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Properties and analysis of dioxin-like compounds in marine samples from Sweden
Umeå University, Faculty of Science and Technology, Department of Chemistry.
2003 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (PCBs) have been assigned toxic equivalency factors (TEFs). These compounds are today routinely analysed with sophisticated analytical techniques. In a near future, there might be other dioxinlike compounds such as polychlorinated naphthalenes (PCNs), alkyl-polychlorodibenzofurans (R-PCDFs), and polychlorinated dibenzothiophenes (PCDTs) added to this list of toxic dioxin-like compounds. It is therefore important to have a readiness to analyse these new compounds in environmental

samples. In this study, a multi-residue non-destructive analytical method for the analyses of these planar dioxin-like compound classes was developed. The use of HPLC PX-21 carbon column fractionation enabled the separation of interfering PCBs from coplanar PCBs and other planar dioxin-like compounds of interest.

The obtained planar fraction containing the dioxin-like compounds was analysed using high-resolution GC-MS. Levels of PCNs in surface sediments and settling particulate matter in the northern Baltic Sea were determined. The concentrations

of PCNs in background surface sediments were approximately 1 ng/g dw and the estimated PCN fluxes were similar to the pre-industrial levels determined in Europe. The PCN congener patterns in the surface sediments suggest that the PCNs deposited in the Baltic Sea originate from similar sources.

Bioaccumulation of PCNs in a benthic food chain (sediment, amphipod, isopod, and four-horned sculpin) from the Gulf of Bothnia was studied. The results indicated that only a few PCN congeners biomagnified. The highest biomagnification factors (BMFs) were found for 2,3,6,7-substituted congeners and those lacking adjacent hydrogen-substituted carbon atoms. The calculated biota to sediment accumulation factors (BSAFs) showed that the tetra- and penta- CNs exhibited BSAF values higher than one, while BSAFs for the more chlorinated PCNs were less than one.

A general difference between the northern and southern parts of the Gulf of Bothnia could be seen in the samples, with the lowest PCN and total PCB concentrations being found in the north and the highest in the south. This gradient is related to distance from the more industrialised and populated regions in the southern parts of Sweden and Finland, and central Europe.

Analysis of R-PCDFs in crustacean samples from the Swedish west coast was performed using HRGC-MS/MS. The ΣR-PCDFs in these samples were present at concentrations up to 10 times higher than the ΣPCDFs. The relatively high

concentrations of R-PCDFs in the crab samples demonstrate that these compounds bioaccumulate.

The fate of a pollutant in the environment and the toxicity of a compound are governed by its physicochemical properties. The information found in a data set of properties can predict a compound’s mode of action. The following physicochemical properties for 87 PCDFs were measured: ultra-violetadsorption, relative retention times on two common gas chromatographic stationary phases, and relative mass spectrometric response factors using EI- and NCI- modes.

Place, publisher, year, edition, pages
Umeå: Kemi , 2003. , 66 p.
Keyword [en]
Environmental chemistry, planar dioxin-like compound, polychlorinated dibenzofuran, polychlorinated biphenyl, polychlorinated naphthalene, alkylated polychlorinated dibenzofuran, high-performance liquid chromatography, PX-21 carbon column, biomagnification factor, biota to sediment accumulation factor, fluxes, relative retention time, mass spectrometry, relative response factor, ultra-violet spectroscopy
Keyword [sv]
Miljökemi
National Category
Environmental Sciences
Research subject
Analytical Chemistry
Identifiers
URN: urn:nbn:se:umu:diva-24ISBN: 91-7305-366-X (print)OAI: oai:DiVA.org:umu-24DiVA: diva2:142777
Public defence
2003-02-07, Umeå, 10:00 (English)
Available from: 2003-02-07 Created: 2003-02-07 Last updated: 2012-06-07Bibliographically approved
List of papers
1. Development of a highperformance liquid chromatography carbon column based method for the fractionation of dioxin-like polychlorinated biphenyls
Open this publication in new window or tab >>Development of a highperformance liquid chromatography carbon column based method for the fractionation of dioxin-like polychlorinated biphenyls
2002 In: Journal of Chromatography A, Vol. 962, 79-93 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:umu:diva-3877 (URN)
Available from: 2003-02-07 Created: 2003-02-07Bibliographically approved
2. Relative retention times (RRTs) on two common gas chromatographic stationary phases and lowresolution mass spectrometric relative response factors (RRFs) for 87 polychlorinated dibenzofurans
Open this publication in new window or tab >>Relative retention times (RRTs) on two common gas chromatographic stationary phases and lowresolution mass spectrometric relative response factors (RRFs) for 87 polychlorinated dibenzofurans
In: Submitted to Journal of Chromatography AArticle in journal (Refereed) Submitted
Identifiers
urn:nbn:se:umu:diva-3878 (URN)
Available from: 2003-02-07 Created: 2003-02-07Bibliographically approved
3. Ultraviolet absorption characteristics of all tetra- to octachlorinated dibenzofurans.
Open this publication in new window or tab >>Ultraviolet absorption characteristics of all tetra- to octachlorinated dibenzofurans.
1993 In: Chemosphere, Vol. 27, 535-546 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:umu:diva-3879 (URN)
Available from: 2003-02-07 Created: 2003-02-07Bibliographically approved
4. Detection of alkylated polychlorodibenzofurans and alkylated polychlorodibenzo-p-dioxins by tandem mass spectrometry for the analysis of crustacean samples
Open this publication in new window or tab >>Detection of alkylated polychlorodibenzofurans and alkylated polychlorodibenzo-p-dioxins by tandem mass spectrometry for the analysis of crustacean samples
1991 In: Chemosphere, Vol. 23, 1591-1604 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:umu:diva-3880 (URN)
Available from: 2003-02-07 Created: 2003-02-07Bibliographically approved
5. Levels of PCBs in the aquatic environment of the Gulf of Bothnia: Benthic species and sediments
Open this publication in new window or tab >>Levels of PCBs in the aquatic environment of the Gulf of Bothnia: Benthic species and sediments
Show others...
1996 In: Marine Pollution Bulletin, Vol. 32, 210-218 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:umu:diva-3881 (URN)
Available from: 2003-02-07 Created: 2003-02-07Bibliographically approved
6. Polychlorinated Naphthalene Levels, Distribution, and Biomagnification in a Benthic Food Chain in the Baltic Sea
Open this publication in new window or tab >>Polychlorinated Naphthalene Levels, Distribution, and Biomagnification in a Benthic Food Chain in the Baltic Sea
Show others...
2002 (English)In: Environmental Science & Technology, Vol. 36, no 23, 5005-13 p.Article in journal (Refereed) Published
Abstract [en]

The scientific literature contains little information regarding bioaccumulation and biomagnification of polychlorinated naphthalenes (PCNs) in food webs. Here we present new information on the food chain transfer of PCNs within a food chain in a subarctic environment. PCNs (tetra- to hepta-chloro congeners) were measured in surface sediments and in a marine benthic food chain, comprising amphipods, isopods, and fourhorned sculpins. Samples were collected from five locations in the Gulf of Bothnia, northern Baltic Sea. PCN concentrations in the sediments were similar to background levels determined previously in sediments from the northern hemisphere. Measurement of the carbon content of the sediments allowed the calculation of biota to sediment accumulation factors (BSAFs). Tetra- and penta-CNs exhibited BSAF values greater than one, while BSAFs for the more chlorinated PCNs were less than one. This suggests more efficient assimilation, by amphipods, of the less chlorinated PCNs. A decrease in PCN concentrations from the lowest to the highest trophic level was demonstrated (amphipods: 10-69 ng/g lw; isopods: 3.9-16 ng/g lw; fourhorned sculpins: 0.54-1.5 ng/g lw). Biomagnification factors (BMFs) were calculated based on the concentrations of the congeners. These indicated that a few congeners biomagnified significantly: the highest BMFs (0.09-1.4) were found for 2,3,6,7-substituted congeners and those lacking adjacent hydrogen-substituted carbon atoms.

Identifiers
urn:nbn:se:umu:diva-8836 (URN)doi:10.1021/es0201146 (DOI)
Available from: 2008-02-18 Created: 2008-02-18 Last updated: 2012-06-07Bibliographically approved
7. Flux estimates and sedimentation of polychlorinated naphthalenes in the northern part of the Baltic sea
Open this publication in new window or tab >>Flux estimates and sedimentation of polychlorinated naphthalenes in the northern part of the Baltic sea
Show others...
2003 (English)In: Environmental Pollution, ISSN 0269-7491, Vol. 126, no 1, 93-105 p.Article in journal (Refereed) Published
Abstract [en]

The concentrations and fluxes of polychlorinated naphthalenes (PCNs) were measured in surface sediments, and settling particulate matter collected in sediment traps, at two coastal and two offshore sampling stations in the Gulf of Bothnia, northern Baltic Sea, Sweden. The PCN concentrations (of tetra- to hepta-chloro congeners) in the surface sediments ranged from 0.27 to 2.8 ng/g dry weight and were of the same order of magnitude as background concentrations reported previously in Europe. The PCN fluxes in the southern basin (0.93 and 0.86 μg/m2/year) of the Gulf of Bothnia were higher than those in the northern basin (0.58 and 0.49 μg/m2/year); they were also higher near the coast than in the open sea. These PCN fluxes are similar to the pre-industrial levels determined from lake sediments in northwest England. The PCN homologue distribution changed from a relatively even distribution in samples collected near the coast, to TeCNs dominating in the samples from the open sea. This indicates that higher chlorinated PCNs are deposited and retained in sediments to a higher degree near the coast. The total annual deposition of PCNs in sediments in the Gulf of Bothnia was estimated to be 91 kg/year.

Background concentrations in sediments, fluxes and annual sedimentation rates of polychlorinated naphthalenes were measured and estimated at two coastal and two offshore remote sampling stations in the Gulf of Bothnia, northern Baltic Sea.

Keyword
Polychlorinated naphthalenes, PCNs, Baltic Sea, Background sediment, Fluxes
Identifiers
urn:nbn:se:umu:diva-9226 (URN)doi:10.1016/S0269-7491(03)00144-1 (DOI)
Available from: 2008-03-12 Created: 2008-03-12 Last updated: 2009-12-03Bibliographically approved

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