| 1. |
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| 2. |
- Bignert, Anders, et al.
(författare)
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Comments Concerning the National Swedish Contaminant Monitoring Programme in Marine Biota, 2015
- 2015
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Rapport (övrigt vetenskapligt/konstnärligt)abstract
- The environmental toxicants examined in this report can be classified into five groups – heavy metals, chlorinated compounds, brominated flame retardants, polyaromatic hydrocarbons and perfluorinated compounds. Each of these contaminants have been examined from various sites for up to six different fish species, in blue mussels, and in guillemot eggs, for varying lengths of time. The following summary examines overall trends, spatial and temporal, for the five groups.Condition and Fat ContentCondition and fat content in different species tended to follow the same pattern at the same sites, with a few exceptions. Most of the fish species generally displayed a decreasing trend in both condition and fat content at most sites examined. Exceptions to this were increases in condition factor seen in cod liver at Fladen, perch muscle at Kvädöfjärden, and for herring at Ängskärsklubb in spring. Also, an increase in fat content was seen during the most recent ten years for herring at Ängskärsklubb in spring. There were also some sites where no log linear trends were seen.Heavy MetalsDue to a change in methods for metal analysis (not mercury) in 2004, values between 2003 and 2007 should be interpreted with care. From 2009 metals are analyzed at ACES, Stockholm University.Generally, higher mercury concentrations are found in the Bothnian Bay, but also from one station in the Northern parts of Baltic Proper, compared to other parts of the Swedish coastline. The time series show varying concentrations over the study period. The longer time series in guillemot egg and spring-caught herring from the southern Bothnian Sea and southern Baltic Proper show significant decreases of mercury. On the other hand, increasing concentrations are seen in e.g., cod muscle, but the concentrations are fairly low compared to measured concentrations in perch from fresh water and coastal sites. In most cases, the mercury concentrations are above the EQSbiota of 20 ng/g wet weight.Lead is generally decreasing over the study period (in time series of sufficient length), supposedly due to the elimination of lead in gasoline. The highest concentrations are seen in the southern part of the Baltic Sea. Elevated lead concentrations between 2003 and 2007 (e.g. Harufjärden) should be viewed with caution (see above regarding change in analysis methods). Lead concentrations are below the suggested target level at all stations.Cadmium concentrations show varying non-linear trends over the monitored period. It is worth noting that despite several measures taken to reduce discharges of cadmium, generally the most recent concentrations are similar to concentrations measured 30 yearsago in the longer time series. Cadmium concentrations in herring and perch are all below the suggested target level of 160 μg/kg wet weight.The reported nickel concentrations show no consistent decreasing trends. Some series begin with two elevated values that exert a strong leverage effect on the regression line and may give a false impression of decreasing trends. Chromium generally shows decreasing concentrations, possibly explained by a shift in analytical method. The essential trace metals, copper and zinc, show no consistent trends during the monitored period.Generally higher concentrations of arsenic and silver are found along the west coast compared to other parts of the Sweadish coast line. However for silver a few stations in the Bothnian Sea and Bothnian Bay show comparable concentrations to the west coast stations.Chlorinated CompoundsGenerally, a decreasing concentrations were observed for all compounds (DDT’s, PCB’s, HCH’s, HCB) in all species examined, with a few exceptions, such as no change in TCDD-equivalents being seen in herring muscle (except at Änskärsklubb where very high concentrations at the beginning of the sampling period were seen and also at the west coast station Fladen). The longer time-series in guillemot also show a marked decrease in TCDD-equivalents from the start in the late 1960s until about 1985 from where no change occurred for many years, however, during the most recent ten years a decrease in the concentration is seen. Concentrations of DDE and CB-118 are for some species and sites still above their respective target levels.The chlorinated compounds generally show higher concentrations in the Bothnian Sea and/or Baltic Proper when compared to the Bothnian Bay and the Swedish west coast.Brominated Flame RetardantsElevated levels of HBCDD are seen in sites from the Baltic Proper, while the investigated PBDEs show higher concentrations in the Bothnian Bay. In addition, lower concentrations of all investigated PBDEs and HBCDD are seen on the Swedish west coast compared to the east coast. Temporally, significant increases in BDE-47, -99 and -100 have been seen in guillemot eggs since the late 1960s until the early 1990s, where concentrations then began to show decreases. Also, the concentration of HBCDD in guillemot eggs shows a decrease during the most recent ten years. For fish and blue mussels, BDE-47, -99, and -153 decreased at some sites and showed no trend at other sites. The concentration of HBCDD in fish and blue mussels showed inconsistent trends. The concentration of HBCDD is below the EQSbiota of 167 μg/kg wet weight for all fish species from all areas, while the concentration of BDE-47 alone is above the EQSbiota for sumPBDE of 0.0085 ng/g wet weight.PAHsOnly blue mussels have been examined for spatial differences in PAH concentrations. Concentration of ΣPAH was found to be higher from Kvädöfjärden in the Baltic Proper compared to stations at the West coast, but individual PAHs showed varying spatial patterns. Over time, acenaphthalene was rarely found above the detection limit. Significant decreasing trends were observed for ΣPAH, chrysene, fluoranthene and pyrene at Fjällbacka; for naphthalene at Kvädöfjärden; and for pyrene at Fladen.All time series where concentrations of various PAHs were compared with the target value based on OSPAR Ecological Assessment Criteria, or EC Environmental Quality Standards were below the target value.PFASsPFHxS and PFOS show a similar spatial pattern, but PFOS concentrations were approximately 25 times higher than PFHxS levels. The distribution of PFOS is quite homogenous along the Swedish coast but with somewhat higher concentrations in the Baltic Proper. PFOS concentrations in guillemot eggs are about 100-200 times higher than in herring liver. An overall increasing concentration of PFOS in guillemot eggs has been observed throughout the whole time period, however, during the most recent ten years, a change of direction is detected. The longer herring time series from Harufjärden, Landsort, and Utlängan show increasing concentrations for PFOS and most carboxylates. For FOSA, on the other hand, decreasing concentrations are seen during the most recent ten years.Organotin compoundsThe majority of the analysed tinorganic compounds showed concentrations below LOQ. However TBT and DPhT showed concentrations above LOQ at all stations with highest reported concentrations in fish from Örefjärden in the northern part of Bothnian Sea.
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| 3. |
- Bizkarguenaga, Ekhine, et al.
(författare)
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Enrichment of perfluorinated alkyl substances on polyethersulfone using 1-methylpyperidine as ion-pair reagent for the clean-up of carrot and amended soil extracts
- 2015
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Ingår i: Talanta. - : Elsevier BV. - 0039-9140 .- 1873-3573. ; 143, s. 263-270
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Tidskriftsartikel (refereegranskat)abstract
- The development of a simple, cheap and environment friendly analytical method for the simultaneous determination of different perfluoroalkyl substances (PFASs) including seven perfluoroalkyl carboxylic acids, three perfluoroalkane sulfonic acids and perfluorooctanesulfonamide in carrot and amended soil was carried out in the present work. The method was based on focused ultrasound solid-liquid extraction followed by extract clean-up through enrichment of the target compounds on a polymeric material using an ion-pair reagent and detection by liquid chromatography-tandem mass spectrometry. The following variables affecting the clean-up step were evaluated: the nature of the polymeric material (polyethersulfone, PES, versus silicone rod), the amount of the polymeric material (from 1 to 9 mg), the ion-pair reagent (1-methylpyperidine, 1-MP, versus tetrabutylammonium salts), the concentration of the ion-pair reagent (from 5 to 50 mM) and the extraction time (from 15 min to 24 h). Optimum clean-up conditions were obtained using preconcentration on 9 mg of PES polymeric material combined with 5 mM 1-MP as ion-pair reagent for 3 h. The method was validated in terms of apparent recoveries in the range of 77-140% and 95-137% at the low concentration (50 ng g(-1)) and in the range of 70-136% and 79-132% at the high concentration (290 ng g(-1)) for amended soil and carrot, respectively, after correction with the corresponding labeled standards. Precision, as relative standard deviation, was within 2-23%, while method detection limits were 0.31-2.85 ng g(-1) for amended soil and 0.11-1.83 ng g(-1) for carrot. In the absence of a certified reference material for the target analytes in the matrices studied, inter-method comparison was carried out and the same samples were processed using two independent clean-up procedures, the one developed in the present work and a classical based on solid-phase extraction. Statistically comparable results were obtained according to the one-way analysis of variance for peel, core, leaves as well as amended soil (F-Calc= 2.59, 5.06, 5.82 and 2.34 < F-Crit= 7.71). Finally, the method was applied for the determination of PFASs in uptake experiments where carrots were cultivated in an amended soil polluted with perfluorooctane sulfonic acid (PFOS) at 500 ng g(-1) level. The highest concentration was measured in the carrot leaves (669 ng g(-1)), while the concentrations in peel and core were at the same level (72 ng g(-1) and 62 ng g(-1) respectively), concluding that translocation of PFOS from the soil to the leaves had occurred.
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| 4. |
- Bogdal, Christian, et al.
(författare)
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Fast Quantification of Chlorinated Paraffins in Environmental Samples by Direct Injection High-Resolution Mass Spectrometry with Pattern Deconvolution
- 2015
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Ingår i: Analytical Chemistry. - : American Chemical Society (ACS). - 0003-2700 .- 1520-6882. ; 87:5, s. 2852-2860
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Tidskriftsartikel (refereegranskat)abstract
- Chlorinated paraffins (CPs) are high production volume chemicals, but data about their environmental fate are scarce. CP mixtures composed of thousands of isomers represent a major challenge for quantification at low levels in environmental samples. Here, we present a novel analytical method for analysis of short-chain, medium-chain, and long-chain CPs in a single injection, that also yields information about congener group pattern. Our detection method is based on direct injection into an atmospheric pressure chemical ionization source operated in negative ion mode under chlorine-enhanced conditions, followed by quadrupole time-of-flight high-resolution mass spectrometry (APCI-qTOF-HRMS) operated in full-scan mode. A mathematical algorithm is applied to deconvolute the CP patterns in the analyzed samples into a linear combination of patterns of technical CP mixtures and to quantify CPs using technical mixtures as external calibration standards. For CP mixtures with known composition, the new method provided concentrations that were within a factor of 1.2 of the target value. Accuracies for CPs spiked to sediment and fish extracts were between 91% and 123%. Concentrations determined in unspiked field samples were within a factor of 5 for short-chain CPs and a factor of 16 for medium-chain CPs of results obtained with an independent method based on gas chromatography/electron capture negative ionization high-resolution mass spectrometry (GC/ECNI-HRMS). The presented APCI-qTOF-HRMS pattern deconvolution method is an interesting alternative for CP analysis in environmental samples. It is particularly sensitive for medium- and long-chain CPs and has the advantage of being extremely fast (instrumental analysis time, less than 1 min).
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| 5. |
- Faxneld, Suzanne, et al.
(författare)
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Temporal Trends and Geographical Differences of Perfluoroalkyl Acids in Baltic Sea Herring and White-Tailed Sea Eagle Eggs in Sweden
- 2016
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Ingår i: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 50:23, s. 13070-13079
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Tidskriftsartikel (refereegranskat)abstract
- 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.
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| 6. |
- Filipovic, Marko, 1985-
(författare)
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Fate of perfluoroalkyl acids in the aquatic environment with a focus on mass balance studies
- 2015
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Perfluoroalkyl substances (PFASs) are man-made chemicals. Their unique properties make them beneficial for a wide range of industrial and consumer product applications, such as in aqueous film forming foam (AFFF), durable water repellent clothing, hydraulic oils and food packaging materials. Perfluoroalkyl acids (PFAAs), a class of PFASs, are highly persistent in the environment, and long chain PFAAs are bioaccumulative and toxic. International regulation and voluntary actions by the industry have been implemented and led to a recent reduction of primary emissions of PFAAs to the environment. However, point sources such as AFFF training sites as well as diffuse sources continue to contaminate water bodies, soil and biota. Reducing environmental pollution with PFAAs has therefore become a regulatory priority. Designing successful measures to reduce the PFAA contamination requires an understanding of the sources, transport and fate of PFAAs in the environment.Four scientific publications are included in this PhD thesis, which aimed at increasing the holistic understanding of the fate of PFAAs in aquatic systems. This was achieved by chemical trace analysis combined with mass balance modeling. The following topics were covered: Dispersion and fate of PFAAs from an AFFF-impacted site (Paper I), recirculation of PFAAs in the aquatic environment with focus on waste water treatment plants (WWTPs, Paper II), mass balance of PFAAs in the Baltic Sea (Paper III) and transport and fate of PFAAs in two pristine boreal stream catchments (Paper IV).Results from Paper I showed that AFFF-impacted sites at a former military airfield, which was abandoned for more than 30 years, continue to be point sources of PFAAs to recipients. The sum of PFAAs in the ground water and surface waters ranged from 740 to 51000 ng L-1 and <0.5 to 79 ng L-1, respectively. PFOS in muscle tissue of European perch from a nearby lake ranged from 77 to 370 ng g-1 wet weight, representing among the highest values reported worldwide for fish muscle. In Paper II the relative importance of environmental recirculation of PFAAs versus new releases from the technosphere was investigated for PFAAs in WWTP influents. It was shown that tap water can be an important source of PFAAs to WWTPs in areas with elevated environmental levels. This needs to be taken into account when calculating emissions via WWTP effluents. PFAA mass balances over the WWTPs suggested that PFHxA and PFOA were formed from precursor compounds within the plants. Assembled PFAA mass balances for the Baltic Sea (Paper III) showed that river inflow and atmospheric deposition were the dominant input pathways, while wastewater treatment plant (WWTP) effluents discharging directly into the Baltic Sea made a minor contribution. The inputs of PFAAs were estimated to be higher than the outputs, suggesting a current increase of the PFAA inventory in the Baltic Sea. Also the mass balance study of PFAAs in two remote stream catchments presented in Paper IV revealed that inputs dominated over outputs for both catchments, indicating that a considerable portion of the PFAAs deposited from the atmosphere is retained in soil or in deep ground water and may be released to surface and marine water environments in the future
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| 7. |
- Filipovic, Marko, et al.
(författare)
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Mass Balance of Perfluorinated Alkyl Acids in a Pristine Boreal Catchment
- 2015
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Ingår i: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 49:20, s. 12127-12135
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Tidskriftsartikel (refereegranskat)abstract
- Mass balances of ten individual perfluorinated alkyl acids (PFAAs) in two nested pristine catchments in Northern Sweden with different sizes and hydrological functions were assembled for 2011-2012. Concentrations of PFAAs in rain and snowmelt, as well as in streamwater at the outlet of the two watersheds were measured and used to calculate PFAA atmospheric inputs to and riverine outputs from the catchments. The results generally showed a great excess of PFAA inputs for both catchments over the whole study year. However, during the spring flood period, the inputs and outputs were within a factor of 2 for several PFAAs and the streamwater showed PFAA patterns resembling the patterns in rain (as opposed to snowmelt), suggesting that snowmelt water infiltrating the ground had displaced water from the previous summer. Comparison of PFAA mass balances between the two catchments further suggested that atmospheric inputs of short-chain (replacement) perfluoroalkyl carboxylic acids had increased in the years before sampling, while inputs of the legacy perfluorooctane sulfonic acid had decreased. Overall, the mass balances indicate that a considerable portion of the PFAAs deposited from the atmosphere are stored in soil and may be released to surface and marine water environments in the future.
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| 8. |
- Gebbink, Wouter A., et al.
(författare)
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Estimating human exposure to PFOS isomers and PFCA homologues : The relative importance of direct and indirect (precursor) exposure
- 2015
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Ingår i: Environment International. - : Elsevier BV. - 0160-4120 .- 1873-6750. ; 74, s. 160-169
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Tidskriftsartikel (refereegranskat)abstract
- Contributions of direct and indirect (via precursors) pathways of human exposure to perfluorooctane sulfonic acid (PFOS) isomers and perfluoroalkyl carboxylic acids (PFCAs) are estimated using a Scenario-Based Risk Assessment (SceBRA) modelling approach. Monitoring data published since 2008 (including samples from 2007) are used. The estimated daily exposures (resulting from both direct and precursor intake) for the general adult population are highest for PFOS and perfluorooctanoic acid (PFOA), followed by perfluorohexanoic add (PFHxA) and perfluorodecanoic acid (PFDA), while lower daily exposures are estimated for perfluorobutanoic acid (PFBA) and perfluorododecanoic acid (PFDoDA). The precursor contributions to the individual perfluoroalkyl acid (PFAA) daily exposures are estimated to be 11-33% for PFOS, 0.1-2.5% for PFBA, 3.7-34% for PFHxA, 13-64% for PFOA, 5.2-66% for PFDA, and 0.7-25% for PFDoDA (ranges represent estimated precursor contributions in a low- and high-exposure scenario). For PFOS, direct intake via diet is the major exposure pathway regardless of exposure scenario. For PFCAs, the dominant exposure pathway is dependent on perfluoroalkyl chain length and exposure scenario. Modelled PFOS and PFOA concentrations in human serum using the estimated intakes from an intermediate-exposure scenario are in agreement with measured concentrations in different populations. The isomer pattern of PFOS resulting from total intakes (direct and via precursors) is estimated to be enriched with linear PFOS (84%) relative to technical PFOS (70% linear). This finding appears to be contradictory to the observed enrichment of branched PFOS isomers in recent human serum monitoring studies and suggests that either external exposure is not fully understood (e.g. there are unknown precursors, missing or poorly quantified exposure pathways) and/or that there is an incomplete understanding of the isomer-specific human pharmacokinetic processes of PFOS, its precursors and intermediates.
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| 9. |
- Gebbink, Wouter A., et al.
(författare)
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Perfluoroalkyl acids and their precursors in Swedish food : The relative importance of direct and indirect dietary exposure
- 2015
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Ingår i: Environmental Pollution. - : Elsevier BV. - 0269-7491 .- 1873-6424. ; 198, s. 108-115
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Tidskriftsartikel (refereegranskat)abstract
- We analyzed food market basket samples obtained in Sweden from 1999, 2005, and 2010 for perfluoroallcyl acids (PFAAs) and a range of precursor compounds. Perfluorooctane sulfonic acid (PFOS) precursors were detected in all food year pools with the highest concentrations in 1999. Six polyfluoroalkyl phosphate diesters (diPAPs, 4:2/6:2, 6:2/6:2, 6:2/8:2, 8:2/8:2, 6:2/10:2, and 10:2/10:2) were detected in the year pools with the highest Sigma diPAP concentrations in 1999 and 2005. All precursors were predominantly found in meat, fish, and/or eggs based on analysis of individual food groups from 1999. Based on year pools, PFOS precursors contributed between 4 and 1% as an indirect source to total dietary PFOS intakes between 1999 and 2010. Perfluorohexanoic acid (PFHxA) exposure originated entirely from diPAPs, whereas for perfluorooctanoic acid (PFOA) and perfluorodecanoic acid (PFDA), diPAPs contributed between 1 and 19% to total exposure. The lowest precursor contributions were generally seen in food samples from 2010.
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| 10. |
- Gebbink, Wouter A., et al.
(författare)
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Perfluoroalkyl Acids (PFAAs) and Selected Precursors in the Baltic Sea Environment : Do Precursors Play a Role in Food Web Accumulation of PFAAs?
- 2016
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Ingår i: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 50:12, s. 6354-6362
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Tidskriftsartikel (refereegranskat)abstract
- 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.
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