Concentrations of perfluorinated carboxylic acids (PFCAs) and sulfonic acids (PFSAs) in liver samples of different marine mammals (1984-2009)

Temporal variations in concentrations of perfluorinated carboxylic acids (PFCAs) and sulfonic acids (PFSAs), including perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) structural isomers, were examined in livers of pilot whale (Globicephala melas), ringed seal (Phoca hispida), minke whale (Balaenoptera acutorostrata), harbor porpoise (Phocoena phocoena), hooded seal (Cystophora cristata), Atlantic white-sided dolphin (Lagenorhynchus acutus) and in muscle tissue of fin whales (Balaenoptera physalus). The sampling spanned over 20 years (1984-2009) and covered a large geographical area of the North Atlantic and West Greenland. Liver and muscle samples were homogenized, extracted with acetonitrile, cleaned up using hexane and solid phase extraction (SPE), and analyzed by liquid chromatography with negative electrospray tandem mass spectrometry (LC-MS/MS). In general, the levels of the long-chained PFCAs (C9-C12) increased whereas the levels of PFOS remained steady over the studied period. The PFOS isomer pattern in pilot whale liver was relatively constant over the sampling years. However, in ringed seals there seemed to be a decrease in linear PFOS (L-PFOS) with time, going from 91% in 1984 to 83% in 2006.

Data compilation of ESOP

The work in this sub-project of ESOP focuses on the advective and convective transforma-tion of water masses in the Greenland Sea and its neighbouring areas. It includes observational work on the sub-mesoscale and analysis of hydrographic data up to the gyre-scale. Observations of active convective plumes were made with a towed chain equipped with up to 80 CTD sensors, giving a horizontal and vertical resolution of the hydrographic fields of a few metres. The observed scales of the penetrative convective plumes compare well with those given by theory. On the mesoscale the structure of homogeneous eddies formed as a result of deep convection was observed and the associated mixing and renewal of the intermediate layers quantified. The relative importance and efficiency of thermal and haline penetrative convection in relation to the surface boundary conditions (heat and salt fluxes and ice cover) and the ambient stratification are studied using the multi year time series of hydro-graphic data in the central Greenland Sea. The modification of the water column of the Greenland Sea gyre through advection from and mixing with water at its rim is assessed on longer time scales. The relative contributions are quantified using modern water mass analysis methods based on inverse techniques. Likewise the convective renewal and the spreading of the Arctic Intermediate Water from its formation area is quantified. The aim is to budget the heat and salt content of the water column, in particular of the low salinity surface layer, and to relate its seasonal and interannual variability to the lateral fluxes and the fluxes at the air-sea-ice interface. This will allow to estimate residence times for the different layers of the Greenland Sea gyre, a quantity important for the description of the Polar Ocean carbon cycle.

(Table 1) Concentrations of the main organochlorine pesticides in liver and plasma samples of ringed seals (Phoca hispida)

The present study investigates the concentrations and patterns of organochlorine pesticides (OCPs) and their metabolites in liver and plasma of two ringed seal populations (Phoca hispida): lower contaminated Svalbard population and more contaminated Baltic Sea population. Among OCPs, p,p'-DDE and sum-chlordanes were the highest in concentration. With increasing hepatic contaminant concentrations and activities of xenobiotic-metabolizing enzymes, the concentrations of 3-methylsulfonyl-p,p'-DDE and the concentration ratios of pentachlorophenol/hexachlorobenzene increased, and the toxaphene pattern shifted more towards persistent Parlar-26 and -50 and less towards more biodegradable Parlar-44. Relative concentrations of the chlordane metabolites, oxychlordane and -heptachlorepoxide, to sum-chlordanes were higher in the seals from Svalbard compared to the seals from the Baltic, while the trend was opposite for cis- and trans-nonachlor. The observed differences in the OCP patterns in the seals from the two populations are probably related to the catalytic activity of xenobiotic-metabolizing enzymes, and also to differences in dietary exposure.

(Table 1) Age determination of sediment core SO147_106KL

Here we present a high-resolution marine sediment record from the El Niño region off the coast of Peru spanning the last 20,000 years. Sea surface temperature, photosynthetic pigments, and a lithic proxy for El Niño flood events on the continent are used as paleo-El Niño-Southern Oscillation proxy data. The onset of stronger El Niño activity in Peru started around 17,000 calibrated years before the present, which is later than modeling experiments show but contemporaneous with the Heinrich event 1. Maximum El Niño activity occurred during the early and late Holocene, especially during the second and third millennium B.P. The recurrence period of very strong El Niño events is 60-80 years. El Niño events were weak before and during the beginning of the Younger Dryas, during the middle of the Holocene, and during medieval times. The strength of El Niño flood events during the last millennium has positive and negative relationships to global and Northern Hemisphere temperature reconstructions.

(Table 1) Sea surface temperature reconstruction for eastern equatorial Pacific surface sediment samples

Significant uncertainties persist in the reconstruction of past sea surface temperatures in the eastern equatorial Pacific, especially regarding the amplitude of the glacial cooling and the details of the post-glacial warming. Here we present the first regional calibration of alkenone unsaturation in surface sediments versus mean annual sea surface temperatures (maSST). Based on 81 new and 48 previously published data points, it is shown that open ocean samples conform to established global regressions of Uk'37 versus maSST and that there is no systematic bias from seasonality in the production or export of alkenones, or from surface ocean nutrient concentrations or salinity. The flattening of the regression at the highest maSSTs is found to be statistically insignificant. For the near-coastal Peru upwelling zone between 11-15°S and 76-79°W, however, we corroborate earlier observations that Uk'37 SST estimates significantly over-estimate maSSTs at many sites. We posit that this is caused either by uncertainties in the determination of maSSTs in this highly dynamic environment, or by biasing of the alkenone paleothermometer toward El Niño events as postulated by Rein et al. (2005).

Physical oceanography during POLARSTERN cruise ARK-XIX/4b

Exchanges between the North Atlantic and the Arctic Ocean result in the most dramatic water mass conversions in the World Ocean: warm and saline Atlantic waters, flowing through the Nordic Seas into the Arctic Ocean, are modified by cooling, freezing and melting to become shallow fresh waters, ice and saline deep waters. The outflow from the Nordic Seas to the south provides the initial driving of the global thermohaline circulation cell. Knowledge of these fluxes and understanding of the modification processes is a major prerequisite for the quantification of the rate of overturning within the large circulation cells of the Arctic and the Atlantic Oceans, and is also a basic requirement for understanding the role of these ocean areas in climate variability on interannual to decadal time scales. The Fram Strait represents the only deep connection between the Arctic Ocean and the Nordic Seas. Just as the freshwater transport from the Arctic Ocean is of major influence on convection in the Nordic Seas and further south, the transport of warm and saline Atlantic water affects the water mass characteristics in the Arctic Ocean which has consequences for the internal circulation and possibly influences also ice and atmosphere. The West Spitsbergen Current carrying Atlantic Water northward. The East Greenland Current, carrying water from the Arctic Ocean southwards has a concentrated core above the continental slope. It is our aim to measure the oceanic fluxes through Fram Strait and to determine their variability in seasonal to decadal time scales. 53 CTD profiles were taken at 51 stations. Two CTD systems from Sea-Bird Electronics Inc SBE911+ were used. Mainly SN 561 with duplicate T and C sensors (temperature sensors SBE3, SN 2685 and 2678, conductivity sensors SBE4, SN 2325 and 2618 and pressure sensor Digiquartz 410K-105 SN 75659) was in service. For the control of the temperature sensors a SBE35 RT digital reversing thermometer, SN 27 was applied. The CTD was connected to a SBE32 Carousel Water Sampler, SN 273 (24 12-liter bottles). For 3 CTD-Stations (726-3, 727-1, 728-1) the Sea-Bird 911+ probe SN 485 was used with temperature sensor SBE3 SN 2460, conductivity sensor SBE4 SN 2054, pressure sensor Digiquartz 410K SN 68997 and the SBE32 Carousel Water Sampler SN 202. Additionally Benthos Altimeters Model 2110-2, SN 189 and SN 208 and Wetlabs C-Star Transmissiometers SN 403 and SN 267 were mounted on the carousels. During the cruise a total number of 184 water samples were analysed with a Guildline Autosal 8400B salinometer, and IAPSO standard seawater batch number P141, K=0.99993. 20 salinity samples were brought back to AWI for onshore analysis. The CTD sensors were calibrated before and after the cruise by Sea-Bird Electronics.

(Table 1) Concentrations of polybrominated diphenyl ethers in liver and plasma samples of ringed seals (Phoca hispida)

The present study investigated the concentrations and patterns of PBDEs and hydroxylated (OH) PBDE analogues in two ringed seal populations: less contaminated Svalbard and more contaminated Baltic Sea. Mean concentration of hepatic sum-PBDE, which was dominated by BDE47, was six times higher in the ringed seals from the Baltic Sea compared to the seals from Svalbard. BDE47/sum-PBDE was higher in the seals from Svalbard compared to that for Baltic seals, while the trend was opposite for BDE153 and 154. The geographical difference in contaminant pattern of PBDEs in ringed seals could be explained by biotransformation via oxidative metabolism and/or by dietary differences. OH-PBDEs were detectable in the majority of plasma samples from both locations, and dominated by bioaccumulation of naturally occurring congeners. Low levels of 3-OH-BDE47 and 4'-OH-BDE49 in the Baltic ringed seals suggested minor oxidative biotransformation of BDE47. In the Baltic seals, BDE153/sum-PBDEs and BDE154/sum-PBDEs increased and BDE28/sum-PBDE decreased with increasing sum-POP concentration, which suggests BDE153 and 154 are more persistent than BDE28. Contrasting diets of the ringed seals in these two locations may influence the PBDE congener pattern due to selective long-range transport and direct effluent emissions to Svalbard and the Baltic, respectively.