A mini-review of the physical recycling methods for plastic parts in end-of-life vehicles.

Although the use of plastic components is increasing in the automotive industry, yet the recovery rates of these materials in end-of-life vehicle (ELV) is lower compared to metals. One of the main problems of ELV plastic waste is poor separation and sorting. Large car plastic parts consist of fibre-reinforced plastics, whereas other components end up in the automotive shredder residue (ASR), featuring a very heterogeneous mix of light materials that contains mostly non-metallic materials such as textiles, plastics, cartridges and wood. Generally, ASR was disposed in landfill or diverted to thermal treatments, such as pyrolysis or gasification, for energy recovery. Currently, the recovery of raw materials from various waste streams plays a key role in new European strategy for plastics in a circular economy. The approach of physical recycling methods described in this mini-review helps to maintain the value of polymer materials in the value chain allowing the reuse in the original or similar application.

Review on the photonic techniques suitable for automatic monitoring of the composition of multi-materials wastes in view of their posterior recycling.

In the increasingly pressing context of improving recycling, optical technologies present a broad potential to support the adequate sorting of plastics. Nevertheless, the commercially available solutions (for example, employing near-infrared spectroscopy) generally focus on identifying mono-materials of a few selected types which currently have a market-interest as secondary materials. Current progress in photonic sciences together with advanced data analysis, such as artificial intelligence, enable bridging practical challenges previously not feasible, for example in terms of classifying more complex materials. In the present paper, the different techniques are initially reviewed based on their main characteristics. Then, based on academic literature, their suitability for monitoring the composition of multi-materials, such as different types of multi-layered packaging and fibre-reinforced polymer composites as well as black plastics used in the motor vehicle industry, is discussed. Finally, some commercial systems with applications in those sectors are also presented. This review mainly focuses on the materials identification step (taking place after waste collection and before sorting and reprocessing) but in outlook, further insights on sorting are given as well as future prospects which can contribute to increasing the circularity of the plastic composites' value chains.

Methods of Responsibly Managing End-of-Life Foams and Plastics Containing Flame Retardants: Part II.

This is Part II of a review covering the wide range of issues associated with all aspects of the use and responsible disposal of foam and plastic wastes containing toxic or potentially toxic flame retardants. We identify basic and applied research needs in the areas of responsible collection, pretreatment, processing, and management of these wastes. In Part II, we explore alternative technologies for the management of halogenated flame retardant (HFR) containing wastes, including chemical, mechanical, and thermal processes for recycling, treatment, and disposal.

Methods of Responsibly Managing End-of-Life Foams and Plastics Containing Flame Retardants: Part I.

Flame retardants (FRs) are added to foams and plastics to comply with flammability standards and test requirements in products for household and industrial uses. When these regulations were implemented, potential health and environmental impacts of FR use were not fully recognized or understood. Extensive research in the past decades reveal that exposure to halogenated FRs, such as those used widely in furniture foam, is associated with and/or causally related to numerous health effects in animals and humans. While many of the toxic FRs have been eliminated and replaced by other FRs, existing products containing toxic or potentially toxic chemical FRs will remain in use for decades, and new products containing these and similar chemicals will permeate the environment. When such products reach the end of their useful life, proper disposal methods are needed to avoid health and ecological risks. To minimize continued human and environmental exposures to hazardous FR chemicals from discarded products, waste management technologies and processes must be improved. This review discusses a wide range of issues associated with all aspects of the use and responsible disposal of wastes containing FRs, and identifies basic and applied research needs in the areas of responsible collection, pretreatment, processing, and management of these wastes.

Characterization of odorous contaminants in post-consumer plastic packaging waste using multidimensional gas chromatographic separation coupled with olfactometric resolution.

The increasing world population with their growing consumption of goods escalates the issue of sustainability concepts with increasing demands in recycling technologies. Recovery of post-consumer packaging waste is a major topic in this respect. However, contamination with odorous constituents currently curtails the production of recycling products that meet the high expectations of both consumers and industry. To guarantee odor-free recyclates, the main prerequisite is to characterize the molecular composition of the causative odorants in post-consumer plastic packaging waste. However, targeted characterization of odorous trace contaminants among an abundance of volatiles is a major challenge and requires specialized and high-resolution analytical approaches. For this aim, post-consumer packaging waste was characterized by sensory analysis and two-dimensional high resolution gas chromatography coupled with mass spectrometry and olfactometry. The 33 identified odorants represent various structural classes as well as a great diversity of smell impressions with some of the compounds being identified in plastics for the first time. Substances unraveled within this study provide insights into sources of odorous contamination that will require specific attention in the future in terms of screening and prevention in recycling products.

Characterisation and materials flow management for waste electrical and electronic equipment plastics from German dismantling centres.

Waste electrical and electronic equipment is a complex waste stream and treatment options that work for one waste category or product may not be appropriate for others. A comprehensive case study has been performed for plastic-rich fractions that are treated in German dismantling centres. Plastics from TVs, monitors and printers and small household appliances have been characterised extensively. Based on the characterisation results, state-of-the-art treatment technologies have been combined to design an optimised recycling and upgrade process for each input fraction. High-impact polystyrene from TV casings that complies with the European directive on the restriction of hazardous substances (RoHS) was produced by applying continuous density separation with yields of about 60%. Valuable acrylonitrile butadiene styrene/polycarbonate can be extracted from monitor and printer casings by near-infrared-based sorting. Polyolefins and/or a halogen-free fraction of mixed styrenics can be sorted out by density separation from monitors and printers and small household appliances. Emerging separation technologies are discussed to improve recycling results.

Rapid identification of polystyrene foam wastes containing hexabromocyclododecane or its alternative polymeric brominated flame retardant by X-ray fluorescence spectroscopy.

The brominated flame retardant hexabromocyclododecane (HBCDD) was added to Annex A of the list of persistent organic pollutants (POPs) of the Stockholm Convention. Thus, production and use of HBCDD will be banned, and the recycling of HBCDD-containing foam waste will be restricted. In reaction a special polymeric brominated flame retardant (PolyFR) was developed to replace HBCDD in expanded and extruded polystyrene foams for building and construction applications. A decision has to be made at some future time whether expanded and extruded polystyrene foam waste is to be subjected to incineration (with HBCDD) or to recycling (without HBCDD). Therefore, an appropriate and rapid field method is required to distinguish between foams containing HBCDD and foams free from HBCDD. Here we present a screening method for identifying HBCDD containing expanded and extruded polystyrene foams. The test principle is based on the fact that PolyFR (a brominated polymeric macromolecule) is not extractable whereas HBCDD (a low molecular weight substance) is extractable. Following rapid extraction of HBCDD the brominated flame retardant is identified and quantified via bromine analysis using a handheld X-ray fluorescence instrument. The method was applied successfully to 27 expanded and extruded polystyrene foam samples (foams and extruded polystyrene foam raw materials), which were provided without any information about the applied flame retardant. The presence of HBCDD was confirmed for all HBCDD-positive samples in the test. A robustness test revealed a high degree of correctness and a high repeatability for the test system: samples containing HBCDD and HBCDD-free samples were identified correctly with relative standard deviations of quantitative results below 14%. Moreover, X-ray fluorescence spectroscopy test results agree well with HBCDD determinations performed in a laboratory with a gas chromatograph coupled to a flame ionisation detector.

Application of chemometric tools in the QSAR development of VOC removal in plastic waste recycling.

Deodorization and, in a broader sense, the removal of volatile organic compounds (VOCs) from plastic waste have become increasingly important in the field of plastic recycling, and various new decontamination techniques have been developed. Both in research and industrial practice, the selection of VOCs has been random or unsubstantiated, making it difficult to compare studies and assess decontamination processes objectively. Thus, this study proposes the use of Statistical Molecular Design (SMD) and Quantitative Structure - Activity Relationship (QSAR) as chemometric tools for the selection of representative VOCs, based on physicochemical properties. Various algorithms are used for SMD; hence, several frequently used D-Optimal Onion Design (DOOD) and Space-Filling (SF) algorithms were assessed. Hereby, it was validated that DOOD, by dividing the layers based on the equal-distance approach without so-called 'Adjacent Layer Bias', results in the most representative selection of VOCs. QSAR models that describe VOC removal by water-based washing of plastic waste as a function of molecular weight, polarizability, dipole moment and Hansen Solubility Parameters Distance were successfully established. An adjusted-R2 value of 0.77 ± 0.09 and a mean absolute error of 24.5 ± 4 % was obtained. Consequently, by measuring a representative selection of VOCs compiled using SMD, the removal of other unanalyzed VOCs was predicted on the basis of the QSAR. Another advantage of the proposed chemometric selection procedure is its flexibility. SMD allows to extend or modify the considered dataset according to the available analytical techniques, and to adjust the considered physicochemical properties according to the intended process.

Tracing the origin of VOCs in post-consumer plastic film bales.

Volatile organic compounds (VOCs), including odors, are still a key issue in plastic recycling, especially in case of flexible packaging. Therefore, this study presents a detailed qualitative and quantitative VOC analysis by applying gas chromatography on 17 categories of flexible plastic packaging that are manually sorted from bales of post-consumer flexible packaging (e.g., beverage shrink wrap, packaging for frozen food, packaging for dairy products, etc.). A total of 203 VOCs are identified on packaging used for food products, while only 142 VOCs are identified on packaging used for non-food products. Especially, more oxygenated compounds (e.g., fatty acids, esters, aldehydes) are identified on food packaging. With more than 65 VOCs, the highest number of VOCs is identified on packaging used for chilled convenience food and ready meals. The total concentration of 21 selected VOCs was also higher on packaging used for food products (totally 9187 µg/kg plastic) compared to packaging used for non-food packaging (totally 3741 µg/kg plastic). Hence, advanced sorting of household plastic packaging waste, e.g., via tracer-based sorting or watermarking, could open the door towards sorting on other properties than polymer type, such as mono- versus multi-material packaging, food versus non-food packaging or even their VOC profile, which might allow for tailoring washing procedures. Potential scenarios showed that sorting the categories with the lowest VOC load, which corresponds to half of the total mass of flexible packaging, could result in a VOC reduction of 56%. By producing less contaminated plastic film fractions and by tailoring washing processes recycled plastics can ultimately be used in a broader market segment.

Recycling process for carbon fiber reinforced plastics with polyamide 6, polyurethane and epoxy matrix by gentle solvent treatment.

Due to the complex composition of carbon fiber reinforced plastics (CFRPs), a complete and useful recovery of such composite material is a real challenge. This paper presents studies on potential solvent-based recycling processes for three CFRP samples comprising polyamide 6 (PA6), polyurethane resin (PUR) and epoxy resin (EP) matrix. Different proprietary CreaSolv® Formulations were applied in laboratory scale and under thermodynamically subcritical conditions in order to dissolve the polymeric matrix and separate the inert carbon fibers. By variation of decisive process parameters, the influence of the temperature-time-load during solvent treatment and solvent recovery was observed carefully. A complete removal of the polymer matrix of all samples was achieved by means of multi-stage solvent extraction without reducing both the length and tensile strength of the recovered carbon fibers. The recovered PA6 matrix polymer revealed no significant decline of its initial average molecular weight. For the dissolved and extracted resin matrices, feedstock recycling was identified as suitable reprocessing. All of the solvent formulations tested were recycled successfully, keeping the initial dissolution properties and, thus, being applicable in a closed loop process design.

Intake of phthalates and di(2-ethylhexyl)adipate: results of the Integrated Exposure Assessment Survey based on duplicate diet samples and biomonitoring data.

Phthalates are ubiquitous environmental chemicals with potential detrimental health effects. The purpose of our study was to quantify dietary intake of phthalates and of DEHA (Di-ethylhexyl adipate) using duplicate diet samples and to compare these data with the calculated data based on urinary levels of primary and secondary phthalate metabolites. 27 female and 23 male healthy subjects aged 14-60 years collected daily duplicate diet samples over 7 consecutive days. Overall, 11 phthalates were measured in the duplicates by GC/MS and LC/MS methods. Urinary levels of primary and secondary phthalate metabolites are also available. The median (95th percentile) daily intake via food was 2.4 (4.0) microg/kg b.w. (Di-2-ethylhexyl phthalate, DEHP), 0.3 (1.4) microg/kg b.w. (Di-n-butyl phthalate, DnBP), 0.6 (2.1) microg/kg b.w. (Di-isobutyl phthalate, DiBP) and 0.7 (2.2) microg/kg b.w. for DEHA. MEPH (Mono-2-ethylhexyl phthalate) was detectable only in minor concentrations in the samples, thus conversion of DEHP to MEHP and dietary intake of MEHP were negligible. When comparing back-calculated intake data of the DEHP metabolites with dietary DEHP intake from the day before significant correlations were observed for most of the metabolites. No correlation was found for DnBP and only a weak but significant correlation for DiBP. The median and 95th percentile daily dietary intake of all target analytes did not exceed the recommended tolerable daily intake. Our data indicated that food was the predominant intake source of DEHP, whilst other sources considerably contributed to the daily intake of DnBP and DiBP in an adult population.

Characterisation of polymer fractions from waste electrical and electronic equipment (WEEE) and implications for waste management.

There is an increasing interest in the end-of-life management of polymers present in waste electrical and electronic equipment (WEEE). This is mainly due to high recycling and recovery quotas set by the European WEEE directive, which can only be fulfilled by including the plastic fraction in recycling and recovery approaches. Previous studies identified a high material diversity and various contaminants in WEEE plastics, including heavy metals, polybrominated biphenyls (PBB), diphenyl ethers (PBDE), as well as polybrominated dibenzodioxins and dibenzofurans (PBDD/F). These substances are regulated by European directives that limit their levels in marketable products. Consequently, both material diversity and contaminants are strong arguments against material recycling and point to hazardous waste treatment. However, recent developments in the production of flame retardants and electrical and electronic goods aimed to reduce contaminants and material diversity. Thus, the present study summarises updated contaminant levels of plastic fractions of European WEEE, as well as data on materials in waste housing polymers. Material characterisation revealed housing fractions to be interesting sources for polymer recycling, which however has to implement potent material separation and/or bromine elimination techniques. With respect to contaminants, our data indicate an effective phase-out of PBB, but still high levels of PBDE and PBDD/F are found. Sources and implications for the material recycling and thermal recovery approaches are discussed in detail.

Post-combustion syntheses of PCDD/F and PBDD/F from halogen-rich fuel is suppressed by a pebble heater technology.

GOAL, SCOPE AND BACKGROUND: Changes in German and European legislation shifted processing of polymer-rich shredding residues (SR) from landfill to thermal treatment. However, when waste of electric and electronic equipment (WEEE) is the source of SR, thermal treatment is complicated by halogens as well as the presence of polybrominated dioxins and furans (PBDD/F) and brominated flame retardants (BFR). Hence, WEEE requires high temperature incineration with sufficient residence times. Post-combustion synthesis of polyhalogenated dioxins and furans (PXDD/F) is dominant in the temperature range between 250-450 degrees C. Thus, a very rapid gas cooling from 450 degrees to 250 degrees C is important for proper raw gas treatment. The pebble heater technology developed by ATZ Entwicklungszentrum (Sulzbach-Rosenberg, Germany) might serve as an alternative to the state-of-the-art quench cooling. It is based on the application of a pebble bed of natural bulk material, which the exhaust gases flows through radially. It provides an excellent heat transfer and a temperature gradient in the range of 1,500-2,000 K/m. The paper presents data of a pilot application of the pebble heater technology for the treatment of raw gas derived from the incineration of polymeric materials from WEEE. METHODS: A liquid fuel was chosen in order to minimise technical modifications of the plant. It was analysed for halogens by x-ray fluorescence, for brominated flame retardants by HPLC-UV/MS and for PXDD/F by GC-HRMS. Combustion gases were rapidly cooled down to temperatures below 200 degrees C and emissions of PBDD/F and PCDD/ F were estimated without further off-gas treatment. PBDD/F emissions were computed as PCDD/F toxicity equivalents applying two different calculation approaches. RESULTS AND DISCUSSION: PCDD/F emissions accounted for 0.04 ng I-TEQ/Nm3 and are in compliance with European emission limits. Calculated PBDD/F toxicity equivalents exceeded the emission limit of 0.1 ng I-TEQ/Nm3 by factors of 75 and 208 depending on the calculation approach. A mass balance of PBDD/F and PCDD/F congeners revealed an efficient elimination of more than 95% in most cases. Lower reduction rates (76% for 2,3,7,8-TeBDF and 82% for 1,2,3,7,8-PeBDF) were attributed to incomplete combustion. An intended recovery of halogens by one-stage scrubbing downstream of the pebble heater was ineffective, recovering 28% of the applied chlorine and 9% of the bromine, only. CONCLUSIONS: Our pilot incineration test indicates that the pebble heater technology can effectively suppress a post-combustion synthesis of PCDD/F and PBDD/F, resulting in low PCDD/F emission levels without further off-gas treatment. The presented data state that WEEE is sensible to incomplete combustion, which will lead to increased PBDD/F emissions without increasing PCDD/F emission limits. This finding is especially relevant for small and low-technical incineration appliances, which have been reported to treat WEEE in developing countries and are considered to serve as a significant source of PXDD/F these days. RECOMMENDATIONS AND PERSPECTIVES: Monitoring of PCDD/F emissions only might considerably underestimate the total emission of dioxins and dioxin-like compounds. It is therefore an ineffective means for assessing resulting health risks, at least for those waste treatment plants which are considered to handle the increasing amounts of PBDD/ F-containing polymers from WEEE in future. Consequently, it is recommended to initiate a screening programme for PXDD/F emissions in large scale incineration facilities which are capable of treating WEEE shredder residues.

Analysis of flame retardant additives in polymer fractions of waste of electric and electronic equipment (WEEE) by means of HPLC-UV/MS and GPC-HPLC-UV.

An HPLC-UV/MS method has been developed to identify and quantify flame retardants in post-consumer plastics from waste of electric and electronic equipment (WEEE). Atmospheric pressure chemical ionisation spectra of 15 brominated and phosphate-based flame retardants were recorded and interpreted. The method was applied to detect flame retardant additives in polymer extracts obtained from pressurised liquid extraction of solid polymers. In addition, a screening method was developed for soluble styrene polymers to isolate a flame retardant fraction through the application of gel permeation chromatography (GPC). This fraction was transferred to an online-coupled HPLC column and detected by UV spectroscopy, which allowed a reliable qualitative and quantitative analysis of brominated flame retardants in the polymer solutions.

Perfluoroalkyl and polyfluoroalkyl substances in consumer products.

Perfluoroalkyl and polyfluoroalkyl substances (PFAS) are used in a wide range of products of all day life. Due to their toxicological potential, an emerging focus is directed towards their exposure to humans. This study investigated the PFAS load of consumer products in a broad perspective. Perfluoroalkyl sulfonic acids (C4, C6-C8, C10-PFSA), carboxylic acids (C4-C14-PFCA) and fluorotelomer alcohols (4:2, 6:2; 8:2 and 10:2 FTOH) were analysed in 115 random samples of consumer products including textiles (outdoor materials), carpets, cleaning and impregnating agents, leather samples, baking and sandwich papers, paper baking forms and ski waxes. PFCA and PFSA were analysed by HPLC-MS/MS, whereas FTOH were detected by GC/CI-MS. Consumer products such as cleaning agents or some baking and sandwich papers show low or negligible PFSA and PFCA contents. On the other hand, high PFAS levels were identified in ski waxes (up to about 2000 µg/kg PFOA), leather samples (up to about 200 µg/kg PFBA and 120 µg/kg PFBS), outdoor textiles (up to 19 µg/m(2) PFOA) and some other baking papers (up to 15 µg/m(2) PFOA). Moreover, some test samples like carpet and leather samples and outdoor materials exceeded the EU regulatory threshold value for PFOS (1 µg/m(2)). A diverse mixture of PFASs can be found in consumer products for all fields of daily use in varying concentrations. This study proves the importance of screening and monitoring of consumer products for PFAS loads and the necessity for an action to regulate the use of PFASs, especially PFOA, in consumer products.

Polybrominated diphenyl ethers listed as Stockholm Convention POPs, other brominated flame retardants and heavy metals in e-waste polymers in Nigeria.

Polybrominated diphenyl ethers (PBDEs) were the first brominated persistent organic pollutants (POPs) listed in the Stockholm Convention. Parties to the convention are currently establishing inventories for developing action plans for the environmentally sound management of PBDE-containing materials. The major use of commercial octabromodiphenyl ether (c-OctaBDE) has been in casings from cathode ray tube (CRT) TVs and computer monitors. Large quantities of used e-waste and electronic equipment have been exported to developing countries with Nigeria being a major importer in Africa. The casings from 382 TVs and computers imported from major world regions to Nigeria were sampled in backyards and waste dumps. The samples were screened with X-ray flourescence (XRF) for bromine and analysed by gas chromatography/ electron capture detection (GC/ECD) for brominated flame retardants (BFRs). A high proportion of the CRT casings (61 %) contained more than 10,000 ppm bromine from BFRs. Decabromodiphenyl ether (DecaBDE) was the major flame retardant used in TV sets and tetrabromobisphenol A (TBBPA) for computer CRTs.The screening suggests that average PBDE levels (of c-OctaBDE + DecaBDE) in Nigerian-stockpiled CRT casings were 1.1 % for TV and 0.13 % for PC CRTs. These are above the Restriction of Hazardous Substances (RoHS) limit and should be separated for RoHS compliant recycling. The Nigerian e-waste inventory of 237,000 t of CRT plastic would therefore contain approx. 594 t c-OctaBDE and 1,880 t of DecaBDE. In Nigeria, as for most developing countries, there is currently no adequate e-waste management, plastic separation or destruction capacity. The data highlight the urgent need to develop environmentally sound management for this large material flow.

Emission of perfluoroalkyl carboxylic acids (PFCA) from heated surfaces made of polytetrafluoroethylene (PTFE) applied in food contact materials and consumer products.

Polytetrafluoroethylene (PTFE) has been widely discussed as a source of perfluorooctanoic acid (PFOA), which has been used in the production of fluoropolymers. PTFE may also contain unintended perfluoroalkyl carboxylic acids (PFCAs) caused by thermolysis of PTFE, which has been observed at temperatures above 300°C. Common PTFE coated food contact materials and consumer goods are operated at temperatures above 200°C. However, knowledge on possible emissions of PFCAs is limited. Therefore, it was the aim of this study to investigate and evaluate the emission of PFCAs from PTFE coated products with both, normal use and overheating scenarios. Four pans, claimed to be PFOA free, and nine consumer products were investigated. At normal use conditions (<230°C), emissions from PTFE surfaces were trapped for 1h. Overheating scenarios (>260°C) recorded emissions during a 30min heating of empty pans on a stove. Emissions were analyzed by LC-ESI-MS. Results indicate the emission of PFCAs, whereas no perfluorinated sulfonic acids were traced. At normal use conditions total emissions of PFCAs accounted for 4.75ng per hour. Overheated pans, however, released far higher amounts with up to 12190ng PFCAs per hour at 370°C. Dominating contributors where PFBA and PFOA at normal use and PFBA and PFPeA during overheating. Temperature seems to be the main factor controlling the emission of PFCAs. A worst case estimation of human exposure revealed that emissions of PFCAs from heated PTFE surfaces would be far below the TDI of 1500ng PFOA per kg body weight.

Presence and sources of anthropogenic perfluoroalkyl acids in high-consumption tap-water based beverages.

This study investigates the presence and sources of perfluorinated alkyl acids (PFAAs) in tap water and corresponding tap-water based beverages such as coffee and cola collected in the city of Amsterdam, The Netherlands. Exposure pathways studies have shown that low concentrations of PFAA in tap water already may pose a high contribution to daily human exposure. Tap water samples (n=4) had higher concentrations of PFAAs than the corresponding post-mixed cola (n=4). The lower PFAA levels in the cola were attributed to the pre-treatment of tap water in the mixing machines and dilution with cola syrup. In coffee samples from a coffee machine perfluorooctanoic acid (PFOA) at 4 ng L(-1) was the dominating analyte (n=12). The concentrations of PFHpA, PFOA and non branched PFOS were found to be significantly higher in manually (self) brewed coffee than in the corresponding tap water (n=4). The contribution from short-chain PFAA analogs could not be quantified due to low recoveries. Leaching experiments at different temperatures were performed with fluoropolymers-containing tubes to investigate the potential of leaching from tubes used in beverage preparation (n=16). Fluoropolymer tubes showed leaching of PFAAs at high (80°C) temperature but its relevance for contamination of beverages in practice is small. The specific contribution from perfluoropolymer tubing inside the beverage preparation machines could not be assessed since no information was available from the manufacturers. The present study shows that although different beverage preparation processes possibly affect the concentrations of PFAAs encountered in the final consumed product, the water used for preparation remains the most important source of PFAAs. This in turn has implications for areas where drinking water is contaminated. Tap-water based beverages will possibly be an additional source of human exposure to PFAAs and need to be considered in exposure modeling.

Impact of industrial production and packaging processes on the concentration of per- and polyfluorinated compounds in milk and dairy products.

Perfluorinated alkylated compounds (PFAA) have been identified in milk and dairy products at sub ppb levels, however, knowledge on the impact of industrial milk processing on PFAA levels is rare. This study examined industrial milk processing first by analytical screening of products of a cooperating dairy, which varied in kind and number of processing steps. Second, amounts of PFAA in raw milk, cream, skim milk, butter milk, and butter were mass balanced in industrial production. For migration testing, unpacked butter was sampled from the production and exposed to original packaging at 5 °C for 45 days. Screening identified dairy products with high fat contents to bear higher loads of PFAA. The mass balance of butter production revealed a significant impact of phase separation processes on concentrations in fat rich and aqueous phases. Storage of butter in packaging coated with a fluorinated polymer increased butter levels of both PFAA and FTOH.

Detection of fluorotelomer alcohols in indoor environments and their relevance for human exposure.

Fluorotelomer alcohols (FTOH) are important precursors of perfluorinated carboxylic acids (PFCA). These neutral and volatile compounds are frequently found in indoor air and may contribute to the overall human exposure to per- and polyfluorinated alkyl substances (PFAS). In this study air samples of ten workplace environments and a car interior were analysed. In addition, extracts and emissions from selected outdoor textiles were analysed in order to establish their potential contribution to the indoor levels of the above-mentioned compounds. Concentrations of FTOHs measured in air ranged from 0.15 to 46.8, 0.25 to 286, and 0.11 to 57.5ng/m(3) for 6:2, 8:2 and 10:2 FTOHs, respectively. The highest concentrations in air were identified in shops selling outdoor clothing, indicating outdoor textiles to be a relevant source of FTOH in indoor workplace environments. Total amounts of FTOH in materials of outdoor textiles accounted for <0.8-7.6, 12.1-180.9 and 4.65-105.7µg/dm(2) for 6:2, 8:2 and 10:2 FTOHs, respectively. Emission from selected textiles revealed emission rates of up to 494ng/h. The measured data show that a) FTOHs are present in indoor textiles (e.g. carpets), b) they are released at ambient temperatures and c) indoor air of shops selling outdoor textiles contains the highest levels of FTOH. Exposure of humans to perfluorooctanoic acid (PFOA) through absorption of FTOH and subsequent degradation is discussed on the basis of indoor air levels. Calculation of indoor air-related exposure using the median of the measured air levels revealed that exposure is on the same order of magnitude as the recently reported dietary intakes for a background-exposed population. On the basis of the 95th percentile, indoor air exposure to PFOA was estimated to exceed dietary exposure. However, indoor air-related intakes of FTOH are far below the tolerable daily intake (TDI) of PFOA, indicating that there is no risk to health, even when assuming an unrealistic complete degradation of FTOH into PFOA.