This report provides information about life cycle based assessments to be used for developing safe and sustainable chemistry as they have been used in the Mistra SafeChem research programme. The requirement to consider a variety of aspects which are anchored in different research communities is rather novel, therefore it can be expected that adjustments and iterations will be necessary based on results from research programmes such as Mistra SafeChem. Background on established assessment contexts for chemical alternatives assessment and life cycle assessment and the integrated chemical footprint assessment is provided. The key models applied for sustainability assessment are USEtox and the framework for life cycle alternatives assessment and ProScale – all of them are under development and testing for a selection of application cases is therefore intended as a contribution to identify user needs, drivers and barriers for application. Separate case study reports are made available through the programme website for further reading on the current state of implementation. This report includes a synthetic case study to showcase application of tools and current challenges providing data, modelling and interpreting results. The Mistra SafeChem research programme will continue with more case studies and address gaps that have been identified in interdisciplinary work so far to enable the implementation of safe and sustainable chemistry principles.

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.

The class-wide restriction proposal on perfluoroalkyl and polyfluoroalkyl substances (PFAS) in the European Union is expected to affect a wide range of commercial sectors, including the lithium-ion battery (LIB) industry, where both polymeric and low molecular weight PFAS are used. The PFAS restriction dossiers currently state that there is weak evidence for viable alternatives to the use of PFAS in LIBs. In this Perspective, we summarize both the peer-reviewed literature and expert opinions from academia and industry to verify the legitimacy of the claims surrounding the lack of alternatives. Our assessment is limited to the electrodes and electrolyte, which account for the most critical uses of PFAS in LIB cells. Companies that already offer or are developing PFAS-free electrode and electrolyte materials were identified. There are also indications that PFAS-free electrolytes are in development by at least one other company, but there is no information regarding the alternative chemistries being proposed. Our review suggests that it is technically feasible to make PFAS-free batteries for battery applications, but PFAS-free solutions are not currently well-established on the market. Successful substitution of PFAS will require an appropriate balance among battery performance, the environmental effects associated with hazardous materials and chemicals, and economic considerations.

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.

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.

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. 

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.

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.

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.