Ulf Järnberg

Isolation of toxic polychlorinated biphenyls by electron donor—acceptor high-performance liquid chromatography on a 2-(1-prenyl)ethyldimethylsilylated silica column

A rapid and simple liquid chromatographic method for the isolation of toxic planar polychlorinated biphenyls from their formulations by electron donor-acceptor high-performance liquid chromatography using a 2-(1-pyrenyl)ethyldimethylsilylated silica column is described. The separation takes less than 15 min and a complete analysis, including quantitation by gas chromatography-mass spectrometry or gas chromatography with electron-capture detection, may be completed in 60 min. Retention data for 105 individual polychlorinated biphenyl congeners are presented and the retention behaviour, as well as the mechanisms of separation, are discussed.

Analytical challenges hamper perfluoroalkyl research

The growing concern over these organohalogens, some of which have been found in human blood and appear to be widespread in the environment, led researchers to gather in Hamburg, Germany, in 2003 to evaluate the current state of methods to analyze for the organic contaminants. Jonathan Martin of the University of Toronto and 20 colleagues from industry, government, and academia summarize the main recommendations from the workshop.

PCBs, PCNs, PCDD/Fs, PAHs and Cl-PAHs in air and water particulate samples--patterns and variations

Methodology for the determination of biologically active polychlorinated biphenyls (PCBs), non-ortho PCBs, polychlorinated naphthalenes (PCNs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polycyclic aromatic hydrocarbons (PAHs) was used to investigate concentrations and patterns of certain chlorinated PAH (Cl-PAH) in source related samples using synthetic reference mixtures. Thus, in addition to the above mentioned compounds, mono-heptachlorosubstituted fluorenes, phenanthrenes/anthracenes and pyrenes/fluoranthenes (Cl-PAHs) were measured in vapour and particulate air samples from urban road tunnels, samples of settling particulate matter (SPM), and in bottom sediment samples from two point source locations (pulp and paper, and Mg-plant/Fe-Mn-smelter/chlor-alkali) and in the Baltic Sea. Concentrations in air samples followed: PAHs>PCBs>PCNs>non-ortho PCBs or Cl-PAHs>PCDD/Fs. SPM samples collected at increasing distance to the urban area of Stockholm showed: PAHs>PCBs>PCNs>PCDD/Fs>non-ortho PCBs or Cl-PAHs. For all compound groups there was a tenfold (Cl-PAHs fivefold) concentration decrease in SPM samples from highest levels in the urban water area to lowest levels at a distance of 26 km from city centre. PCB profiles of SPM showed similarities with combined profiles of Aroclor 1242 and 1254. PCN profiles of SPM showed similarities with combined profiles of Halowax 1099 and 1014. A correlation with concentration of all tested Cl-PAH and their corresponding parent PAH was found only for Cl-fluorene.

Gas chromatographic retention behaviour of polychlorinated naphthalenes on non-polar, polarizable, polar and smectic capillary columns

Six commercially available gas chromatography columns were investigated for performance in separating polychlorinated naphthalenes (PCNs). Retention behaviour on the investigated phases is compared and retention data for 40 congeners on a 5% phenyl-methylpolysiloxane column is reported. For all columns, except the octylmethylpolysiloxane and the smectic, a relation between substitution pattern and retention was found, where substitution in adjacent positions as well as alpha-substitution increase the retention time. A mathematical model based on these findings was developed and used to predict the relative retention of all congeners from di- up to octachloronaphthalene, on a 5% phenyl-methylpolysiloxane column.

Peer Reviewed: Analytical Challenges Hamper Perfluoroalkyl Research

The growing concern over these organohalogens, some of which have been found in human blood and appear to be widespread in the environment, led researchers to gather in Hamburg, Germany, in 2003 to evaluate the current state of methods to analyze for the organic contaminants. Jonathan Martin of the University of Toronto and 20 colleagues from industry, government, and academia summarize the main recommendations from the workshop.

Seasonal Variations of DDT Compounds and PCB in a Eutrophic and an Oligotrophic Lake in Relation to Algal Biomass

Abstract Interactions between eutrophication and organic pollutants (PCB, DDTs and γ-HCH) were investigated during 1996-1997 in two lakes, one eutrophic (Lake E) and one oligotrophic (Lake O) but with otherwise similar morphometry and water chemistry. Soil samples from the watersheds indicated similar atmospheric exposure of the lakes. No biomass dilution was observed in Lake E compared to Lake O. Lake E had higher levels of PCB based on organic carbon and lipid mass in sedimenting matter (1.5×), surface sediment (1.4×) and perch (Perca fluviatilis) (2.4×), and also higher settling fluxes of particulate matter and PCB measured in sediment traps and in surface sediment. Phytoplankton was responsible for most of the PCB transport to the sediment in Lake E. Higher DDD/DDE ratios seemed to correlate to a high load of p,p′-DDT more than to that of anaerobic conditions. A high DDD/DDE ratio was recorded in the deep sediment core from Lake O together with high levels of sDDT and was also highest in the sediment traps during periods with, probably, the highest runoff of parental DDT from the watershed.

Characterisation of humic substances by acid catalysed transesterification

Abstract The chemical composition of low molecular weight moieties linked to the core structures of humic substances (HS) are of substantial importance for the understanding of the chemical structures and mode of interactions of HS with other substances in the environment. In this study a novel approach to characterise certain low molecular weight compounds bound to HS is suggested. The method includes transesterification (TE) of ester and amide bound structures, and esterification (E) of free carboxylic groups using acid catalysed methanolysis followed by gas chromatography (GC)–mass spectrometry (MS) and GC-FID analysis. Methanolysis of five HS of different origin, demonstrated the presence of multifunctional hydroxy-substituted benzoic acids, hexoses, and long chain fatty acids. Based on GC-FID and addition of the internal standard before methanolysis, the total amounts of low molecular weight material could be estimated. In case of HS from the aqueous sources the yields were below 1%, whereas in case of the HS derived from lignite the yield was significantly higher. The hydrophobic long chain fatty acids constituted about one-third of this material. Principal component analysis (PCA), which was used for extended data evaluation, differentiated between the samples in terms of chemical composition.

Increasing Concentrations of Perfluoroalkyl Acids in Scandinavian Otters (Lutra lutra) between 1972 and 2011: A New Threat to the Otter Population?

Liver samples from 140 otters (Lutra lutra) from Sweden and Norway were analyzed for 10 perfluoroalkyl carboxylic acids (PFCAs; C6-C15), 4 perfluoroalkane sulfonic acids (PFSAs; C4,C6,C8,C10) and perfluorooctane sulfonamide (FOSA). Perfluorooctane sulfonic acid (PFOS) was the dominant compound accounting for approximately 80% of the fluorinated contaminants and showing concentrations up to 16 μg/g wet weight. Perfluorononanoic acid (PFNA) was the dominant PFCA (up to 640 ng/g wet weight) closely followed by the C10 and C11 homologues. A spatial comparison between otters from southwestern Norway, southern and northern Sweden sampled between 2005 and 2011 revealed that the samples from southern Sweden had generally the largest contaminant load, but two PFCAs and FOSA were higher concentrated in the Norwegian samples. A temporal trend study was performed on otters from southern Sweden collected between 1972 and 2011. Seven PFCAs (C8-C14), PFOS and perfluorodecane sulfonic acid (PFDS) showed significantly increasing trends with doubling times between 5.5 and 13 years. The PFCAs also showed significantly increasing trends over the period 2002 to 2011. These findings together with the exceptionally high liver concentrations of PFOS are of great concern for the Scandinavian otter populations.

Organic geochemistry of lipids in marine sediments in the Canary Basin: Implications for origin and accumulation of organic matter

Abstract The Canary basin consists of the continental margin off the coast of Northwest Africa, the deep basin, the Madeira Abyssal Plain (MAP) and the volcanic Canary Islands. The continental margin has an area of upwelling marine productivity with special characteristics: (a) a wide shelf area, (b) a wide irregular zone of upwelling, and (c) proximity to a large dust source—the Saharan desert. The Canary Islands divide the continental slope into a northern area and a southern area of primary productivity and accumulation of organic matter (OM). Accumulation of marine OM in the northern area is augmented by input of Saharan dust containing adsorbed terrigenous OM. n -Alkane distributions show a pronounced maximum around C 29 and C 31 with a strong odd-to-even predominance typical of terrigenous OM. There are less pronounced maxima near C 15 -C 17 , indicating a recent marine origin for the OM. Fatty acids show carbon number distributions similar to the n -alkanes, with a higher content and substantially higher C 16 /C 26 ratios in near-surface sediments of the slope samples, which decrease with depth in the sediment. The above data from the slope sediments can be compared to the most recent organic turbidite “a” on the MAP. Turbidite “a” was emplaced about 1000 years ago, incorporating slope derived material representing a 200,000-year time period. TOC and biomarker signatures of sediments on the slope are comparable to turbidite “a”. Biomarker analyses of deeper sediments on the MAP show similar data continuing back to early Miocene. Comparison of recent seafloor surface biomarkers with deeper samples indicates a varying contribution of terrigenous OM and a strong degradation of marine OM components in favor of leaving the long-chained compounds that increase a terrigenous signature of the sediments. The marine component is higher than analysis of deeper biomarkers tends to indicate. Polyaromatic hydrocarbons (PAH) are low in concentration, and no human pollution effects were detected. Perylene data suggest active diagenesis down the sediment core.

Cytological and biochemical biomarkers in adult female perch (Perca fluviatilis) in a chronically polluted gradient in the Stockholm recipient (Sweden).

By measuring a battery of cytological and biochemical biomarkers in adult female perch (Perca fluviatilis), the city of Stockholm (Sweden) was investigated as a point source of anthropogenic aquatic pollution. The investigation included both an upstream gradient, 46 km westwards through Lake Mälaren, and a downstream gradient, 84 km eastwards through the Stockholm archipelago. Indeed, there was a graded response for most of the biomarkers and for the muscle concentrations of ΣPBDE, four organotin compounds and PFOS in the perch. The results indicated severe pollution in central Stockholm, with poor health of the perch, characterised by increased frequency of micronucleated erythrocytes, altered liver apoptosis, increased liver catalase activity, decreased brain aromatase activity, and decreased liver lysosomal membrane stability. Some biomarker responses were lowest in the middle archipelago and increased again eastwards, indicating a second, partly overlapping, gradient of toxic effects from the Baltic Sea.