ALBERT

Description: A seasonally-varying sedimentation pattern was observed for the alkenone flux measured with sediment traps in the northern North Atlantic. In the Norwegian Sea (traps were set at 500, 1000 and 3000 m) the alkenone flux varied between 0.1 and 7.1 μg m−2 d−1 and followed the seasonal pattern of the bulk parameters. Maximum fluxes occurred from mid-October until mid-November and were also high in May. A surprising result was that considerably higher particle fluxes were observed at 3000 m. For the alkenone flux, the highest additional input of 250% was observed during the period when sediment resuspension was greatest in summer. At the Barents Sea continental margin (traps at 1840 and 1950 m) the alkenone fluxes follow the sedimentation pattern of the bulk parameters, with a less visible signal of distinct seasonality observed in the 1950 m trap. The sedimentation of total alkenones varied between 0.8 and 144 μg m−2 d−1 at 1840 m and between 0.5 and 31.0 μg m−2 d−1 at 1950 m. Resuspension and lateral advection contributed significantly to measured fluxes in the two near-bottom traps. Alkenone concentrations were determined in faecal pellets of Appendicularia, ostracods and euphausids from selected samples at the Barents Sea site. The alkenone flux in pellets (4% to 24% of total) was 5 to 6 times higher at 1950 m depth than at 1840 m and the major part (77–78%) of the total flux of C37:3 reaching the near-bottom trap at 1950 m was associated with faecal pellets of the meso-zooplankton. Spatial and temporal variations of the U37k′ signals were observed, indicating that the imprint in the alkenone signal depends on the origin and transport pathway of the organic material. Strong deviations occur in areas where nepheloid layers contribute particles of long residence times to the primary flux.

Description: Concentrations of 23 individual chlorobiphenyls (CBs) and 6 polyaromatic hydrocarbons (PAHs) were determined in different water masses of the North Atlantic Ocean around Iceland. The study was carried out in the framework of the second Intergovernmental Oceanographic Commission (IOC) baseline studies of contaminants in the North Atlantic Ocean, involving trace organics and trace elements. Concentrations of individual CBs were extremely low. In solution, they varied between 〈2 and 126 fg dm−3 and in suspension between 〈2 and 1400 fg dm−3. The values for their sum (∑CB) were between 10 and 1048 in solution, and 286–11 241 fg dm−3 in suspension. ∑PAHs were present in the 〈5–65 pg dm−3 range, p,p′-DDE and hexachlorobenzene were 〈2 fg dm−3. The concentrations of CBs and PAHs decreased from the surface towards the bottom at each station. The lowest concentrations were found in Norwegian Sea Deep Water (∑CB 10 fg dm−3), concurrent with the lowest halocarbon concentrations found during the cruise. Values in near-surface waters were considerably lower than those determined at mid-latitudes of the North Atlantic. These findings reflect the mixing of water bodies with higher CB concentrations from the central North Atlantic with less contaminated waters from the Arctic Ocean. Concentrations in suspension exceeded those in solution in most samples, as a result of the relatively high suspended matter concentrations in the waters around Iceland. Particulate CB and PAH concentrations were positively correlated with particulate organic carbon concentrations. This suggests that suspended organic material is a carrier for these relatively apolar organic compounds in the water column. The data do not support the co-distillation concept suggested in the literature.

Description: A system for in-situ filtration and extraction of organics in natural waters has been developed and tested down to 4000 m in the Atlantic Ocean. Up to 2000 dm3 water can be filtered and extracted at low suspended matter concentrations. The sampling equipment has new features for the analysis of trace organic compounds: contamination is extremely low, this can be checked and cured, if necessary, and water flow can be selected and maintained at a constant rate. Various resins can be applied, with different optimum flow rates for the efficient extraction of the compounds of interest. The properties of the resin (here XAD-2) do not change with depth. The operation of the unit is controlled by menu-driven software. All relevant data are stored for later evaluation. Tests in the deep Atlantic resulted in total procedural blanks, including sampling, as low as 0/003 pg dm−3 for individual chlorobiphenyls (CBs), HCB and DDE and 0.5 pg dm−3 for individual PAHs. Actual dissolved concentrations were in the range 0.005–0.1 pg dm−3 for CBs, HCB and DDE and 0.5–140 pg dm−3 for PAHs.

Description: Metabolism of chlorobiphenyls (CBs) was studied in harbour porpoise by comparing patterns of CB-X/CB-153 ratios in blood, brain, liver and blubber with the patterns in herring, the main food source. The CBs were classified in five groups, based on the presence/absence of vicinal H-atoms (vic. Hs) in meta,para (m,p) and/or ortho,meta (o,m) positions and the number of ortho-Cl-atoms (ortho-Cls). Plots of CB-X/CB-153 ratios in porpoise tissue vs the ratios in herring appeared to be linear for each CB group in all tissues. Slopes of these plots (metabolic slopes) were used as quantitative indicators of metabolic activity. In this way, activity of PB-type isozymes of the P450 monooxygenase system was apparent: in contrast to existing literature data, harbour porpoise appears to be able to metabolize congeners with m,p vic. Hs, even in the presence of more than 2 ortho-Cls. The presence of 3-MC-type (MC-type) isozymes was also detected. The metabolic slopes were also used as basis for risk assessment. Due to their metabolism the most toxic non-ortho CBs were not present in the tissues at detectable levels. We suggest a risk assessment approach which takes this into account. It is considered to be an alternative and more reliable basis for risk assessment than the use of toxic equivalent factors. The results support the model of equilibrium distribution of CBs in harbour porpoise and the role of blood as central transport medium. The model has been developed for persistent compounds; it appears to hold for metabolizable CB congeners as well.

Description: A PYE 2-(1-pyrenyl)ethyldimethylsilylated silica gel] column HPLC in combination with MDGC-ECD has been developed for a sensitive and selective determination of toxic mono- and non-ortho PCBs in environmental samples. This technique was applied to environmental samples such as coastal water, suspended particulate material (SPM), coastal sediment, mussels, fish, bird and marine mammal. Determination of PCB 156 along with non-ortho congeners acted as matrix-integrated quality control parameter. This hyphenated technique offers one of the most sensitive way of determining non-ortho PCBs but also reveals the immense complexity of the coelution problem which unnoticed results in over estimation of toxic PCBs in the environmental samples.

Description: The effect of the supply of chlorinated biphenyls by the river Oder into some adjacent areas of Baltic Sea was studied in nine sediment cores and in 10 suspended matter samples. Congener-specific analysis was carried out on 28 individual chlorobiphenyls (CBs). ∑CB concentrations in suspension ranged from 2.4 pg dm-3 in the southern Bornholm Basin to 986 pg dm-3 in the Achterwasser. ∑CB contents in surface sediment decreased with increasing distance from the river mouth. Highest contents were found in the Oderhaff (18 ng g-1 dw) decreasing to 2 ng g-1 dw in the Bornholm Basin. The ∑CB contents generally decreased more or less regularly with increasing depth. The compositions of the CB mixtures in surficial sediment and suspension samples were rather similar, suggesting a common source. Compositions of the CB mixtures in the sediment cores showed distinct differences. These may reflect variations in source strength over time. Mass balance considerations on the basis of the 28 CBs resulted in an estimation of a total storage of approximate 733±158 kg ∑CBs in the Oderhaff, Achterwasser, Greifswalder Bodden, Oder Rinne, Arkona Basin and Bornholm Basin in the past 65 years, covering the time period since CBs were first produced. Based on river data about 500 kg of ∑CBs were supplied during this time by river Oder, that may thus be the major source of these compounds for the southern Baltic Sea.

Description: Individual chlorinated biphenyls (CBs) and chlorinated pesticides (p,p′-DDT and metabolites, HCHs and HCB) were determined in blubber samples of 40 harbour porpoises (Phocoena phocoena) of different age and sex from the North Sea, the Baltic Sea and Greenland coastal waters. Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were analysed in a selected group of animals. ΣCB concentrations (medians) in North Sea immature specimens were similar (14.9 μg/g lipid) to those from the Baltic Sea (17.0 μg/g lipid) and exceeding those in Greenland specimens by an order of magnitude (1.3 μg/g lipid). The median concentrations (μg/g lipid) of HCB, p,p′-DDE, p,p′-DDD and γ-HCH were in the order Greenland〈North Sea〈Baltic Sea. The highest concentrations of α-HCH (0.14 μg/g lipid) were found in the Greenland population, and p,p′-DDT was detected only in this group. The North Sea and Baltic Sea populations were identified as distinctly separate on the basis of levels and compositions of these contaminants. The ecological risk associated with dioxin-like toxicity was dominated by the CB congeners 118 and 170; the PCDD/Fs were playing only a minor role.

Description: Arabian Sea sediments record changes in the upwelling system off Arabia, which is driven by the monsoon circulation system over the NW Indian Ocean. In accordance with climate models, and differing from other large upwelling areas of the tropical ocean, a 500,000-yr record of productivity at ODP Site 723 shows consistently stronger upwelling during interglaciations than during glaciations. Sea-surface temperatures (SSTs) reconstructed from the alkenone unsaturation index (U K′ 37) are high (up to 27°C) during interglaciations and low (22-24°C) during glaciations, indicating a glacial-interglacial temperature change of 〉3°C in spite of the dampening effect of enhanced or weakened upwelling. The increased productivity is attributed to stronger monsoon winds during interglacial times relative to glacial times, whereas the difference in SSTs must be unrelated to upwelling and to the summer monsoon intensity. The winter (NE) monsoon was more effective in cooling the Arabian Sea during glaciations then it is now.

Description: Single and multidimensional GC-ECD techniques were applied to determine individual chlorobiphenyls (CBs) in solution and in suspended particles in the Baltic Sea (some data were also obtained for the adjacent German Bight in the North Sea). Large volumes (up to 1100 dm3) were analysed in transects in November 1988 and 1989 and in spring 1991. Salinity and temperature were measured continuously along the sampling tracks in all three cruises; nutrients and pH only in the latter two cruises. Concentrations of individual CBs in solution were in the sub- and low pg dm−3 range (detection limit being 0.05 pg dm−3), and of their sum between 2 and 237 pg dm−3. These concentrations are considerably lower than previously reported data. This is mainly the result of the elimination of contamination and interference problems in the sampling, clean-up and GC-ECD procedures. It may also partly reflect the reduction in the production and use of PCBs in the last decade. The highest concentrations in solution originated from local sources in the Belt Sea and the Gulf of Finland. Regional differences were found for the compositions of the CB mixtures in solution. The lowest concentrations of CBs in solution were found in areas and periods of plankton production (spring 1991), with ΣCB concentrations between 2 and 14 pg dm−3. The compositions of the CB mixtures showed regional differences in each cruise. These could be interpreted in terms of mixing between different water bodies. The classification of transects on the basis of these CB patterns agreed well with the distinction of water bodies on the basis of T-S diagrams and hydrochemical data. Concentrations of individual CBs in suspension were generally 0.1–0.5 pg dm−3, those of their sum (ΣCB) between 4 and 6 pg dm−3 during the autumn cruises. Extremely high values were found in the Belt Sea-Kattegat area in spring 1991 (up to 589 pg dm−3 for individual CBs and up to 2859 pg dm−3 for ΣCB). This probably reflects the uptake of CBs into particulates during a plankton bloom. Primary production may effectively remove CBs from the water column into the sediments. The amounts of chlorobiphenyls presently stored in the sediments of the Baltic Sea exceed the amounts in the water column by several orders of magnitude. The compositions of the CB mixtures differed considerably between solution and suspension. The relations between log K′d (apparent particle/water partition coefficient) and log Kow (octanol-water distribution coefficient) suggest the existence of (quasi-)equilibrium conditions in autumn. Deviations from this behaviour arise from biological activity in spring. The contribution of toxic congeners to the CB mixtures was dominated by the mono- and di-ortho-Cl substituted derivatives of the most toxic non-ortho-Cl CBs. The toxicity of the CB mixtures in solution was between 0.01 and 12fg dm−3 TEQs (TCDD toxic equivalents). CBs-77, -118, -105 and -156 had the largest contributions to TEQs.