EEE201 Handout 11: Microplastics & PFAS Environmental Fate, Effects & Mitigation Strategies PDF

EEE201 Biogeochemische Kreisläufe und globale Umweltveränderungen Microplastics & PFAS Environmental Fate, Effects and Mitigation Strategies Gilda Dell’Ambrogio, Stefanie Lutz, Marcel van der Heijden University of Zurich and Agroscope 06.12.2024 Contents 1. Microplastics: Description and environmental fate 2. Microplastics: Environmental effects 3. PFAS: Description and environmental fate 4. PFAS : Environmental effects 5. Microplastics and PFAS: mitigation strategies Learning goals 1. Microplastics What are microplastic and how do they behave in the environment? What are the effects on living organisms? 2. PFAS What are PFAS and how do they behave in the environment? What are the effects on living organisms? 3. Mitigation strategies What are the main challenges for the risk assessment of PFAS/microplastics? Learning goals 1. Microplastics What are microplastic and how do they behave in the environment? What are the effects on living organisms? 2. PFAS What are PFAS and how do they behave in the environment? What are the effects on living organisms? 3. Mitigation strategies What are the main challenges for the risk assessment of PFAS/microplastics? Plastics 1955 Life magazine article celebrates the: «Throwaway living» Mostly thanks to disposable plastics Celebrates the beginning of new «Golden Age» Cleaning is a waste of time Tossing used-once items into the thrash is a sign of modernity https://time.com/ What are microplastics? Total amount of plastic ever produced (1950-2015) in million tons Geyer et al. 2017 What are microplastics? Total amount of plastic ever produced (1950-2015) in million tons 91% of the produced plastic is not recycled! 79% 12% 9% 6300 Waste Geyer et al. 2017 What are microplastics? Estimated amount of primary plastic waste (1950-2015 and 20250) in million tons Geyer et al. 2017 What are microplastics? Greek: plastikos (to mould) Plastics: A polymer which can be molded into desired shape and size when soft and can be hardened to produce durable articles Plastics are produced from the polymerization of monomers derived from oil or gas (made of carbon and hydrogen) Additives are often included during plastic production to enhance their properties to last longer to burn slowly to be more flexible to degrade slower/faster What are microplastics? Greek: plastikos (to mould) Plastics: A polymer which can be molded into desired shape and size when soft and can be hardened to produce durable articles Different types of plastics with different shapes, size, compositions and physical and chemical properties Ahmed et al. 2022 Chemosphere 293(4):133557 What are microplastics? Plastics classification by size Nanoplastik Mikroplastik «bulk» Plastik < 1 Mikrometer < 5 Millimeter > 5 Millimeter https://www.forbes.com/ © Bundesamt für Gewässerkunde, Deutschland Cortes et al 2020 What are microplastics? Plastics classification by size Nanoplastik Mikroplastik «bulk» Plastik < 1 Mikrometer < 5 Millimeter > 5 Millimeter https://www.forbes.com/ © Bundesamt für Gewässerkunde, Deutschland Cortes et al 2020 Main sources of microplastics Already produced in Fragmentation of small size larger size-particles Adapted from Borah et al. 2023 Environmental Effects What are the effects on living organisms and the ecosystem? Type of substance Dose Mixture Contaminant 1 3 Environmental conditions Organism traits 2 Bioavailability Exposure Habitat quality Detoxification/regulation Environmental Effects What are the effects on living organisms and the ecosystem? Type of substance Dose Mixture Contaminant 1 3 Environmental conditions Organism traits 2 Bioavailability Exposure Habitat quality Detoxification/regulation Environmental Fate Transfer and distribution depends on physico-chemical properties of the compound and of the environment Equilibrium between different phases (partitioning) Key physico-chemical properties: Mobility Persistence Bioaccumulation Environmental Fate - Mobility Adsorption Hydrophobic & lipophilic. i.e. likely to adsorb to: Soil/sediments Persistent (hydrophobic) organic pollutants Metals General rule: the smaller the size the higher the adsorption to soil/sediment particles Solubility and volatilization Very low Environmental Fate - Persistence Degradation Complete degradation is extremely slow Partial degradation can induce important changes: Release of additives Polarization of plastic surfaces: interaction with water/chemicals Plastics persist for very long time in the environment Considering their degree of degradation is crucial for assessing their properties and effects Environmental Fate - Bioaccumulation Bioaccumulation and bioagnification Wide range of BCF/BAF Depends on: Particle size & shape Additives Organisms Trophic level … Hydrophobic & lipophilic: usually partition into lipids within body compartments Smaller size more likely to bind to lipids and to be transferred through trophic chain Fibers more likely to be retained in the organisms rather than beads Environmental Fate Plastics end up in all compartments: Ocean and sediments Freshwaters Atmosphere Soil Biota Environmental Fate Plastics end up in all compartments: Ocean and sediments Freshwaters Atmosphere Soil Biota Pictures: https://www.nationalgeographic.com/ Input pathways: Directly from land (e.g. rivers, wastewater treatment effluents) Stormwater, atmospheric deposition Marine (e.g. fishing nets, lines, ropes) The ocean is a major sink of plastics: In principle floating (low density) Can be colonized by organisms (biofouling) and settle into sediments Kooi et al. 2017 Environmental Fate Plastics end up in all compartments: Ocean and sediments Freshwaters Atmosphere Soil Biota Input pathways: Effluent (e.g. waste water treatment) Littering Refuse site leachate Mani et al. 2016 Example: Rhine river https://www.unibas.ch/ Environmental Fate Plastic end up in all compartments: Ocean and sediments Freshwaters Atmosphere Soil Biota Input pathways: Industry emissions City dust Burning of plastics in open landfills Microplastics can travel long distances through wind transportation and can be found in remote areas such as mountains and Arctics (e.g. Bergmann et al. 2019, Allen et al. 2019) Environmental Fate Plastics end up in all compartments: Ocean and sediments Freshwaters Atmosphere Soil Biota Input pathways: Discarded plastic litter, fragmentation (Rilllig 2012, Kwak and An 2021) Aerial deposition (Brahney et al. 2020) Plastic mulching, other agricultural products (Bläsing and Amelung 2018) Compost or sewage sludge addition (Weithmann et al. 2018) Roads (tire abrasion) (Baensch-Baltruschat et al. 2020) Bläsing and Amelung 2018 Environmental Fate Plastics end up in all compartments: Ocean and sediments Freshwaters Atmosphere Soil Biota 1. Direct ingestion of plastics (bioaccumulation) 2. Ingestion of animals that ingested plastics (biomagnification) Environmental Fate Plastics end up in all compartments: Ocean and sediments Freshwaters Atmosphere Soil Biota 1. Direct ingestion of plastics (bioaccumulation) 2. Ingestion of animals that ingested plastics (biomagnification) Example: Zooplankton: Collected from the Ocean Microplastics detected in two zooplankton species are in the same size range as their natural prey items → mistaken for food Desforges et al. 2015 Environmental Fate Plastics end up in all compartments: Ocean and sediments Freshwaters Atmosphere Soil Biota Zooplankton (Tintinnopsis lobiancoi) 1. Direct ingestion of plastics (bioaccumulation) with ingested fluorescent beads 2. Ingestion of animals that ingested plastics (biomagnification) Example: Zooplankton to mysid shrimps (Setälä et al. 2015): Zooplankton labelled with ingested microspheres offered as food to mysid shrimps Presence of zooplankton prey and microspheres after 3 h incubation Contents of a mysid shrimp (Mysis relicta) intestine after 3 h incubation with zooplankton labelled with Potential of microplastic transfer from one trophic level fluorescent microspheres (mesozooplankton) to a higher level (macrozooplankton) Environmental Fate Plastics end up in all compartments: Ocean and sediments Freshwaters Atmosphere Soil Biota Horton et al. 2018 1. Direct ingestion of plastics (bioaccumulation) 2. Ingestion of animals that ingested plastics (biomagnification) Example: Freshwater fish: Of 64 sampled R. rutilus from River Thames, 33% contained at least one microplastic particle in their gut content The majority were fibres (75%), followed by fragments (22.7%) and pellets (2.3%) Probably assimilated through ingestion of algae and molluscs which contained the microplastics Environmental Fate Plastics end up in all compartments: Ocean and sediments Freshwaters Atmosphere Soil Biota 1. Direct ingestion of plastics (bioaccumulation) 2. Ingestion of animals that ingested plastics (biomagnification) Example: Seabirds: Review on microplastic found in stomach of seabirds Avery-Gomm et al. 2018 Ecological Quality Objective (EcoQO): exceeded when more than 10% of individuals exceed 0.1 g of plastic in the stomach https://www.birdingplaces.eu/ Environmental Fate Plastics end up in all compartments: Ocean and sediments Freshwaters Atmosphere Soil Biota 1. Direct ingestion of plastics (bioaccumulation) 2. Ingestion of animals that ingested plastics (biomagnification) Environmental Fate Plastics end up in all compartments: Ocean and sediments Freshwaters Atmosphere Soil Biota 1. Direct ingestion of plastics (bioaccumulation) 2. Ingestion of animals that ingested plastics (biomagnification) https://www.20min.ch/wissen/news/story/Menschen-nehmen-52-000- Mikroplastik-Partikeln-ein-19111793 Environmental Effects What are the effects on living organisms and the ecosystem? Type of substance Dose Mixture Contaminant 1 3 Environmental conditions Organism traits 2 Bioavailability Exposure Habitat quality Detoxification/regulation Effects: Observed/measured at different levels of biological organisation Sophie Campiche, EcotoxCentre DNA Effects: Observed/measured at different levels of biological organisation Effects: Subindividual level Mode of Action: how do microplastics affect organisms? Most chemicals have a specific effect/mode of action Microplastics effect is more complex to assess: Different types have different effects Mechanical effect through surface interaction Effects due to transporting chemicals Effects: Subindividual level Mode of Action: how do microplastics affect organisms? Most chemicals have a specific effect/mode of action Microplastics effect is more complex to assess: Different types have different effects Mechanical effect through surface interaction Effects due to transporting chemicals Example: Microalgae Mechanical effect: Small particles (nano) can be adsorbed on the surface of microalgae and either encapsulate microalgae cells or enter the cell wall Larger particles (micro) can mechanically damage the cell wall (e.g. surface abrasion) Li et al. 2023 Loss of membrane integrity DNA damage Oxidative stress Photosynthesis inhibition Effects: Subindividual level – transporting chemicals Mode of Action: how do microplastics affect organisms? Most chemicals have a specific effect/mode of action Microplastics effect is more complex to assess: Different types have different effects Mechanical effect through surface interaction Effects due to transporting chemicals Example: Additives in Tire and road wear particles (TRWP) Additives are employed in the production of tires to improve their reactivity (e.g. vulcanizers, antioxidants) Tire particles and their additives are released from the abrasion of tires and are subjected to degradation/aging https://www.ufz.de/ TRWP artificially aged in the lab: of 11 tested Ex: tire‐associated chemicals, two were estrogenic, N‐(1,3‐dimethylbutyl)‐N′‐phenyl‐ three were genotoxic, and several inhibited p‐phenylenediamine (6PPD), diphenylguanidine (DPG) bacterial luminescence (Bergmann et al. 2024) Effects: Subindividual level – transporting chemicals Mode of Action: how do microplastics affect organisms? Most chemicals have a specific effect/mode of action Microplastics effect is more complex to assess: Different types have different effects Mechanical effect through surface interaction Effects due to transporting chemicals Example: Metals Plastics are expected to be a vehicle for transport of metals in aquatic systems and be potentially ingested by living organisms (Holmes et al. 2012) Copper interaction with aged microplastics causes oxidative stress to microalgae Chlorella vulgaris: content of antioxidative enzymes (SOD) after 10 days increased under single compound exposure while it decreased under mixture exposure Fu et al. 2019 Effects: Observed/measured at different levels of biological organisation Effects: Individual level Microplastic effects to individuals/populations are multiple: 1. Contrasting effects depending on the organism/species Example: Algae Review: growht inhibited or promoted depending on: type of plastic species of algae environmental conditions (marine VS freshwater) Song et al., 2020 Effects: Individual level Microplastic effects to individuals/populations are multiple: 1. Contrasting effects depending on the organism/species Example: Algae Review: growht inhibited or promoted depending on: type of plastic species of algae environmental conditions (marine VS freshwater) But why growth promotion? 1. Substrate for growth and colonization 2. Light scattering 3. Adsorption of toxicants (make less available) 4. Adsorption and release of nutrients Song et al., 2020 Effects: Individual/population level Microplastic effects to individuals/populations are multiple: 1. Contrasting effects depending on the organism/species 2. Effects of transporting chemicals: additives and time-delay Example: Nematode reproduction Inhibition of reproduction was mainly attributed to the extractable additives: when the additives were extracted, the toxic effects of each microplastic disappeared The harmful effects increased when the microplastics were maintained in the soil for a long-term period with frequent wet−dry cycles → additives released with time Effects: Individual/population level Microplastic effects to individuals/populations are multiple: 1. Contrasting effects depending on the organism/species 2. Effects of transporting chemicals: additives and time-delay Additives are slowly released by the plastics during their useful life and this continues once discarded to the environment Effects: Individual/population level Microplastic effects to individuals/populations are multiple: 1. Contrasting effects depending on the organism/species 2. Effects of transporting chemicals: additives and time-delay 3. Indirect effects Example: Plant growth Changes in soil physical properties (structure, bulk density water holding capacity) Especially fibers have negative effects on soil aggregation (Machado et al. 2018, Rillig et al. 2021) Microplastic fibers interact with soil aggregates affecting soil structure (Pictures from Matthias C. Rillig) Effects: Individual/population level Microplastic effects to individuals/populations are multiple: 1. Contrasting effects depending on the organism/species 2. Effects of transporting chemicals: additives and time-delay arbuscular mycorrhizal fungi (AMF) 3. Indirect effects Example: Plant growth Changes in soil physical properties Effects on microbial community (e.g. symbionts) Direct (toxic) effects Transport of contaminants Change in soil properties Carbon pool Effects: Individual/population level Microplastic effects to individuals/populations are multiple: 1. Contrasting effects depending on the organism/species 2. Effects of transporting chemicals: additives and time-delay 3. Indirect effects Example: Plant growth Changes in soil physical properties Effects on microbial community Different indirect effects on plant growth: Growth stimulation (e.g. Machado et al. 2019, Lozano et al. 2020) Growth inhibition (e.g. Kleunen et al. 2020) Rillig et al. 2020 Effects: Observed/measured at different levels of biological organisation Effects: Population/community level Microplastic effects to individuals/populations are multiple: 1. Contrasting effects depending on the organism/species 2. Effects of transporting chemicals: additives and time-delay 3. Indirect effects Example: Plant growth Changes in soil physical properties Effects on microbial community Different indirect effects on plant growth: Growth stimulation (e.g. Machado et al. 2019, Lozano et al. 2020) Growth inhibition (e.g. Kleunen et al. 2020) Shift in plant community (Lozano and Rillig 2020) Effects: Observed/measured at different levels of biological organisation Effects: Ecosystem level Factor of global change: effects on ecosystem functions Example: Soil system (Rillig et al. 2021) Microplastics have a influence on key ecosystem functions, such as cycling of nutrients and carbon Images - Le sol forestier vit – diversité et fonctions des organisms vivants du sol. WSL – Notice pour le practicien 2018 Effects: Ecosystem level Factor of global change: effects on ecosystem functions Example: Soil system (Rillig et al. 2021) Microplastics have a influence on key ecosystem functions, such as cycling of nutrients and carbon Example: Shift in litter quality Plant grow increased but unrelated to nutrient availability More plant material has less and less nutrients Litter is less rich in nutrients (dilution effect) Litter «diluted» Adapted from https://ess.science.energy.gov/ Effects: Ecosystem level Factor of global change: effects on ecosystem functions Example: Soil system (Rillig et al. 2021) Microplastics have a influence on key ecosystem functions, such as cycling of nutrients and carbon Example: Shift in litter quality Change in communities of organisms involved in the litter decomposition (e.g. microorganisms, earthworms): Altered soil properties Direct toxic effects Supply of organic carbon Effects: Ecosystem level Microplastics are not only a pollutant inducing toxicity… …Because of their ubiquity, they should be considered as a: Ecotoxicology traditional approach: Focus on current contamination Factor of global change: levels Linked with human activity Negative effects Affects biota Focus on highly controlled Exerts effects at the global scale experiments Readouts from individual (model) Consider future contamination levels organisms Any effects (positive&negative) = deviation from natural state Focus on ecological relevance, ecosystems → long-term effects Communities, ecosystem functions → Earth system feedbacks Rillig and Lehmann 2020 Rillig et al. 2021 Effects: Ecosystem level Factor of global change: consequences for the Earth system feedback? Consequences for process rates and net primary production (NPP), causing feedbacks to the atmosphere, including greenhouse gases emissions Rillig and Lehmann 2020 Learning goals 1. Microplastics What are microplastic and how do they behave in the environment? What are the effects on living organisms? 2. PFAS What are PFAS and how do they behave in the environment? What are the effects on living organisms? 3. Mitigation strategies What are the main challenges for the risk assessment of PFAS/microplastics? What are PFAS? Per- and Polyfluoroalkyl Substances: large and complex group of millions of industrial substances “PFASs are defined as fluorinated substances that contain at least one fully fluorinated methyl or methylene carbon atom (without any H/Cl/Br/I atom attached to it), i.e. with a few noted exceptions, any chemical with at least a perfluorinated methyl group (–CF3) or a perfluorinated methylene group (– CF2–) is a PFAS” (OECD 2021) > 1400 PFAS listed in the US Toxic Substances Control Act Inventory > 4700 PFSA in revised OECD list > 8000 known chemical structures (Evich et al. 2022) Main properties: Water repellent Fat and dirt repellent Chemical and thermal stability High polyvalence https://www.mn-net.com/ch/ch/pfas What are PFAS? Per- and Polyfluoroalkyl Substances: large and complex group of millions of industrial substances Perfluoroalkyl substances are fully fluorinated (perfluoro-) alkane (carbon-chain) molecules. Their basic chemical structure is a chain (or tail) of two or more carbon atoms with a charged functional group (or head) attached at one end. Common functional groups are carboxylates or sulfonates, but other forms are also detected in the environment Examples: https://pfas-1.itrcweb.org/ What are PFAS? Per- and Polyfluoroalkyl Substances: large and complex group of millions of industrial substances Perfluoroalkyl acids (PFAAs) are some of the least complex PFAS and currently are the class of PFAS most commonly tested for in the environment. Biotic and abiotic transformation of many polyfluoroalkyl substances may result in the formation of PFAAs. As a result, PFAAs are sometimes referred to as “terminal PFAS” or “terminal transformation products,” meaning no further transformation products will form from them under normal environmental conditions. Polyfluoroalkyl PFAS that transform to create terminal PFAAs are referred to as “precursors.” Examples: PFOS, PFOA, PFBA, PFBS… https://pfas-1.itrcweb.org/ What are PFAS? Per- and Polyfluoroalkyl Substances: large and complex group of millions of industrial substances Polyfluoroalkyl substances are distinguished from perfluoroalkyl substances by not being fully fluorinated. Instead, they are aliphatic substances for which all hydrogen atoms attached to at least one (but not all) carbon atom have been replaced by fluorine atoms, in such a manner that they contain the perfluoroalkyl moiety CnF2n+1. The carbon-hydrogen (or other non- fluorinated) bond in polyfluoroalkyl molecules creates a “weak” point in the carbon chain that is susceptible to biotic or abiotic transformation. As a result, many polyfluoroalkyl substances that contain a perfluoroalkyl CnF2n+1 moiety are potential precursor compounds that have the potential to be transformed into PFAAs Example: polyfluoroalkyl substance https://pfas-1.itrcweb.org/ What are PFAS? Per- and Polyfluoroalkyl Substances: large and complex group of millions of industrial substances Polymers are large molecules formed by combining many identical smaller molecules (or monomers) in a repeating pattern. Subclasses in the polymer class include fluoropolymers, polymeric perfluoropolyethers (PFPE), and side-chain fluorinated polymers. Some polymer PFAS are currently believed to pose less immediate human health and ecological risk relative to some nonpolymer PFAS. As stated previously, most compounds of interest at environmental release sites are nonpolymers https://pfas-1.itrcweb.org/ What are PFAS? Per- and Polyfluoroalkyl Substances: large and complex group of millions of industrial substances https://pfas-1.itrcweb.org/ What are PFAS? Per- and Polyfluoroalkyl Substances: large and complex group of millions of industrial substances Some are very old… 1947: PFOA, 3M 1949: PFOS, 3M 1951: Teflon, produced with PFOA: DuPont From early 1970, started to be largely used at industrial scale PFOA, PFOS, and PFHxS: Mostly banned today in Europe because classified as Substances of Very High Concern Classified as Persistent Organic Pollutant in the Stockholm Convention Main usages and sources Used because of their non-sticky and tensid-like properties for various purposes: Textiles, textile coating, e.g., seat covers, carpets, outdoor clothing Fire extinguisher foams Food packaging, e.g., pizza cartons, paper cups Paper finishing Fibre coating Cookware Building material, e.g., water resistant lacquer Further consumer products, such as: furniture, polishing and cleaning agents and creams https://www.mn-net.com/ch/ch/pfas Environmental Fate Transfer and distribution depends on physico-chemical properties of the compound and of the environment Equilibrium between different phases (partitioning) Key physico-chemical properties: Mobility Persistence Bioaccumulation Environmental Fate: mobility Large diversity of structures → large diversity of properties Lipo- & hydrophobic tail Polar & hydrophilic anionic head Amphilic structure Environmental Fate - Mobility Large diversity of structures → large diversity of properties Adsorption Long-chain PFAS more likely to partition to soil/ sediment than short-chain PFAS Solubility Short-chain PFAS more soluble than long-chain PFAS Amphilic structure make them behave like surfactants, i.e. accumulate to the fluid-fluid interface (e.g. air-water) Volatilization Mostly non volatile As a general rule, short-chain PFAS are more mobile https://pfas-1.itrcweb.org/ Environmental fate: persistence Persistence: «forever chemicals» The perfluorinated tail is highly resistant to environmental degradation due to the strength of the C-F bond Precursors (e.g. polyfluorinated substances) are subjected to partial degradation through biotic and abiotic transformation → transformed into PFAAS which are extremely persistant in the environment (“terminal PFAS”) → Most commonly tested for in the environment Environmental Fate: bioaccumulation/biomagnification Bioaccumulation and biomagnification Wide range of BCF/BAF Depends on: PFAS type Organisms Medium Trophic level … Amphiphilic PFAS are more likely to interact with other organic molecules with both polar and nonpolar regions (e.g. proteins , phospholipids) Long-chain PFAS more likely to bioaccumulate in animals than short-chain PFAS Short-chain PFAS tend to bioaccumulate more in plants Environmental Fate Where do PFAS end up? Ocean and sediments Freshwaters Atmosphere Soil Biota Environmental Fate https://pfas-1.itrcweb.org/ Environmental Fate Where do PFAS end up? Ocean and sediments Freshwaters Atmosphere Soil Biota Example: Glatt River Efﬂuents from waste water treatmnet plants and Glatt River water were dominated by PFOS, which was detected in all samples, followed by PFHxS and PFOA The mass ﬂows of ﬂuorochemicals emanating from WWTPs were found to be conserved within the 35 km Glatt River Input from the WWTPs is additive Removal within the Glatt River is not signiﬁcant Huset et al. 2008 Environmental Fate Where do PFAS end up? Limit value for drinking water = 0.1 µg/l Ocean and sediments Freshwaters Atmosphere Soil Biota Example: Groundwater PFAS detected in ~half of the 550 points measured by the NAQUA program for monitoring groundwater quality in Switzerland 90% of the measurement points containing PFAS are in urban area 13 PFAS identified in total, highest concentrations: PFOS and PFHxS https://www.bafu.admin.ch/ Environmental Fate Where do PFAS end up? Ocean and sediments Freshwaters (atmosphere) Soil Biota Example: Switzerland PFOA and PFOS found in all 146 soil samples used for different purposes, from different regions and climates Mainly long chain PFAS More mobile short-chain more likely to move to groundwaters but mechanisms on do they do that still unclear Cause: probably rainfall and atmospheric deposition Thalmann et al. 2022 Environmental Fate Where do PFAS end up? Ocean and sediments Freshwaters Atmosphere Soil Biota Environmental Fate Where do PFAS end up? Ocean and sediments Freshwaters Atmosphere Soil Houde et al. 2011 Biota Example: Fish, birds and marine mammals PFOS detected in all samples Remote zones from Greenland and the Faroe Islands Bossi et al. 2005 Environmental Fate Where do PFAS end up? Ocean and sediments Freshwaters Atmosphere Soil Biota Example: Plants Short-chain PFAS found to accumulate in plants (Ghisi et al. 2019) Main sources: Irrigation with contaminated water Use of polluted sewage sludges or industrial wastes as soil conditioners May lead to increases in human dietary exposure (consumption of vegetables) Environmental Fate Where do PFAS end up? Ocean and sediments Freshwaters Atmosphere Soil Biota Example: Humans Main sources: Water and food consumption (especially fish) Absorption from air and air-suspended dust https://www.eea.europa.eu/ Effects: Observed/measured at different levels of biological organisation Effects: Subindividual level Mode of Action: how do PFAS affect organisms? The research on toxicity of PFAS has mainly been focused on their and their effects on humans Most studied: PFOS, PFOA, and PFHxS Per- and Polyfluoroalkyl Substances (PFASs) | UNEP - UN Environment Programme https://www.eea.europa.eu/ Effects: Subindividual level Mode of Action: how do PFAS affect organisms? Large diversity of structures → large diversity of properties → large diversity of toxicity Fish: Lipid degradation pathways, including upregulation of enzymes in fatty acid degradation, such as fatty acid β- oxidation, and oxidative markers such as CAT and glutathione S-transferase were significantly affected by PFAS confirming lipid homeostasis disruption in Atlantic cod G. morhua PFAA mixtures (PFOS, PFOA, PFNA, and PFBS) potentially disrupted the endocrine system at a multigenerational scale, as observed in the Japanese medaka (Oryzias latipes) Turtles/Birds/Mammals: Few studies available The available studies suggest a relationship between PFAS concentration (e.g. in blood) and immune system, oxidative stress status, body condition and hormone balance. These studies are based on field observation to related to low-environmental concentrations and chronic exposure (From the recent draft dossier for the derivation of Environmental Quality Standards for PFAS, JRC 2021) Terrestrial organisms: Do not seem to be highly toxic but data are limited Data gaps on many ecotoxicological effects Effects: Observed/measured at different levels of biological organisation Effects: Individual/population level Large diversity of structures → large diversity of properties → large diversity of toxicity Example: mortality (acute) & reproduction (chronic) for aquatic species: heterogeneity of effects Acute: Fishes are the most sensitive 12 mg/l Chronic: Crustacean are most sensitive 0.3 mg/l Slide: Alexandra Kroll, EcotoxCentre Effects: Individual/population level Large diversity of structures → large diversity of properties → large diversity of toxicity Since bioaccumulative, the potential risk is expected to be higher for the upper levels of the trophic chain (final consumers) Focus is generally on these upper levels (esp. humans) PFOS: can cause significant health problems in birds, mammals and humans – ranging from changes in organ and/or body weights, cancer, and developmental abnormalities to death (Environment Agency, 2019) PFAS in general: “From existing evaluations, it is known that PFOS, PFOA and other PFAS have a relatively low toxicity to water organisms, but they may pose a problem when entering the food chain via fish. Therefore, the analysis was mainly focused on deriving human health-based quality standards for fish consumption” (From the recent draft dossier for the derivation of Environmental Quality Standards for PFAS, JRC 2021) Data gaps on many ecotoxicological effects for different groups of organisms Effects: Observed/measured at different levels of biological organisation Data gaps on effects on community/ecosystem Learning goals 1. Microplastics What are microplastic and how do they behave in the environment? What are the effects on living organisms? 2. PFAS What are PFAS and how do they behave in the environment? What are the effects on living organisms? 3. Mitigation strategies What are the main challenges for the risk assessment of PFAS/microplastics? What are possible alternatives? Mitigation: risk assessment Risk : exposure vs. hazard Step 1 Step 2 Step 3 Step 4 Establish effects Establish threshold Determine exposure Calculate based on effects and Risk quotient (RQ) = uncertainty Environmental concentration Effect-based threshold e.g. Growth inhibition e.g. Environmental Quality Standard (EQS) (Chriesbach; Image: Goran Basic / NZZ) Predicted env. conc. (PEC) Risk management Slide: Alexandra Kroll, EcotoxCentre Measured env. conc. (MEC) Mitigation: risk assessment Assumption: Effects can be extrapolated from lab experiments to the environment Top consumers Secondary consumers «Basic data» Fish Primary consumers Crustaceans (Daphnids) Algae, higher plants Primary producers © Prof. David Lavigne Slide: Alexandra Kroll, EcotoxCentre Mitigation: risk assessment Monitoring is a useful tool to complementary tool in risk assessment Prospective assessment Ok? Production/ Release on Manufacture the market Authorization Not so strong for PFAS & plastics (impossible to evaluate all substances) Mitigation: risk assessment Monitoring is a useful tool to complementary tool in risk assessment Prospective assessment Retrospective assessment Ok? Ok? Production/ Release on Risk Manufacture the market mitigation Authorization Monitoring Regulation: e.g. derivation of Environmental Quality Standards (EQS)) Mitigation: risk assessment Assumptions of the effect-based approach: For a compound of interest: No effect occurs above a certain threshold Effects can be measured for proxy organisms A threshold value (e.g. EQS) can be determined based on the effects on the most sensitive organism The threshold value can be compared with Predicted or Measured Environmental Concentrations Mitigation: risk assessment Main challenges of PFAS & plastics for risk assessment 1. Large and complex groups of substances Impossible to test every molecule Heterogeneity of mechanisms of effects/mode of actions Heterogeneity of measured effects (esp. PFAS) Data gaps (esp. PFAS) Difficulty of defining threshold values which would cover all compounds Standard toxicity tests for chemicals cannot cover all the potential effects of particles No admission/registration data available Mitigation: risk assessment Main challenges of PFAS & plastics for risk assessment 1. Large and complex groups of substances 2. Heterogenous physicochemical properties due to molecular structure Solubility Sorption Uptake into organisms/tissues Detection with analytical methods Difficulty of assessing exposure Mitigation: risk assessment Main challenges of PFAS & plastics for risk assessment 1. Large and complex groups of substances 2. Heterogenous physicochemical properties due to molecular structure 3. Accumulation in organisms and food chains Effects are strongest at the end of the food chains Difficulty of predicting concentrations & effects for predators Mitigation: risk assessment Main challenges of PFAS & plastics for risk assessment 1. Large and complex groups of substances 2. Heterogenous physicochemical properties due to molecular structure 3. Accumulation in organisms and food chains 4. Occurr in complex mixtures Example: complex mixture of PFAS found in surface waters (A) Overview of (tentatively) identified PFAS in this study at levels 1–3, grouped according to their classification in the OECD PFAS database,(1) (B) proposed chemical structures of novel compounds including related PubChem CIDs, and (C) chemical structure of the identified insecticide flubendiamide, typically not included in PFAS research. Joerss et al 2022 Environ. Sci. Technol. 2022, 56, 9, 5456–5465 Slide: Alexandra Kroll, EcotoxCentre Mitigation: risk assessment - PFAS Main challenges of PFAS & plastics for risk assessment 1. Large and complex groups of substances 2. Heterogenous physicochemical properties due to molecular structure 3. Accumulation in organisms and food chains 4. Occurr in complex mixtures 5. Regulated under different frameworks PFAS: Only most (known) toxic PFAS regulated Different goals (e.g. human health, animals) Different context (e.g. environmental media, industrial products, cosmetics) Different toxicity data used (dietary exposure, effects to animals) Different threshold values Most PFAS still used without restriction Slide: Alexandra Kroll, EcotoxCentre Mitigation: risk assessment - plastics Main challenges of PFAS & plastics for risk assessment 1. Large and complex groups of substances 2. Heterogenous physicochemical properties due to molecular structure 3. Accumulation in organisms and food chains 4. Occurr in complex mixtures Packaging 5. Regulated under different frameworks Waste Directive Packaging and Packaging Single-Use Waste Plastics Directive Plastics Marine Strategy Directive (Directive (EU) Only some type of plastics or hazardous Framework 2019/904) contaminants contained in plastic addressed REACH Regulation Directive Different goals, context, toxicity data, etc. (Registration, (2008/56/EC) Different threshold values Evaluation, Most plastic still used without restriction Authorisation, and Restriction of Chemicals) (Directive 94/62/EC) Mitigation: risk assessment -PFAS Some strategies to cope with these challenges 1. Large and complex groups of substances Concept for extrapolation between substances needed Example: PFOS & similar PFOS and few other long-chain PFAS are the most frequently detected and at highest concentrations Also expected to be the most toxic and for which most data are available EQS have been derived under several frameworks (e.g. EU Water Framework Directive, Casado et al. 2022, EFSA 2018): EQSbiota,HH = 9.1 ng/kg for human health (based on consumption of fishery products) for PFOS only Tolerable Weekly Intake (TWI) = 4.4 ng/kg for sum of PFOA, PFOS, PFNA, PFHxS Mitigation: risk assessment -PFAS Example: PFAS in birds and piscivore mammals PFOS and other PFAS measured in fish chair from lakes in the Alps region PFOS measured concentrations compared with limit values for human health: EQSbiota,HH (WFD) and TWI (EFSA) Already exceeded in some lakes EQSbiota,HH TWI Valsecchi et al. 2021 Mitigation: risk assessment -PFAS Example: PFAS in birds and piscivore mammals PFOS and other PFAS measured in fish chair from lakes in the Alps region PFOS measured concentrations compared with limit values for human health: EQSbiota,HH (WFD) and TWI (EFSA) Already exceeded in some lakes EQSbiota,HH TWI What about all other PFAS? Valsecchi et al. 2021 Mitigation: risk assessment -PFAS Some strategies to cope with these challenges 1. Large and complex groups of substances Concept for extrapolation between substances needed Example: Current proposal for PFAS EQS (JRC 2021) Based on data on 24 PFAS Uses the relative toxicity approach, i.e. PFOA-equivalent New EQS proposed to be included in the EU Water Framework Directive: EQSbiota,HH = 77 ng/kg for human health (based on consumption of fishery products) Currently under evaluation Mitigation: authorization & monitoring PFOA, PFOS, and PFHxS: Classified as Persistent Organic Pollutant in the Stockholm Convention Mitigation: authorization & monitoring Annex XVII to Regulation (EC) No Development of Limit Values for PFAS 1907/2006 of the European Parliament under European Directives and and of the Council on the Registration, authorities Evaluation, Authorisation and Restriction of Chemicals (REACH): Placing on the market and use of chemicals 2008: PFOS restricted with few exemptions because persistent, bioaccumulative, toxic 2008: PFOA identified as a Substance of Very High Concern because persistent, 2013: PFOS added to priority list bioaccumulative, toxic of the Water Framework Directive with EQS for surface waters 2020: Drinking Water Directive introduced limit values for PFAS 2021: European Food Safety 2020: PFOA restricted with few exemptions Authority introduced new because persistent, bioaccumulative, toxic Tolerable Weekly Intake (TWI) 2021: Draft proposal of several EQS for 24 PFAS under Water for PFOS and PFOA Framework Directive Hamid et al. 2024 Mitigation: authorization and restriction Proposition of restriction of > 10’000 PFAS at the European scale REACH: Registration, Evaluation and Authorization of Chemicals Nearly complete restriction on the manufacture, placing on the market and use of PFAS Registry of restriction intentions until outcome - ECHA Mitigation: alternatives What can be the alternatives to PFAS/plastics? 1. PFAS 2. Plastics Mitigation: alternatives What can be the alternatives to PFAS/plastics? 1. PFAS 2. Plastics The most (known) toxic PFAS (long-chain) are currently under regulation/restriction Other PFAS (short-chain) are used as alternatives Spatial distribution: → Are they really less problematic? Widespread distribution of short- chain and Polyfluoroalkyl PFAS Toxicity to aquatic organisms: Bioaccumulation Oxidative stress, hepatoxicity, neurotoxicity, histopathological alterations, behavioral and growth, abnormalities, reproductive toxicity and metabolism defects Ecological risks for freshwater and marine species: Higher for phytoplankton compared to invertebrates Mitigation: alternatives What can be the alternatives to PFAS/plastics? 1. PFAS 2. Plastics Non plastic-based products (e.g. bioplastic) Plastic use/production is decreasing Recycling of plastic is increasing Bioplastic production is increasing → Is it enough? The Circular Economy for Plastics – A European Analysis 2024 Plastics Europe Europe’s share of plastic production Microplastics: summary Environmental fate: Microplastics are a wide range of compounds having different shape, size, and composition The origin of microplastic can be direct production (primary) or fragmentation of larger pieces (secondary) Microplastics are persistent and occurr for very long time in the environment, with partial degradation/aging leading to important changes in their physico-chemical properties Microplastics are found in all environmental compartments, including remote regions (e.g. Arctic) and bioaccumulate in living organisms at all trophic levels Environmental effects: The toxic effects of microplastics are complex to be assessed due to the large diversity of plastic type and depends on their composition, size, shape, degradation/aging status Effects can be direct, such as morphological changes/harm to the cell membrane, oxidative stress, genotoxity, etc. Effects can be due to contaminants sorbed to plastics (e.g. additives, organic contaminants, metals) Effects can be indirects, e.g. by changing soil properties which affects microbial activity and plant growth Microplastics are now a factor of global change, leading to shifts in communities and consequent impacts on ecosystem functions PFAS: summary Environmental fate: PFAS represent a large variety of compounds having a large variety of properties PFAS are extremely persistent («forever chemicals»), mobile and bioaccumulative PFAS are found in all environmental compartments and they accumulate in living organisms Environmental effects: The toxic effects of PFAS are complex to be assessed due to the large diversity of PFAS and depend mainly on their type Aquatic and terrestrial invertebrates not particularly sensitive to PFAS but also knowledge gap Effects are mostly expected at higher levels of the trophic chain (fish, mammals, birds…) PFAS research has mainly been focused on human health PFAS and mitigation strategies: summary Mitigation strategies: PFAS & plastic: difficult to assess the risk for all compounds (different properties, effects, exposures) Plastics: only some substances (e.g. hazardous additives) are regulated PFAS: only most known toxic substances (e.g. PFOS, PFOA, PFHxS) are regulated Different frameworks with different protection goals/context result in different threshold values PFAS: EU is on the process of setting more conservative limit values and (hopefully) ban most PFAS References Allen, S., Allen, D., Phoenix, V.R. et al. 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