An Outdoor Aging Study to Investigate the Release of Per- And Polyfluoroalkyl Substances (PFAS) from Functional Textiles.

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.

An (Eco)Toxicity Life Cycle Impact Assessment Framework for Per- And Polyfluoroalkyl Substances.

A framework for characterizing per- and polyfluoroalkyl substances (PFASs) in life cycle impact assessment (LCIA) is proposed. Thousands of PFASs are used worldwide, with special properties imparted by the fluorinated alkyl chain. Our framework makes it possible to characterize a large part of the family of PFASs by introducing transformation fractions that translate emissions of primary emitted PFASs into the highly persistent terminal degradation products: the perfluoroalkyl acids (PFAAs). Using a PFAA-adapted characterization model, human toxicity as well as marine and freshwater aquatic ecotoxicity characterization factors are calculated for three PFAAs, namely perfluorooctanoic acid (PFOA) perfluorohexanoic acid (PFHxA) and perfluorobutanesulfonic acid (PFBS). The model is evaluated to adequately capture long-term fate, where PFAAs are predicted to accumulate in open oceans. The characterization factors of the three PFAAs are ranked among the top 5% for marine ecotoxicity, when compared to 3104 chemicals in the existing USEtox results databases. Uncertainty analysis indicates potential for equally high ranks for human health impacts. Data availability constitutes an important limitation creating uncertainties. Even so, a life cycle assessment (LCA) case study illustrates practical application of our proposed framework, demonstrating that even low emissions of PFASs can have large effects on LCA results.

Release of Side-Chain Fluorinated Polymer-Containing Microplastic Fibers from Functional Textiles During Washing and First Estimates of Perfluoroalkyl Acid Emissions.

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.

Physical-chemical properties and evaluative fate modelling of 'emerging' and 'novel' brominated and organophosphorus flame retardants in the indoor and outdoor environment.

Several groups of flame retardants (FRs) have entered the market in recent years as replacements for polybrominated diphenyl ethers (PBDEs), but little is known about their physical-chemical properties or their environmental transport and fate. Here we make best estimates of the physical-chemical properties and undertake evaluative modelling assessments (indoors and outdoors) for 35 so-called 'novel' and 'emerging' brominated flame retardants (BFRs) and 22 organophosphorus flame retardants (OPFRs). A QSPR (Quantitative Structure-Property Relationship) based technique is used to reduce uncertainty in physical-chemical properties and to aid property selection for modelling, but it is evident that more, high quality property data are required for improving future assessments. Evaluative modelling results show that many of the alternative FRs, mainly alternative BFRs and some of the halogenated OPFRs, behave similarly to the PBDEs both indoors and outdoors. These alternative FRs exhibit high overall persistence (Pov), long-range transport potential (LRTP) and POP-like behaviour and on that basis cannot be regarded as suitable replacements to PBDEs. A group of low molecular weight alternative BFRs and non-halogenated OPFRs show a potentially better environmental performance based on Pov and LRTP metrics. Results must be interpreted with caution though since there are significant uncertainties and limited data to allow for thorough model evaluation. Additional environmental parameters such as toxicity and bioaccumulative potential as well as functionality issues should be considered in an industrial substitution strategy.

Emissions and fate of brominated flame retardants in the indoor environment: a critical review of modelling approaches.

This review explores the existing understanding and the available approaches to estimating the emissions and fate of semi-volatile organic compounds (SVOCs) and in particular focuses on the brominated flame retardants (BFRs). Volatilisation, an important emission mechanism for the more volatile compounds can be well described using current emission models. More research is needed, however, to better characterise alternative release mechanisms such as direct material-particle partitioning and material abrasion. These two particle-mediated emissions are likely to result in an increased chemical release from the source than can be accounted for by volatilisation, especially for low volatile compounds, and emission models need to be updated in order to account for these. Air-surface partitioning is an important fate process for SVOCs such as BFRs however it is still not well characterised indoors. In addition, the assumption of an instantaneous air-particle equilibrium adopted by current indoor fate models might not be valid for high-molecular weight, strongly sorbing compounds. A better description of indoor particle dynamics is required to assess the effect of particle-associated transport as this will control the fate of low volatile BFRs. We suggest further research steps that will improve modelling precision and increase our understanding of the factors that govern the indoor fate of a wide range of SVOCs. It is also considered that the appropriateness of the selected model for a given study relies on the individual characteristics of the study environment and scope of the study.