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| 2. |
- Assefa, Anteneh, et al.
(författare)
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Airborne dioxins and other POPs in the Baltic Sea environment: the potential of using metals as source markers
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Annan publikation (övrigt vetenskapligt/konstnärligt)abstract
- Atmospheric sources are major contributors of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in the Baltic Sea environment. In this study, we investigated the potential of using trace metals along with PCDD/F levels and seasonal trends as markers of important source types for PCDD/Fs in air. Levels of PCDD/F congeners (n=17) and metals (n=16) were measured in summer and winter air using high volume sampling at a rural field station (Aspvreten, Sweden). During winter, levels were on average 20 times higher than in summer (5.1 ± 5.8 fg TEQ m-3 and 0.26 ± 0.18 fg TEQ m-3, respec- tively) mostly due to a higher fraction of PCDFs. The increased levels were pronounced in air masses from southern (S) and eastern (E) compass sectors. Most of the detected metals (n=12) were positively and significantly correlated with the PCDF congeners for all compass sectors (Cd, Co, Cu, Fe, K, Mn, Pb, Sb, and Zn) during winter season. The average correlation coefficient (r) value for the correlation between PCDF congeners and these metals was 0.85 and p values generally below <0.05. In contrast, polychlorinated biphenyls (PCBs) and hexachlorobenzene (HCB) showed no significant correlations with detected metals except for HCB and Cr (r=0.60 and p<0.01). 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 various sources, limited the use of the metals as source markers in the current study. Although, the study was not able to pin-point primary PCDD/F sources for Baltic air, we demonstrated a promising approach for source tracing of PCDD/F in air.
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| 3. |
- Assefa, Anteneh, et al.
(författare)
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Source-apportionment shows why dioxin levels have not declined in Baltic fish
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Annan publikation (övrigt vetenskapligt/konstnärligt)abstract
- Levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs, “dioxins”) in fatty fish of the Baltic Sea have remained high despite declines in environmental levels since the 1980s. This has raised human health concerns and restricted marketing of Baltic herring and salmon within the European Union. Thus, there is an urgent need to identify and control current PCDD/F emission sources. Analysis presented here explains why PCDD/Fs levels in fish have stopped declining or even increased in recent decades. We show that contributions of “thermal” sources (e.g., waste incineration) of PCDD/Fs to Baltic fish have declined since the 1990s, but not contributions of sources associated with the manufacture and use of chlorophenols (particularly tetrachlorophenol and pentachlorophenol, TCP and PCP, respectively). Moreover, the discrepancy between declines in levels of dioxins in abiotic compartments (e.g. sediments and air), and stable or increasing levels in biota can be explained by the persistently high bioavailability of PCDD/Fs associated with TCP and PCP type sources.
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| 4. |
- Assefa, Anteneh, et al.
(författare)
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Sources of dioxins in Baltic Sea herring: A modelling study for identification of dioxin sources and quantification of their temporal and spatial impacts
- 2018
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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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| 5. |
- Assefa, Anteneh, 1983-
(författare)
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Tracing and apportioning sources of dioxins using multivariate pattern recognition techniques
- 2015
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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. |
- Badea, Silviu-Laurentiu, 1980-
(författare)
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Association of hydrophobic organic compounds to organic material in the soil system
- 2013
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Licentiatavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Contaminated soils and sediments have been identified as significant secondary sources of organic contaminants. Leaching tests may be useful tools to estimate the mobility of contaminants via the water phase and thereby the risk for groundwater and surface water contamination. The influence of soil composition (peat and clay content) on the leachability was investigated in batch leaching experiments for chemically diverse hydrophobic organic compounds (HOCs: PCP, PAHs, HCB, HCHs, PCBs, and TCDD/Fs). The above mentioned compounds were analyzed by both GC-LRMS (gas chromatography coupled with low resolution mass spectrometry (GC-HRMS) and GC-HRMS (gas chromatography coupled with high resolution mass spectrometry). Also the the leachability of eleven selected PCBs from naturally aged soil (Västervik, Sweden) was investigated in relation to the composition and concentration of dissolved organic matter at different pH (2 to 9), using a pH static test with initial acid/base addition. The the composition and of dissolved organic matter (DOM) at different pH values was explored by FTIR spectroscopy. The results were evaluated by orthogonal projections to latent structures (OPLS).Generally, for all model compounds studies, the Kd-values showed a variability of 2-3 orders of magnitude depending on the matrix composition. The Kd-values of moderately hydrophobic compounds, (e.g. HCHs, PCP and Phe), were correlated mainly with the organic matter content of soil. For more hydrophobic compounds (e.g.BaA, HCB and PCB 47), the leachability decreased as the proportions of OM and clay contents increased. The Kd-values of 1,3,6,8-TCDD and 1,3,6,8-TCDF were positively correlated with peat content but negatively correlated with clay content, while for PCB 153 and PCB 155 the correlations were reversed. The log Kd-values of all target PCBs decreased with increased pH values and the log Kd-values were highly correlated with the concentration of total organic carbon (TOC) in the leachates. The FTIR analysis of DOM showed that the least chlorinated and hydrophobic PCB congeners (i.e. PCB 28) might be associated with the hydrophilic fraction (i.e. carboxylic groups) of DOM. Our study demonstrated how complex interaction between the organic matter, clay components, pH and DOC influences the leachability of HOCs in a compound-specific manner.
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| 7. |
- Badea, Silviu-Laurentiu, et al.
(författare)
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Leachability of PCBs in soil and its pH and dissolved organic matter (DOM) dependency
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Annan publikation (övrigt vetenskapligt/konstnärligt)abstract
- The leachability of eleven selected PCBs from naturally aged soil (Västervik, Sweden) was investigated in relation to the composition and concentration of dissolved organic matter at different pH (2 to 9), using a pH static test with initial acid/base addition. The batch leaching tests were performed on 50 g aliquots of a PCBs contaminated soil at a liquid to solid ratio (L/S) of 10 L/Kg. The PCBs were analyzed by gas chromatography coupled with high resolution mass spectrometry (GC-HRMS). The composition and of dissolved organic matter (DOM) at different pH values was explored by FTIR spectroscopy. The correlation between the FTIR data obtained for DOM and the log Kd values of PCBs was explored by orthogonal projections to latent structures (OPLS). The log Kd-values of all target PCBs decreased with increased pH values and the log Kd-values were highly correlated with the concentration of total organic carbon (TOC) in the leachates. For the lower chlorinated congener, PCB 28, this correlation was weaker. The variation of fractions of concentrations of mono-ortho to di-ortho PCBs (PCB 66 to PCB 52 and PCB 105 to PCB 101) indicated an influence of the ortho-chlorine atoms through pH effects on their leachability. The FTIR analysis of DOM showed that the least chlorinated and hydrophobic PCB congeners (i.e. PCB 28) might be associated with the hydrophilic fraction (i.e. carboxylic groups) of the DOM.
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| 8. |
- Bergknut, Magnus, 1973-
(författare)
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Characterization of PAH-contaminated soils focusing on availability, chemical composition and biological effects
- 2006
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The risks associated with a soil contaminated by polycyclic aromatic hydrocarbons (PAHs) are generally assessed by measuring individual PAHs in the soil and correlating the obtained amounts to known adverse biological effects of the PAHs. The validity of such a risk estimation is dependent on the presence of additional compounds, the availability of the compounds (including the PAHs), and the methods used to correlate the measured chemical data and biological effects. In the work underlying this thesis the availability, chemical composition and biological effects of PAHs in samples of soils from PAH-contaminated environments were examined. It can be concluded from the results presented in the included papers that the PAHs in the studied soils from industrial sites were not generally physically trapped in soil material, indicating that the availability of the PAHs was not restricted in this sense. However, the bioavailable fraction of the PAHs, as assessed by bioassays with the earthworm Eisenia Fetida, could not be assessed by a number of abiotic techniques (including: solid phase micro extraction, SPME; use of semi-permeable membrane devices, SPMDs; leaching with various solvent mixtures, leaching using additives, and sequential leaching) and it seems to be difficult to find a chemical method that can accurately assess the bioavailability of PAHs. Furthermore, it was shown that PAH-polluted samples may be extensively chemically characterized by GC-TOFMS using peak deconvolution, and over 900 components can be resolved in a single run. The chemical characterization also revealed that samples that appeared to be similar in terms of their PAH composition were heterogeneous in terms of their overall composition. Finally, single compounds from this large set of compounds, which correlated with different biological effects, could be identified using the multivariate technique partial least squares projections to latent structures (PLS). This indicates that PLS may provide a valid alternative to Effect Directed Analysis (EDA), an established method for finding single compounds that correlate to the toxicity of environmental samples. Thus, the instrumentation and data evaluation tools used in this thesis are clearly capable of providing a broad chemical characterization as well as linking the obtained chemical data to results from bioassays. However, the link between the chemical analyses and the biological tests could be improved as as an organic solvent that solubilised virtually all of the contaminants was used during the chemical analysis while the biological tests were performed in an aqueous solution with limited solubility for a number of compounds. Consequently the compounds probably have a different impact in the biological tests than their relative abundance in profiles obtained by standard chemical analyses suggests. The availability and bioavailability of contaminants in soil also has to be studied further, and such future studies should focus on the molecular interactions between the contaminants and different compartments of the soil. By doing so, detailed knowledge could be obtained which could be applied to a number of different contaminants and soil types. Such studies would generate the data needed for molecular-based modelling of availability and bioavailability, which would be a big step forward compared to current risk assessment practices.
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| 9. |
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| 10. |
- Eriksson, Johan, 1956-
(författare)
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Polybrominated diphenyl ethers and Tetrabromobisphenol A : Chemical synthesis, X-ray crystallography and Photochemical degradation
- 2004
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- In the 1960s’ several manmade chemicals were detected in the environment, far from their sources. The most well known, and most likely those with the largest impact on the society, were DDT and its related compounds, and PCBs. These anthropogenic compounds were characterised as persistent organic pollutants (POPs). Following these POPs, several other chemicals have found their way to the environment. Over the last two decades, brominated flame retardants (BFRs) have become a matter of concern. Among all BFRs being commercially produced, tetrabromobisphenol A (TBBPA) and polybrominated diphenyl ethers (PBDEs) are the ones with the largest annual production. TBBPA is a very well defined compound while PBDEs consist of a large number of isomers and homologues (congeners). TBBPA does not seem to accumulate in biota as the PBDEs do, but is still of concern since it is found in e.g. sediments. The PBDEs can reach accumulation levels up in the ppm range. Still there is a lack of basic data for both TBBPA and PBDEs. Hence the present thesis is aimed to fill some of the data gaps by pursuing work on 1) photochemical degradation of TBBPA, some related compounds, and PBDEs; 2) synthesis of PBDE congeners and of TBBPA degradation products and 3) structural identifications of a selected set of BFRs by X-ray crystallography.An apparatus was designed for carrying out photochemical degradation test of chemicals in general but in particular for BFRs. Quantum yield, rate of degradation and to some extent, identification of degradation products were performed on TBBPA, the corresponding chlorinated compound and a number of TBBPA degradation products and on 15 single PBDE congeners. In order to make this work possible all three nonaBDE isomers were synthesised via a reductive pathway applying sodium borohydride as a reducing agent. The three nona-BDEs were all characterised by X-ray crystallography. The results of the photochemical degradation of TBBPA in water show a rapidly degradable compound also at pH’s that are environmentally relevant. Hence it is likely that TBBPA is not transported long distances, when exposed to sunlight, without undergoing photochemical degradation. It is notable that the TBBPA is degraded through cleavage between the two phenol rings. When the method was applied to study quantum yields and rate constants for the reaction of PBDE congeners it is evident that the decabromodiphenyl ether (BDE-209) is rapidly transformed. The reaction rate differ drastically from PBDEs with four or five bromine substituents that have very long half-lives when subjected to UV-light under the same conditions as for BDE-209. Lower brominated diphenyl ethers and polybrominated dibenzofurans were identified as PBDE degradation products. The synthesis of PBDEs and of TBBPA degradation products expanded the study as did the X-ray structure identifications.
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