Per- and polyfluoroalkyl substances (PFAS) in white-tailed sea eagle eggs from Sweden: temporal trends (1969-2021), spatial variations, fluorine mass balance, and suspect screening.

Temporal and spatial trends of 15 per- and polyfluoroalkyl substances (PFAS) were determined in white-tailed sea eagle (WTSE) eggs (Haliaeetus albicilla) from two inland and two coastal regions of Sweden between 1969 and 2021. PFAS concentrations generally increased from ∼1969 to ∼1990s-2010 (depending on target and site) and thereafter plateaued or declined, with perfluorooctane sulfonamide (FOSA) and perfluorooctane sulfonate (PFOS) declining faster than most perfluoroalkyl carboxylic acids (PFCAs). The net result was a shift in the PFAS profile from PFOS-dominant in 1969-2010 to an increased prevalence of PFCAs over the last decade. Further, during the entire period higher PFAS concentrations were generally observed in coastal populations, possibly due to differences in diet and/or proximity to more densely populated areas. Fluorine mass balance determination in pooled samples from three of the regions (2019-2021) indicated that target PFAS accounted for the vast majority (i.e. 81-100%) of extractable organic fluorine (EOF). Nevertheless, high resolution mass-spectrometry-based suspect screening identified 55 suspects (31 at a confidence level [CL] of 1-3 and 24 at a CL of 4-5), of which 43 were substances not included in the targeted analysis. Semi-quantification of CL ≤ 2 suspects increased the identified EOF to >90% in coastal samples. In addition to showing the impact of PFAS regulation and phase-out initiatives, this study demonstrates that most extractable organofluorine in WTSE eggs is made up of known (legacy) PFAS, albeit with low levels of novel substances.

Characterizing the Organohalogen Iceberg: Extractable, Multihalogen Mass Balance Determination in Municipal Wastewater Treatment Plant Sludge.

The large number and diversity of organohalogen compounds (OHCs) occurring in the environment poses a grand challenge to analytical chemists. Since no single targeted method can identify and quantify all OHCs, the size of the OHC "iceberg" may be underestimated. We sought to address this problem in municipal wastewater treatment plant (WWTP) sludge by quantifying the unidentified fraction of the OHC iceberg using targeted analyses of major OHCs together with measurements of total and extractable (organo)halogen (TX and EOX, respectively; where X = F, Cl, or Br). In addition to extensive method validation via spike/recovery and combustion efficiency experiments, TX and/or EOX were determined in reference materials (BCR-461 and NIST SRMs 2585 and 2781) for the first time. Application of the method to WWTP sludge revealed that chlorinated paraffins (CPs) accounted for most (∼92%) of the EOCl, while brominated flame retardants and per- and polyfluoroalkyl substances (PFAS) accounted for only 54% of the EOBr and 2% of the EOF, respectively. Moreover, unidentified EOF in nonpolar CP extracts points to the existence of organofluorine(s) with physical-chemical properties unlike those of target PFAS. This study represents the first multihalogen mass balance in WWTP sludge and offers a novel approach to prioritization of sample extracts for follow-up investigation.

Levels of per- and polyfluoroalkyl substances (PFAS) in ski wax products on the market in 2019 indicate no changes in formulation.

In the summer of 2019, eleven of the best-selling fluorinated ski wax products were purchased from one of Norway's largest sports stores and soon after analysed for a suite of 26 per- and polyfluoroalkyl substances (PFAS). The waxes were shown to contain a wide range of perfluoroalkyl acids, including perfluoroalkyl carboxylic acids with up to 25 carbons. Of particular concern was the finding that perfluorooctanoic acid (PFOA) levels in nine of the eleven ski lubrication products analysed were above the EU limit values of 25 ng g-1, which came into force on 4th July 2020. The ski wax with the highest PFOA levels had a concentration that was 1215 times higher than the EU restrictions. Although some of the ski wax manufacturers have indicated that they have switched to formulations that contain chemistries based on shorter perfluoroalkyl chains, the analytical results show that this is not the case.

Fluorine Mass Balance and Suspect Screening in Marine Mammals from the Northern Hemisphere.

There is increasing evidence that the ∼20 routinely monitored perfluoroalkyl and polyfluoroalkyl substances (PFASs) account for only a fraction of extractable organofluorine (EOF) occurring in the environment. To assess whether PFAS exposure is being underestimated in marine mammals from the Northern Hemisphere, we performed a fluorine mass balance on liver tissues from 11 different species using a combination of targeted PFAS analysis, EOF and total fluorine determination, and suspect screening. Samples were obtained from the east coast United States (US), west and east coast of Greenland, Iceland, and Sweden from 2000 to 2017. Of the 36 target PFASs, perfluorooctane sulfonate (PFOS) dominated in all but one Icelandic and three US samples, where the 7:3 fluorotelomer carboxylic acid (7:3 FTCA) was prevalent. This is the first report of 7:3 FTCA in polar bears (∼1000 ng/g, ww) and cetaceans (<6-190 ng/g, ww). In 18 out of 25 samples, EOF was not significantly greater than fluorine concentrations derived from sum target PFASs. For the remaining 7 samples (mostly from the US east coast), 30-75% of the EOF was unidentified. Suspect screening revealed an additional 37 PFASs (not included in the targeted analysis) bringing the total to 63 detected PFASs from 12 different classes. Overall, these results highlight the importance of a multiplatform approach for accurately characterizing PFAS exposure in marine mammals.

Temporal trends of suspect- and target-per/polyfluoroalkyl substances (PFAS), extractable organic fluorine (EOF) and total fluorine (TF) in pooled serum from first-time mothers in Uppsala, Sweden, 1996-2017.

A combined method for quantitative analysis, along with suspect and non-target screening of per- and polyfluoroalkyl substances (PFAS) was developed using ultra-high pressure liquid chromatography-ultra-high resolution (Orbitrap) mass spectrometry. The method was applied together with measurements of total- and extractable organofluorine (TF and EOF, respectively), to pooled serum samples from 1996-2017 from first-time mothers living in the county of Uppsala, Sweden, some of which (i.e. 148 of 472 women sampled 1996-2012) were exposed to drinking water contaminated with perfluorohexane sulfonate (PFHxS) and other PFAS until mid-2012. Declining trends were observed for all target PFAS as well as TF, with homologue-dependent differences in year of onset of decline. Only 33% of samples displayed detectable EOF, and amongst these samples the percentage of EOF explained by target PFAS declined significantly (-3.5% per year) over the entire study period. This finding corroborates prior observations in Germany after the year 2000, and may reflect increasing exposure to novel PFAS which have not yet been identified. Suspect screening revealed the presence of perfluoro-4-ethylcyclohexanesulfonate (PFECHS), which displayed declining trends since the year 2000. Non-target time trend screening revealed 3 unidentified features with time trends matching PFHxS. These features require further investigation, but may represent contaminants which co-occurred with PFHxS in the contaminated drinking water.

Spatio-temporal variation of metals and organic contaminants in bank voles (Myodes glareolus).

Environmental contamination with metals and organic compounds is of increasing concern for ecosystem and human health. Still, our knowledge about spatial distribution, temporal changes and ecotoxicological fate of metals and organic contaminants in wildlife is limited. We studied concentrations of 69 elements and 50 organic compounds in 300 bank voles (Myodes glareolus), Europe's most common mammal, sampled in spring and autumn 2017-2018 in five monitoring areas, representing three biogeographic regions. In addition, we compared measured concentrations with previous results from bank voles sampled within the same areas in 1995-1997 and 2001. In general, our results show regional differences, but no consistent patterns among contaminants and study areas. The exception was for the lowest concentrations of organic contaminants (e.g. perfluorooctane sulfonate, PFOS), which were generally found in the northern Swedish mountain area. Concentrations of metals and organic contaminants in adults varied seasonally with most organic contaminants being higher in spring; likely induced by diet shifts but potentially also related to age differences. In addition, metal concentrations varied between organs (liver vs. kidney), age classes (juveniles vs. adults; generally higher in adults) as well as between males and females. Concentrations of chromium and nickel in kidney and liver in the northernmost mountain area were lower in 2017-2018 than in 1995-1997 and in three of four areas, lead concentrations were lower in 2017-2018 than in 2001. Current metal concentrations (except mercury) are not expected to negatively affect the voles. Concentrations of hexachlorobenzene displayed highest concentrations in 2001 in the mountains, while it was close to detection limit in 2017-2018. Likewise, PFOS concentrations decreased in the mountains and in south-central lowland forests between 2001 and 2017-2018. Our results suggest that season, age class and sex need to be considered when designing and interpreting results from monitoring programs targeting inorganic and organic contaminants in wildlife.

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

The quantity and composition of fibers released from functional textiles during accelerated washing were investigated using the GyroWash method. Two fabrics [polyamide (PA) and polyester/cotton (PES/CO)] were selected and coated with perfluorohexane-based side-chain fluorinated polymers. Fibers released during washing ranged from ∼10 to 500 µ with a similar distribution for the two textile types. The PA-based fabric released considerably more fibers >20 µm in length compared to the PES/CO-based fabric (>1000/GyroWash for PA vs ∼200/GyroWash fibers for PES/CO). After one GyroWash (2-15 domestic washes), fibers that contained approximately 240 and 1300 µg total fluorine per square meter (µg F/m2) were released from the PA and PES/CO fabrics, respectively. Current understanding of the fate of microplastic fibers suggests that a large fraction of these fibers reach the environment either in effluent wastewater or sewage sludge applied to land. In the environment, the fluorinated side chains will be slowly cleaved from the backbone of the side-chain fluorinated polymers coated on the fibers and then transformed into short-chain perfluoroalkyl acids. On the European scale, emissions of up to ∼0.7 t of fluorotelomer alcohol (6:2 FTOH) per year were estimated for outdoor rain jackets treated with fluorotelomer-based side-chain fluorinated polymers.

Effects of Leachates from UV-Weathered Microplastic in Cell-Based Bioassays.

Standard ecotoxicological testing of microplastic does not provide insight into the influence that environmental weathering by, e.g., UV light has on related effects. In this study, we leached chemicals from plastic into artificial seawater during simulated UV-induced weathering. We tested largely additive-free preproduction polyethylene, polyethylene terephthalate, polypropylene, and polystyrene and two types of plastic obtained from electronic equipment as positive controls. Leachates were concentrated by solid-phase extraction and dosed into cell-based bioassays that cover (i) cytotoxicity; (ii) activation of metabolic enzymes via binding to the arylhydrocarbon receptor (AhR) and the peroxisome proliferator-activated receptor (PPARγ); (iii) specific, receptor-mediated effects (estrogenicity, ERα); and (iv) adaptive response to oxidative stress (AREc32). LC-HRMS analysis was used to identify possible chain-scission products of polymer degradation, which were then tested in AREc32 and PPARγ. Explicit activation of all assays by the positive controls provided proof-of-concept of the experimental setup to demonstrate effects of chemicals liberated during weathering. All plastic leachates activated the oxidative stress response, in most cases with increased induction by UV-treated samples compared to dark controls. For PPARγ, polyethylene-specific effects were partially explained by the detected dicarboxylic acids. Since the preproduction plastic showed low effects often in the range of the blanks future studies should investigate implications of weathering on end consumer products containing additives.

A strategic screening approach to identify transformation products of organic micropollutants formed in natural waters.

Many transformation products (TPs) from organic micropollutants are not included in routine environmental monitoring programs due to limited knowledge of their occurrence and fate. An efficient method to identify and prioritize critical compounds in terms of environmental relevance is needed. In this study, we applied a strategic screening approach based on a case-control concept to identify TPs formed along wastewater-impacted rivers. Time-integrated samples were collected over one week at both ends of a river stretch downstream of a wastewater treatment plant (WWTP) outfall and were analyzed by ultrahigh performance liquid chromatography interfaced with quadrupole time-of-flight mass spectrometry (UHPLC-QToF-MS/MS). The screening procedure of the high-resolution MS (HRMS) datasets consisted of three major steps: (i) screening for parent compounds (PCs) attenuated along the stretch; (ii) prediction of potential TPs from these PCs; and (iii) screening for TPs from this list with an increasing trend along the stretch. In total, 32 PCs decreased along the investigated river stretches. From these PCs, eight TPs had increasing concentrations along the studied stretches and could be tentatively identified. The identification of one TP (benzamide) was confirmed by its corresponding reference standard, while no standards were available for the remaining TPs.

Bioconcentration and Biotransformation of Amitriptyline in Gilt-Head Bream.

Extensive global use of the serotonin-norepinephrine reuptake inhibitor Amitriptyline (AMI) for treatment of mental health problems has led to its common occurrence in the aquatic environment. To assess AMI bioconcentration factors, tissue distribution, and metabolite formation in fish, we exposed gilt-head bream (Sparus aurata) to AMI in seawater for 7 days at two concentrations (0.2 µg/L and 10 µg/L). Day 7 proportional bioconcentration factors (BCFs) ranged from 6 (10 µg/L dose, muscle) to 127 (0.2 µg/L dose, brain) and were consistently larger at the low dose level. The relative tissue distribution of AMI was consistent at both doses, with concentrations decreasing in the order brain ≈ gill > liver > plasma > bile ≫ muscle. Using a suspect screening workflow based on liquid chromatography-high resolution (Orbitrap) mass spectrometry we identified 33 AMI metabolites (both Phase I and Phase II), occurring mostly in bile, liver and plasma. Ten structures are reported for the first time. Remarkably, all 33 metabolites retained the tricyclic ring structure common to tricyclic antidepressants, which may be toxicologically relevant. Collectively these data indicate that, in addition to AMI, a broad suite of metabolites should be included in biomonitoring campaigns in order to fully characterize exposure in aquatic wildlife.

Non-target time trend screening: a data reduction strategy for detecting emerging contaminants in biological samples.

Non-targeted mass spectrometry-based approaches for detecting novel xenobiotics in biological samples are hampered by the occurrence of naturally fluctuating endogenous substances, which are difficult to distinguish from environmental contaminants. Here, we investigate a data reduction strategy for datasets derived from a biological time series. The objective is to flag reoccurring peaks in the time series based on increasing peak intensities, thereby reducing peak lists to only those which may be associated with emerging bioaccumulative contaminants. As a result, compounds with increasing concentrations are flagged while compounds displaying random, decreasing, or steady-state time trends are removed. As an initial proof of concept, we created artificial time trends by fortifying human whole blood samples with isotopically labelled standards. Different scenarios were investigated: eight model compounds had a continuously increasing trend in the last two to nine time points, and four model compounds had a trend that reached steady state after an initial increase. Each time series was investigated at three fortification levels and one unfortified series. Following extraction, analysis by ultra performance liquid chromatography high-resolution mass spectrometry, and data processing, a total of 21,700 aligned peaks were obtained. Peaks displaying an increasing trend were filtered from randomly fluctuating peaks using time trend ratios and Spearman's rank correlation coefficients. The first approach was successful in flagging model compounds spiked at only two to three time points, while the latter approach resulted in all model compounds ranking in the top 11 % of the peak lists. Compared to initial peak lists, a combination of both approaches reduced the size of datasets by 80-85 %. Overall, non-target time trend screening represents a promising data reduction strategy for identifying emerging bioaccumulative contaminants in biological samples. Graphical abstract Using time trends to filter out emerging contaminants from large peak lists.

Detecting a wide range of environmental contaminants in human blood samples--combining QuEChERS with LC-MS and GC-MS methods.

Exposure to environmental pollution and consumer products may result in an uptake of chemicals into human tissues. Several studies have reported the presence of diverse environmental contaminants in human blood samples. However, previously developed multi-target methods for the analysis of human blood include a fairly limited amount of compounds stemming from one or two related compound groups. Thus, the sample preparation method QuEChERS (quick easy cheap effective rugged and safe) was tested for the extraction of 64 analytes covering a broad compound domain followed by detection using liquid and gas chromatography coupled to mass spectrometry (LC- and GC-MS). Forty-seven analytes showed absolute recoveries above 70% in the first QuEChERS step, being a simple liquid-liquid extraction (LLE) using acetonitrile and salt. The second QuEChERS step, being a dispersive solid phase extraction, did not result in an overall improvement of recoveries or removal of background signals. Using solely the LLE step, eight analytes could subsequently be detected in human blood samples from the German Environmental Specimen Bank. Using a LC-multiple reaction monitoring (MRM) method with a triple quadrupole instrument, better recoveries were achieved than with an older LC-high-resolution (HR) MS full scan orbitrap instrument, which required a higher concentration factor of the extracts. However, the application of HRMS full scan methods could be used for the detection of additional compounds retrospectively.

Pathways for degradation of plastic polymers floating in the marine environment.

Each year vast amounts of plastic are produced worldwide. When released to the environment, plastics accumulate, and plastic debris in the world's oceans is of particular environmental concern. More than 60% of all floating debris in the oceans is plastic and amounts are increasing each year. Plastic polymers in the marine environment are exposed to sunlight, oxidants and physical stress, and over time they weather and degrade. The degradation processes and products must be understood to detect and evaluate potential environmental hazards. Some attention has been drawn to additives and persistent organic pollutants that sorb to the plastic surface, but so far the chemicals generated by degradation of the plastic polymers themselves have not been well studied from an environmental perspective. In this paper we review available information about the degradation pathways and chemicals that are formed by degradation of the six plastic types that are most widely used in Europe. We extrapolate that information to likely pathways and possible degradation products under environmental conditions found on the oceans' surface. The potential degradation pathways and products depend on the polymer type. UV-radiation and oxygen are the most important factors that initiate degradation of polymers with a carbon-carbon backbone, leading to chain scission. Smaller polymer fragments formed by chain scission are more susceptible to biodegradation and therefore abiotic degradation is expected to precede biodegradation. When heteroatoms are present in the main chain of a polymer, degradation proceeds by photo-oxidation, hydrolysis, and biodegradation. Degradation of plastic polymers can lead to low molecular weight polymer fragments, like monomers and oligomers, and formation of new end groups, especially carboxylic acids.

Extending analysis of environmental pollutants in human urine towards screening for suspected compounds.

Today there is a large difference in the number of chemicals of commerce and the number of chemicals being monitored in environmental and human samples. During the last decades suspect screening methods have been developed to increase the number of monitored analytes. Peaks detected during high resolution mass spectrometry full scan measurements are compared to a list of suspect chemicals with known exact masses. These methods, however, have so far focused on environmental samples. Thus we present a method development for a suspect screening of human urine samples. The sample preparation techniques and instrumental analysis were tested by target chemicals with a wide range of properties. A combination of direct injection and QuEChERS extraction followed by liquid chromatography coupled to high resolution mass spectrometry was able to detect 33 of the 40 spiked target compounds at 30-120% absolute recovery. For suspect evaluation peaks were deconvoluted and aligned with the software MZmine followed by R script processing. Comparing detected and in-silico fragmentation, nine suspect chemicals could be tentatively identified in a pooled human urine sample and four of these were confirmed by a reference standard.

Perfluoroalkyl carboxylic acids with up to 22 carbon atoms in snow and soil samples from a ski area.

The use of fluorinated ski waxes as a direct input route of perfluoroalkyl carboxylic acids (PFCAs) to the environment was investigated. PFCA homologues with 6-22 carbon atoms (C6-22 PFCAs) were detected in fluorinated ski waxes and their raw materials by liquid chromatography coupled to tandem mass spectrometry. Snow and soil samples from a ski area in Sweden were taken after a skiing competition and after snowmelt, respectively. In both snow and soil samples C6-22 PFCAs were detected, representing the first report of PFCAs with up to 22 carbon atoms in environmental samples. Single analyte concentrations in snow (analyzed as melt water) and soil ranged up to 0.8µgL(-1) and 5ngg(-1) dry weight, respectively. ∑PFCA concentrations in snow and soil decreased from the start to the finish of the ski trail. Distinct differences in PFCA patterns between snow (prevalence of C14-20 PFCAs) and soil samples (C6-14 PFCAs dominating) were observed. Additionally, a PFCA pattern change from the start to about two third of the distance of the ski trail was found both for snow and soil, with a larger fraction of longer chain homologues present in samples from the start. These observations are probably a result of differences in PFCA homologue patterns present in different types of waxes. The calculated PFCA input from snow affected by the skiing competition was smaller than the PFCA inventory in soil for all chain lengths and markedly smaller for C6-15 PFCAs, presenting evidence for long-term accumulation in soil.

Environmental occurrence and fate of semifluorinated n-alkanes in snow and soil samples from a ski area.

Semifluorinated n-alkanes (SFAs) with carbon chain lengths of 22 to approximately 36 atoms are present in fluorinated ski waxes to reduce the friction between ski base and snow, resulting in a better glide. Semifluorinated n-alkenes (SFAenes) are byproducts in the production process of SFAs and are also found in ski waxes. Snow and soil samples from a ski area in Sweden were taken after a large skiing competition and after snowmelt, respectively, and analyzed for SFAs and SFAenes. Single analyte concentrations in snow (analyzed as melt water) ranged from a few ng L(-1) up to 300 µg L(-1). ∑SFA concentrations decreased significantly from the start to the finish of the ski trail. Single analyte concentrations in soil ranged up to 9 ng g(-1)dw. ∑SFA concentrations in soil did not show a trend along the ski trail. This may be due to the fact that concentrations in soil, although strongly influenced by the competition, reflect inputs during the whole skiing season. The chemical inventory in snow was greater than the inventory in soil for shorter chain SFAs (C(22)C(28)) and for all SFAenes. Additionally, a significant change in SFA patterns between snow and soil samples was found. These observations suggested volatilization of shorter chain SFAs and of SFAenes during snowmelt. Evidence for long-term accumulation of SFAs in surface soil over several skiing seasons was not found.

Laboratory studies on the fate of perfluoroalkyl carboxylates and sulfonates during snowmelt.

Perfluoroalkyl acids (PFAAs) are anthropogenic chemicals that occur in snow from both remote and source regions. Experiments were conducted to determine how PFAAs are released from a melting snowpack. Different PFAAs eluted from the snowpack at different times, those with short chains eluting early, those with long chains eluting late. The concentrations in the meltwater of PFAAs with medium chain lengths of 6 to 9 perfluorinated carbon atoms first increased and then decreased during the melt period. Such a peak elution had not been previously observed for any other chemicals. The specific snow surface area (SSA) influenced this elution type, with peak concentrations occurring earlier in a snowpack with lower SSA. Model simulations suggested that the snow surface decrease during the melt alone was insufficient to explain the observations. It was ruled out that the calcium concentration affected PFAA sorption to the snow surface in a similar way as sorption to sediments. Adsorption coefficients of PFAAs to the snow surface were estimated by fitting the measured and modeled elution profiles.

Theoretical and experimental simulation of the fate of semifluorinated n-alkanes during snowmelt.

Semifluorinated n-alkanes (SFAs) are highly fluorinated anthropogenic chemicals that are released into the environment through their use in ski waxes. Nothing is known about their environmental partitioning in general and their fate during snowmelt in particular. Properties were estimated for a range of SFAs with different chain lengths and degrees of fluorination using the SPARC calculator and poly parameter linear free energy relationships (ppLFERs). The calculations resulted in very low water solubility and vapor pressures and, consequently, high log KOW and log KOA values. Artificially produced snow in a cold room was spiked with a range of SFAs and subsequently melted with infrared lamps. Melt water, particles, and air samples taken during melting were analyzed. Both calculations and experiments showed that SFAs used in ski waxes will bind to particles or snow grain surfaces during snowmelt and thus are predicted to end up on the soil surface in skiing areas.

Trace analytical methods for semifluorinated n-alkanes in snow, soil, and air.

Semifluorinated n-alkanes (SFAs) are anthropogenic chemicals that are used in ski waxes and, thus, are released directly into the environment, but their subsequent fate and distribution are as yet unknown. Therefore, simple, selective, and sensitive methods were developed for analyzing trace amounts of SFAs in snow/water, soil, and air samples by gas chromatography coupled to electron capture negative ionization mass spectrometry (GC/ECNI-MS). Recoveries were generally in the range of 70-120%, depending on the compound and matrix. The analytical sensitivity was higher for SFAs with longer fluorinated chains, and the instrumental limits of detection ranged from 0.3 to 260 pg injected, providing method detection limits of 0.54-311 ng L(-1), 0.004-9.86 ng g(-1), and 0.4-531 ng m(-3) for snow (analyzed as its meltwater), soil, and air samples, respectively. Using the developed procedures, SFAs were found in snow (meltwater) and soil samples from a small cross-country ski area in Sweden at concentrations up to 1.3 microg L(-1) and 47 pg g(-1), respectively.