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We investigated associations between serum perfluoroalkyl acid (PFAA) concentrations in children aged 4, 8, and 12 years (sampled in 2008-2015; n = 57, 55, and 119, respectively) and exposure via placental transfer, breastfeeding, and ingestion of PFAA-contaminated drinking water. Sampling took place in Uppsala County, Sweden, where the drinking water has been historically contaminated with perfluorobutanesulfonate (PFBS), perfluorohexanesulfonate (PFHxS), perfluorooctanesulfonate (PFOS), perfluoroheptanoate (PFHpA), and perfluorooctanoate (PFOA). PFOS showed the highest median concentrations in serum (3.8-5.3 ng g(-1) serum), followed by PFHxS (1.6-5.0 ng g(-1) serum), PFOA (2.0-2.5 ng g(-1) serum), and perfluorononanoate (PFNA) (0.59-0.69 ng g(-1) serum) in children. Including all children, serum PFOA, PFHxS, and PFOS concentrations (adjusted mean), respectively, per unit (ng g(-1) serum) of increase in the maternal serum level (at delivery), the associations being strongest for 4 year-old children. PFHxS and PFOS significantly increased 3.9 and 3.8%, respectively, per month of nursing, with the highest increase for 4 year-olds. PFOA, PFBS, PFHxS, and PFOS increased 1.2, 207, 7.4, and 0.93%, respectively, per month of cumulative drinking water exposure. Early life exposure to PFOA, PFHxS, and PFOS is an important determinant of serum concentrations in children, with the strongest influence on younger ages. Drinking water with low to moderate PFBS, PFHxS, PFOS, and PFOA contamination is an important source of exposure for children with background exposure from other sources.

We investigated associations between serum perfluoroalkyl acid (PFAA) concentrations in children aged 4, 8, and 12 years (sampled in 2008–2015; n = 57, 55, and 119, respectively) and exposure via placental transfer, breastfeeding, and ingestion of PFAA-contaminated drinking water. Sampling took place in Uppsala County, Sweden, where the drinking water has been historically contaminated with perfluorobutanesulfonate (PFBS), perfluorohexanesulfonate (PFHxS), perfluorooctanesulfonate (PFOS), perfluoroheptanoate (PFHpA), and perfluorooctanoate (PFOA). PFOS showed the highest median concentrations in serum (3.8–5.3 ng g–1 serum), followed by PFHxS (1.6–5.0 ng g–1 serum), PFOA (2.0–2.5 ng g–1 serum), and perfluorononanoate (PFNA) (0.59–0.69 ng g–1 serum) in children. Including all children, serum PFOA, PFHxS, and PFOS concentrations in children increased 10, 10, and 1.3% (adjusted mean), respectively, per unit (ng g–1 serum) of increase in the maternal serum level (at delivery), the associations being strongest for 4 year-old children. PFHxS and PFOS significantly increased 3.9 and 3.8%, respectively, per month of nursing, with the highest increase for 4 year-olds. PFOA, PFBS, PFHxS, and PFOS increased 1.2, 207, 7.4, and 0.93%, respectively, per month of cumulative drinking water exposure. Early life exposure to PFOA, PFHxS, and PFOS is an important determinant of serum concentrations in children, with the strongest influence on younger ages. Drinking water with low to moderate PFBS, PFHxS, PFOS, and PFOA contamination is an important source of exposure for children with background exposure from other sources.

Perfluoroalkyl acids (PFAAs) are persistent, ubiquitous environmental contaminants and their long-chain representatives are bioaccumulative. The phase-out of these compounds (e.g. PFOA and PFOS) shifted the production to alternatives. However, little is known about the bioaccumulative behaviour of the alternatives, which are still highly fluorinated. PFAAs are predominantly detected in blood, where they bind to the transport protein serum albumin. This sorption can be described by the albumin/water partition coefficient. It is unclear whether the partition coefficients of the alternatives are lower than or in the same range as those of classical PFAAs. We determined albumin/water partition coefficients for seven perfluoroalkyl carboxylates, three perfluoroalkane sulfonates and four alternatives by dialysis experiments in a physiologically representative system. Quantification was done by LC-MS/MS and a mass balance approach. Logarithmic albumin/water partition coefficients for PFAAs range from 2.8 to 4.8 [Lwater kgalbumin−1] and increase with increasing chain length. Perfluorinated sulfonates sorb more strongly than their carboxylate counterparts. The albumin/water partition coefficients for the alternatives (HFPO-DA, DONA, 9Cl-PF3ONS and PFECHS) are in the same range as for classical PFAAs. Structural modifications such as the introduction of ether groups into the chain do not reduce sorption to albumin, whereas the chlorine atom in 9Cl-PF3ONS seems to even increase the sorption to albumin. We further investigated whether the sorption strength could be affected in the presence of medium- or long-chain fatty acids. Binding competition between medium-chain fatty acids and PFAAs appeared to be possible. However, the presence of physiologically more relevant long-chain fatty acids should not alter the albumin/water partition coefficients of PFAAs.

We investigated if maternal body burdens of perfluoroalkyl acids (PFAAs) at the time of delivery are associated with birth outcome and if early life exposure (in utero/nursing) is associated with early childhood growth and weight gain. Maternal PFAA body burdens were estimated by analysis of serum samples from mothers living in Uppsala County, Sweden (POPUP), sampled three weeks after delivery between 1996 and 2011. Data on child length and weight were collected from medical records and converted into standard deviation scores (SDS). Multiple linear regression models with appropriate covariates were used to analyze associations between maternal PFAA levels and birth outcomes (n=381). After birth Generalized Least Squares models were used to analyze associations between maternal PFAA and child growth (n=200). Inverse associations were found between maternal levels of perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), and perfluoroundecanoic acid (PFUnDA), and birth weight SDS with a change of -0.10 to -0.18 weight SDS for an inter-quartile range (IQR) increase in ng/g PFAA. After birth, weight and length SDS were not significantly associated with maternal PFAA. However, BMI SDS was significantly associated with PFOA, PFNA, and PFHxS at 3 and 4years of age, and with PFOS at 4 and 5years of age. If causal, these associations suggest that PFAA affects fetal and childhood body development in different directions.

Little is known about factors influencing infant perfluorinated alkyl acid (PFAA) concentrations. Associations between serum PFAA concentrations in 2-4-month-old infants (n = 101) and determinants were investigated by multiple linear regression and general linear model analysis. In exclusively breastfed infants, maternal serum PFAA concentrations 3 weeks after delivery explained 13% (perfluoroundecanoic acid, PFUnDA) to 73% (perfluorohexanesulfonate, PFHxS) of infant PFAA concentration variation. Median infant/maternal ratios decreased with increasing PFAA carbon chain length from 2.8 for perfluoroheptanoic acid and perfluorooctanoic acid (PFOA) to 0.53 for PFUnDA and from 1.2 to 0.69 for PFHxS and perfluorooctanesulfonate (PFOS). Infant PFOA, perfluorononanoic acid (PFNA), and PFOS levels increased 0.7-1.2% per day of gestational age. Bottle-fed infants had mean concentrations of PFAAs 2 times lower than and a mean percentage of branched (%br) PFOS isomers 1.3 times higher than those of exclusively breast-fed infants. PFOA, PFNA, and PFHxS levels increased 8-11% per week of exclusive breast-feeding. Infants living in an area receiving PFAA-contaminated drinking water had 3-fold higher mean perfluorobutanesulfonate (PFBS) and PFHxS concentrations and higher mean %br PFHxS. Prenatal PFAA exposure and postnatal PFAA exposure significantly contribute to infant PFAA serum concentrations, depending on PFAA carbon chain length. Moderately PFBS- and PFHxS-contaminated drinking water is an important indirect exposure source.

Studies suggest negative health impacts from early life exposure to per- and polyfluoroalkyl substances (PFASs). However, information on longitudinal exposure to PFASs during childhood is scarce for background-exposed individuals. This study sought to fill this gap by investigating children's longitudinal exposure trends through measurement of PFAS serum concentrations and calculation of body burdens (mu g, total in body). Blood of 54 Finnish children was sampled 2005-2015 and analyzed for 20 PFASs at 1, 6 and 10.5 years of age. The body burden was calculated by multiplying the serum concentration by the volume of distribution and the bodyweight for each individual. Associations between serum concentrations or body burdens and parameters, such as sex, breastfeeding duration, body mass index as well as indoor dust and air PFAS concentrations, were evaluated. Serum concentrations of perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA) and perfluorohexane sulfonic acid (PFHxS) decreased significantly (p < 0.001) with age. In contrast to serum concentrations, body burdens stayed unchanged or even increased significantly (p < 0.05), except for PFOA in female children. Breastfeeding duration was positively correlated (p < 0.001) with serum concentrations of PFHxS, PFOS, PFOA and PFNA at 1 year of age. Some associations were found at 10.5 years with sex and indoor PFAS concentrations. Observations of longitudinal decreasing trends of serum concentrations can be misleading for understanding exposure levels from external media during childhood, as the serum concentration is influenced by parallel temporal changes and growth dilution. Body burdens account for growth dilution and thus better reflect differences in early-life to adolescence exposure than serum concentrations.

Chemicals that are persistent in the environment,mobile in the aquatic environment and toxic may be critical for the quality of raw waters. In the present study, a list of 167 REACHregistered substances were assessed with respect to their intrinsic substance properties persistence in the aquatic environment (Paq),mobility in the aquatic environment (M) and toxicity (T) usingmodified criteria earlier defined by Kalberlah et al. (2014).This was done by comprehensive manual research of all relevant information and data in all available data sources including mathematical models.Additionally, the substances were assessed and ranked with respect to their potential for environmental emissions based on the evaluation approach developed by Schulze et al. (2018).The present study provides a consolidated list of substances assessed according to the above criteria, including 8 substances assessed as PaqMT substances and 21 substances assessed as PaqMsubstances with suspected T. Further 105 suspected PaqMT substances were identified.Consequently, a total of 134 substances based on suspected PaqMT properties combined with expected environmental emissions are recommended to the German Environment Agency (UBA) for further investigation and scientific and  regulatory scrutiny.However, this result may not be suitable to indicate the need for regulatory measures.The study identified considerable data gaps (especially for experimental data) that in many cases hampered the assessment of the criteria, especially for Mand T.Manufacturers, importers and downstream users of substances should strive to obtain and report data of better quality in order to carry out a more accurate assessment. Further, the results of this project will support the ongoing discussion to define PMT criteria under REACH.Stoffe, die persistent in der Umwelt,mobil im Wasserkreislauf und toxisch sind, könnten die Qualität der Rohwässer zur Trinkwassergewinnung gefährden. Im Rahmen des vorliegenden Vorhabens

Per- and polyfluoroalkyl substances (PFASs) are man-made chemicals that contain at least one perfluoroalkyl moiety, –CnF2n–. 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.

Little is known about factors influencing infant perfluorinated alkyl acid (PFAA) concentrations. Associations between serum PFAA concentrations in 2–4-month-old infants (n = 101) and determinants were investigated by multiple linear regression and general linear model analysis. In exclusively breast-fed infants, maternal serum PFAA concentrations 3 weeks after delivery explained 13% (perfluoroundecanoic acid, PFUnDA) to 73% (perfluorohexanesulfonate, PFHxS) of infant PFAA concentration variation. Median infant/maternal ratios decreased with increasing PFAA carbon chain length from 2.8 for perfluoroheptanoic acid and perfluorooctanoic acid (PFOA) to 0.53 for PFUnDA and from 1.2 to 0.69 for PFHxS and perfluorooctanesulfonate (PFOS). Infant PFOA, perfluorononanoic acid (PFNA), and PFOS levels increased 0.7–1.2% per day of gestational age. Bottle-fed infants had mean concentrations of PFAAs 2 times lower than and a mean percentage of branched (%br) PFOS isomers 1.3 times higher than those of exclusively breast-fed infants. PFOA, PFNA, and PFHxS levels increased 8–11% per week of exclusive breast-feeding. Infants living in an area receiving PFAA-contaminated drinking water had 3-fold higher mean perfluorobutanesulfonate (PFBS) and PFHxS concentrations and higher mean %br PFHxS. Prenatal PFAA exposure and postnatal PFAA exposure significantly contribute to infant PFAA serum concentrations, depending on PFAA carbon chain length. Moderately PFBS- and PFHxS-contaminated drinking water is an important indirect exposure source.

Organic chemicals that are persistent and mobile in the aquatic environment exhibit a hazard to contaminate drinking water resources. In this study an emission score model was developed to rank the potential of substances registered under the REACH legislation to be emitted into the environment. It was applied to a list of 2167 REACH registered substances that were previously identified to be persistent and mobile organic chemicals (PMOCs) in groundwater or to be hydrolyzed to form transformation products fulfilling the PMOC criteria. The emission score model is based on the tonnage placed on the European market and on seven emission-related use characteristics (high release to environment, wide dispersive use, intermediate use, closed system use, professional use, consumer use, and substance in article), reported in the companies' registrations under REACH. Applying the model resulted in a list of 1110 substances (936 PMOCs and 174 precursors to PMOCs) that were estimated to be released into the environment, while 1054 substances had indicators of negligible environmental emissions and 3 substances could not be evaluated due to severe data gaps. The 936 PMOCs and the 174 precursors were ranked in two lists with regard to their emission potential. The model was shown to be fit for purpose in terms of suggesting and prioritizing substances for scientific investigations with a focus on environmental water quality. Though targeted for PMOCs, the presented scoring system is illustrative of how REACH registration data can be used to assess the emission potential of various substances.

Accurate quantification of short-chain chlorinated paraffins (SCCPs) poses an exceptional challenge to analytical chemists. SCCPs are complex mixtures of chlorinated alkanes with variable chain length and chlorination level; congeners with a fixed chain length (n) and number of chlorines (m) are referred to as a congener group CnClm Recently, we resolved individual CnClm by mathematically deconvolving soft ionization high-resolution mass spectra of SCCP mixtures. Here we extend the method to quantifying CnClm by introducing CnClm specific response factors (RFs) that are calculated from 17 SCCP chain-length standards with a single carbon chain length and variable chlorination level. The signal pattern of each standard is measured on APCI-QTOF-MS. RFs of each CnClm are obtained by pairwise optimization of the normal distribution's fit to the signal patterns of the 17 chain-length standards. The method was verified by quantifying SCCP technical mixtures and spiked environmental samples with accuracies of 82-123% and 76-109%, respectively. The absolute differences between calculated and manufacturer-reported chlorination degrees were 0.9 to 1.0%Cl for SCCP mixtures of 49-71%Cl. The quantification method has been replicated with ECNI magnetic sector MS and ECNI-Q:Orbitrap-MS. CnClm concentrations determined with the three instruments were highly correlated (R-2 > 0.90) with each other.

The volatilisation of perfluorooctanoic acid (PFOA) was measured experimentally at a range of pH valuesusing a previously published laboratory method. Water-to-air transfer was studied for five structuralisomers, namely: the linear isomer (n-PFOA) and the four most commonly occurring branched isomers(3-, 4-, 5- and 6-PFOA). The influence of water concentration and water type on the pH-dependent waterto-air transfer was also investigated for n-PFOA. The water-to-air transfer was studied over the course of 48 h at pH values ranging from 0.2 to 5.5. Under all experimental conditions tested, the volatilisation ofPFOA was negligible at pH > 2.5. In experiments performed with MilliQ water, volatilisation increasedwith decreasing water pH. In experiments performed with tap water and lake water, maximum volatilisationwas observed at pH 1. The concentration of PFOA in water had no influence on the pH value atwhich water-to-air transfer was observed (i.e. at pH < 2.5) for the concentration range tested (0.1e50 mg/L PFOA in deionised water). Although the percentage of PFOA volatilised was significantly different forthe four branched isomers at low pH, volatilisation was not observed above pH 2.5 for any branchedisomer suggesting that all PFOA isomers have a low pKa. Overall, these laboratory results demonstratethat volatilisation of any structural isomer of PFOA from water is negligible at environmentally-relevantconditions. It is unlikely that PFOA isomers will be fractionated in the environment as a result of volatilisationbecause it is a process of negligible environmental relevance.

The contamination levels and patterns of perfluoroallcyl acids (PFAAs) and their precursors in indoor air of children's bedrooms in Finland, Northern Europe, were investigated. Our study is among the most comprehensive indoor air monitoring studies (n = 57) and to our knowledge the first one to analyse air in children's bedrooms for PFASs (17 PFAAs and 9 precursors, including two acrylates, 6:2 FTAC and 6:2 FTMAC). The most frequently detected compound was 8:2 fluorotelomer alcohol (8:2 FTOH) with the highest median concentration (3570 pg/m(3)). FTOH concentrations were generally similar to previous studies, indicating that in 2014/2015 the impact of the industrial transition had been minor on FTOH levels in indoor air. However, in contrast to earlier studies (with one exception), median concentrations of 6:2 FTOH were higher than 10:2 FTOH. The C8 PFAAs are still the most abundant acids, even though they have now been phased out by major manufacturers. The mean concentrations of FOSE/As, especially MeFOSE (89.9 pg/m(3)), were at least an order of magnitude lower compared to previous studies. Collectively the comparison of FTOHs, PFAAs and FOSE/FOSAs with previous studies indicates that indoor air levels of PFASs display a time lag to changes in production of several years. This is the first indoor air study investigating 6:2 FTMAC, which was frequently detected (58%) and displayed some of the highest maximum concentrations (13 000 pg/m(3)). There were several statistically significant correlations between particular house and room characteristics and PFAS concentrations, most interestingly higher EtFOSE air concentrations in rooms with plastic floors compared to wood or laminate.

Due to the dynamic developmental processes during pregnancy, infancy, childhood and adolescence, exposure to PFASs is hypothesized to have the most pronounced negative effects during this period. In this review we critically evaluate the current state of the science regarding human early life exposure processes (until 18 years of age) to per- and polyfluoroalkyl substances (PFASs). Efficient placental transfer of perfluoroalkyl acids (PFAAs) results in relatively high prenatal exposure compared with many neutral organic contaminants. The few biomonitoring studies that specifically target infants, toddlers and other children suggest relatively high serum concentrations of perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) in early life with peak concentrations occurring sometime before the child reaches 20 months. This peak in serum concentrations is most likely explained by exposure via breastfeeding, ingestion of house dust and/or specific contact events with consumer products leading to high body weight normalized estimated daily intakes (EDIs). Although children have higher EDIs of PFASs than adults, these are not always reflected by higher serum levels of PFASs in children in cross-sectional biomonitoring studies due to the confounding effect of age and birth cohort, and different exposure histories due to production changes. Longitudinal exposure studies measuring internal and external exposure (for multiple pathways and PFASs) at several time points during early life are strongly encouraged to understand temporal changes in exposure of individual children. A better quantitative understanding of early life exposure processes would help to improve the validity of epidemiological studies and allow informed decisions regarding setting of regulatory thresholds and appropriate mitigation actions.

The contamination levels and patterns of perfluoroallcyl acids (PFAAs) and their precursors in indoor air of children's bedrooms in Finland, Northern Europe, were investigated. Our study is among the most comprehensive indoor air monitoring studies (n = 57) and to our knowledge the first one to analyse air in children's bedrooms for PFASs (17 PFAAs and 9 precursors, including two acrylates, 6:2 FTAC and 6:2 FTMAC). The most frequently detected compound was 8:2 fluorotelomer alcohol (8:2 FTOH) with the highest median concentration (3570 pg/m(3)). FTOH concentrations were generally similar to previous studies, indicating that in 2014/2015 the impact of the industrial transition had been minor on FTOH levels in indoor air. However, in contrast to earlier studies (with one exception), median concentrations of 6:2 FTOH were higher than 10:2 FTOH. The C8 PFAAs are still the most abundant acids, even though they have now been phased out by major manufacturers. The mean concentrations of FOSE/As, especially MeFOSE (89.9 pg/m(3)), were at least an order of magnitude lower compared to previous studies. Collectively the comparison of FTOHs, PFAAs and FOSE/FOSAs with previous studies indicates that indoor air levels of PFASs display a time lag to changes in production of several years. This is the first indoor air study investigating 6:2 FTMAC, which was frequently detected (58%) and displayed some of the highest maximum concentrations (13 000 pg/m(3)). There were several statistically significant correlations between particular house and room characteristics and PFAS concentrations, most interestingly higher EtFOSE air concentrations in rooms with plastic floors compared to wood or laminate. (C) 2016 Published by Elsevier Ltd.

We investigated if maternal body burdens of perfluoroalkyl acids (PFAAs) at the time of delivery are associated with birth outcome and if early life exposure (in utero/nursing) is associated with early childhood growth and weight gain. Maternal PFAA body burdens were estimated by analysis of serum samples from mothers living in Uppsala County, Sweden (POPUP), sampled three weeks after delivery between 1996 and 2011. Data on child length and weight were collected from medical records and converted into standard deviation scores (SDS). Multiple linear regression models with appropriate covariates were used to analyze associations between maternal PFAA levels and birth outcomes (n = 381). After birth Generalized Least Squares models were used to analyze associations between maternal PFAA and child growth (n = 200). Inverse associations were found between maternal levels of perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), and perfluoroundecanoic acid (PFUnDA), and birth weight SDS with a change of − 0.10 to − 0.18 weight SDS for an inter-quartile range (IQR) increase in ng/g PFAA. After birth, weight and length SDS were not significantly associated with maternal PFAA. However, BMI SDS was significantly associated with PFOA, PFNA, and PFHxS at 3 and 4 years of age, and with PFOS at 4 and 5 years of age. If causal, these associations suggest that PFAA affects fetal and childhood body development in different directions.

The contaminants that have the greatest chances of appearing in drinking water are those that are mobile enough in the aquatic environment to enter drinking water sources and persistent enough to survive treatment processes. Herein a screening procedure to rank neutral, ionizable and ionic organic compounds for being persistent and mobile organic compounds (PMOCs) is presented and applied to the list of industrial substances registered under the EU REACH legislation as of December 2014. This comprised 5155 identifiable, unique organic structures. The minimum cut-off criteria considered for PMOC classification herein are a freshwater half-life >40 days, which is consistent with the REACH definition of freshwater persistency, and a logDoc < 4.5 between pH 4–10 (where Doc is the organic carbon–water distribution coefficient). Experimental data were given the highest priority, followed by data from an array of available quantitative structure–activity relationships (QSARs), and as a third resort, an original Iterative Fragment Selection (IFS) QSAR. In total, 52% of the unique REACH structures made the minimum criteria to be considered a PMOC, and 21% achieved the highest PMOC ranking (half-life > 40 days, logDoc < 1.0 between pH 4–10). Only 9% of neutral substances received the highest PMOC ranking, compared to 30% of ionizable compounds and 44% of ionic compounds. Predicted hydrolysis products for all REACH parents (contributing 5043 additional structures) were found to have higher PMOC rankings than their parents, due to increased mobility but not persistence. The fewest experimental data available were for ionic compounds; therefore, their ranking is more uncertain than neutral and ionizable compounds. The most sensitive parameter for the PMOC ranking was freshwater persistency, which was also the parameter that QSARs performed the most poorly at predicting. Several prioritized drinking water contaminants in the EU and USA, and other conta

Accurate quantification of short-chain chlorinated paraffins (SCCPs) poses an exceptional challenge to analytical chemists. SCCPs are complex mixtures of chlorinated alkanes with variable chain length and chlorination level; congeners with a fixed chain length (n) and number of chlorines (m) are referred to as a “congener group” CnClm. Recently, we resolved individual CnClm by mathematically deconvolving soft ionization high-resolution mass spectra of SCCP mixtures. Here we extend the method to quantifying CnClm by introducing CnClm specific response factors (RFs) that are calculated from 17 SCCP chain-length standards with a single carbon chain length and variable chlorination level. The signal pattern of each standard is measured on APCI-QTOF-MS. RFs of each CnClm are obtained by pairwise optimization of the normal distribution’s fit to the signal patterns of the 17 chain-length standards. The method was verified by quantifying SCCP technical mixtures and spiked environmental samples with accuracies of 82–123% and 76–109%, respectively. The absolute differences between calculated and manufacturer-reported chlorination degrees were –0.9 to 1.0%Cl for SCCP mixtures of 49–71%Cl. The quantification method has been replicated with ECNI magnetic sector MS and ECNI-Q-Orbitrap-MS. CnClm concentrations determined with the three instruments were highly correlated (R2 > 0.90) with each other.

Experimental work was undertaken to test whether gaseous perfluorooctanoic acid (PFOA) sorbs to glass fibre filters (GFFs) during air sampling, causing an incorrect measure of the gas-particle equilibrium distribution. Furthermore, tests were performed to investigate whether deactivation by siliconisation prevents sorption of gaseous PFOA to filter materials. An apparatus was constructed to closely simulate a high-volume air sampler, although with additional features allowing introduction of gaseous test compounds into an air stream stripped from particles. The set-up enabled investigation of the sorption of gaseous test compounds to filter media, eliminating any contribution from particles. Experiments were performed under ambient outdoor air conditions at environmentally relevant analyte concentrations. The results demonstrate that gaseous PFOA sorbs to GFFs, but that breakthrough of gaseous PFOA on the GFFs occurs at trace-level loadings. This indicates that during high volume air sampling, filters do not quantitatively capture all the PFOA in the sampled air. Experiments with siliconised GFFs showed that this filter pre-treatment reduced the sorption of gaseous PFOA, but that sorption still occurred at environmentally relevant air concentrations. We conclude that deactivation of GFFs does not allow for the separation of gaseous and particle bound perfluorinated carboxylic acids (PFCAs) during active air sampling. Consequently, the well-recognised theory that PFCAs do not prevail as gaseous species in the atmosphere may be based on biased measurements. Caution should be taken to ensure that this artefact will not bias the conclusions of future field studies.

Perfluoroalkyl acids (PFAAs) are found globally in environmental samples and have been studied in various species. In this study, we compare the sensitivity of three avian species to the toxic effects of perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA). Eggs of great cormorant (Phalacrocorax carbo sinensis), herring gull (Larus argentatus) and the domestic White Leghorn chicken (Gallus gallus domesticus) were exposed in ovo by injection into the air sac. Effects on embryo survival were observed following exposure to PFOS and PFOA in chicken and herring gull. Chicken was found to be the most sensitive species with 50 % reduced embryo survival at 8.5 μg/g egg for PFOS and 2.5 μg/g egg for PFOA. Cormorant was shown to be the least sensitive species. The difference in sensitivity between chicken and herring gull was a factor of 2.7 for PFOS and 3.5 for PFOA. Between chicken and great cormorant, the sensitivity difference was 2.6 for PFOS and 8.2 for PFOA. Effects on embryo survival were seen at egg injection doses of PFOS close to levels found in environmental samples from wild birds, indicating that PFOS could be having effects in highly exposed populations of birds. This study also shows that there are differences in species sensitivity to PFOS and PFOA that should be taken into consideration in avian wildlife risk assessment.

We describe and illustrate a three-step data-processing approach that enables individual congener groups of chlorinated-paraffins (CPs) to be resolved in mass spectra obtained from either-of two soft ionization methods: electron capture negative-ionization mass spectrometry (ECNI-MS) or atmospheric pressure chemical ionization mass spectrometry (APCI-MS). In the first step, general fragmentation pathways of CPs are deduced from analysis of mass spectra of individual CP congeners. In the-Second step, all possible fragment ions in the general fragmentation pathways of CPs with 10 to 20 carbon atoms are enumerated and compared to mass spectra of CP mixture standards, and a deconvolution algorithm is applied to identify fragment ions that are actually observed. In the third step, isotope permutations of the observed fragment ions are calculated and used to identify isobaric overlaps, so that mass intensities of indivichial CP congener groups can be deconvolved from the unresolved isobaric ion signal intensities in mass spectra. For a specific instrument; the three steps only need to be done once to enable deconvolution of CPs in unknown samples. This approach enables congener group-level resolution of CP mixtures in environmental samples, and: it opens up the possibility, for quantification of congener group.

Perfluoroalkyl phosphonic and phosphinic acids (PFPAs and PFPiAs) are sub-groups of per- and polyfluoroalkyl substances (PFASs) that have been commercialized since the 1970s, particularly as defoamers in pesticide formulations and wetting agents in consumer products. Recently, C-4/C-4 PFPiA and its derivatives have been presented as alternatives to long-chain PFASs in certain applications. In this study, we systematically assess the publicly available information on the hazardous properties, occurrence, and exposure routes of PFPAs and PFPiAs, and make comparisons to the corresponding properties of their better-known carboxylic and sulfonic acid analogs (i.e. PFCAs and PFPAs). This comparative assessment indicates that [i] PFPAs likely have high persistence and long-range transport potential; [ii] PFPiAs may transform to PFPAs (and possibly PFCAs) in the environment and biota; [iii] certain PFPAs and PFPiAs can only be slowly eliminated from rainbow trout and rats, similarly to long-chain PFCAs and PFPAs; [iv] PFPAs and PFPiAs have modes-of-action that are both similar to, and different from, those of PFCAs and PFSAs; and [v] the measured levels of PFPAs/PFPiAs in the global environment and biota appear to be low in comparison to PFCAs and PFPAs, suggesting, for the time being, low risks from PFPAs and PFPiAs alone. Although risks from individual PFPAs/PFPiAs are currently low, their ongoing production and use and high persistence will lead to increasing exposure and risks over time. Furthermore, simultaneous exposure to PFPAs, PFPiAs and other PFASs may result in additive effects necessitating cumulative risk assessments. To facilitate effective future research, we highlight possible strategies to overcome sampling and analytical challenges.

Temporal and spatial trends of perfluoroalkyl acids (PFAAs) were investigated in Baltic Sea herring liver (Clupea harengus) from three sites, and white-tailed sea eagle (WTSE) eggs (Haliaeetus albicilla) from two freshwater and two marine areas in Sweden. Trends of most quantifiable PFAAs increased over the monitored period (1980-2014 in herring, 1960s/1980s-2010 in WTSE). No significant decreasing trends were observed for the most recent ten years for any substances, except perfluorooctane sulfonamide (FOSA). Concentrations of perfluorooctanesulfonic acids (PFOS) in herring showed a distinct decreasing spatial trend moving from the more southern site toward the more northern site, indicating main input of PFOS into the southern Baltic Sea. For WTSE, PFOS concentration was higher in the marine compared to the freshwater environment, explained by the cumulative historic contamination of the Baltic Sea. Similarly, concentrations in WTSE were lower in the northern part of the Baltic Sea compared to further south. Concentrations of PFUnDA, representing long-chain perfluoroalkyl carboxylic acids (PFCAs), showed a more homogeneous spatial distribution compared to PFOS for both herring and WTSE, indicating that atmospheric inputs (via precursors) of the long-chain PFCAs are important contributors in the study areas.

The present study examined the presence of perfluoroalkyl acids (PFAAs) and selected precursors in the Baltic Sea abiotic environment and guillemot food web, and investigated the relative importance of precursors in food web accumulation of PFAAs. Sediment, water, zooplankton, herring, sprat, and guillemot eggs were analyzed for perfluoroalkane sulfonic acids (PFSAs; C-4,C-6,C-8,C-10) and perfluoroalkyl carboxylic acids (PFCAs; C6-15) along with six perfluorooctane sulfonic acid (PFOS) precursors and 11 polyfluoroalkyl phosphoric acid diesters (diPAPs). FOSA, FOSAA. and its methyl and ethyl derivatives (Me- and EtFOSAA), and 6:2/6:2 diPAP were detected in sediment and water. While FOSA and the three FOSAAs were detected in all biota, a total of nine diPAPs were only detected in zooplankton. Concentrations of PFOS precursors and diPAPs exceeded PFOS and PFCA concentrations, respectively, in zooplankton, but not in fish and guillemot eggs. Although PFOS precursors were present at all trophic levels, they appear to play a minor role in food web accumulation of PFOS based on PFOS precursor/PFOS ratios and PFOS and FOSA isomer patterns. The PFCA pattern in fish could not be explained by the intake pattern based on PFCAs and analyzed precursors, that is, diPAPs. Exposure to additional precursors might therefore be a dominant exposure pathway compared to direct PFCA exposure for fish.