(Figure 1 and 2) Phosphorus pools in the investigated sediments quantified by SEDEX sequential extraction and distribution of recovered 33P spike between sedimentary P pools after incubation

Phosphorus is an essential nutrient for life. In the ocean, phosphorus burial regulates marine primary production**1, 2. Phosphorus is removed from the ocean by sedimentation of organic matter, and the subsequent conversion of organic phosphorus to phosphate minerals such as apatite, and ultimately phosphorite deposits**3, 4. Bacteria are thought to mediate these processes**5, but the mechanism of sequestration has remained unclear. Here, we present results from laboratory incubations in which we labelled organic-rich sediments from the Benguela upwelling system, Namibia, with a 33P-radiotracer, and tracked the fate of the phosphorus. We show that under both anoxic and oxic conditions, large sulphide-oxidizing bacteria accumulate 33P in their cells, and catalyse the nearly instantaneous conversion of phosphate to apatite. Apatite formation was greatest under anoxic conditions. Nutrient analyses of Namibian upwelling waters and sediments suggest that the rate of phosphate-to-apatite conversion beneath anoxic bottom waters exceeds the rate of phosphorus release during organic matter mineralization in the upper sediment layers. We suggest that bacterial apatite formation is a significant phosphorus sink under anoxic bottom-water conditions. Expanding oxygen minimum zones are projected in simulations of future climate change**6, potentially increasing sequestration of marine phosphate, and restricting marine productivity.

Iron and manganese in bottom sediments and interstitial waters sampled in the White Sea on August 21-30, 2003

Iron and manganese in bottom sediments studied along the sublatitudinal transect from Kandalaksha to Arkhangelsk are characterized by various contents and speciations depending on sedimentation environment, grain size of sediments, and diagenetic processes. The latter include redistribution of reactive forms leading to enrichment in Fe and Mn of surface sediments, formation of films, incrustations, and ferromanganese nodules. Variations in total Fe content (2-8%) are accompanied by changes in concentration of its reactive forms (acid extraction) and concentration of dissolved Fe in interstitial waters (1-14 µM). Variations in Mn content in bottom sediments (0.03-3.7%) and interstitial waters (up to 500 µM) correspond to high diagenetic mobility of this element. Changes in oxidation degree of chemical elements result in redox stratification of sediment strata with maximum concentrations of Fe, Mn, and sulfides. Organic matter of bottom sediments with considerable terrestrial constituent is oxidized by bottom water oxygen mainly at the sediment surface or in anaerobic conditions within the sediment strata. The role of inorganic components in organic matter oxidation changes from surface layer bottom sediments (where manganese oxyhydroxide dominates among oxidants) to deeper layers (where sulfate of interstitial water serves as the main oxidant). Differences in river runoff and hydrodynamics are responsible for geochemical asymmetry of the transect. The deep Kandalaksha Bay serves as a sediment trap for manganese (Mn content in sediments varies within 0.5-0.7%), whereas the sedimentary environment in the Dvina Bay promotes its removal from bottom sediments (Mn 0.05%).

(Table 3) Concentrations of polybrominated diphenyl ether and congeners in blubber samples from whales, seals and porpoises between 1986-2009

A selection of PBDE congeners was analyzed in pooled blubber samples of pilot whale (Globicephala melas), ringed seal (Phoca hispida), minke whale (Balaenoptera acutorostrata), fin whale (Balaenoptera physalus), harbor porpoise (Phocoena phocoena), hooded seal (Cystophora cristata) and Atlantic white-sided dolphin (Lagenorhynchus acutus), covering a time period of more than 20 years (1986-2009). The analytes were extracted and cleaned-up using open column extraction and multi-layer silica gel column chromatography, and the analysis was performed on a GC-MS system operating in the NCI mode. The highest PBDE levels were found in the toothed whale species pilot whale and white-sided dolphin, and the lowest levels in fin whales and ringed seals. One-sided analyses of variance (ANOVA) followed by Tukey comparisons of means were applied to test for differences between years and sampling areas. Due to inter-year sampling variability, only general comparisons of PBDE concentrations between different sampling areas could be made. Differences in PBDE concentrations between three sampling periods, from 1986 to 2007, were evaluated in samples of pilot whales, ringed seals, white-sided dolphins and hooded seals. The highest PBDE levels were found in samples from the late 1990s or beginning of 2000, possibly reflecting the increase in the global production of technical PBDE mixtures in the 1990s. The levels of BDE #153 and #154 increased relative to the total PBDE concentration in some of the species in recent years, which may indicate an increased relative exposure to higher brominated congeners. In order to assess the effect of measures taken in legally binding international agreements, it is important to continuously monitor POPs such as PBDEs in sub-Arctic and Arctic environments.

Mean chemical characteristics and volcano signatures of ice cores from Belukha, the Everest and three Svalbard sites

Ice cores from outside the Greenland and Antarctic ice sheets are difficult to date because of seasonal melting and multiple sources (terrestrial, marine, biogenic and anthropogenic) of sulfates deposited onto the ice. Here we present a method of volcanic sulfate extraction that relies on fitting sulfate profiles to other ion species measured along the cores in moving windows in log space. We verify the method with a well dated section of the Belukha ice core from central Eurasia. There are excellent matches to volcanoes in the preindustrial, and clear extraction of volcanic peaks in the post-1940 period when a simple method based on calcium as a proxy for terrestrial sulfate fails due to anthropogenic sulfate deposition. We then attempt to use the same statistical scheme to locate volcanic sulfate horizons within three ice cores from Svalbard and a core from Mount Everest. Volcanic sulfate is <5% of the sulfate budget in every core, and differences in eruption signals extracted reflect the large differences in environment between western, northern and central regions of Svalbard. The Lomonosovfonna and Vestfonna cores span about the last 1000 years, with good extraction of volcanic signals, while Holtedahlfonna which extends to about AD1700 appears to lack a clear record. The Mount Everest core allows clean volcanic signal extraction and the core extends back to about AD700, slightly older than a previous flow model has suggested. The method may thus be used to extract historical volcanic records from a more diverse geographical range than hitherto.

Measurements of seawater and aerosol particles during POLARSTERN cruise ANT-XXVII/4

An analytical method for the determination of the alpha dicarbonyls glyoxal (GLY) and methylglyoxal (MGLY) from seawater and marine aerosol particles is presented. The method is based on derivatization with o-(2,3,4,5,6-Pentafluorobenzyl)-hydroxylamine (PFBHA) reagent, solvent extraction and GC-MS (SIM) analysis. The method showed good precision (RSD < 10%), sensitivity (detection limits in the low ng/l range), and accuracy (good agreement between external calibration and standard addition). The method was applied to determine GLY and MGLY in oceanic water sampled during the Polarstern cruise ANT XXVII/4 from Capetown to Bremerhaven in spring 2011. GLY and MGLY were determined in the sea surface microlayer (SML) of the ocean and corresponding bulk water (BW) with average concentrations of 228 ng/l (GLY) and 196 ng/l (MGLY). The results show a significant enrichment (factor of 4) of GLY and MGLY in the SML. Furthermore, marine aerosol particles (PM1) were sampled during the cruise and analyzed for GLY (average concentration 0.19 ng/m**3) and MGLY (average concentration 0.15 ng/m**3). On aerosol particles, both carbonyls show a very good correlation with oxalate, supporting the idea of a secondary formation of oxalic acid via GLY and MGLY. Concentrations of GLY and MGLY in seawater and on aerosol particles were correlated to environmental parameters such as global radiation, temperature, distance to the coastline and biological activity. There are slight hints for a photochemical production of GLY and MGLY in the SML (significant enrichment in the SML, higher enrichment at higher temperature). However, a clear connection of GLY and MGLY to global radiation as well as to biological activity cannot be concluded from the data. A slight correlation between GLY and MGLY in the SML and in aerosol particles could be a hint for interactions, in particular of GLY, between seawater and the atmosphere.

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.

(Table 2) Polybrominated diphenyl ether concentration in blubber samples from whales, seals and porpoises between 1986-2009

A selection of MeO-BDE and BDE congeners were analyzed in pooled blubber samples of pilot whale (Globicephala melas), ringed seal (Phoca hispida), minke whale (Balaenoptera acutorostrata), fin whale (Balaenoptera physalus), harbor porpoise (Phocoena phocoena), hooded seal (Cystophora cristata), and Atlantic white-sided dolphin (Lagenorhynchus acutus), covering a time period of more than 20 years (1986-2009). The analytes were extracted and cleaned-up using open column extraction and multi-layer silica gel column chromatography. The analysis was performed using both low resolution and high resolution GC-MS. MeO-PBDE concentrations relative to total PBDE concentrations varied greatly between sampling periods and species. The highest MeO-PBDE levels were found in the toothed whale species pilot whale and white-sided dolphin, often exceeding the concentration of the most abundant PBDE, BDE-47. The lowest MeO-PBDE levels were found in fin whales and ringed seals. The main MeO-BDE congeners were 6-MeO-BDE47 and 2'-MeO-BDE68. A weak correlation only between BDE47 and its methoxylated analog 6-MeO-BDE47 was found and is indicative of a natural source for MeO-PBDEs.

Land based mesocosm experiment studying the simultaneous impact of warming and acidification on the planktonic food web of the Eastern Mediterranean

A land based mesocosm experiment focusing on the study of the simultaneous impact of warming and acidification on the planktonic food web of the Eastern Mediterranean took place in August-September 2013 at the mesocosm facilities of HCMR in Crete (CRETACOSMOS). Two different pCO2 (present day and predicted for year 2100) were applied in triplicate mesocosms of 3 m**3. This was tested in two different temperatures (ambient seawater T and ambient T plus 3°C). Twelve mesocosms in total were incubated in two large concrete tanks. Temperature was controlled by sophisticated, automated systems. A large variety of chemical, biological and biochemical variables were studied, including salinity, temperature, light and alkalinity measurements, inorganic and organic, particulate and dissolved, nutrient analyses, biological stock (Chla concentration, enumeration and community composition of microbial, phyto- and zooplankton organisms) and rate (primary, bacterial, viral production, copepod egg production, zooplankton grazing, N2 fixation, P uptake) measurements, bacterial DNA extraction and phytoplankton transcriptomics, calcifiers analyses. Twenty three scientists from 6 Institutes and 5 countries participated in this experiment.

Polyaromatic hydrocarbons in sediments from the Barents and White Seas

Polycyclic aromatic hydrocarbons (PAHs) are common environmental contaminants which can be derived from anthropogenic sources, such as combustion and discharges from extraction and transport, and natural processes, including leakage and erosion of fossil carbon. Natural PAH sources contribute, along with biological activities and terrestrial run-off, to the organic carbon content in sediments.The Barents Sea region is far from many anthropogenic sources of PAH, but production and trans-shipment of hydrocarbons is increasing. We present data for polycyclic aromatic hydrocarbon (PAH) concentrations in bottom sediments from 510 stations in the Barents and White Seas, and along the northern coast of Norway.

(Table 1, page 1376) Chemical analyses of manganese nodules and crusts from the Pacific Ocean

A compilation of chemical analyses of Pacific Ocean nodules using an x-ray fluorescence technique. The equipment used was a General Electric XRD-5 with a tungsten tube. Lithium fluoride was used as the diffraction element in assaying for all elements above calcium in the atomic table and EDDT was used in conjunction with a helium path for all elements with an atomic number less than calcium. Flow counters were used in conjunction with a pulse height analyzer to eliminate x-ray lines of different but integral orders in gathering count data. The stability of the equipment was found to be excellent by the author. The equipment was calibrated by the use of standard ores made from pure oxide forms of the elements in the nodules and carefully mixed in proportion to the amounts of these elements generally found in the manganese nodules. Chemically analyzed standards of the nodules themselves were also used. As a final check, a known amount of the element in question was added to selected samples of the nodules and careful counts were taken on these samples before and after the addition of the extra amount of the element. The method involved the determination and subsequent use of absorption and activation factors for the lines of the various elements. All the absorption and activation factors were carefully determined using the standard ores. The chemically analyzed samples of the nodules by these methods yielded an accuracy to at least three significant figures.

He isotope, U/Th isotope, Calcium carbonate, biogenic opal, rare earth element concentrations, and grain size distribution measured on core-top sediments during SONNE cruise SO202 (INOPEX)

Eolian dust is a significant source of iron and other nutrients that are essential for the health of marine ecosystems and potentially a controlling factor of the high nutrient-low chlorophyll status of the Subarctic North Pacific. We map the spatial distribution of dust input using three different geochemical tracers of eolian dust, 4He, 232Th and rare earth elements, in combination with grain size distribution data, from a set of core-top sediments covering the entire Subarctic North Pacific. Using the suite of geochemical proxies to fingerprint different lithogenic components, we deconvolve eolian dust input from other lithogenic inputs such as volcanic ash, ice-rafted debris, riverine and hemipelagic input. While the open ocean sites far away from the volcanic arcs are dominantly composed of pure eolian dust, lithogenic components other than eolian dust play a more crucial role along the arcs. In sites dominated by dust, eolian dust input appears to be characterized by a nearly uniform grain size mode at ~4 µm. Applying the 230Th-normalization technique, our proxies yield a consistent pattern of uniform dust fluxes of 1-2 g/m**2/yr across the Subarctic North Pacific. Elevated eolian dust fluxes of 2-4 g/m**2/yr characterize the westernmost region off Japan and the southern Kurile Islands south of 45° N and west of 165° E along the main pathway of the westerly winds. The core-top based dust flux reconstruction is consistent with recent estimates based on dissolved thorium isotope concentrations in seawater from the Subarctic North Pacific. The dust flux pattern compares well with state-of-the-art dust model predictions in the western and central Subarctic North Pacific, but we find that dust fluxes are higher than modeled fluxes by 0.5-1 g/m**2/yr in the northwest, northeast and eastern Subarctic North Pacific. Our results provide an important benchmark for biogeochemical models and a robust approach for downcore studies testing dust-induced iron fertilization of past changes in biological productivity in the Subarctic North Pacific.

(Figure 4) Stable carbon isotopic values and relative contents of biphytanes and sugars from sediment sample from the Peru margin and from the Pakistan margin

Glycolipids are prominent constituents in the membranes of cells from all domains of life. For example, diglycosyl-glycerol dibiphytanyl glycerol tetraethers (2Gly-GDGTs) are associated with methanotrophic ANME-1 archaea and heterotrophic benthic archaea, two archaeal groups of global biogeochemical importance. The hydrophobic biphytane moieties of 2Gly-GDGTs from these two uncultivated archaeal groups exhibit distinct carbon isotopic compositions. To explore whether the isotopic compositions of the sugar headgroups provide additional information on the metabolism of their producers, we developed a procedure to analyze the d13C values of glycosidic headgroups. Successful determination was achieved by (1) monitoring the contamination from free sugars during lipid extraction and preparation, (2) optimizing the hydrolytic conditions for glycolipids, and (3) derivatizing the resulting sugars into aldononitrile acetate derivatives, which are stable enough to withstand a subsequent column purification step. First results of d13C values of sugars cleaved from 2Gly-GDGTs in two marine sediment samples, one containing predominantly ANME-1 archaea and the other benthic archaea, were obtained and compared with the d13C values of the corresponding biphytanes. In both samples the dominant sugar headgroups were enriched in 13C relative to the corresponding major biphytane. This 13C enrichment was significantly larger in the putative major glycolipids from ANME-1 archaea (~15 per mil) than in those from benthic archaea (<7 per mil). This method opens a new analytical window for the examination of carbon isotopic relationships between sugars and lipids in uncultivated organisms.