Description: Kanechlor-300, -400, -500 and -600, Phenoclor DP-3, -4, -5 and -6 and Sovol mixtures were analyzed for their chlorobiphenyl (CB) composition using high-resolution one-dimensional and multidimensional gas chromatography-electron capture detection (MDGC-ECD) techniques. The congener patterns of tested Kanechlor and Phenoclor mixtures resembled Aroclor 1016, 1242, 1254 and 1260. However, differences in the percentage contribution of minor constituents were noticed among these mixtures, which could be due to variations in the boiling-point fractionation of these commercial products. CB pattern of Sovol was different from the rest of the mixtures tested. It showed a composition in between ca. 30%, 40%, 50% and 60% overall chlorine levels. MDGC-ECD study showed the presence of hitherto unnoticed non-CB compounds coeluting with CBs in some commercial PCBs. The use of these mixtures as quantitation standards should be considered with caution. CB patterns of Sovol and a water extract of the Gulf of Finland matched closely, indicating a point source contamination to these waters.

Description: Eine Analysenmethode, die für die organische Spurenstoff-Bestimmung im Meerwasser konzipiert ist, wurde auf die Analytik von Grund- und Trinkwasser übertragen. Es zeigte sich, daß mit den üblichen Meßmethoden keine ausreichenden Analysen möglich sind. Hauptprobleme sind zu geringe Probenvolumina (1-10 1), ungenügende Clean-up Methoden und unvollständige gaschromatographische Trennungen von koeluierenden Verbindungen. Die Konzentrationen an Chlorbiphenylen im untersuchten Trinkwasser lagen zwischen 0,1 und 50 pg/1 und somit weit unter den nach der Trinkwasserverordnung vom Dezember 1990 zulässigen Höchstmengen. Die Gehalte waren aber zum Teil höher als im Meerwasser der als sehr belastet angesehenen Nordsee und Ostsee. Unter diesen Gesichtspunkten, wie auch unter Berücksichtigung der unterschiedlichen Toxizitäten der Einzelkomponenten, erscheint der in der Trinkwasserverordnung vorgeschriebene Grenzwert viel zu hoch

Description: Environmental context: Halocarbons are trace gases important in atmospheric ozone chemistry whose biogenic production – among other factors – depends on light-induced stress of marine algae. Several studies have confirmed this effect in laboratory experiments but knowledge in natural systems remains sparse. In mesocosm experiments, which are a link between field and laboratory studies, we observed that the influence of natural levels of ultraviolet radiation on halocarbon dynamics in the marine surface waters was either insignificant or concealed by the complex interactions in the natural systems. Abstract: The aim of the present study was to evaluate the influence of different light quality, especially ultraviolet radiation (UVR), on the dynamics of volatile halogenated organic compounds (VHOCs) at the sea surface. Short term experiments were conducted with floating gas-tight mesocosms of different optical qualities. Six halocarbons (CH3I, CHCl3, CH2Br2, CH2ClI, CHBr3 and CH2I2), known to be produced by phytoplankton, together with a variety of biological and environmental variables were measured in the coastal southern Baltic Sea and in the Raunefjord (North Sea). These experiments showed that ambient levels of UVR have no significant influence on VHOC dynamics in the natural systems. We attribute it to the low radiation doses that phytoplankton cells receive in a normal turbulent surface mixed layer. The VHOC concentrations were influenced by their production and removal processes, but they were not correlated with biological or environmental parameters investigated. Diatoms were most likely the dominant biogenic source of VHOCs in the Baltic Sea experiment, whereas in the Raunefjord experiment macroalgae probably contributed strongly to the production of VHOCs. The variable stable carbon isotope signatures (δ13C values) of bromoform (CHBr3) also indicate that different autotrophic organisms were responsible for CHBr3 production in the two coastal environments. In the Raunefjord, despite strong daily variations in CHBr3 concentration, the carbon isotopic ratio was fairly stable with a mean value of –26 ‰. During the declining spring phytoplankton bloom in the Baltic Sea, the δ13C values of CHBr3 were enriched in 13C and showed noticeable diurnal changes (–12 ‰ ± 4). These results show that isotope signature analysis is a useful tool to study both the origin and dynamics of VHOCs in natural systems.

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: In order to investigate temporal changes in combination with the influence of different environmental parameters on the concentration and the composition of volatile organic compounds (VOCs), seawater samples from the coastal Baltic Sea were weekly measured from January to November 2008. In most cases, concentrations of VOCs varied seasonally and were influenced by changes in temperature and light conditions or biological species composition. A nearly two-fold increase in the mean concentration was noticed for isoprene, iodomethane and bromoform in the season with higher water temperature. The strongest flux of dimethylsulfide to the atmosphere appeared in May and July. Its high production was related to the presence of Prymnesiophyceae. The highest concentrations of diiodomethane and chloroiodomethane were observed with the spring and autumn phytoplankton bloom; their distribution was strongly controlled by light intensity. Flux calculations showed that coastal regions can affect local atmosphere, especially during biologically active periods. The strongest emission of bromoform and iodomethane was in July and August. The data presented here highlights the need to include seasonal cycles when calculating the global budgets and modelling sea-air fluxes of trace gases.

Description: Environmental context: Once released to the atmosphere, halocarbons are involved in key chemical reactions. Stable carbon isotope measurements of halocarbons can provide valuable information on their sources and fate in the atmosphere. Here, we report δ13C values of 13 polyhalomethanes released from brown algae, which may provide a basis for inferring their sources and fate in future studies. Abstract: Halocarbons are important vectors of reactive halogens to the atmosphere, where the latter participate in several key chemical processes. An improved understanding of the biogeochemical controls of the production–destruction equilibrium on halocarbons is of vital importance to address potential future changes in their fluxes to the atmosphere. Carbon stable isotope ratios of halocarbons could provide valuable additional information on their sources and fate that cannot be derived from mixing ratios alone. We determined the δ13C values of 13 polyhalomethanes from three brown algae species (Laminaria digitata, Fucus vesiculosus, Fucus serratus) and one seagrass species (Zostera noltii). The δ13C values were determined in laboratory incubations under variable environmental conditions of light, water levels (to simulate tidal events) and addition of hydrogen peroxide (H2O2). The δ13C values of the polyhalomethanes ranged from –42.2 ‰ (±3.5 s.d.) for CHCl3 to 6.9 ‰ (±4.5) for CHI2Br and showed a systematic effect of the halogen substituents that could empirically be described in terms of linear free energy relationships. We further observed an enrichment in the δ13C of the polyhalomethanes with decreasing polyhalomethane yield that is attributed to the competing formation of halogenated ketones. Though variable, the isotopic composition of polyhalomethanes may provide useful additional information to discriminate between marine polyhalomethane sources.

Description: Long-term observations of the deep ocean particle flux from three sites in the northeast Atlantic (33 degrees N, 22 degrees W; 47 degrees N, 20 degrees W; 54 degrees N, 20 degrees W) provide the basis for comparison and characterization of the biogeochemical provinces in terms of sedimentation pattern. Deep ocean particle flux data (2000 in) for fluxes of total mass and the flux composition are presented and compared to published sediment trap data from this area to consider regional-scale variations in the quantity and composition of settling material. The observations show that in the northeast Atlantic gradient of decreasing mass flux from North to South, exists consistent with known changes of biological productivity in surface waters. This gradient is associated with similar trends in opal and particulate organic carbon, whereas calcium carbonate shows trend in the opposite direction. The changes in the composition of the settling material found along the transect are indicating that the calcium carbonate flux is critical in removing organic matter from the upper ocean to the deeper sink. Its role declines from the subtropical ocean (60-80% of the particle flux) towards North (〈 40%) reflecting the decreasing importance of coccolithophorid/foraminiferal blooms for particle flux from the subtropical to the subpolar North Atlantic. In contrast, the role of biogenic silica (opal) in regard to the ballasting effect increases towards North. The northern sites have much higher percentage of biogenic silica than the sites in the South, because of the deep winter mixing and the seasonality of phytoplankton dominated by diatom blooms during spring and summer. The comparison of the seasonal pattern of particle flux with the seasonal pattern of surface chlorophyll a concentrations from SeaWiFS together with the similarity of the pattern observed in calcium carbonate and opal leads to the conclusion that the particle flux at two positions (33 degrees N, 22 degrees W; 47 degrees N, 20 degrees W) is fast and directly coupled to the phytoplankton dynamics in the overlying euphotic zone.

Description: The subtropical northeast Atlantic has previously been identified as a marine environment with an apparent imbalance between low nitrate supply to the surface and concurrent high export production. To better constrain the sources and fluxes of mixed layer nitrate and to assess the potential role of N2 fixation in providing new nitrogen (N), we investigated the depth distribution of nitrate δ15N and δ18O at six stations across the Azores Front in the NE Atlantic. In addition, we measured the δ15N of dissolved organic N (DON) in surface waters and of sinking particulate N collected in sediment traps at 2000 m depth between 2003 and 2005 at Station KIEL276. The nitrate isotope profiles at the majority of the hydrographic stations displayed a decrease in the δ15N from depth toward low-nitrate surface waters, concomitant with an increase in δ18O. Given that nitrate uptake by phytoplankton leads to a proportional increase in nitrate δ15N and δ18O, the observed surface water nitrate isotope anomalies (Δ(15;18) up to −6‰) indicate that nitrate assimilation is not the sole process controlling the isotopic composition of nitrate in the photic zone and implicate a significant addition of newly fixed N that is remineralized in surface and subsurface waters. Both the concentration of DON and its δ15N in surface water were spatially invariant, showing mean values of 4.7 ± 0.5 μmol L−1 and 2.6 ± 0.4‰ (n = 35), respectively, supporting the conjecture of a mostly recalcitrant DON pool. The weighted biannual mean δ15N of sinking particulate N (1.8 ± 0.8‰, n = 33) was low with respect to thermocline nitrate. The anomalous dual nitrate isotope signatures together with the low δ15N of export production and elevated nitrate-to-phosphate ratios in surface and subsurface waters strongly suggest that N2 fixation represents a substantive source of N in this part of the subtropical northeast Atlantic. Simple isotope mass balance suggests that, locally, N2 fixation supplies between 56 and 259 mmol N m−2 a−1 for phytoplankton growth in the photic zone, accounting for up to ∼40% of the estimated export production.

Description: Under the EC sponsored research project ODER (Oder Discharge-Environmental Response) first investigations have been carried out to estimate the chlorinated biphenyls (CB) input into Oderhaff via the Oder river. For this purpose, vertical profiles of CB content and composition were analysed on samples of three sediment cores. In two water samples, the content of suspended particulate material as weil as the particulate CB content and congener-specific composition were measured. In the Oderhaff the CB concentrations of particulate material were between 700 to 800 pg/dm3. Significant differences in the composition of the components were not observed. In sediments, CB contents were as high as 17 to 24 ngig dry weight in near surface sediment layers. They decreased with increasing sediment depth and were below detection limits at 15 to 21 cm depth. Based on the size of the 49 accumulation area and related hydrographic conditions, we estimated an input of 95 kg into the Oderhaff for the last 65 years since the onset of CB production. Applying the present prevailing conditions, we calculated an average transport of about 825 kg CB by the Oder river during this period. Comparing these two estimates, we observed that at least 15 % of the CB transported by the Oder river was deposited in the Oderhaff. The remaining 85 % (-730 kg), have been further transported into the South Pomeranian Bight and Southern Baltic Sea.

Description: The effect of dissolution from particulates into the supernatant solution in sediment trap sample cups has been measured for fatty acids. A mooring array with time series sediment traps was deployed in the northeast Atlantic Ocean (59°N, 21°W) for 14 months. Selected representative samples from the trap at 2200 m (poisoned with NaN3) were analyzed for total and free fatty acids in both the solution and particulate phase by means of gas chromatography‐mass spectrometry with an ion trap detector. The flux contribution of the dissolved total fatty acids (∑ DTFA) was found to be between 15 and 75% of the total flux (∑ TTFA, sum of the fluxes of total fatty acids in both particles and supernatants). Dissolved free fatty acids (∑ DFFA) represented 25–88% of the total flux of free fatty acids (∑ TFFA). Absolute concentrations of total and free fatty acids in both compartments are discussed in terms of the processes controlling the distribution between the two phases, for example, readsorption. Sample handling, poisoning, bacterial activity, and swimmers may also affect fatty acid distribution. Flux data (sum of particulate and dissolved fluxes) are presented for individual fatty acids. Also, the degree of dissolution of individual fatty acids is shown for one sample (dissolved fraction ranging between 16 and 98% of total flux).