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1.
  • Bidleman, Terry F., et al. (författare)
  • Bromoanisoles and Methoxylated Bromodiphenyl Ethers in Macroalgae from Nordic Coastal Regions
  • 2019
  • Ingår i: Environmental Science. - London : Royal Society of Chemistry. - 2050-7887 .- 2050-7895. ; , s. 881-892
  • Tidskriftsartikel (refereegranskat)abstract
    • Marine macroalgae are used worldwide for human consumption, animal feed, cosmetics and agriculture. In addition to beneficial nutrients, macroalgae contain halogenated natural products (HNPs), some of which have toxic properties similar to those of well-known anthropogenic contaminants. Sixteen species of red, green and brown macroalgae were collected in 2017–2018 from coastal waters of the northern Baltic Sea, Sweden Atlantic and Norway Atlantic, and analyzed for bromoanisoles (BAs) and methoxylated bromodiphenyl ethers (MeO-BDEs). Target compounds were quantified by gas chromatography-low resolution mass spectrometry (GC-LRMS), with qualitative confirmation in selected species by GC-high resolution mass spectrometry (GC-HRMS). Quantified compounds were 2,4-diBA, 2,4,6-triBA, 2′-MeO-BDE68, 6-MeO-BDE47, and two tribromo-MeO-BDEs and one tetrabromo-MeO-BDE with unknown bromine substituent positions. Semiquantitative results for pentabromo-MeO-BDEs were also obtained for a few species by GC-HRMS. Three extraction methods were compared; soaking in methanol, soaking in methanol–dichloromethane, and blending with mixed solvents. Extraction yields of BAs did not differ significantly (p > 0.05) with the three methods and the two soaking methods gave equivalent yields of MeO-BDEs. Extraction efficiencies of MeO-BDEs were significantly lower using the blend method (p < 0.05). For reasons of simplicity and efficiency, the soaking methods are preferred. Concentrations varied by orders of magnitude among species: ∑2BAs 57 to 57 700 and ∑5MeO-BDEs < 10 to 476 pg g−1 wet weight (ww). Macroalgae standing out with ∑2BAs >1000 pg g−1 ww were Ascophyllum nodosum, Ceramium tenuicorne, Ceramium virgatum, Fucus radicans, Fucus serratus, Fucus vesiculosus, Saccharina latissima, Laminaria digitata, and Acrosiphonia/Spongomorpha sp. Species A. nodosum, C. tenuicorne, Chara virgata, F. radicans and F. vesiculosus (Sweden Atlantic only) had ∑5MeO-BDEs >100 pg g−1ww. Profiles of individual compounds showed distinct differences among species and locations.
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2.
  • Andersson, Agneta, et al. (författare)
  • Projected future climate change and Baltic Sea ecosystem management
  • 2015
  • Ingår i: Ambio. - : Springer. - 0044-7447 .- 1654-7209. ; 44:Supplement 3, s. S345-S356
  • Tidskriftsartikel (refereegranskat)abstract
    • Climate change is likely to have large effects on the Baltic Sea ecosystem. Simulations indicate 2-4 degrees C warming and 50-80 % decrease in ice cover by 2100. Precipitation may increase similar to 30 % in the north, causing increased land runoff of allochthonous organic matter (AOM) and organic pollutants and decreased salinity. Coupled physical-biogeochemical models indicate that, in the south, bottom-water anoxia may spread, reducing cod recruitment and increasing sediment phosphorus release, thus promoting cyanobacterial blooms. In the north, heterotrophic bacteria will be favored by AOM, while phytoplankton production may be reduced. Extra trophic levels in the food web may increase energy losses and consequently reduce fish production. Future management of the Baltic Sea must consider the effects of climate change on the ecosystem dynamics and functions, as well as the effects of anthropogenic nutrient and pollutant load. Monitoring should have a holistic approach, encompassing both autotrophic (phytoplankton) and heterotrophic (e.g., bacterial) processes.
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3.
  • Assefa, Anteneh, et al. (författare)
  • Sources of dioxins in Baltic Sea herring: A modelling study for identification of dioxin sources and quantification of their temporal and spatial impacts
  • 2018
  • Rapport (övrigt vetenskapligt/konstnärligt)abstract
    • This study presents a step-by-step statistical analysis for tracing dioxins sources that have contributed to levels in Baltic herring during the last decades. The study is based on the concentrations of the 17 toxic (2,3,7,8-substituted) dioxin congeners in herring and sediment from the Baltic Sea, and it evaluates how the impacts of the sources may have changed during the studied periods, i.e. 1990–2009 in the Bothnian Bay, 1979–2009 in the Bothnian Sea and 1988–2009 in the Baltic Proper. The modelling technique used (PMF) extracted three dioxin patterns in herring that could be used to obtain source patterns after applying transformation factors. The transformed patterns were compared to real dioxin source patterns available through previous measurement and modelling studies. The identified sources included tetrachlorophenol (TCP), pentachlorophenol/atmospheric background (PCP/AB) and emissions from thermal activities.The results indicate that the thermal source type has been the major contributor of dioxins to Baltic herring during the pre-and post-2000 periods (72% and 59%, respectively). Its impact appears, however, to have declined by 19% in the Bothnian Bay, by 67% in the Bothnian Sea, and by 48% in the Baltic Proper (TEQ-basis). On the other hand, the relative importance of TCP and PCP/AB appear to have increased over time, from 1.4% and 1.5% to 19% and 6.6% in the Bothnian Bay, from 3.3% and 7.2% to 12% and 10% in the Bothnian Sea, and from 8.9% and <1% to 33% and 13% in the Baltic Proper. Comparisons using absolute values (pg TEQ g-1 lipid weight) indicate an increase of the TCP source by five times in the Bothnian Bay from the pre-2000 to the post-2000 period, a slight increase in the Bothnian Sea, and more than a doubling of the levels in the Baltic Proper. The agreement between the trends in the three sub-basins is a good indication for an increased impact of the TCP source during recent years (post-2000). Corresponding analysis for the PCP/AB source type, indicate slightly decreased TEQ levels from the PCP/AB source type in the Bothnian Sea (by ~50%), more than twice as high in the Bothnian Bay, and more than triplicated in the Baltic Proper. While the declining trends of the thermal source type encourages continuing management efforts for air emissions, the apparent increase of TCP and PCP/AB call for more attention to such sources in the Baltic Sea. As the use of technical products containing TCP and PCP have been banned/restricted since the 1970s and 1980s, more focus on contaminated sites may be required in the mitigation actions of such sources.
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4.
  • Assefa, Anteneh, et al. (författare)
  • Sources of polychlorinated dibenzo-p-dioxins and dibenzofurans to Baltic Sea herring
  • 2019
  • Ingår i: Chemosphere. - : Elsevier. - 0045-6535 .- 1879-1298. ; 218, s. 493-500
  • Tidskriftsartikel (refereegranskat)abstract
    • Levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in herring (Clupea harengus) remain high in several parts of the Baltic Sea, despite declines in PCDD/F emissions since the 1980s. The reasons behind this are not well understood. This study applied a statistical modeling approach where sources of PCDD/Fs that contaminate Baltic biota were quantitatively assessed by analyzing existing datasets. PCDD/F patterns were extracted from a herring dataset using positive matrix factorization (PMF). The extracted biota patterns were transformed into sediment patterns using fish-to-sediment transformation factors, and the resulting patterns were compared with known source PCDD/F patterns. The model distinguished three model patterns, which explained 85% of the data. These patterns were matched to tetra-chlorophenol (TCP), penta-chlorophenol/atmospheric background (PCP/AB), and thermal source patterns, respectively. The thermal source was the largest contributor to toxic equivalents (TEQ) in herring, but the level decreased from 42 ± 9.0 pg TEQ g−1 lipid weight (lw) before year 2000 (pre-2000) to 15 ± 2.4 pg TEQ g−1 lw post-2000, i.e., a decline of around one-third in the original TEQ concentration. The contribution of TCP more than doubled, from 2.1 ± 0.62 pg TEQ g−1 lw to 5.6 ± 1.1 pg TEQ g−1 lw, and the relative contribution of PCP/AB also increased. These increasing trends suggest that, as primary air emissions of PCDD/Fs are managed and levels decline, the impact of TCP and PCP/AB sources on Baltic Sea biota will become more important over time and that PCDD/F-contaminated sites in coastal areas and marine environments require more attention.
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5.
  • Assefa, Anteneh, 1983- (författare)
  • Tracing and apportioning sources of dioxins using multivariate pattern recognition techniques
  • 2015
  • Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
    • High levels of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in edible fish in the Baltic Sea have raised health concerns in the Baltic region and the rest of Europe. Thus, there are urgent needs to characterize sources in order to formulate effective mitigation strategies. The aim of this thesis is to contribute to a better understanding of past and present sources of PCDD/Fs in the Baltic Sea environment by exploring chemical fingerprints in sediments, air, and biota. The spatial and temporal patterns of PCDD/F distributions in the Baltic Sea during the 20th century were studied in Swedish coastal and offshore sediment cores. The results showed that PCDD/F levels peaked in 1975 (± 7 years) in coastal and 1991 (± 5 years) in offshore areas. The time trends of PCDD/Fs in the sediment cores also showed that environmental half-lives of these pollutants have been shorter in coastal than in offshore areas (15 ± 5 and 29 ± 14 years, respectively). Consequently, there have been remarkable recoveries in coastal areas, but slower recovery in offshore areas with 81 ± 12% and 38 ± 11% reductions from peak levels, respectively.Source-to-receptor multivariate modeling by Positive Matrix Factorization (PMF) showed that six types of PCDD/F sources are and have been important for the Baltic Sea environment: PCDD/Fs related to i) atmospheric background, ii) thermal processes, iii) manufacture and use of tetra-chlorophenol (TCP) and iv) penta-chlorophenol (PCP), v) industrial use of elementary chlo- rine and the chloralkali-process (Chl), and vi) hexa-CDD sources. The results showed that diffuse sources (i and ii) have consistently contributed >80% of the total amounts in the Southern Baltic Sea. In the Northern Baltic Sea, where the biota is most heavily contaminated, impacts of local sources (TCP, PCP and Chl) have been higher, contributing ca. 50% of total amounts. Among the six sources, only Thermal and chlorophenols (ii-iv) have had major impacts on biota. The impact of thermal sources has, however, been declining as shown from source apportioned time-trend data of PCDD/Fs in Baltic herring. In contrast, impacts of chlorophenol-associated sources generally increased, remained at steady-state or slowly decreased during 1990-2010, suggesting that these sources have substantially contributed to the persistently high levels of PCDD/Fs in Baltic biota.Atmospheric sources of PCDD/Fs for the Baltic region (Northern Europe) were also investigated, and specifically whether the inclusion of parallel measurements of metals in the analysis of air would help back-tracking sources. PCDD/Fs and metals in high-volume air samples from a rural field station near the shore of the central Baltic Sea were measured. The study focused on the winter season and air from the S and E sectors, as these samples showed elevated levels of PCDD/Fs, particularly PCDFs. Several metals were found to correlate significantly with the PCDFs. The wide range of candidate metals as source markers for PCDD/F emissions, and the lack of an up-to-date extensive compilation of source characteristics for metal emission from vari- ous sources, limited the use of the metals as source markers. The study was not able to pin-point primary PCDD/F sources for Baltic air, but it demonstrated a new promising approach for source tracing of air emissions. The best leads for back-tracking primary sources of atmospheric PCDD/Fs in Baltic air were seasonal trends and PCDD/F congener patterns, pointing at non-industrial related thermal sources related to heating. The non-localized natures of the sources raise challenges for managing the emissions and thus societal efforts are required to better control atmospheric emissions of PCDD/Fs.
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6.
  • Assefa, Anteneh, et al. (författare)
  • Tracing the sources of PCDD/Fs in Baltic Sea air by using metals as source markers
  • 2018
  • Ingår i: Environmental Science. - Cambridge : Royal Society of Chemistry. - 2050-7887 .- 2050-7895. ; 20:3, s. 544-552
  • Tidskriftsartikel (refereegranskat)abstract
    • The atmosphere is the major contributor of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in the Baltic Sea environment. In this study, we investigated the potential of using metals along with PCDD/Fs as markers of important emission sources of PCDD/Fs in air. The air concentrations of PCDD/F congeners (n = 17), other persistent organic pollutants (n = 8) and metals (n = 16) were determined in summer and winter air using high volume samplers at a rural field station (Aspvreten, Sweden) located close to the Baltic Sea coast. During winter, PCDD/F levels were on average 20 times higher than in summer (5.1 +/- 5.8 fg toxicity equivalents (TEQ) m-3 and 0.26 +/- 0.18 fg TEQ m-3, respectively) mostly due to a higher fraction of PCDFs. The increased levels of PCDD/Fs were pronounced mainly in air masses that had travelled from southern (S) and eastern (E) compass sectors. A principal component analysis (PCA) of metal levels in Scots pine (Pinus sylvestris) needles sampled to reflect various air emission source types helped to identify potential marker metals for selected known atmospheric emission sources of PCDD/Fs and to rank among the candidate source types. Brown coal burning, domestic burning and heavy oil burning appeared to be the source types that contribute most of the PCDD/Fs in Baltic Sea air. The current study demonstrates a successful approach for source tracing of PCDD/Fs in air, where integrated indices from seasonal and spatial patterns of PCDD/Fs as well as metal source markers were used to trace and rank sources.
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7.
  • Bengtsson-Palme, Johan, 1985, et al. (författare)
  • Elucidating selection processes for antibiotic resistance in sewage treatment plants using metagenomics
  • 2016
  • Ingår i: Science of the Total Environment. - : Elsevier BV. - 0048-9697 .- 1879-1026. ; 572, s. 697-712
  • Tidskriftsartikel (refereegranskat)abstract
    • Sewage treatment plants (STPs) have repeatedly been suggested as “hotspots” for the emergence and dissemination of antibiotic-resistant bacteria. A critical question still unanswered is if selection pressures within STPs, caused by residual antibiotics or other co-selective agents, are sufficient to specifically promote resistance. To address this, we employed shotgun metagenomic sequencing of samples from different steps of the treatment process in three Swedish STPs. In parallel, concentrations of selected antibiotics, biocides and metals were analyzed. We found that concentrations of tetracycline and ciprofloxacin in the influent were above predicted concentrations for resistance selection, however, there was no consistent enrichment of resistance genes to any particular class of antibiotics in the STPs, neither for biocide and metal resistance genes. The most substantial change of the bacterial communities compared to human feces occurred already in the sewage pipes, manifested by a strong shift from obligate to facultative anaerobes. Through the treatment process, resistance genes against antibiotics, biocides and metals were not reduced to the same extent as fecal bacteria. The OXA-48 gene was consistently enriched in surplus and digested sludge. We find this worrying as OXA-48, still rare in Swedish clinical isolates, provides resistance to carbapenems, one of our most critically important classes of antibiotics. Taken together, metagenomics analyses did not provide clear support for specific antibiotic resistance selection. However, stronger selective forces affecting gross taxonomic composition, and with that resistance gene abundances, limit interpretability. Comprehensive analyses of resistant/non-resistant strains within relevant species are therefore warranted.
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8.
  • Bidleman, Terry, 1942-, et al. (författare)
  • A review of halogenated natural products in Arctic, Subarctic and Nordic ecosystems
  • 2019
  • Ingår i: Emerging Contaminants. - : Elsevier. - 2405-6650 .- 2405-6642. ; 5, s. 89-115
  • Tidskriftsartikel (refereegranskat)abstract
    • Halogenated natural products (HNPs) are organic compounds containing bromine, chlorine, iodine, andrarely fluorine. HNPs comprise many classes of compounds, ranging in complexity from halocarbons tohigher molecular weight compounds, which often contain oxygen and/or nitrogen atoms in addition tohalogens. Many HNPs are biosynthesized by marine bacteria, macroalgae, phytoplankton, tunicates,corals, worms, sponges and other invertebrates. This paper reviews HNPs in Arctic, Subarctic and Nordicecosystems and is based on sections of Chapter 2.16 in the Arctic Monitoring and Assessment Program(AMAP) assessment Chemicals of Emerging Arctic Concern (AMAP, 2017) which deal with the highermolecular weight HNPs. Material is updated and expanded to include more Nordic examples. Much ofthe chapter is devoted to “bromophenolic” HNPs, viz bromophenols (BPs) and transformation productsbromoanisoles (BAs), hydroxylated and methoxylated bromodiphenyl ethers (OH-BDEs, MeO-BDEs) andpolybrominated dibenzo-p-dioxins (PBDDs), since these HNPs are most frequently reported. Othersdiscussed are 2,20-dimethoxy-3,30,5,50-tetrabromobiphenyl (2,20-dimethoxy-BB80), polyhalogenated 10-methyl-1,20-bipyrroles (PMBPs), polyhalogenated 1,10-dimethyl-2,20-bipyrroles (PDBPs), polyhalogenatedN-methylpyrroles (PMPs), polyhalogenated N-methylindoles (PMIs), bromoheptyl- and bromooctylpyrroles, (1R,2S,4R,5R,10E)-2-bromo-1-bromomethyl-1,4-dichloro-5-(20-chloroethenyl)-5-methylcyclohexane (mixed halogenated compound MHC-1), polybrominated hexahydroxanthene derivatives(PBHDs) and polyhalogenated carbazoles (PHCs). Aspects of HNPs covered are physicochemicalproperties, sources and production, transformation processes, concentrations and trends in the physicalenvironment and biota (marine and freshwater). Toxic properties of some HNPs and a discussion of howclimate change might affect HNPs production and distribution are also included. The review concludeswith a summary of research needs to better understand the role of HNPs as “chemicals of emergingArctic concern”.
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9.
  • Bidleman, Terry, et al. (författare)
  • Atmospheric pathways of chlorinated pesticides and natural bromoanisoles in the northern Baltic Sea and its catchment
  • 2015
  • Ingår i: Ambio. - : Springer Science and Business Media LLC. - 0044-7447 .- 1654-7209. ; 44, s. 472-483
  • Tidskriftsartikel (refereegranskat)abstract
    • Long-range atmospheric transport is a major pathway for delivering persistent organic pollutants to the oceans. Atmospheric deposition and volatilization of chlorinated pesticides and algae-produced bromoanisoles (BAs) were estimated for Bothnian Bay, northern Baltic Sea, based on air and water concentrations measured in 2011-2012. Pesticide fluxes were estimated using monthly air and water temperatures and assuming 4 months ice cover when no exchange occurs. Fluxes were predicted to increase by about 50 % under a 2069-2099 prediction scenario of higher temperatures and no ice. Total atmospheric loadings to Bothnian Bay and its catchment were derived from air-sea gas exchange and bulk'' (precipitation ? dry particle) deposition, resulting in net gains of 53 and 46 kg year(-1) for endosulfans and hexachlorocyclohexanes, respectively, and net loss of 10 kg year(-1) for chlordanes. Volatilization of BAs releases bromine to the atmosphere and may limit their residence time in Bothnian Bay. This initial study provides baseline information for future investigations of climate change on biogeochemical cycles in the northern Baltic Sea and its catchment.
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10.
  • Bidleman, Terry F., et al. (författare)
  • Atmospheric transport and deposition of bromoanisoles along a temperate to arctic gradient
  • 2017
  • Ingår i: Environmental Science and Technology. - Washington : American Chemical Society (ACS). - 1086-931X .- 1520-6912 .- 0013-936X .- 1520-5851. ; 51:19, s. 10974-10982
  • Tidskriftsartikel (refereegranskat)abstract
    • Bromoanisoles (BAs) arise from O-methylation of bromophenols, produced by marine algae and invertebrates. BAs undergo sea-air exchange and are transported over the oceans. Here we report 2,4-DiBA and 2,4,6-TriBA in air and deposition on the Swedish west coast (Råö) and the interior of arctic Finland (Pallas). Results are discussed in perspective with previous measurements in the northern Baltic region in 2011−2013. BAs in air decreased from south to north in the order Råö > northern Baltic > Pallas. Geometric mean concentrations at Pallas increased significantly (p < 0.05) between 2002 and 2015 for 2,4-DiBA but not for 2,4,6-TriBA. The logarithm of BA partial pressures correlated significantly to reciprocal air temperature at the coastal station Råö and over the Baltic, but only weakly (2,4-DiBA) or not significantly (2,4,6-TriBA) at inland Pallas. Deposition fluxes of BAs were similar at both sites despite lower air concentrations at Pallas, due to greater precipitation scavenging at lower temperatures. Proportions of the two BAs in air and deposition were related to Henry’s law partitioning and source regions. Precipitation concentrations were 10−40% of those in surface water of Bothnian Bay, northern Baltic Sea. BAs deposited in the bay catchment likely enter rivers and provide an unexpected source to northern estuaries. BAs may be precursors to higher molecular weight compounds identified by others in Swedish inland lakes.
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