Studies. Environ. Sci. Technol. 2022, 56, 6232, DOI: 10.1021/acs.est.1c03732There is no corresponding record for this reference.
- 58Holmquist, H.; Schellenberger, S.; van der Veen, I.; Peters, G. M.; Leonards, P. E. G.; Cousins, I. T. Properties, Performance and Associated Hazards of State-of-the-Art Durable Water Repellent (DWR) Chemistry for Textile Finishing. Environ. Int. 2016, 91, 251– 264, DOI: 10.1016/j.envint.2016.02.03558https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XkvVeltbw%253D&md5=a5dc27663a15529c7e517da1486ddaceProperties, performance and associated hazards of state-of-the-art durable water repellent (DWR) chemistry for textile finishingHolmquist, H.; Schellenberger, S.; van der Veen, I.; Peters, G. M.; Leonards, P. E. G.; Cousins, I. T.Environment International (2016), 91 (), 251-264CODEN: ENVIDV; ISSN:0160-4120. (Elsevier Ltd.)Following the phase-out of long-chain per- and polyfluoroalkyl substances (PFASs), the textile industry had to find alternatives for side-chain fluorinated polymer based durable water repellent (DWR) chemistries that incorporated long perfluoroalkyl side chains. This phase-out and subsequent substitution with alternatives has resulted in a market where both fluorinated and non-fluorinated DWRs are available. These DWR alternatives can be divided into four broad groups that reflect their basic chem.: side-chain fluorinated polymers, silicones, hydrocarbons and other chemistries (includes dendrimer and inorg. nanoparticle chemistries). In this crit. review, the alternative DWRs are assessed with regards to their structural properties and connected performance, loss and degrdn. processes resulting in diffuse environmental emissions, and hazard profiles for selected emitted substances. Our review shows that there are large differences in performance between the alternative DWRs, most importantly the lack of oil repellence of non-fluorinated alternatives. It also shows that for all alternatives, impurities and/or degrdn. products of the DWR chemistries are diffusively emitted to the environment. Our hazard ranking suggests that hydrocarbon based DWR is the most environmentally benign, followed by silicone and side-chain fluorinated polymer-based DWR chemistries. Industrial commitments to reduce the levels of impurities in silicone based and side-chain fluorinated polymer based DWR formulations will lower the actual risks. There is a lack of information on the hazards assocd. with DWRs, in particular for the dendrimer and inorg. nanoparticle chemistries, and these data gaps must be filled. Until environmentally safe alternatives, which provide the required performance, are available our recommendation is to choose DWR chem. on a case-by-case basis, always weighing the benefits connected to increased performance against the risks to the environment and human health.
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Supporting Information
Supporting Information
The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.est.4c09088.
Additional details on the methods followed to build up the database and additional analysis of the data on alternatives to PFAS, including extracts of the database (PDF)
Applications of PFAS listed in the database; links between applications of PFAS listed in the database and the uses identified by Glüge et al.; composition of alternative products to uses of PFAS; list of applications of PFAS without identified alternatives; list of PFAS used as fluorinated gases; list of functions delivered by PFAS used as fluorinated gases; and list of alternatives to PFAS used as fluorinated gases (XLSX)
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