Given their extensive production volumes and potential to form persistent perfluoroalkyl acids (PFAAs), there is concern surrounding the ongoing use of side-chain fluorinated polymers (SFPs) in consumer products. Targeted SFP quantification relies on matrix-assisted laser desorption ionization time-of-flight mass spectrometry, which can suffer from poor accuracy and high detection limits. Alternatively, total fluorine (TF)-based methods may be used, but these approaches report concentrations on a "fluorine equivalent"basis (e.g., fluorine per square meter in the case of textiles) and are incapable of elucidating structure or chain length. Here a new method for comprehensive characterization of SFPs is presented, which makes use of the total oxidizable precursor assay for fingerprint-based structural elucidation and combustion ion chromatography for TF quantification. When used in parallel, quantitative determination of SFPs (in units of mass of CnF2n+1 per square meter of textile) is achieved. Expressing SFP concentrations in terms of the mass of the side chain (as opposed to fluorine equivalents) facilitates estimation of both the structure and quantity of PFAA degradation products. As a proof of principle, the method was applied to six unknown SFP-coated medical textiles from Sweden. Four products contained C6-fluorotelomer-based SFPs (concentration range of 36-188 mg of C6F13/m2), one contained a C4-sulfonamide-based SFP (718 mg of C4F9/m2), and one contained a C8-fluorotelomer-based SFP (249 mg of C8F17/m2). © 2021 The Authors.

Recycling of lithium-ion batteries (LIBs) is a rapidly growing industry, which is vital to address the increasing demand for metals, and to achieve a sustainable circular economy. Relatively little information is known about the environmental risks posed by LIB recycling, in particular with regards to the emission of persistent (in)organic fluorinated chemicals. Here we present an overview on the use of fluorinated substances - in particular per- and polyfluoroalkyl substances (PFAS) - in state-of-the-art LIBs, along with recycling conditions which may lead to their formation and/or release to the environment. Both organic and inorganic fluorinated substances are widely reported in LIB components, including the electrodes and binder, electrolyte (and additives), and separator. Among the most common substances are LiPF6 (an electrolyte salt), and the polymeric PFAS polyvinylidene fluoride (used as an electrode binder and a separator). Currently the most common LIB recycling process involves pyrometallurgy, which operates at high temperatures (up to 1600 °C), sufficient for PFAS mineralization. However, hydrometallurgy, an increasingly popular alternative recycling approach, operates under milder temperatures (<600 °C), which could favor incomplete degradation and/or formation and release of persistent fluorinated substances. This is supported by the wide range of fluorinated substances detected in bench-scale LIB recycling experiments. Overall, this review highlights the need to further investigate emissions of fluorinated substances during LIB recycling and suggests that substitution of PFAS-based materials (i.e. during manufacturing), or alternatively post-treatments and/or changes in process conditions may be required to avoid formation and emission of persistent fluorinated substances.

Consumer products such as clothes and footwear sometimes contain chemical substances with properties that pose a risk to human health and the environment. These substances, restricted by law or company policy, are in focus for chemicals management processes by textile retailers. However, complex and non-transparent supply chains, and limited chemical knowledge, makes chemicals management challenging. Therefore, a function-based approach for life cycle management (LCM) of chemicals was developed, based on results of previous projects and evaluated using a two-step Delphi process. The resulting approach aims to help retailers identify and substitute hazardous substances in products, and consists of three parts: (i) a function-based chemicals management concept model for different levels of chemical information within the supply chain, (ii) tools for non-chemists which explain chemical information, and (iii) a continuous provision of knowledge to stakeholders (e.g., retailers) in a network. This approach is successfully implemented by over 100 retailers in the Nordic countries, providing the textile industry with practical and robust tools to manage and substitute hazardous chemicals in products and production processes. We conclude that the developed approach provides an explicit link, communication, and knowledge sharing between actors in the supply chain, which has proven important in chemicals LCM.

Fluorinated durable water repellent (DWR) agents are used to obtain water and stain repellent textiles. Due to the on-going phase-out of DWRs based on side-chain fluorinated polymers (SFP) with “long” perfluoroalkyl chains, the textile industry lacks suitable alternatives with comparable material characteristics. The constant development and optimization of SFPs for textile applications initiated more than half a century ago has resulted in a robust and very efficient DWR-technology and textiles with exceptional hydro- and oleo-phobic properties. The industry is now in the predicament that the long-chain SFPs with the best technical performance have undesirable toxicological and environmental behaviour. This study provides a comprehensive overview of the technical performance of presently available fluorinated and non-fluorinated DWRs as part of a chemical alternatives assessment (CAA). The results are based on a study with synthetic outdoor fabrics treated with alternative DWRs and tested for repellency using industrial standard and complementary methods. Using this approach, the complex structure-property relationships of DWR-polymers could be explained on a molecular level. Both short-chain SFPs and non-fluorinated DWRs showed excellent water repellency and durability in some cases while short-chain SFPs were the more robust of the alternatives to long-chain SFPs. A strong decline in oil repellency and durability with perfluoroalkyl chain length was shown for SFP DWRs. Non-fluorinated alternatives were unable to repel oil, which might limit their potential for substitution in textile application that require repellency towards non-polar liquids.

Ongoing regulation of, and concerns regarding, per- and polyfluoroalkyl substances (also popularly known as “highly fluorinated chemicals”), has driven the textile market to search for sustainable alternative chemistries that can provide similar liquid repellency to per- and polyfluoroalkyl substances in performance textiles. This paper aims to inform the potential substitution of fluorochemicals with more environmentally friendly durable water repellents, taking a case-by-case approach and evaluating protection needs for consumer outdoor clothing and medical protective clothing separately. Recently developed non-fluorinated durable water repellents, some based on green chemistry principles, were evaluated in an in-depth assessment for their functionality against fluorinated short-chain alternatives (with hydro-and oleophobic moieties of carbon chain length of six or less). Repellency towards water and non-polar liquids was evaluated with established standard test methods and by measuring the roll-off angle of liquid droplets with a novel sample holder setup. This improved method allowed an enhanced mechanistic understanding of the droplets’ roll-off processes on woven textiles. The best non-fluorinated alternatives demonstrated high water repellency equal to fluorinated side-chain polymers with ‘short’ fluorinated carbon chains ≤6 carbons, and should be considered as suitable substitutes for consumer outdoor clothing. These results are supported by a survey of end-use requirements indicating water repellency and durability were the most important purchasing criteria. For polar liquids, with lower surface tensions, the repellency provided by non-fluorinated alternatives was clearly reduced, although they had a moderate repellency towards liquids with intermediate polarity (e.g. red wine or synthetic blood). Only fluorinated side-chain polymers with ‘short’ fluorinated carbon chains ≤6 carbons were seen to provide sufficient protection to polar liquids with very low surface tension (olive oil or gastric fluid). Since occupational protective clothing (e.g. medical clothing) often must provide protection against liquid of a wider range of polarities (e.g. in the case of medical clothing, to bodily fluids and protect the wearer from the transmission of diseases), current non-fluorinated DWRs do not provide sufficient liquid repellency. This implies that innovations in textile technology are still needed to substitute PFASs in some types of occupational protective clothing and other end uses where oil and stain repellency is essential.

The quantity and composition of fibers released from functional textiles during accelerated washing were investigated using the GyroWash method. Two fabrics [polyamide (PA) and polyester/cotton (PES/CO)] were selected and coated with perfluorohexane-based side-chain fluorinated polymers. Fibers released during washing ranged from ∼10 to 500 μ with a similar distribution for the two textile types. The PA-based fabric released considerably more fibers >20 μm in length compared to the PES/CO-based fabric (>1000/GyroWash for PA vs ∼200/GyroWash fibers for PES/CO). After one GyroWash (2-15 domestic washes), fibers that contained approximately 240 and 1300 μg total fluorine per square meter (μg F/m²) were released from the PA and PES/CO fabrics, respectively. Current understanding of the fate of microplastic fibers suggests that a large fraction of these fibers reach the environment either in effluent wastewater or sewage sludge applied to land. In the environment, the fluorinated side chains will be slowly cleaved from the backbone of the side-chain fluorinated polymers coated on the fibers and then transformed into short-chain perfluoroalkyl acids. On the European scale, emissions of up to ∼0.7 t of fluorotelomer alcohol (6:2 FTOH) per year were estimated for outdoor rain jackets treated with fluorotelomer-based side-chain fluorinated polymers.

The emission of per- and polyfluoroalkyl substances (PFAS) from functional textiles was investigated via an outdoor weathering experiment in Sydney, Australia. Polyamide (PA) textile fabrics treated with different water-repellent, side-chain fluorinated polymers (SFPs) were exposed on a rooftop to multiple natural stressors, including direct sunlight, precipitation, wind, and heat for 6-months. After weathering, additional stress was applied to the fabrics through abrasion and washing. Textile characterization using a multiplatform analytical approach revealed loss of both PFAS-containing textile fragments (e.g., microfibers) as well as formation and loss of low molecular weight PFAS, both of which occurred throughout weathering. These changes were accompanied by a loss of color and water repellency of the textile. The potential formation of perfluoroalkyl acids (PFAAs) from mobile residuals was quantified by oxidative conversion of extracts from unweathered textiles. Each SFP-textile finish emitted a distinct PFAA pattern following weathering, and in some cases the concentrations exceeded regulatory limits for textiles. In addition to transformation of residual low molecular weight PFAA-precursors, release of polymeric PFAS from degradation and loss of textile fibers/particles contributed to overall PFAS emissions during weathering. © 2022 The Authors. 

Total fluorine was determined in 45 consumer product samples from the Swedish market which were either suspected or known to contain fluorinated polymers. Product categories included cookware (70–550 000 ppm F), textiles (10–1600 ppm F), electronics (20–2100 ppm F), and personal care products (10–630 000 ppm F). To confirm that the fluorine was organic in nature, and deduce structure, a qualitative pyrolysis-gas chromatography-mass spectrometry (pyr-GC/MS) method was validated using a suite of reference materials. When applied to samples with unknown PFAS content, the method was successful at identifying polytetrafluoroethylene (PTFE) in cookware, dental products, and electronics at concentrations as low as 0.1–0.2 wt%. It was also possible to distinguish between 3 different side-chain fluorinated polymers in textiles. Several products appeared to contain high levels of inorganic fluorine. This is one of the few studies to quantify fluorine in a wide range of consumer plastics and provides important data on the concentration of fluorine in materials which may be intended for recycling, along with insights into the application of pyr-GC/MS for structural elucidation of fluorinated polymers in consumer products.

To make outdoor clothing water- or dirt-repellent, durable water-repellent (DWR) coatings based on side-chain fluorinated polymers (SFPs) are used. During use of outdoor clothing, per- and polyfluoroalkyl substances (PFASs) can be emitted from the DWR to the environment. In this study, the effects of aging, washing, and tumble drying on the concentration of extractable PFASs in the DWR of perfluorohexane-based short-chain SFPs (FC-6 chemistry) and of perfluorooctane-based long-chain SFPs (FC-8 chemistry) were assessed. For this purpose, polyamide (PA) and polyester (PES) fabrics were coated with FC-6- and FC-8-based DWRs. Results show that aging of the coated fabrics causes an increase in concentration and formation of perfluoroalkyl acids (PFAAs). The effect of aging on the volatile PFASs depends on the type of fabric. Washing causes a decrease in PFAA concentrations, and in general, volatile PFASs are partly washed out of the textiles. However, washing can also increase the extractable concentration of volatile PFASs in the fabrics. This effect becomes stronger by a combination of aging and washing. Tumble drying does not affect the PFAS concentrations in textiles. In conclusion, aging and washing of fabrics coated with the DWR based on SFPs release PFASs to the environment.

This report contains a life cycle assessment, LCA, of recycling of lithium-ion battery, LIB, cells. It was performed in the context of the Swedish Scope-lib project. The study aims to highlight environmental hotspots with LIB recycling and shows the potential of LIB recycling. In short, the results indicate that: • the Scope-lib process operated in full scale, can potentially recover almost half of the climate impacts of producing a new NMC traction battery, the currently most common traction battery chemistry. The main reason is that the climate impact (data) of cobalt production has four folded since 2018. It emphasizes the importance of recycling scarce battery materials. • the Scope-lib process is not dependent on carbon-lean electricity to achieve a lot of climate impact avoidance. Using average European electricity mix (around 400 g CO2-eq/kWh) instead of Swedish electricity mix (around 40 g CO2-eq/kWh) only decrease the climate impact avoidance with less than 1 kg CO2-eq/kg cell or less than 10%. • recovery and recycling of ethylene carbonate (used as solvent in LIB electrolytes) shows much smaller potential climate benefits than recovery and recycling of the metals. • the resource depletion gains of the Scope-lib process follow the same trend as the climate impact gains, with the exception of aluminium. To complement the LCA, a life cycle-based risk mapping was performed which identified a particular high risk with fluorinated materials present in binders and electrolytes in NMC batteries which could potentially form hazardous chemical emissions during recycling (such as persistent PFAS) and thus need special attention.

In the end-of-life phase the risks related to toxicity, fire and high voltage inherent in the traction LIB life cycle become apparent and amplified. LIBs are a green technology but contain different hazardous substances, that can be emitted especially during fire events. These emissions are of high risks since chemical transformation processes are not well understood so far. Additional risk occurs during production of raw materials such as highly fluorinated organic chemicals used in LIBs e.g. for binder materials. Due to the electrochemical stability of fluorinated materials their use might be unavoidable to produce batteries with a long life. However, their production, use and disposal need to be controlled. A high temperature treatment in recycling is a possibility to control emissions in the end-of-life phase. Any laboratory, recycling facility or actor involved in the end-of-life phase of LIBs must carry out risk assessment for their unique activities and equipment and develop and maintain site specific safety protocols for their personal.