Fluorinated Precursor Compounds in Sediments as a Source of Perfluorinated Alkyl Acids (PFAA) to Biota.

The environmental behavior of perfluorinated alkyl acids (PFAA) and their precursors was investigated in lake Tyrifjorden, downstream a factory producing paper products coated with per- and polyfluorinated alkyl substances (PFAS). Low water concentrations (max 0.18 ng L-1 linear perfluorooctanesulfonic acid, L-PFOS) compared to biota (mean 149 µg kg-1 L-PFOS in perch livers) resulted in high bioaccumulation factors (L-PFOS BAFPerch liver: 8.05 × 105-5.14 × 106). Sediment concentrations were high, particularly for the PFOS precursor SAmPAP diester (max 1 872 µg kg-1). Biota-sediment accumulation factors (L-PFOS BSAFPerch liver: 22-559) were comparable to elsewhere, and concentrations of PFAA precursors and long chained PFAA in biota were positively correlated to the ratio of carbon isotopes (13C/12C), indicating positive correlations to dietary intake of benthic organisms. The sum fluorine from targeted analyses accounted for 54% of the extractable organic fluorine in sediment, and 9-108% in biota. This, and high trophic magnification factors (TMF, 3.7-9.3 for L-PFOS), suggests that hydrophobic precursors in sediments undergo transformation and are a main source of PFAA accumulation in top predator fish. Due to the combination of water exchange and dilution, transformation of larger hydrophobic precursors in sediments can be a source to PFAA, some of which are normally associated with uptake from water.

Bioaccumulation of Fluorotelomer Sulfonates and Perfluoroalkyl Acids in Marine Organisms Living in Aqueous Film-Forming Foam Impacted Waters.

The use of aqueous film-forming foams (AFFFs) has resulted in hot spots polluted with poly- and perfluorinated alkyl substances (PFASs). The phase out of long-chained perfluoroalkyl acids (PFAAs) from AFFFs resulted in the necessity for alternatives, and short-chained PFAAs and fluorotelomer-based surfactants have been used. Here, the distribution of PFAS contamination in the marine environment surrounding a military site in Norway was investigated. Up to 30 PFASs were analyzed in storm, leachate, and fjord water; marine sediments; marine invertebrates (snails, green shore crab, great spider crab, and edible crab); and teleost fish (Atlantic cod, European place, and Lemon sole). Perfluorooctanesulfonic acid (PFOS) was the most abundantly detected PFAS. Differences in PFAS accumulation levels were observed among species, likely reflecting different exposure routes among trophic levels and different capabilities for depuration and/or enzymatic degradation. In agreement with previous literature, almost no 6:2 fluorotelomer sulfonate (6:2 FTS) was detected in teleost fish. However, this study is one of the first to report considerable concentrations of 6:2 FTS in marine invertebrates, suggesting bioaccumulation. Biota monitoring and risk assessments of sites contaminated with fluorotelomer sulfonates (FTSs) and related compounds should not be limited to fish, but should also include invertebrates.

Sequestration of Antimony on Calcite Observed by Time-Resolved Nanoscale Imaging.

Antimony, which has damaging effects on the human body and the ecosystem, can be released into soils, ground-, and surface waters either from ore minerals that weather in near surface environments, or due to anthropogenic releases from waste rich in antimony, a component used in batteries, electronics, ammunitions, plastics, and many other industrial applications. Here, we show that dissolved Sb can interact with calcite, a widespread carbonate mineral, through a coupled dissolution-precipitation mechanism. The process is imaged in situ, at room temperature, at the nanometer scale by using an atomic force microscope equipped with a flow-through cell. Time-resolved imaging allowed following the coupled process of calcite dissolution, nucleation of precipitates at the calcite surface and growth of these precipitates. Sb(V) forms a precipitate, whereas Sb(III) needs to be oxidized to Sb(V) before being incorporated in the new phase. Scanning-electron microscopy and Raman spectroscopy allowed identification of the precipitates as two different calcium-antimony phases (Ca2Sb2O7). This coupled dissolution-precipitation process that occurs in a boundary layer at the calcite surface can sequester Sb as a solid phase on calcite, which has environmental implications as it may reduce the mobility of this hazardous compound in soils and groundwaters.

Effect-Directed Analysis Based on Transthyretin Binding Activity of Per- and Polyfluoroalkyl Substances in a Contaminated Sediment Extract.

Only a fraction of the total number of per- and polyfluoroalkyl substances (PFAS) are monitored on a routine basis using targeted chemical analyses. We report on an approach toward identifying bioactive substances in environmental samples using effect-directed analysis by combining toxicity testing, targeted chemical analyses, and suspect screening. PFAS compete with the thyroid hormone thyroxin (T4 ) for binding to its distributor protein transthyretin (TTR). Therefore, a TTR-binding bioassay was used to prioritize unknown features for chemical identification in a PFAS-contaminated sediment sample collected downstream of a factory producing PFAS-coated paper. First, the TTR-binding potencies of 31 analytical PFAS standards were determined. Potencies varied between PFAS depending on carbon chain length, functional group, and, for precursors to perfluoroalkyl sulfonic acids (PFSA), the size or number of atoms in the group(s) attached to the nitrogen. The most potent PFAS were the seven- and eight-carbon PFSA, perfluoroheptane sulfonic acid (PFHpS) and perfluorooctane sulfonic acid (PFOS), and the eight-carbon perfluoroalkyl carboxylic acid (PFCA), perfluorooctanoic acid (PFOA), which showed approximately four- and five-times weaker potencies, respectively, compared with the native ligand T4 . For some of the other PFAS tested, TTR-binding potencies were weak or not observed at all. For the environmental sediment sample, not all of the bioactivity observed in the TTR-binding assay could be assigned to the PFAS quantified using targeted chemical analyses. Therefore, suspect screening was applied to the retention times corresponding to observed TTR binding, and five candidates were identified. Targeted analyses showed that the sediment was dominated by the di-substituted phosphate ester of N-ethyl perfluorooctane sulfonamido ethanol (SAmPAP diester), whereas it was not bioactive in the assay. SAmPAP diester has the potential for (bio)transformation into smaller PFAS, including PFOS. Therefore, when it comes to TTR binding, the hazard associated with this substance is likely through (bio)transformation into more potent transformation products. Environ Toxicol Chem 2024;43:245-258. © 2023 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Life cycle assessment to evaluate the environmental impact of biochar implementation in conservation agriculture in Zambia.

Biochar amendment to soil is a potential technology for carbon storage and climate change mitigation. It may, in addition, be a valuable soil fertility enhancer for agricultural purposes in sandy and/or weathered soils. A life cycle assessment including ecological, health and resource impacts has been conducted for field sites in Zambia to evaluate the overall impacts of biochar for agricultural use. The life cycle impacts from conservation farming using cultivation growth basins and precision fertilization with and without biochar addition were in the present study compared to conventional agricultural methods. Three different biochar production methods were evaluated: traditional earth-mound kilns, improved retort kilns, and micro top-lit updraft (TLUD) gasifier stoves. The results confirm that the use of biochar in conservation farming is beneficial for climate change mitigation purposes. However, when including health impacts from particle emissions originating from biochar production, conservation farming plus biochar from earth-mound kilns generally results in a larger negative effect over the whole life cycle than conservation farming without biochar addition. The use of cleaner technologies such as retort kilns or TLUDs can overcome this problem, mainly because fewer particles and less volatile organic compounds, methane and carbon monoxide are emitted. These results emphasize the need for a holistic view on biochar use in agricultural systems. Of special importance is the biochar production technique which has to be evaluated from both environmental/climate, health and social perspectives.

Antimony (Sb) contaminated shooting range soil: Sb mobility and immobilization by soil amendments.

Antimony (Sb) in lead bullets poses a major environmental risk in shooting range soils. Here we studied the effect of iron (Fe)-based amendments on the mobility of Sb in contaminated soil from shooting ranges in Norway. Untreated soil showed high Sb concentrations in water extracts from batch tests (0.22-1.59 mg L(-1)) and soil leachate from column tests (0.3-0.7 mg L(-1)), occurring exclusively as Sb(V). Sorption of Sb to different iron-based sorbents was well described by the Freundlich equation (Fe2(SO4)3, log KF = 6.35, n = 1.51; CFH-12 (Fe oxyhydroxide), log KF = 4.16-4.32, n = 0.75-0.76); Fe(0) grit, log KF = 3.26, n = 0.47). These sorbents mixed with soil (0.5 and 2% w/w), showed significant sorption of Sb in batch tests (46-92%). However, for Fe2(SO4)3 and CFH-12 liming was also necessary to prevent mobilization of lead, copper, and zinc. Column tests showed significant retention of Sb (89-98%) in soil amended with CFH-12 (2%) mixed with limestone (1%) compared to unamended soil. The sorption capacity of soils amended with Fe(0) (2%) increased steadily up to 72% over the duration period of the column test (64 days), most likely due to the gradual oxidation of Fe(0) to Fe oxyhydroxides. Based on the experimental results, CFH-12 and oxidized Fe(0) are effective amendments for the stabilization of Sb in shooting range soils.

Effect of activated carbon amendment on bacterial community structure and functions in a PAH impacted urban soil.

We collected urban soil samples impacted by polycyclic aromatic hydrocarbons (PAHs) from a sorbent-based remediation field trial to address concerns about unwanted side-effects of 2% powdered (PAC) or granular (GAC) activated carbon amendment on soil microbiology and pollutant biodegradation. After three years, total microbial cell counts and respiration rates were highest in the GAC amended soil. The predominant bacterial community structure derived from denaturing gradient gel electrophoresis (DGGE) shifted more strongly with time than in response to AC amendment. DGGE band sequencing revealed the presence of taxa with closest affiliations either to known PAH degraders, e.g. Rhodococcus jostii RHA-1, or taxa known to harbor PAH degraders, e.g. Rhodococcus erythropolis, in all soils. Quantification by real-time polymerase chain reaction yielded similar dioxygenases gene copy numbers in unamended, PAC-, or GAC-amended soil. PAH availability assessments in batch tests showed the greatest difference of 75% with and without biocide addition for unamended soil, while the lowest PAH availability overall was measured in PAC-amended, live soil. We conclude that AC had no detrimental effects on soil microbiology, AC-amended soils retained the potential to biodegrade PAHs, but the removal of available pollutants by biodegradation was most notable in unamended soil.

Large-scale field study on thin-layer capping of marine PCDD/F-contaminated sediments in Grenlandfjords, Norway: physicochemical effects.

A large-scale field experiment on in situ thin-layer capping was carried out in the polychlorinated dibenzodioxin and dibenzofuran (PCDD/F) contaminated Grenlandsfjords, Norway. The main focus of the trial was to test the effectiveness of active caps (targeted thickness of 2.5 cm) consisting of powdered activated carbon (AC) mixed into locally dredged clean clay. Nonactive caps (targed thickness of 5 cm) consisting of clay without AC as well as crushed limestone were also tested. Fields with areas of 10,000 to 40,000 m(2) were established at 30 to 100 m water depth. Auxiliary shaken laboratory batch experiments showed that 2% of the applied powdered AC substantially reduced PCDD/F porewater concentrations, by >90% for tetra-, penta- and hexa-clorinated congeners to 60-70% for octachlorinated ones. In-situ AC profiles revealed that the AC was mixed into the sediment to 3 to 5 cm depth in 20 months. Only around 25% of the AC was found inside the pilot fields. Sediment-to-water PCDD/F fluxes measured by in situ diffusion chambers were significantly lower at the capped fields than at reference fields in the same fjord, reductions being largest for the limestone (50-90%) followed by clay (50-70%), and the AC + clay (60%). Also reductions in overlying aqueous PCDD/F concentrations measured by passive samplers were significant in most cases (20-40% reduction), probably because of the large size of the trial fields. The AC was less effective in the field than in the laboratory, probably due to prolonged sediment-to-AC mass transfer times for PCDD/Fs and field factors such as integrity of the cap, new deposition of contaminated sediment particles, and bioturbation. The present field data indicate that slightly thicker layers of limestone and dredged clay can show as good physicochemical effectiveness as thin caps of AC mixed with clay, at least for PCDD/Fs during the first two years after cap placement.

A review of PFAS fingerprints in fish from Norwegian freshwater bodies subject to different source inputs.

The extensive use of per- and polyfluorinated alkyl substances (PFAS) has resulted in many environmental point and diffuse sources. Identifying the source responsible for a pollution hot spot is vital for assessing remediation measures, however, as there are many possible sources of environmental PFAS pollution, this can be challenging. Chemical fingerprinting has been proposed as an approach to identify contamination sources. Here, concentrations and profiles (relative distribution profiles) of routinely targeted PFAS in freshwater fish from eight sites in Norway, representing three different sources: (1) production of paper products, (2) the use of aqueous film forming foams (AFFF), and (3) long-range atmospheric transport, were investigated. The data were retrieved from published studies. Results showed that fingerprinting of PFAS in fish can be used to identify the dominant exposure source(s), and the profiles associated with the different sources were described in detail. Based on the results, the liver was concluded to be better suited for source tracking compared to muscle. PFAS fingerprints originating from AFFF were dominated by perfluorooctanesulfonate (PFOS) and other perfluoroalkanesulfonic acids (PFSA). Fingerprints originating from both long-range atmospheric transport and production of paper products were associated with high percentages of long chained perfluoroalkyl carboxylic acids (PFCA). However, there were differences between the two latter sources with respect to the ∑PFAS concentrations and ratios of specific PFCA pairs (PFUnDA/PFDA and PFTrDA/PFDoDA). Low ∑PFAS concentrations were detected in fish exposed mainly to PFAS via long-range atmospheric transport. In contrast, ∑PFAS concentrations were high and high percentages of PFOS were detected in fish exposed to pollution from production of paper products. The source-specific fingerprints described here can be used for source tracking.

Use of life cycle assessments to evaluate the environmental footprint of contaminated sediment remediation.

Ecological and human risks often drive the selection of remedial alternatives for contaminated sediments. Traditional human and ecological risk assessment (HERA) includes assessing risk for benthic organisms and aquatic fauna associated with exposure to contaminated sediments before and after remediation as well as risk for human exposure but does not consider the environmental footprint associated with implementing remedial alternatives. Assessment of environmental effects over the whole life cycle (i.e., Life Cycle Assessment, LCA) could complement HERA and help in selecting the most appropriate sediment management alternative. Even though LCA has been developed and applied in multiple environmental management cases, applications to contaminated sediments and marine ecosystems are in general less frequent. This paper implements LCA methodology for the case of the polychlorinated dibenzo-p-dioxins and -furans (PCDD/F)-contaminated Grenland fjord in Norway. LCA was applied to investigate the environmental footprint of different active and passive thin-layer capping alternatives as compared to natural recovery. The results showed that capping was preferable to natural recovery when analysis is limited to effects related to the site contamination. Incorporation of impacts related to the use of resources and energy during the implementation of a thin layer cap increase the environmental footprint by over 1 order of magnitude, making capping inferior to the natural recovery alternative. Use of biomass-derived activated carbon, where carbon dioxide is sequestered during the production process, reduces the overall environmental impact to that of natural recovery. The results from this study show that LCA may be a valuable tool for assessing the environmental footprint of sediment remediation projects and for sustainable sediment management.

In situ measurement of PCB pore water concentration profiles in activated carbon-amended sediment using passive samplers.

Vertical pore water profiles of in situ PCBs were determined in a contaminated mudflat in San Francisco Bay, CA, 30 months after treatment using an activated carbon amendment in the upper layer of the sediment. Pore water concentrations were derived from concentrations of PCBs measured in two passive samplers; polyethylene (PE, 51 µm thick) and polyoxymethylene (POM, 17 µm thick) at different sediment depths. To calculate pore water concentrations from PCB contents in the passive samplers, an equilibrium approach and a first-order uptake model were applied, using five performance reference compounds to estimate pore water sampling rates. Vertical pore water profiles showed good agreement among the measurement and calculation methods with variations within a factor of 2, which seems reasonable for in situ measurements. The close agreements of pore water estimates for the two sampler materials (PE and POM) and the two methods used to translate uptake in samplers to pore water concentrations demonstrate the robustness and suitability of the passive sampling approach. The application of passive samplers in the sediment presents a promising method for site monitoring and remedial treatment evaluation of sorbent amendment or capping techniques that result in changes of pore water concentrations in the sediment subsurface.

Remediation of contaminated marine sediment using thin-layer capping with activated carbon--a field experiment in Trondheim harbor, Norway.

In situ amendment of contaminated sediments using activated carbon (AC) is a recent remediation technique, where the strong sorption of contaminants to added AC reduces their release from sediments and uptake into organisms. The current study describes a marine underwater field pilot study in Trondheim harbor, Norway, in which powdered AC alone or in combination with sand or clay was tested as a thin-layer capping material for polycyclic aromatic hydrocarbon (PAH)-contaminated sediment. Several novel elements were included, such as measuring PAH fluxes, no active mixing of AC into the sediment, and the testing of new manners of placing a thin AC cap on sediment, such as AC+clay and AC+sand combinations. Innovative chemical and biological monitoring methods were deployed to test capping effectiveness. In situ sediment-to-water PAH fluxes were measured using recently developed benthic flux chambers. Compared to the reference field, AC capping reduced fluxes by a factor of 2-10. Pore water PAH concentration profiles were measured in situ using a new passive sampler technique, and yielded a reduction factor of 2-3 compared to the reference field. The benthic macrofauna composition and biodiversity were affected by the AC amendments, AC + clay having a lower impact on the benthic taxa than AC-only or AC + sand. In addition, AC + clay gave the highest AC recoveries (60% vs 30% for AC-only and AC + sand) and strongest reductions in sediment-to-water PAH fluxes and porewater concentrations. Thus, application of an AC-clay mixture is recommended as the optimal choice of the currently tested thin-layer capping methods for PAHs, and more research on optimizing its implementation is needed.

Excavated vs novel in situ soil washing as a remediation strategy for sandy soils impacted with per- and polyfluoroalkyl substances from aqueous film forming foams.

In situ soil washing at the field scale has not yet been investigated as a remediation strategy for soils impacted by per- and polyfluoroalkyl substances (PFAS). This remediation strategy is a promising low-cost alternative to other costlier remediation options like excavating, transporting and landfilling large amounts of PFAS contaminated soil. However, it is unclear if it is effective at the field scale, where large areas of heterogenous soil can be challenging to saturate with infiltration water and then pump to a treatment facility. To address this for the first time, herein we established three different trials involving in situ washing of an undisturbed, 3 m deep, sandy vadose zone soil contaminated with aqueous film forming foam (AFFF). The trials were performed at a site with an established pump and treat system for treating PFAS contaminated groundwater. In situ soil washing was compared to the more conventional practice of washing excavated soil on top of an impermeable bottom lining where the PFAS contaminated water was collected and monitored in a drainage system before treatment. The measured amount of perfluorooctane sulfonate (PFOS) removed was compared with expectations based on a non-calibrated, 1-D first order rate saturated soil model using only the local soil-to-water distribution coefficient as well as the volume and irrigation rate of wash water as input. This model predicted results within a factor of 2. The suspected reasons for small discrepancies between model predictions and excavated vs in situ washing was a combination of the heterogeneity of PFOS distribution in the soil as well as preferential flow paths during soil washing that prevented full saturation. This analysis showed that in situ soil washing was more efficient and less costly than washing excavated sandy soil, particularly if a pump-and-treat system is already in place.

The fate of poly- and perfluoroalkyl substances in a marine food web influenced by land-based sources in the Norwegian Arctic.

Although poly- and perfluorinated alkyl substances (PFAS) are ubiquitous in the Arctic, their sources and fate in Arctic marine environments remain unclear. Herein, abiotic media (water, snow, and sediment) and biotic media (plankton, benthic organisms, fish, crab, and glaucous gull) were sampled to study PFAS uptake and fate in the marine food web of an Arctic Fjord in the vicinity of Longyearbyen (Svalbard, Norwegian Arctic). Samples were collected from locations impacted by a firefighting training site (FFTS) and a landfill as well as from a reference site. Mean concentration in the landfill leachate was 643 ± 84 ng L-1, while it was 365 ± 8.0 ng L-1 in a freshwater pond and 57 ± 4.0 ng L-1 in a creek in the vicinity of the FFTS. These levels were an order of magnitude higher than in coastal seawater of the nearby fjord (maximum level , at the FFTS impacted site). PFOS was the most predominant compound in all seawater samples and in freshly fallen snow (63-93% of ). In freshwater samples from the Longyear river and the reference site, PFCA ≤ C9 were the predominant PFAS (37-59%), indicating that both local point sources and diffuse sources contributed to the exposure of the marine food web in the fjord. concentrations increased from zooplankton (1.1 ± 0.32 µg kg-1 ww) to polychaete (2.8 ± 0.80 µg kg-1 ww), crab (2.9 ± 0.70 µg kg-1 ww whole-body), fish liver (5.4 ± 0.87 µg kg-1 ww), and gull liver (62.2 ± 11.2 µg kg-1). PFAS profiles changed with increasing trophic level from a large contribution of 6:2 FTS, FOSA and long-chained PFCA in zooplankton and polychaetes to being dominated by linear PFOS in fish and gull liver. The PFOS isomer profile (branched versus linear) in the active FFTS and landfill was similar to historical ECF PFOS. A similar isomer profile was observed in seawater, indicating major contribution from local sources. However, a PFOS isomer profile enriched by the linear isomer was observed in other media (sediment and biota). Substitutes for PFOS, namely 6:2 FTS and PFBS, showed bioaccumulation potential in marine invertebrates. However, these compounds were not found in organisms at higher trophic levels.

Field measurement of diffusional mass transfer of HOCs at the sediment-water interface.

The sediment to water diffusive flux of PAHs and PCBs was measured under field conditions with a novel infinite-sink benthic flux chamber that deployed semipermeable membrane devices (SPMD) as a sorbing material. Fluxes were measured before and after in situ capping of sediments in Oslo Harbour with clean clay. The fluxes of native pyrene and PCB 52 from uncapped contaminated sediment measured with the flux chamber were 0.3-1.6 microg m(-2) d(-1) and 2-8 ng m(-2) d(-1), respectively. Fluxes from the capped sediment were reduced by 93-97%. The in situ measured fluxes were compared to fluxes independently calculated from freely dissolved concentrations in pore water and overlying water, measured using equilibrium passive samplers, diffusive boundary layer (DBL) thickness, measured by an alabaster dissolution method and literature values of diffusion coefficients. Measured fluxes from the uncapped sediment agreed well with calculated fluxes, the median of the ratio of the measured flux over the calculated flux was 0.9 with an inter quartile range of 0.5-1.6.

The presence, emission and partitioning behavior of polychlorinated biphenyls in waste, leachate and aerosols from Norwegian waste-handling facilities.

Even though production and open use of polychlorinated biphenyls (PCBs) have been phased out in Western industrialised countries since the 1980s, PCBs were still present in waste collected from different waste handling facilities in Norway in 2013. Sums of seven indicator-PCBs (I-PCB7: PCB-28, -52, -101, -118, -138, -153 and -180) were highest in plastic waste (3700 ±1800 µg/kg, n=15), waste electrical and electronic equipment (WEEE) (1300 ± 400 µg/kg, n=12) and fine vehicle fluff (1800 ± 1400 µg/kg, n=4) and lowest in glass waste, combustibles, bottom ash and fly ash (0.3 to 65 µg/kg). Concentrations in leachate water varied from 1.7 to 2900 ng/L, with higher concentrations found at vehicle and WEEE handling facilities. Particles in leachate water exhibited similar PCB sorption properties as solid waste collected on site, with waste-water partitioning coefficients ranging from 105 to 107. I-PCB7 in air samples collected at the sites were mostly in the gas phase (100-24000 pg/m3), compared to those associated with particles (9-1900 pg/m3). In contrast, brominated flame retardants (BFRs) in the same samples were predominantly found associated with particles (e.g. sum of 10 brominated diethyl ethers, ΣBDE10, associated with particles 77-194,000 pg/m3) compared to the gas phase (ΣBDE10 6-473 pg/m3). Measured gas-phase I-PCB7 concentrations are less than predicted, assuming waste-air partitioning in equilibrium with predominant waste on site. However, the gas-particle partitioning behavior of PCBs and BFRs could be predicted using an established partitioning model for ambient aerosols. PCB emissions from Norwegian waste handling facilities occurred primarily in the form of atmospheric vapor or leachate particles.

Paper product production identified as the main source of per- and polyfluoroalkyl substances (PFAS) in a Norwegian lake: Source and historic emission tracking.

The entirety of the sediment bed in lake Tyrifjorden, Norway, is contaminated by per- and polyfluoroalkyl substances (PFAS). A factory producing paper products and a fire station were investigated as possible sources. Fire station emissions were dominated by the eight carbon perfluoroalkyl sulfonic acid (PFSA), perfluorooctanesulfonic acid (PFOS), from aqueous film forming foams. Factory emissions contained PFOS, PFOS precursors (preFOS and SAmPAP), long chained fluorotelomer sulfonates (FTS), and perfluoroalkyl carboxylic acids (PFCA). Concentrations and profiles in sediments and biota indicated that emissions originating from the factory were the main source of pollution in the lake, while no clear indication of fire station emissions was found. Ratios of linear-to branched-PFOS increased with distance from the factory, indicating that isomer profiles can be used to trace a point source. A dated sediment core contained higher concentrations in older sediments and indicated that two different PFAS products have been used at the factory, referred to here as Scotchban and FTS mixture. Modelling, based on the sediment concentrations, indicated that 42-189 tons Scotchban, and 2.4-15.6 tons FTS mixture, were emitted. Production of paper products may be a major PFAS point source, that has generally been overlooked. It is hypothesized that paper fibres released from such facilities are important vectors for PFAS transport in the aquatic environment.

Leaching and transport of PFAS from aqueous film-forming foam (AFFF) in the unsaturated soil at a firefighting training facility under cold climatic conditions.

The contaminant situation at a Norwegian firefighting training facility (FTF) was investigated 15 years after the use of perfluorooctanesulfonic acid (PFOS) based aqueous film forming foams (AFFF) products had ceased. Detailed mapping of the soil and groundwater at the FTF field site in 2016, revealed high concentrations of per- and polyfluoroalkyl substances (PFAS). PFOS accounted for 96% of the total PFAS concentration in the soil with concentrations ranging from <0.3 µg/kg to 6500 µg/kg. The average concentration of PFOS in the groundwater down-gradient of the site was 22 µg/l (6.5-44.4 µg/l), accounting for 71% of the total PFAS concentration. To get a better understanding of the historic fate of AFFF used at the site, unsaturated column studies were performed with pristine soil with a similar texture and mineralogy as found at the FTF and the same PFOS containing AFFF used at the site. Transport and attenuation processes governing PFAS behavior were studied with focus on cold climate conditions and infiltration during snow melting, the main groundwater recharge process at the FTF. Low and high water infiltration rates of respectively 4.9 and 9.7 mm/day were applied for 14 and 7 weeks, thereby applying the same amount of water, but changing the aqueous saturation of the soil columns. The low infiltration rate represented 2 years of snow melting, while the high infiltration rate can be considered to mimic the extra water added in the areas with intensive firefighting training. In the low infiltration experiment PFOS was not detected in the column leachate over the complete 14 weeks. With high infiltration PFOS was detected after 14 days and concentrations increased from 20 ng/l to 2200 ng/l at the end of the experiment (49 days). Soil was extracted from the columns in 5 cm layers and showed PFOS concentrations in the range < 0.21-1700 µg/kg in the low infiltration column. A clear maximum was observed at a soil depth of 30 cm. No PFOS was detected below 60 cm depth. In the high infiltration column PFOS concentration ranged from 7.4 to 1000 µg/kg, with highest concentrations found at 22-32 cm depth. In this case PFOS was detected down to the deepest sample (~90 cm). Based on the field study, retardation factors for the average vertical transport of PFOS in the unsaturated zone were estimated to be 33-42 and 16-21 for the areas with a low and high AFFF impact, respectively. The estimated retardation factors for the column experiments were much lower at 6.5 and 5.8 for low and high infiltration, respectively. This study showed that PFOS is strongly attenuated in the unsaturated zone and mobility is dependent on infiltration rate. The results also suggest that the attenuation rate increases with time.

Vertical profiles of sedimentary polycyclic aromatic hydrocarbons and black carbon in the Gulf of Gdansk (Poland) and Oslofjord/Drammensfjord (Norway), and their relation to regional energy transitions.

The analysis of undisturbed sediment cores is a powerful tool for understanding spatial and temporal impacts of anthropogenic emissions from the energy and transport sectors at a regional scale. The spatial and vertical distribution of polycyclic aromatic hydrocarbons (PAHs) and black carbon (BC) were determined in 12 cores of recent (up to 20cm long) sediments from the Gulf of Gdansk in Poland, and Oslofjord/Drammensfjord in Norway. The Σ12PAHs levels in individual sediment layers varied from 250 to 4500ng/g d.w. in the Gulf of Gdansk, and from 210 to 4580ng/g d.w. in the Norwegian fjords. Analysis of PAH ratios indicates that PAHs in both studied areas originated mainly from pyrogenic sources. The BC concentrations in sediments were up to 0.9% and were generally higher in the Gulf of Gdansk (mean - 0.39%) than in Oslofjord/Drammensfjord (mean - 0.19%). The deposition history of anthropogenic emissions over the last 100years was reconstructed based on the analysis of dated and well-laminated sediment cores from two stations from the Gulf of Gdansk and two stations from the Norwegian fjords. The evolution in energy structure was especially evident in the Oslofjord, where transition from fossil fuel combustion to hydropower after 1960 coincided with a sharp decrease in sedimentary PAHs. Despite significant changes in the economic development in Poland, temporal patterns in PAH concentrations/profiles in the Gulf of Gdansk were not as obvious. The historical PAH trends in the Gulf of Gdansk may be related to the overwhelming PAH inputs from domestic combustion of solid fuels (coal, wood) for heating purposes. The implementation of legislation and other activities addressed to restrict the use of solid fuels in residential heating should reduce PAH emissions.

Passive samplers versus surfactant extraction for the evaluation of PAH availability in sediments with variable levels of contamination.

The purpose of this study was to test the efficiency of passive solid samplers, polyoxymethylene (POM) strips and polydimethylsiloxane (PDMS) silicon tubing, to predict the bioavailability of native PAHs in contaminated sediments. Results were compared with worm bioaccumulation data and solid/liquid extraction using the surfactant Brij((R)) 700 (B700). The two passive samplers were found to act differently. The PDMS sampler overestimated the availability of PAHs in all studied sediments. The POM method provided results in accordance with those obtained with the B700 extraction. However, POM and B700 methods underestimated PAH availability in low contaminated sediments where biological factors (digestible organic matter) become important. Bioavailability of total PAHs was correctly predicted by POM and B700 in highly contaminated aluminum smelter sediments. A closer examination of individual PAH results indicated that both techniques overestimated the availability of large molecules with logK(ow)>6 suggesting a biological mechanism limiting uptake of larger PAHs which seems to be related to the molecular size of compounds.