Contiunous surface water uncorrected and quench-corrected active fluorescence and derived chlorophyll a concentration using calibration by HPLC pigments during POLARSTERN cruise ANT-XXV/1

The relationship between phytoplankton assemblages and the associated optical properties of the water body is important for the further development of algorithms for large-scale remote sensing of phytoplankton biomass and the identification of phytoplankton functional types (PFTs), which are often representative for different biogeochemical export scenarios. Optical in-situ measurements aid in the identification of phytoplankton groups with differing pigment compositions and are widely used to validate remote sensing data. In this study we present results from an interdisciplinary cruise aboard the RV Polarstern along a north-to-south transect in the eastern Atlantic Ocean in November 2008. Phytoplankton community composition was identified using a broad set of in-situ measurements. Water samples from the surface and the depth of maximum chlorophyll concentration were analyzed by high performance liquid chromatography (HPLC), flow cytometry, spectrophotometry and microscopy. Simultaneously, the above- and underwater light field was measured by a set of high spectral resolution (hyperspectral) radiometers. An unsupervised cluster algorithm applied to the measured parameters allowed us to define bio-optical provinces, which we compared to ecological provinces proposed elsewhere in the literature. As could be expected, picophytoplankton was responsible for most of the variability of PFTs in the eastern Atlantic Ocean. Our bio-optical clusters agreed well with established provinces and thus can be used to classify areas of similar biogeography. This method has the potential to become an automated approach where satellite data could be used to identify shifting boundaries of established ecological provinces or to track exceptions from the rule to improve our understanding of the biogeochemical cycles in the ocean.

Atmospheric nitrate concentrations and isotope composition for samples collected in the marine boundary layer in 2006 and 2007

The comprehensive isotopic composition of atmospheric nitrate (i.e., the simultaneous measurement of all its stable isotope ratios: 15N/14N, 17O/16O and 18O/16O) has been determined for aerosol samples collected in the marine boundary layer (MBL) over the Atlantic Ocean from 65°S (Weddell Sea) to 79°N (Svalbard), along a ship-borne latitudinal transect. In nonpolar areas, the d15N of nitrate mostly deriving from anthropogenically emitted NOx is found to be significantly different (from 0 to 6 per mil) from nitrate sampled in locations influenced by natural NOx sources (-4 ± 2) per mil. The effects on d15N(NO3-) of different NOx sources and nitrate removal processes associated with its atmospheric transport are discussed. Measurements of the oxygen isotope anomaly (D17O = d17O - 0.52 × d18O) of nitrate suggest that nocturnal processes involving the nitrate radical play a major role in terms of NOx sinks. Different D17O between aerosol size fractions indicate different proportions between nitrate formation pathways as a function of the size and composition of the particles. Extremely low d15N values (down to -40 per mil) are found in air masses exposed to snow-covered areas, showing that snowpack emissions of NOx from upwind regions can have a significant impact on the local surface budget of reactive nitrogen, in conjunction with interactions with active halogen chemistry. The implications of the results are discussed in light of the potential use of the stable isotopic composition of nitrate to infer atmospherically relevant information from nitrate preserved in ice cores.

Mesocosm experiment 2012 on warming and acidification effects on phytoplankton biomass and chemical composition

We investigated the impacts of predicted ocean acidification and future warming on the quantity and nutritional quality of a natural phytoplankton autumn bloom in a mesocosm experiment. Since the effects of CO2-enrichment and temperature have usually been studied independently, we were also interested in the interactive effects of both aspects of climate change. Therefore, we used a factorial design with two temperature and two acidification levels in a mesocosm experiment with a Baltic Sea phytoplankton community. Our results show a significant time-dependent influence of warming on phytoplankton carbon, chlorophyll a as well as POC. Phytoplankton carbon for instance decreased by more than a half with increasing temperature at bloom time. Additionally, elemental carbon to phosphorus ratios (C:P) increased significantly by approximately 5-8 % under warming. Impacts of CO2 or synergetic effects of warming and acidification could not be detected. We suggest that temperature-induced stronger grazing pressure was responsible for the significant decline in phytoplankton biomass. Our results suggest that biological effects of warming on Baltic Sea phytoplankton are considerable and will likely have fundamental consequences for the trophic transfer in the pelagic food-web.

Composition of pore water and diagenetic carbonates of ODP Site 123-765

Degradation of organic matter in slightly organic-rich (1 wt% organic carbon) Neogene calcareous turbidites of the Argo Basin at Site 765 by sulfate reduction results in pore-water phosphate, ammonium, manganese, and carbonate alkalinity maxima. Pore-water calcium and magnesium decrease in the uppermost 100 meters below seafloor (mbsf) in response to the precipitation of calcian dolomite with an average composition of Ca1.15Mg0.83Fe0.02(CO3)2. Clear, euhedral dolomite rhombs range from <1 to 40 µm in diameter and occur in trace to minor amounts (<1-2 wt%) in Pleistocene to Pliocene sediment (62-210 mbsf) The abundance of dolomite increases markedly (2-10 wt%) in Miocene sediment (210-440 mbsf). The dolomite is associated with diagenetic sepiolite and palygorskite, as well as redeposited biogenic low-Mg calcite and aragonitic benthic foraminifers. Currently, dolomite is precipitating at depth within the pore spaces of the sediment, largely as a result of aragonite dissolution. The rate of aragonite dissolution, calculated from the pore-water strontium profile, is sufficient to explain the amount of dolomite observed at Site 765. A foraminiferal aragonite precursor is further supported by the carbon and oxygen isotopic compositions of the dolomite, which are fairly close to the range of isotopic compositions observed for Miocene benthic foraminifers. Dolomite precipitation is promoted by the degradation of organic matter by sulfate-reducing bacteria because the lower pore-water sulfate concentration reduces the effect of sulfate inhibition on the dolomite reaction and because the higher carbonate alkalinity increases the degree of saturation of the pore waters with dolomite. Organic matter degradation also results in the precipitation of pyrite and trace amounts of apatite (francolite), and the release of iron and manganese to the pore water by reduction of Fe and Mn oxides. Spherical, silt-sized aggregates of microcrystalline calcian rhodochrosite occur in trace to minor amounts in Lower Cretaceous sediment from 740 to 900 mbsf at Site 765. A negative carbon isotopic composition suggests that the rhodochrosite formed early in the sulfate reduction zone, but a depleted oxygen isotopic composition suggests that the rhodochrosite may have recrystallized at deeper burial depths.

Chemical composition of sediments from the Indian Ocean

Intensive reduction processes within bottom sediments from the Bay of Bengal lead to marked enrichment of the oxidized layer in iron and manganese. This is not observed in sediments from the Arabian Sea. Oxidized bottom sediments in central areas of the Indian Ocean show high iron concentrations, but fraction of reactive Fe in total Fe is lower. Manganese concentration increases steadily with distance from the shore to the pelagic region of the ocean, and fraction of reactive manganese also increases in the same direction. There is close correlation between total Mn and Mn(4+) in these sediments.

Pb concentrations, Pb isotopic composition, and amount of metalliferous components in pelagic sediments from the Pacific Ocean

The amount of lead annually transferred from oceanic crust to metalliferous sediments was estimated in order to test the hypothesis that a non-magmatic flux of lead causes the Pb surplus in the continental crust. A Pb surplus has been inferred from global crust-mantle lead mass balances derived from lead concentration correlations with other trace elements and from lead isotope systematics in oceanic basalts. DSDP/ODP data on the amount of metalliferous sediments in the Pacific Ocean and along a South Atlantic traverse are used to calculate the mean worldwide thickness of 3 (+/-1) m for purely metalliferous sediment componens. Lead isotope ratios of 39 metalliferous sediments from the Pacific define mixing lines between continent-derived (seawater) and mantle-derived (basaltic) lead, with the most metal-rich sediments usually having the most mantle-like Pb isotope composition. We used this isotope correlation and the Pb content of the 39 metalliferous sediments to derive an estimate of 130 (+/-70) µg/g for the concentration of mantle-derived lead in the purely metalliferous end-member. Mass balance calculations show that at least 12 (+/-8)% of the lead, annually transferred from upper mantle to oceanic crust at the ocean ridges, is leached out by hydrothermal processes and re-deposited in marine sediments. If all of the metalliferous lead is ultimately transferred to the continental crust during subduction, the annual flux of this lead from mantle to continental crust is 2.6 (+/-2.0) * 10**6 kg. Assuming this transfer rate to be proportional to the rate of oceanic plate production, one can fit the lead transfer to models of plate production rate variations through time. Integrating over 4 Ga, hydrothermal lead transfer to the continental crust accounts for a significant portion of the Pb surplus in the continental crust. It therefore appears to be one of the main reasons for the anomalous behavior of lead in the global crust-mantle system.

Dissolved organic matter molecular composition and concentrations from a large scale mesocosm study KOSMOS 2013 Kristineberg) on ocean acidification

Marine dissolved organic matter (DOM) represents one of the largest active carbon reservoirs on Earth. Changes in pool size or composition could have major impacts on the global carbon cycle. Ocean acidification is a potential driver for these changes because it influences marine primary production and heterotrophic respiration. Here we show that ocean acidification as expected for a 'business-as-usual' emission scenario in the year 2100 (900 µatm) does not affect the DOM pool with respect to its size and molecular composition. We applied ultrahigh-resolution mass spectrometry to monitor the production and turnover of 7,360 distinct molecular DOM features in an unprecedented long-term mesocosm study in a Swedish Fjord, covering a full cycle of marine production. DOM concentration and molecular composition did not differ significantly between present-day and year 2100 CO2 levels. Our findings are likely applicable to other coastal and productive marine ecosystems in general.

Chlorine concentration and isotopic data for sediments and serpentine seamount material from ODP Legs 125, 129, 185, and 195

Chlorine isotope ratios were determined for volcanic gas, geothermal well, ash, and lava samples along the Izu-Bonin-Mariana volcanic front, serpentinite clasts and muds from serpentine seamounts (Conical, South Chamorro, Torishima), basalts from the Guguan cross-chain, and sediments from Ocean Drilling Program (ODP) Sites 800, 801, 802, and 1149. There is no systematic variation in d37Cl values along the volcanic front in either gas or ash samples. In contrast, distinct variations occur across the arc, implying variations in the fluid source at different depths within the subduction zone. Serpentinite clasts and serpentine muds from the seamounts tap a source of ~30 km depth and have d37Cl values of structurally bound chloride of +0.4 per mil +/- 0.4 per mil (n = 24), identical to most seafloor serpentinites, suggesting a serpentinite (chrysotile and/or lizardite to antigorite transition) fluid source. Tapping deeper levels of the subduction zone (~115-130 km depth), volcanic gases and ashes have d37Cl values averaging -1.1 per mil +/- 1.0 per mil (n = 29), precisely overlapping the range measured in sediments from ODP cores (-1.1 per mil +/- +0.7 per mil, n = 11) and limited altered oceanic crust (AOC). Both sediments and AOC are possible Cl sources in the volcanic front. The Guguan cross-chain basalts come from the greatest depths and have an average d37Cl value of +0.2 per mil +/- 0.2 per mil (n = 3), suggesting a second serpentine-derived source, in this case from antigorite breakdown at ~200 km depth.