(Table 1) Concentration of organohalogenated compounds in clean and contaminated hair of polar bears (Ursus maritimus) from East Greenland

In this pilot study, we report on levels of persistent organohalogenated contaminants (OHCs) in hair of polar bears (Ursus maritimus) from East Greenland sampled between 1999 and 2001. To our knowledge, this is the first study on the validation of polar bear hair as a non-invasive matrix representative of concentrations and profiles in internal organs and blood plasma. Because of low sample weights (13-140 mg), only major bioaccumulative OHCs were detected above the limit of quantification: five polychlorinated biphenyl (PCB) congeners (CB 99, 138, 153, 170 and 180), one polybrominated diphenyl ether (PBDE) congener (BDE 47), oxychlordane, trans-nonachlor and ß-hexachlorocyclohexane. The PCB profile in hair was similar to that of internal tissues (i.e. adipose, liver, brain and blood), with CB 153 and 180 as the major congeners in all matrices. A gender difference was found for concentrations in hair relative to concentrations in internal tissues. Females (n = 6) were found to display negative correlations, while males (n = 5) showed positive correlations, although p-values were not found significant. These negative correlations in females may reflect seasonal OHC mobilisation from periphery adipose tissue due to, for example, lactation and fasting. The lack of significance in most correlations may be due to small sample sizes and seasonal variability of concentrations in soft tissues. Further research with larger sample weights and sizes is therefore necessary to draw more definitive conclusions on the usefulness of hair for biomonitoring OHCs in polar bears and other fur mammals.

Long-term chemical characterization of aerosols at CVAO from 2007 to 2011

The first long-term aerosol sampling and chemical characterization results from measurements at the Cape Verde Atmospheric Observatory (CVAO) on the island of São Vicente are presented and are discussed with respect to air mass origin and seasonal trends. In total 671 samples were collected using a high-volume PM10 sampler on quartz fiber filters from January 2007 to December 2011. The samples were analyzed for their aerosol chemical composition, including their ionic and organic constituents. Back trajectory analyses showed that the aerosol at CVAO was strongly influenced by emissions from Europe and Africa, with the latter often responsible for high mineral dust loading. Sea salt and mineral dust dominated the aerosol mass and made up in total about 80% of the aerosol mass. The 5-year PM10 mean was 47.1 ± 55.5 µg/m**2, while the mineral dust and sea salt means were 27.9 ± 48.7 and 11.1 ± 5.5 µg/m**2, respectively. Non-sea-salt (nss) sulfate made up 62% of the total sulfate and originated from both long-range transport from Africa or Europe and marine sources. Strong seasonal variation was observed for the aerosol components. While nitrate showed no clear seasonal variation with an annual mean of 1.1 ± 0.6 µg/m**3, the aerosol mass, OC (organic carbon) and EC (elemental carbon), showed strong winter maxima due to strong influence of African air mass inflow. Additionally during summer, elevated concentrations of OM were observed originating from marine emissions. A summer maximum was observed for non-sea-salt sulfate and was connected to periods when air mass inflow was predominantly of marine origin, indicating that marine biogenic emissions were a significant source. Ammonium showed a distinct maximum in spring and coincided with ocean surface water chlorophyll a concentrations. Good correlations were also observed between nss-sulfate and oxalate during the summer and winter seasons, indicating a likely photochemical in-cloud processing of the marine and anthropogenic precursors of these species. High temporal variability was observed in both chloride and bromide depletion, differing significantly within the seasons, air mass history and Saharan dust concentration. Chloride (bromide) depletion varied from 8.8 ± 8.5% (62 ± 42%) in Saharan-dust-dominated air mass to 30 ± 12% (87 ± 11%) in polluted Europe air masses. During summer, bromide depletion often reached 100% in marine as well as in polluted continental samples. In addition to the influence of the aerosol acidic components, photochemistry was one of the main drivers of halogenide depletion during the summer; while during dust events, displacement reaction with nitric acid was found to be the dominant mechanism. Positive matrix factorization (PMF) analysis identified three major aerosol sources: sea salt, aged sea salt and long-range transport. The ionic budget was dominated by the first two of these factors, while the long-range transport factor could only account for about 14% of the total observed ionic mass.

Cuttlebone morphometry measurements

Changes in seawater carbonate chemistry that accompany ongoing ocean acidification have been found to affect calcification processes in many marine invertebrates. In contrast to the response of most invertebrates, calcification rates increase in the cephalopod Sepia officials during long-term exposure to elevated seawater pCO2. The present trial investigated structural changes in the cuttlebones of S. officinalis calcified during 6 weeks of exposure to 615 Pa CO2. Cuttlebone mass increased sevenfold over the course of the growth trail, reaching a mean value of 0.71 ± 0.15 g. Depending on cuttlefish size (mantle lengths 44-56 mm), cuttlebones of CO2-incubated individuals accreted 22-55% more CaCO3 compared to controls at 64 Pa CO2. However, the height of the CO2- exposed cuttlebones was reduced. A decrease in spacing of the cuttlebone lamellae, from 384 ± 26 to 195 ± 38 lm, accounted for the height reduction The greater CaCO3 content of the CO2-incubated cuttlebones can be attributed to an increase in thickness of the lamellar and pillar walls. Particularly, pillar thickness increased from 2.6 ± 0.6 to 4.9 ± 2.2 lm. Interestingly, the incorporation of non-acidsoluble organic matrix (chitin) in the cuttlebones of CO2- exposed individuals was reduced by 30% on average. The apparent robustness of calcification processes in S. officials, and other powerful ion regulators such as decapod cructaceans, during exposure to elevated pCO2 is predicated to be closely connected to the increased extracellular [HCO3 -] maintained by these organisms to compensate extracellular pH. The potential negative impact of increased calcification in the cuttlebone of S. officials is discussed with regard to its function as a lightweight and highly porous buoyancy regulation device. Further studies working with lower seawater pCO2 values are necessary to evaluate if the observed phenomenon is of ecological relevance.

Non-isoprenoidal intact polar lipids, isoprenoidal and non-isoprenoidal core lipids, isoprenoidal intact polar lipids of the Black Sea site GeoB15105 sampled during Meteor cruise M84/1 in February 2011

This PhD thesis focused on the analysis and application of microbial membrane lipids as biomarkers in marine sediments. Existing protocols for lipid extraction from marine sediments and biomass were modified. In addition, recent protocols based on high-performance liquid chromatography coupled to mass spectrometry (HPLC-MS) as well as state-of-the-art mass spectrometric analysis by quadrupole time-of-flight (MSqTOF) and the triple quadrupole (MSQQQ) mass spectrometer were used to investigate matrix effects and evaluate the reliability of quantitative analysis in marine environmental samples. The improved lipid extraction and quantification were used to analyze Black Sea water column and sediments samples to a depth of 8 meters from site GeoB 15105 taken during cruise M84/1 (DARCSEAS) with R/V Meteor to apply lipid analysis in benthic bio systems. With this component specific differentiation between planktonic and benthic lipid signature we assessed possible lipid sources. Here, this high detail lipid fingerprinting allowed us to observe changes in the head group and lipid core structures of the intact polar lipids according to the geochemical zonation.