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Per- and polyfluoroalkyl substances (PFASs) were one of the priority substance groups selected which have been investigated under the ambitious European Joint programme HBM4EU (2017–2022). In order to answer policy relevant questions concerning exposure and health effects of PFASs in Europe several activities were developed under HBM4EU namely i) synthesis of HBM data generated in Europe prior to HBM4EU by developing new platforms, ii) development of a Quality Assurance/Quality Control Program covering 12 biomarkers of PFASs, iii) aligned and harmonized human biomonitoring studies of PFASs. In addition, some cohort studies (on motherchild exposure, occupational exposure to hexavalent chromium) were initiated, and literature researches on risk assessment of mixtures of PFAS, health effects and effect biomarkers were performed. The HBM4EU Aligned Studies have generated internal exposure reference levels for 12 PFASs in 1957 European teenagers aged 12–18 years. The results showed that serum levels of 14.3% of the teenagers exceeded 6.9 μg/L PFASs, which corresponds to the EFSA guideline value for a tolerable weekly intake (TWI) of 4.4 ng/kg for some of the investigated PFASs (PFOA, PFOS, PFNA and PFHxS). In Northern and Western Europe, 24% of teenagers exceeded this level. The most relevant sources of exposure identified were drinking water and some foods (fish, eggs, offal and locally produced foods). HBM4EU occupational studies also revealed very high levels of PFASs exposure in workers (P95: 192 μg/L in chrome plating facilities), highlighting the importance of monitoring PFASs exposure in specific workplaces. In addition, environmental contaminated hotspots causing high exposure to the population were identified. In conclusion, the frequent and high PFASs exposure evidenced by HBM4EU strongly suggests the need to take all possible measures to prevent further contamination of the European population, in addition to adopting remediation measures in hotspot areas, to protect human health and the environment. HBM4EU findings also support the restriction of the whole group of PFASs. Further, research and definition for additional toxicological dose-effect relationship values for more PFASs compounds is needed, European Union’s Horizon 2020 research and innovation program under grant agreement No 733032

Fluoropolymers are a group of polymers within the class of per- and polyfluoroalkyl substances (PFAS). The objective of this analysis is to evaluate the evidence regarding the environmental and human health impacts of fluoropolymers throughout their life cycle(s). Production of some fluoropolymers is intimately linked to the use and emissions of legacy and novel PFAS as polymer processing aids. There are serious concerns regarding the toxicity and adverse effects of fluorinated processing aids on humans and the environment. A variety of other PFAS, including monomers and oligomers, are emitted during the production, processing, use, and end-of-life treatment of fluoropolymers. There are further concerns regarding the safe disposal of fluoropolymers and their associated products and articles at the end of their life cycle. While recycling and reuse of fluoropolymers is performed on some industrial waste, there are only limited options for their recycling from consumer articles. The evidence reviewed in this analysis does not find a scientific rationale for concluding that fluoropolymers are of low concern for environmental and human health. Given fluoropolymers’ extreme persistence; emissions associated with their production, use, and disposal; and a high likelihood for human exposure to PFAS, their production and uses should be curtailed except in cases of essential uses.

This commentary presents a scientific basis for managing as one chemical class the thousands of chemicals known as PFAS (per- and polyfluoroalkyl substances). The class includes perfluoroalkyl acids, perfluoroalkylether acids, and their precursors; fluoropolymers and perfluoropolyethers; and other PFAS. The basis for the class approach is presented in relation to their physicochemical, environmental, and toxicological properties. Specifically, the high persistence, accumulation potential, and/or hazards (known and potential) of PFAS studied to date warrant treating all PFAS as a single class. Examples are provided of how some PFAS are being regulated and how some businesses are avoiding all PFAS in their products and purchasing decisions. We conclude with options for how governments and industry can apply the class-based approach, emphasizing the importance of eliminating non-essential uses of PFAS, and further developing safer alternatives and methods to remove existing PFAS from the environment., Environmental Science & Technology Letters, 7 (8), ISSN:2328-8930

Background: Safe and clean drinking water is essential for human life. Persistent, mobile and toxic (PMT) substances and/or very persistent and very mobile (vPvM) substances are an important group of substances for which additional measures to protect water resources may be needed to avoid negative environmental and human health effects. PMT/vPvM substances do not sufficiently biodegrade in the environment, they can travel long distances with water and are toxic (those that are PMT substances) to the environment and/or human health. PMT/vPvM substance research and regulation is arguably in its infancy and in order to get in control of these substances the following (non-exhaustive list of) knowledge gaps should to be addressed: environmental occurrence; the suitability of currently available analytical methods; the effectiveness and availability of treatment technologies; the ability of regional governance and industrial stewardship to contribute to safe drinking water while supporting innovation; the ways in which policies and regulations can be used most effectively to govern these substances; and, the identification of safe and sustainable alternatives. Methods: The work is the outcome of the third PMT workshop, held in March 2021, that brought together diverse scientists, regulators, NGOs, and representatives from the water sector and the chemical sector, all concerned with protecting the quality of our water resources. The online workshop was attended by over 700 people. The knowledge gaps above were discussed in the presentations given and the attendees were invited to provide their opinions about knowledge gaps related to PMT/vPvM substance research and regulation. Results: Strategies to closing the knowledge, technical and practical gaps to get in control of PMT/vPvM substances can be rooted in the Chemicals Strategy for Sustainability Towards a Toxic Free Environment from the European Commission, as well as recent advances in the research and industrial stewardship. Key to closing these gaps are: (i) advancing remediation and removal strategies for PMT/vPvM substances that are already in the environment, however this is not an effective long-term strategy; (ii) clear and harmonized definitions of PMT/vPvM substances across diverse European and international legislations; (iii) ensuring wider availability of analytical methods and reference standards; (iv) addressing data gaps related to persistence, mobility and toxicity of chemical substances, particularly transformation products and those within complex substance mixtures; and (v) advancing monitoring and risk assessment tools for stewardship and regulatory compliance. The two most effective ways to get in control were identified to be source control through risk governance efforts, and enhancing market incentives for alternatives to PMT/vPvM substances by using safe and sustainable by design strategies., Environmental Sciences Europe, 34, ISSN:2190-4715, ISSN:2190-4707

TheSABYDOMA project, funded by the EU H2020 programme (grant agreement no. 862296), organised virtually its workshop ”A Stakeholder’s Perspective ofSafe-and-Sustainable-by-Design (SSbD), on18thFebruary 2022. Around 100 participants from all over the world (Asia, America, Africa, Europe) and from a wide range of stakeholders (scientists, industry, consultants, market researchers, NGO representatives, regulators, policy makers/advisors, lawyers, trade associations, etc.) , joint the workshop with the expectation of increasing their knowledge in SSbD, in knowing more about the point of view of SSbD from other stakeholder’s perspectives and to foster on the policy consequences of adopting one concrete “concept”. After a warm welcome to the workshop by the moderatorMr Anthony Bochon, from Gil Robles – San Bartolome & Partners (Brussels), SABYDOMA’s coordinator,Prof. Andrew Nelson, from the University of Leeds, gave a short presentation about the project. After a summary of the output of the 1st Legal Workshop on Safe-by-Design organised by SABYDOMA in January 2021, by Anthony Bochon, Beatriz Alfaro Serrano (from BioNanoNet Forschungsgesellschaft GmbH) warmly welcomed and presented all renowned invited speakers, who shortly presented their visions/definitions of SSbD. The invited speakers were: Victor Puntes, Applied Nanoparticles, Spain Mario Pansera, University of Vigo, Spain Eva Valsami-Jones, University of Birmingham, UK Denis Sarigiannis, PARC project Jana Drbohlavová, European Commission Xenia Trier,European Environmental Agency (EEA) Anne Chloe Devic, European Chemical Industry Council (CEFIC), Belgium Henrik Edin, ChemSec, SE Blanca Suarez,TEMAS Solutions GmbH, Switzerland Sean Kelly, Nanotechnology Industries Association, Belgium The workshop continued with a life survey, moderated by Beatriz Alfaro, where the workshop participants were invited to choose, based on the definitions given by the workshop speakers, those they mostly agreed / felt most comfortable with. Furthermore, the participants were asked to name which words they mostly associate with SSbD, giving as result a heterogenous word cloud. The workshop ended with a very interactiveRound Table, where eight panellists (all speakers with the exception of Eva Valsami-Jones and Xenia Trier) were interviewed by the moderator of the session Mr Ignasi Gispert Pi (from Applied Nanoparticles S.L.) discussing about different aspects of SSbD. Relevant publications suggested by the workshop speakers can be found here. You can find the presentations below. The recordings of the workshop can be found in SABYDOMA’s YouTube channel (SSbD Workshop – Part 1 (Speakers) & Part 2 (Round Table)).

Per- and polyfluoroalkyl substances (PFAS) are a class of substances for which there are widespread concerns about their extreme persistence in combination with toxic effects. It has been argued that PFAS should only be employed in those uses that are necessary for health or safety or are critical for the functioning of society and where no alternatives are available (“essential-use concept”). Implementing the essential-use concept requires a sufficient understanding of the current uses of PFAS and of the availability, suitability, and hazardous properties of alternatives. To illustrate the information requirements under the essential-use concept, we investigate seven different PFAS uses, three in consumer products and four industrial applications. We investigate how much information is available on the types and functions of PFAS in these uses, how much information is available on alternatives, their performance and hazardous properties and, finally, whether this information is sufficient as a basis for deciding on the essentiality of a PFAS use. The results show (i) the uses of PFAS are highly diverse and information on alternatives is often limited or lacking; (ii) PFAS in consumer products often are relatively easy to replace; (iii) PFAS uses in industrial processes can be highly complex and a thorough evaluation of the technical function of each PFAS and of the suitability of alternatives is needed; (iv) more coordination among PFAS manufacturers, manufacturers of alternatives to PFAS, users of these materials, government authorities, and other stakeholders is needed to make the process of phasing out PFAS more transparent and coherent., Environmental Science & Technology, 56 (10), ISSN:0013-936X, ISSN:1520-5851

Despite decades of research on per- and polyfluoroalkyl substances (PFAS), fundamental obstacles remain to addressing worldwide contamination by these chemicals and their associated impacts on environmental quality and health. Here we propose six urgent questions relevant to science, technology, and policy that must be tackled in order to address the “PFAS problem”: (1) What are the global production volumes of PFAS, and where are PFAS used? (2) Where are the unknown PFAS hotspots in the environment? (3) How can we make the measurement of PFAS globally accessible? (4) How can we safely manage PFAS-containing waste? (5) How do we understand and describe the health effects of PFAS exposure? And (6) Who pays the costs of PFAS contamination? The importance of each question and barriers to progress are briefly described, and several potential paths forward are proposed. Given the diversity of PFAS and their uses, the extreme persistence of most PFAS, the striking ongoing lack of fundamental information, and the inequity of the health and environmental impacts from PFAS contamination, there is a need for scientific and regulatory communities to work together, with cooperation from PFAS-related industries, to fill in critical data gaps and protect human health and the environment.

Per- and polyfluoroalkyl substances (PFAS) are of concern because of their high persistence (or that of their degradation products) and their impacts on human and environmental health that are known or can be deduced from some well-studied PFAS. Currently, many different PFAS (on the order of several thousands) are used in a wide range of applications, and there is no comprehensive source of information on the many individual substances and their functions in different applications. Here we provide a broad overview of many use categories where PFAS have been employed and for which function; we also specify which PFAS have been used and discuss the magnitude of the uses. Despite being non-exhaustive, our study clearly demonstrates that PFAS are used in almost all industry branches and many consumer products. In total, more than 200 use categories and subcategories are identified for more than 1400 individual PFAS. In addition to well-known categories such as textile impregnation, fire-fighting foam, and electroplating, the identified use categories also include many categories not described in the scientific literature, including PFAS in ammunition, climbing ropes, guitar strings, artificial turf, and soil remediation. We further discuss several use categories that may be prioritised for finding PFAS-free alternatives. Besides the detailed description of use categories, the present study also provides a list of the identified PFAS per use category, including their exact masses for future analytical studies aiming to identify additional PFAS., Environmental Science: Processes & Impacts, 22 (12), ISSN:2050-7887, ISSN:2050-7895

Purpose: Limiting exposure to potentially toxic chemicals in food packaging can lead to environmental impact trade-offs. No available tool, however, considers trade-offs between environmental impacts of packaging systems and exposure to potentially toxic chemicals in food packaging. This study therefore explores the research needs for extending life cycle impact assessment (LCIA) to include exposure to chemicals in food packaging. Methods: The LCIA framework for human toxicity was extended for the first time to include consumer exposure to chemicals in food packaging through the product intake fraction (PiF) metric. The related exposure pathway was added to LCIA without other modifications to the existing toxicity characterization framework used by USEtox®, i.e., effect factor derivation. The developed method was applied to a high impact polystyrene (HIPS) container case study with the functional unit of providing 1 kg of yogurt in single servings. Various exposure scenarios were considered, including an evidence-based scenario using concentration data and a migration model. Human toxicity impact scores in comparative toxic units (CTUh ) for the use stage were evaluated and then compared to human toxicity impact scores from a conventional LCIA methodology. Results and discussion: Data allowed toxicity characterization of use stage exposure to only seven chemicals in HIPS out of fourty-four identified. Data required were the initial concentration of chemicals in food packaging, chemical mass transfer from packaging into food, and relevant toxicity information. Toxicity characterization demonstrated that the combined CTUh for HIPS material acquisition, manufacturing, and disposal stages exceeded the toxicity scores related to consumer exposure to previously estimated concentrations of the seven characterizable chemicals in HIPS, by about two orders of magnitude. The CTUh associated with consumer exposure became relevant when migration was above 0.1% of the European regulatory levels. Results emphasize missing data for chemical concentrations in food contact materials and a need to expand the current USEtox method for effect factor derivation (e.g., to consider endocrine disruption, mixture toxicity, background exposure, and thresholds when relevant). Conclusions: An LCIA method was developed to include consumer exposure to chemicals in food packaging. Further study is required to assess realistic scenarios to inform decisions and policies, such as circular economy, which can lead to trade-offs between environmental impacts and potentially toxic chemicals in packaging. To apply the developed method, data regarding occurrence, concentration, and toxicity of chemicals in food packaging are needed. Revisiting the derivation of effect factors in future work could improve the interpretation of human toxicity impact scores.

Because of the extreme persistence of per- and polyfluoroalkyl substances (PFASs) and their associated risks, the Madrid Statement argues for stopping their use where they are deemed not essential or when safer alternatives exist. To determine 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 determine 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, constant 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 chemicals, or groups of chemicals, of concern., Environmental Science: Processes & Impacts, 21 (11), ISSN:2050-7887, ISSN:2050-7895

Poly- and perfluorinated alkyl substances (PFAS) are used in paper and board food contact materials (FCMs) and they have been found to be highly persistent, bioaccumulative and toxic. The purpose o ...

Per- and polyfluoroalkyl substances (PFASs) are man-made chemicals that contain at least one perfluoroalkyl moiety, [Formula: see text]. To date, over 4,000 unique PFASs have been used in technical applications and consumer products, and some of them have been detected globally in human and wildlife biomonitoring studies. Because of their extraordinary persistence, human and environmental exposure to PFASs will be a long-term source of concern. Some PFASs such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) have been investigated extensively and thus regulated, but for many other PFASs, knowledge about their current uses and hazards is still very limited or missing entirely. To address this problem and prepare an action plan for the assessment and management of PFASs in the coming years, a group of more than 50 international scientists and regulators held a two-day workshop in November, 2017. The group identified both the respective needs of and common goals shared by the scientific and the policy communities, made recommendations for cooperative actions, and outlined how the science-policy interface regarding PFASs can be strengthened using new approaches for assessing and managing highly persistent chemicals such as PFASs. https://doi.org/10.1289/EHP4158.

High resolution mass spectrometry (HRMS) was successfully applied to elucidate the structure of a polyfluorinated polyether (PFPE)-based formulation. The mass spectrum generated from direct injection into the MS was examined by identifying the different repeating units manually and with the aid of an instrument data processor. Highly accurate mass spectral data enabled the calculation of higher-order mass defects. The different plots of MW and the nth-order mass defects (up to n = 3) could aid in assessing the structure of the different repeating units and estimating their absolute and relative number per molecule. The three major repeating units were -C2H4O-, -C2F4O-, and -CF2O-. Tandem MS was used to identify the end groups that appeared to be phosphates, as well as the possible distribution of the repeating units. Reversed-phase HPLC separated of the polymer molecules on the basis of number of nonpolar repeating units. The elucidated structure resembles the structure in the published manufacturer technical data. This analytical approach to the characterization of a PFPE-based formulation can serve as a guide in analyzing not just other PFPE-based formulations but also other fluorinated and non-fluorinated polymers. The information from MS is essential in studying the physico-chemical properties of PFPEs and can help in assessing the risks they pose to the environment and to human health. Graphical Abstract ᅟ Electronic supplementary material The online version of this article (doi:10.1007/s13361-015-1269-9) contains supplementary material, which is available to authorized users.

Background: Food contact articles (FCAs) are manufactured from food contact materials (FCMs) that include plastics, paper, metal, glass, and printing inks. Chemicals can migrate from FCAs into food during storage, processing, and transportation. Food contact materials’ safety is evaluated using chemical risk assessment (RA). Several challenges to the RA of FCAs exist. Objectives: We review regulatory requirements for RA of FCMs in the United States and Europe, identify gaps in RA, and highlight opportunities for improving the protection of public health. We intend to initiate a discussion in the wider scientific community to enhance the safety of food contact articles. Discussion: Based on our evaluation of the evidence, we conclude that current regulations are insufficient for addressing chemical exposures from FCAs. RA currently focuses on monomers and additives used in the manufacture of products, but it does not cover all substances formed in the production processes. Several factors hamper effective RA for many FCMs, including a lack of information on chemical identity, inadequate assessment of hazardous properties, and missing exposure data. Companies make decisions about the safety of some food contact chemicals (FCCs) without review by public authorities. Some chemical migration limits cannot be enforced because analytical standards are unavailable. Conclusion: We think that exposures to hazardous substances migrating from FCAs require more attention. We recommend a) limiting the number and types of chemicals authorized for manufacture and b) developing novel approaches for assessing the safety of chemicals in FCAs, including unidentified chemicals that form during or after production. ISSN:1552-9924 ISSN:0091-6765

open access article Food contact materials (FCM) are any type of item intended to come into contact with foods and thus represent a potential source for human exposure to chemicals. Regarding FCMs made of paper and board, information pertaining to their chemical constituents and the potential impacts on human health remains scarce, which hampers safety evaluation. We describe an effect-directed strategy to identify and characterize emerging chemicals in paper and board FCMs. Twenty FCMs were tested in eight reporter gene assays, including assays for the AR, ER, AhR, PPARγ, Nrf2 and p53, as well as mutagenicity. All FCMs exhibited activities in at least one assay. As proof-of-principle, FCM samples obtained from a sandwich wrapper and a pizza box were carried through a complete step-by-step multi-tiered approach. The pizza box exhibited ER activity, likely caused by the presence of bisphenol A, dibutyl phthalate, and benzylbutyl phthalate. The sandwich wrapper exhibited AR antagonism, likely caused by abietic acid and dehydroabietic acid. Migration studies confirmed that the active chemicals can transfer from FCMs to food simulants. In conclusion, we report an effect-directed strategy that can identify hazards posed by FCMs made from paper and board, including the identification of the chemical(s) responsible for the observed activity.

Polyfluoroalkyl phosphate surfactants (PAPS) are widely used in food contact materials (FCMs) of paper and board and have recently been detected in 57% of investigated materials. Human exposure occurs as PAPS have been measured in blood; however knowledge is lacking on the toxicology of PAPS. The aim of this study was to elucidate the effects of six fluorochemicals on sex hormone synthesis and androgen receptor (AR) activation in vitro. Four PAPS and two metabolites, perfluorooctanoic acid (PFOA) and 8:2 fluorotelomer alcohol (8:2 FTOH) were tested. Hormone profiles, including eight steroid hormones, generally showed that 8:2 diPAPS, 8:2 monoPAPS and 8:2 FTOH led to decreases in androgens (testosterone, dehydroepiandrosterone, and androstenedione) in the H295R steroidogenesis assay. Decreases were observed for progesterone and 17-OH-progesterone as well. These observations indicated that a step prior to progestagen and androgen synthesis had been affected. Gene expression analysis of StAR, Bzrp, CYP11A, CYP17, CYP21 and CYP19 mRNA showed a decrease in Bzrp mRNA levels for 8:2 monoPAPS and 8:2 FTOH indicating interference with cholesterol transport to the inner mitochondria. Cortisol, estrone and 17β-estradiol levels were in several cases increased with exposure. In accordance with these data CYP19 gene expression increased with 8:2 diPAPS, 8:2 monoPAPS and 8:2 FTOH exposures indicating that this is a contributing factor to the decreased androgen and the increased estrogen levels. Overall, these results demonstrate that fluorochemicals present in food packaging materials and their metabolites can affect steroidogenesis through decreased Bzrp and increased CYP19 gene expression leading to lower androgen and higher estrogen levels.

International audience; Migration of chemicals from packaging materials to foods may lead to human exposure. Polyfluoroalkyl substances (PFAS) can beused in technical mixtures (TMs) for use in food packaging of paper and board, and PFAS have been detected in human serum andumbilical cord blood. The specific structures of the PFAS in TMs are often unknown, but polyfluorinated alkyl phosphate esters(PAPs) have been characterized in TMs, food packaging, and in food. PAPs can be metabolized into fluorotelomer alcohols (FTOHs)and perfluoroalkyl carboxylic acids (PFCAs). Some PFAS have endocrine activities, highlighting the need to investigate these effects.Herein, we studied the endocrine activity of less characterized PFAS, including short-chain PFCAs and FTOHs, PAPs, and TMs ofunknown chemical composition. Long-chain PFCAs were also included. We applied seven assays covering effects on estrogen, gluco-corticoid, androgen, and peroxisome proliferator-activated receptor (PPAR) activity, as well as steroidogenesis in vitro and ex vivo. Ingeneral, PAPs, FTOHs, TMs, and long-chain PFCAs showed estrogenic activity through receptor activation and/or increasing 17b-estradiol levels. Furthermore, short- and long-chain PFCAs activated PPARaand PPARc. Collectively, this means that (i) PAPs,FTOHs, and PFCAs exhibit endocrine activity through distinct and sometimes different mechanisms, (ii) two out of three tested TMsexhibited estrogenic activity, and (iii) short-chain FTOHs showed estrogenic activity and short-chain PFCAs generally activate bothPPARaand PPARcwith similar potency and efficacy as long-chain PFCAs. In conclusion, several new and divergent toxicologicaltargets were identified for different groups of PFAS.

Hazardous chemicals in packaging, including ‘eco-friendly’ and recycled food packaging, can migrate into food and expose humans. LCA has been fundamental to indicate more ‘eco-friendly’ packages, but currently LCA does not consider exposure to chemical migrants and methods have not yet been developed. In this study we question if exposure to chemicals in food packaging should be considered as a sustainable design consideration, i.e. if this human health risk is relevant in a life cycle context. To answer this question, we focus on developing methods to quantify exposure to chemicals in food packaging in a life cycle impact assessment (LCIA) framework. To put exposure during use in a life cycle context we perform a screening-level LCA of several life cycle stages of high impact polystyrene packaging (HIPS), with a functional unit of containing and delivering one kilogram of yogurt for consumption. For screening, we include exposure via environmental emissions from the production of the raw material HIPS, thermoforming into packaging, 14 day refrigeration by consumers, and disposal via incineration. The purpose of this screening is not to obtain a detailed and accurate LCA of HIPS but to provide life cycle context to compare the magnitude of characterized exposure to chemicals in packaging, in order to elucidate if this exposure pathway is important. We detail estimates of life cycle exposure to one known hazardous chemical in polystyrene packaging (styrene) that has data available on concentrations in yogurt packaged in HIPS and life cycle inventory releases. We also extend this analysis, given data limitations, to include exposure to three other chemicals in HIPS packaging through food. Given that data on concentrations of food packaging chemicals in food are often missing, we also explore methods to model the product intake fraction (PiF) as the fraction of chemical mass taken in through food packaging versus its initial mass in the food packaging. Results demonstrated that in the given cases consumer exposure to chemicals in packaging through consuming packaged food can be greater than population-level exposure mediated by the life cycle releases of such chemicals, even when only considering one or several chemicals in packaging that expose consumers. Occupational exposure was not consid ered in this study, but could be a focus of future work.Thus, this initial exploration indicates that exposure to chemicals in food packaging can be an essential consideration for burden shifting and quantifying design trade-offs in a life cycle context.

In this study, we explore the identity of a range of polyfluorinated surfactants (PFS) used for food contact materials, primarily to impart oil and water repellency on paper and board. PFS are of interest, as they can be precursors of poly- and perfluorinated alkyl substances (PFAS), of which several are persistent and are found worldwide in human blood and in the environment. To determine the elemental composition of PFS, we combined information from patents, chemical suppliers and analyses of industrial blends using ultra performance liquid chromatography-negative electrospray ionisation quadrupole time-of-flight mass spectrometry. At a high pH of 9.7, both non-ionic and anionic PFS were ionised and were recognised by negative mass defects of exact masses, and neutral fragment losses of n × 20 or n × 100 Da. More than 115 molecular structures were found in industrial blends from the EU, US and China, belonging to the groups of polyfluoroalkyl-mono- and di-ester phosphates (monoPAPS, diPAPS and S-diPAPS), -ethoxylates, -acrylates, -amino acids, -sulfonamide phosphates and -thio acids, together with residuals and synthesis byproducts. In addition, a number of starting materials such as perfluorooctane sulfonamide N-alkyl esters were analysed. Di- and trialkylated PAPS and S-diPAPS were found in migrates from European food contact materials. This study highlights the need to monitor for more types of PFS in order to map the sources of PFAS in humans and the environment.

In this discussion paper, the transition from long-chain poly- and perfluorinated alkyl substances (PFASs) to fluorinated alternatives is addressed. Long-chain PFASs include perfluoroalkyl carboxylic acids (PFCAs) with 7 or more perfluorinated carbons, perfluoroalkyl sulfonic acids (PFSAs) with 6 or more perfluorinated carbons, and their precursors. Because long-chain PFASs have been found to be persistent, bioaccumulative and toxic, they are being replaced by a wide range of fluorinated alternatives. We summarize key concerns about the potential impacts of fluorinated alternatives on human health and the environment in order to provide concise information for different stakeholders and the public. These concerns include, amongst others, the likelihood of fluorinated alternatives or their transformation products becoming ubiquitously present in the global environment; the need for more information on uses, properties and effects of fluorinated alternatives; the formation of persistent terminal transformation products including PFCAs and PFSAs; increasing environmental and human exposure and potential of adverse effects as a consequence of the high ultimate persistence and increasing usage of fluorinated alternatives; the high societal costs that would be caused if the uses, environmental fate, and adverse effects of fluorinated alternatives had to be investigated by publicly funded research; and the lack of consideration of non-persistent alternatives to long-chain PFASs., Chemosphere, 114, ISSN:0045-6535, ISSN:1879-1298

Primary aromatic amines (PAAs) were analysed by liquid chromatography-tandem mass spectrometry (LC-MS/MS) in migrates from 234 samples of food-contact materials, including black nylon (polyamide) kitchen utensils (n = 136), coloured plastics (28), and clear/printed multilayer film/laminates (41), from retailers, importers, and food producers. A further 29 utensils in use were obtained from colleagues. Very high PAA migration was found from black nylon kitchen utensils to the food simulant 3% acetic acid: the 'non-detectable' limit (20 microg aniline equivalents kg(-1) food) was exceeded by up to 2100 times. All the other materials were compliant. The majority of the non-compliant utensils came from China. The predominant PAAs were aniline and 4,4'-methylenedianiline (4,4'-MDA). The frequency of violations decreased from the year 2004 (55%) to the autumn of 2005 (13%), possibly due to increased demands for in-house documentation, but they remained almost constant from 2005 to 2009. The validity of the results was shown by recovery studies, participation in proficiency testing, and comparative testing of utensils by two laboratories. Migration modelling was used to compare how various compliance migration test conditions influenced the final test results. Long-term release of PAAs was fitted by diffusion modelling experiments and long-term release was also seen as expected from used utensils. Toxicologists consider these migration levels of the suspected carcinogenic PAAs as a problem of major concern.

Environmental Health Perspectives, 123 (5), ISSN:1552-9924, ISSN:0091-6765

Environmental Health Perspectives, 123 (7), ISSN:1552-9924, ISSN:0091-6765

Paper and board used as food contact materials (FCMs) are chemically complex matrices, partly due to the naturally occurring substances in paper and board, but also due to the chemical treatment of the paper used to make it suitable for food contact. In order to assure the safety of packaging materials, information on the exposure as well as on the toxicity of substances in the packaging must be obtained. This study describes a comprehensive method for the extraction and fractionation of substances present in paper and board FCMs for further investigation by in vitro testing and chemical analysis. The extraction efficiency and the fractionation process were validated by determining recoveries in extracts from paper and board fortified with five surrogates of known concentration. The recoveries for the five surrogates were between 20% and 104% in the raw extract and between 21% and 109% after extraction and fractionation. The fractionation both reduces the number of compounds to be identified and works as a sample clean-up by reducing matrix effects. Raw extracts and fractions from two paper and board FCMs were furthermore tested in the aryl hydrocarbon receptor (AhR) reporter gene assay. Both raw extracts and two of the fractions of the raw extracts gave a positive response in the AhR assay. The strategy of extraction followed by fractionation offers a powerful tool in order to make the workflow for screening FCMs for potentially adverse effects more efficient.

A technique based on capillary electrophoresis and amperometric detection (CE-AD) has been developed for the speciation of mercury. This technique has the unique capability to detect only cationic mercury species that are electrochemically active. Capillary electrophoresis with electrokinetic injection allows efficient separation of inorganic mercury and organomercury cations in 8 min. Selective detection of these electrochemically active species is attained by controlling the reduction potential applied on the micro-electrode. For Hg 2+ , an optimal potential of −0.2 V can be used to prevent interference by less electroactive toxic metals and other substances found in complex environmental samples. The amperometric signal is linearly proportional to the Hg 2+ concentration over three orders of magnitude, with a detection limit of 0.2 ng/ml. The mass detection limit corresponds to 8 fg of Hg 2+ in an injection volume of 40 nl. For CH 3 Hg + , the detection limit is 3 ng/ml when a potential of −0.5 V is used. These detection sensitivities are attractive for environmental monitoring of contaminated sediments in ecosystems. Steam distillation is evaluated for the extraction of CH 3 Hg + from the sediment matrix. It yields an unknown mercury species which is unsuitable for CE-AD determination under the specified conditions.

This Tema Nord report presents a study based on open information and custom market research to review the most common perfluorinated substances (PFC) with less focus on PFOS and PFOA.The study incl ...

This Tema Nord report presents a study based on open information and custom market research to review the most common perfluorinated substances (PFC) with less focus on PFOS and PFOA.The study includes three major parts:1) Identification of relevant per-and polyfluorinated substances and their use in various industrial sectors in the Nordic market by interviews with major players and database information2) Emissions to and occurence in the Nordic environment of the substances described in 1)3) A summary of knowledge of the toxic effects on humans and the environment of substances prioritized in 2)There is a lack of physical chemical data, analystical reference substances, human and environmental occurrence and toxicology data, as well as market information regarding PFCs other than PFOA and PFOS and the current legislation cannot enforce disclosure of specific PFC substance information.

A tiered approach is proposed for the discovery of unknown anionic and nonionic polyfluorinated alkyl surfactants (PFASs) by reversed phase ultra high performance liquid chromatography (UHPLC)--negative electrospray ionisation--quadrupole time of flight mass spectrometry (UHPLC-ESI(-)-QTOF-MS). The chromatographic separation, ionisation and detection of PFASs mixtures, was achieved at high pH (pH=9.7) with NH(4)OH as additive. To distinguish PFASs from other chemicals we used the characteristic negative mass defects of PFASs, their specific losses of 20 Da (HF) and the presence of series of chromatographic peaks, belonging to homologues series with m/z of n×50 Da (CF(2)) or n×100 Da (CF(2)CF(2)). The elemental composition of the precursor ions were deducted from the accurate m/z values of the deprotonated molecules [M-H](-). In case of in-source fragmentation, the presence of dimers, e.g. [M(2)-H](-) and adduct ions such as [M-H+solvent](-) and [(M-H)(M-H+Na)(n)](-) were used to confirm the identity of the precursor ions. In relation to quantification of PFASs, we discuss how their surfactancy influence the ESI processes, challenge their handling in solution and choices of precursor-to-product ions for MSMS of e.g., structural PFAS isomers. The method has been used to discover PFASs in industrial blends and in extracts from food contact materials.

In this study, we provide strategies for detecting and quantifying the structural isomers of polyfluorinated di- and tri-alkyl surfactants (PFAS) by mass spectrometry (MS). We specifically investigate polyfluorinated dialkylated phosphate ester surfactants (x:2/y:2 diPAPS, (F(CF2) x CH2CH2O-P(O)(O)−-OCH2CH2(CF2) y F)) and their thioether analogues (x:2/y:2 S-diPAPS, F(CF2) x CH2CH2SCH2-C[CH2O)2P(O)(O)−]-CH2SCH2CH2(CF2) y F), which are used for industrial applications, such as oil- and water-repellent coatings on paper and board. DiPAPS have been found in human blood and are metabolised to the persistent perfluoroalkyl carboxylic acids (PFCA) in rats. A microwave popcorn bag extract was analysed by ultrahigh-pressure liquid chromatography coupled to a negative electrospray ionisation-quadrupole time-of-flight MS. The extract contained S-diPAPS, diPAPS and trialkylated (triPAPS) impurities. TriPAPS were also present in industrial and synthetic diPAPS standards, and were verified with an 8:2/8:2/8:2 triPAPS standard. The eight elemental compositions (m/z’s) of diPAPS in the extract represent 19 precursor ion structures, and the six S-diPAPS m/z’s represent at least 13 structures. The diPAPS had [M-H]− precursor ions of m/z 789, 889,…1,489 and the S-diPAPS of m/z 921, 1,021,…1,421, corresponding to fluorinated chains from C6–18. Each m/z appeared as one to three chromatographic peaks of structural isomers, where, e.g. m/z 1,189 was present as 10:2/10:2, 8:2/12:2 and 6:2/14:2 diPAPS. The isomers formed different products ions, thus only half of the m/z 1,189 diPAPS concentration was measured with one precursor ion > product ion transition. In general, knowledge about structural isomers of poly-alkylated PFAS is needed for the estimation of types and amounts of perfluorinated degradation products, such as PFCA from diPAPS.

A multi-analyte method without any pre-treatment steps using reversed-phase liquid chromatography–electrospray ionization-tandem mass spectrometry (LC–ESI-MS/MS) was developed and applied for the determination of 20 primary aromatic amines (PAA) associated with polyurethane (PUR) products or azo-colours. The method was validated in-house for water and 3% acetic acid food simulants using spiked migrates from plastic laminates. Detection limits ranged from 0.27 to 3 μg amine/L food simulants, and RSD values of within-laboratory reproducibility at the 2 μg PAA/L level ranged from 3.9 to 19%. PAA migration from plastic laminates and black nylon cooking utensils were determined with the method, and high levels of 4,4′-methylenedianiline and aniline were found in migrates from about half of the tested cooking utensils. The method fulfils present legislative demands in the EU for screening and verification of PAA migration from food contact materials.

A few years ago, it became accepted that the plastics industry could use migration modelling for compliance testing. When a calculation confirms that the migration of a compound from a plastic material or article is below the specific migration limit, this is considered sufficient documentation for compliance with legislation. In the case of non-compliance, the result needs to be verified experimentally. The European Commission recommends that the enforcement authorities use migration modelling as well to avoid long and expensive analysis. The aim of the present work was to investigate the practical possibilities of implementing migration-modelling software as a tool in official food control and possibly in improving the own-check programmes of Danish plastic-converting plants. Food inspectors from nine regional food control centres initially attended a training course in the use of a commercial modelling software package and were supported further during the project period of about 1 year. They visited 40 producers of final plastic materials and articles, but mainly due to a lack of elementary knowledge of the detailed composition of the materials only 16 full migration calculations were performed. A major reason was a lack of information from those in the raw material supply chain who considered their products protected by commercial confidentiality. In general, the food inspectors were in favour of using migration modelling for future control visits.

Fluorinated polymers are used in a variety of applications providing benefits to the society, but at the same time also causing risks of irreversible pollution and impacts on the environment and human health in different stages of the lifecycle. The main aim of the study was to provide information on impacts of fluorinated polymers along their lifecycles in a low carbon, circular and toxic-free economy, which could be relevant to consider in future assessments. An important part of the work was also to discuss options for risk governance and to identify knowledge gaps. The work was based on a literature survey of recently published reports and selected peer-reviewed articles on the topic. The report presents the results of the work carried out by the ETC/WMGE and ETC/CME.

Danmarks hidtil største forskningsprojekt om kemikaliers cocktaileffekter, Cocktail, har tilvejebragt nødvendig viden om cocktaileffekter af kemiske stoffer i fødevarer. I projektet er en pålidelig metode eksempelvis skabt til at beregne cocktaileffekter af kemikalier i fødevarer, ligesom en ny strategi til gruppering af kemikalier og vurdering af fødevareemballage og forureninger i fødevarer er udviklet. Den nye viden er afgørende i en national kontekst, men spiller også en vigtig rolle i videreudviklingen af EU’s kemikaliestrategi.