Dag Broman

Field testing of equilibrium passive samplers to determine freely dissolved native polycyclic aromatic hydrocarbon concentrations

Equilibrium passive samplers are promising tools to determine freely dissolved aqueous concentrations (C(W,free)) of hydrophobic organic compounds. Their use in the field, however, remains a challenge. In the present study on native polycyclic aromatic hydrocarbons (PAHs) in Oslo Harbor, Norway, two different passive sampler materials, polyoxymethylene (POM; thickness, 55 microm [POM-55] and 500 microm [POM-500]) and polydimethylsiloxane (PDMS; thickness, 200 microm), were used to determine in the laboratory C(W,free) in sediment pore water (C(PW,free)), and the suitability of five passive samplers for determination of C(W,free) in overlying surface water was tested under field conditions. For laboratory determinations of C(PW,free), both POM-55 and PDMS turned out to be suitable. In the field, the shortest equilibrium times (approximately one month) were observed for POM-55 and PDMS (thickness, 28 microm) coatings on solid-phase microextraction fibers, with PDMS tubing as a good alternative. Low-density polyethylene (thickness, 100 microm) and POM-500 did not reach equilibrium within 119 d in the field. Realistic values were obtained for dissolved organic carbon-water partition coefficients in the field (approximately one log unit under log K(OW)), which strengthened the conclusion that equilibrium was established in field-exposed passive samplers. At all four stations, chemical activity ratios between pore water and overlying water were greater than one for all PAHs, indicating that the sediment was a PAH diffusion source and that sediment remediation may be an appropriate treatment for PAH contamination in Oslo Harbor.

A review of processes involved in the exchange of persistent organic pollutants across the air-sea interface

Abstract Atmospheric deposition across the air–sea interface is the main input route for persistent organic pollutants (POPs) to the marine environment and its ecosystems. The main processes contributing to air–sea exchange of POPs are diffusive vapour exchange, precipitation scavenging of vapours and particle-sorbed chemicals, and dry deposition with particles. Additional processes within the atmosphere and surface water affecting this exchange are aerosol–vapour partitioning, and partitioning and sedimentation in the water-column. These processes are discussed and recent findings are summarised. Commonly employed expressions used for describing these processes in models are presented, with a special focus on the influence of temperature and other seasonal parameters. Research gaps are identified which have to be addressed to gain a solid understanding of the environmental transport and distribution of POPs. This is needed to implement and evaluate the effectiveness of recent international agreements to protect the marine environment from the deleterious effects of POPs.

Eutrophication and Contaminants in Aquatic Ecosystems

Abstract Eutrophication and persistent pollutants are two of the main environmental problems in European marine and freshwater ecosystems. As they tend to co-occur, interactive processes between eutrophication and contaminants are suggested, that may lead to environmental effects that cannot be predicted from each process alone. In order to predict the consequences of remedial measures (changing the input of organic matter, nutrients and contaminants) it is important to understand mechanisms that alter the bioavailability and fate of contaminants. The environmental risks will depend on the speciation of contaminants and their association to media and matter and by that means affect exposure. Furthermore, the risks will depend on the mobility of the substances and their pathways in food chains. In 1995, the Swedish Environmental Protection Agency initiated a 5-year research program Interactions between EUtrophication and CONtaminants (EUCON). A background document was prepared listing a number of relevant questions and hypotheses. On the basis of this document a program was launched, addressing the problems related to the interaction between eutrophication and contaminants (persistent organic compounds and trace metals) in the marine environment, with focus on the Baltic Sea, and in lakes. This paper summarizes the state-of-the-art, hypotheses and highlights from the research program with emphasis on the implications and applications of the results.

Soot-water distribution coefficients for polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and polybrominated diphenylethers determined with the soot cosolvency-column method.

For many types of hydrophobic compounds, sorption non-linearity and solid-water distributions in the field well above expectations from organic matter partitioning models have lead to the proposition that strong adsorption to soot surfaces may not be limited to polycyclic aromatic hydrocarbons but may extend as a significant process for many aromatic compound classes. Here, the soot-water distribution coefficients (Ksc) were determined with the soot cosolvency-column method for homolog series of five polychlorinated dibenzo-p-dioxins (PCDDs), five polychlorinated dibenzofurans (PCDFs) and for two polybrominated diphenylethers (PBDEs). All compounds exhibited significantly stronger association with soot carbon than expected from estimates of their bulk organic-carbon normalized partition coefficients (Koc). The Ksc/Koc ratios (at aqueous concentrations of around 0.1-1 microg/l) were for PCDDs (up to tetrachlorination) 19-130 (median 25), for PCDFs (also up to tetrachlorination) 150-490 (median 300), and for both the tetra- and pentabrominated PBDEs a factor of 60. The particularly strong soot sorption for the PCDFs is of similar enhancement factors as previously elucidated for polycyclic aromatic hydrocarbons. Compound-class specific correlations between log Ksc and octanol-water partition coefficients (log Kow) were significant for both PCDDs and PCDFs (and with R2 > 98%). These may prove useful for anticipating variable fractions of dissolved exposures between different environmental regimes and putative remediation objects.

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.

Toxicity and EROD-inducing potency of 24 polycyclic aromatic hydrocarbons (PAHs) in chick embryos

The toxicities (embryolethality) of 24 polycyclic aromatic hydrocarbons (PAHs) were determined in chick embryos using a 72-h test. The substances, dissolved in peanut oil, were injected into the air sacs of eggs preincubated for 7 days. LD50 values were determined for the four most toxic of the 24 compounds. Benzo [k] fluoranthene proved to be the most potent, with an LD50 of 14 μg (56 nmol)/kg egg. Dibenz[a,h]anthracene, benz[a]anthracene and benzo[b]naphtho[2,3-d]thiophene were a few times less toxic [LD50=39 μg (140 nmol)/kg, 79 μg (349 nmol)/kg and 82 μg (350 nmol)/kg, respectively]. The LD50 of benzo [k] fluoranthene was only about 5 times higher than that previously found for the most potent coplanar polychlorinated biphenyl (PCB), 3,3′,4,4′,5-pentachlorobiphenyl [LD50=3.1 μg (9.4 nmol)/kg], in the same kind of test. The toxicities of 18 of the PAHs in this study have also been evaluated previously using a 2-week test in chick embryos. Dibenz[a,h]anthracene, which had not been studied earlier in the 2-week test, proved to be almost as toxic as previously found for benzo [k] fluoranthene in that test. Several of the PAHs studied induced EROD activity in chick embryos, and, in general, the most toxic PAHs were also the most potent inducers of EROD. The highest enzyme activities were found after treatment with indeno[1,2,3-c,d]pyrene (12 times the control value) and dibenz[a,h]anthracene (8 times the control value). However, due to the high toxicity of dibenz[a,h]anthracene, the dose used was 7 times lower than that of indeno [1,2,3-c,d]pyrene. Following injection of PAHs on day 7, the EROD activities on day 10 were considerably lower than those obtained after a corresponding treatment with coplanar PCBs in an earlier study. Of the PAHs studied, some exhibited very high embryotoxicity. The most toxic PAHs induced EROD activity, suggesting that their toxicity was at least partly mediated via binding to the Ah receptor.

Biomagnification of organic pollutants in benthic and pelagic marine food chains from the Baltic Sea.

The trophic transfer of organic pollutants with varying physical chemical properties was determined in both a pelagic and benthic food chain using delta 15N as a continuous variable for assessing trophic levels. The trophic transfer of organic pollutants through the entire food chain in terms of food chain magnification factors (FCMFs) was quantified from the slope of the regression between ln [concentration] and delta 15N. Organic pollutants with statistically significant FCMFs >1 were considered to biomagnify within the food chain, whereas those with FCMFs <1 were considered to trophically dilute. Statistically significant FCMFs >1 were found for PCB congeners and organochlorine pesticides in the Baltic food chains whereas statistically significant FCMFs <1 were found for PAHs and PCNs due to trophic dilution resulting from metabolism. FCMFs were generally greater in the pelagic food chain than in the benthic food chain. However, estimated FCMFs for the benthic food chain are likely in error, as the delta 15N method suggested a food chain structure which was not consistent with the known dietary patterns of the species. Biomagnification factors (BMFs) were additionally calculated as the ratio of the lipid normalized concentrations in the predator and prey species with adjustment for trophic level and were generally consistent with the FCMFs with BMF >1 for PCBs and organochlorines.

A multi-sediment trap study on the temporal and spatial variability of polycyclic aromatic hydrocarbons and lead in an anthropogenic influenced archipelago.

Sixteen sediment traps have been used to collect seston for more than 8 months to study the spatial and temporal distribution of 18 PAH compounds and lead in the Stockholm archipelago (Baltic Proper). Concentrations and especially fluxes exhibit a steep logarithmic decline with distance from urban areas. PAH concentrations and fluxes are higher during the winter-spring period than during the summer due to increased emissions, more extensive washout of land-deposited PAH during snow melting, and resuspension caused by nonstratified water conditions and mixing zone effects. Microbial degradation and photooxidation during summer are of secondary importance to the lower concentrations during that period. Results indicate that air-transported black carbon particles from a variety of nonpoint pollution sources are the probably main carriers of PAH in combination with particles from direct runoff for the stations in the immediate surroundings of the urban area.

Potential biomagnification of PCDD/Fs - new possibilities for quantitative assessment using stable isotope trophic position

Abstract The transport of PCDD/Fs in two Baltic food chains is studied with a new method which quantitatively estimates biomagnification. Metabolic fractionation of stable isotopes of nitrogen is used to numerically estimate the trophic position of organisms. An application of the method to PCDD/F data from two Baltic food chains indicates that summed whole body concentrations of 2378-substituted PCDD/Fs decrease with increasing trophic position. The sum of TEQs however increases with trophic position. The main reason for this is the decrease in OCDD concentrations and a selective biomagnification of the three most toxic isomers 2378-TCDD, 23478-PnCDF and 12378-PnCDD.

Wild birds of declining European species are dying from a thiamine deficiency syndrome.

Wild birds of several species are dying in large numbers from an idiopathic paralytic disease in the Baltic Sea area. Here, we demonstrate strong relationships between this disease, breeding failure, and thiamine (vitamin B1) deficiency in eggs, pulli, and full-grown individuals. Thiamine is essential for vertebrates, and its diphosphorylated form functions as a cofactor for several life sustaining enzymes, whereas the triphosphorylated form is necessary for the functioning of neuronal membranes. Paralyzed individuals were remedied by thiamine treatment. Moreover, thiamine deficiency and detrimental effects on thiamine-dependent enzymes were demonstrated in the yolk, liver, and brain. We propose that the mortality and breeding failure are part of a thiamine deficiency syndrome, which may have contributed significantly to declines in many bird populations during the last decades.