(Table 1) Micro-inclusion counts and ion concentrations in the five GRIP ice-core sections

We provide the first direct evidence that a number of water-soluble compounds, in particular calcium sulfate (CaSO4 2H2O) and calcium carbonate (CaCO3), are present as solid, micron-sized inclusions within the Greenland GRIP ice core. The compounds are detected by two independent methods: micro-Raman spectroscopy of a solid ice sample, and energy-dispersive X-ray spectroscopy of individual inclusions remaining after sublimation. CaSO4 2H2O is found in abundance throughout the Holocene and the last glacial period, while CaCO3 exists mainly in the glacial period ice. We also present size and spatial distributions of the micro-inclusions. These results suggest that water-soluble aerosols in the GRIP ice core are dependable proxies for past atmospheric conditions.

Characteristics and aldehyde concentrations of diamond dust events near Barrow, Alaska

Diamond dust (DD) refers to tiny ice crystals that form frequently in the Polar troposphere under clear sky conditions. They provide surfaces for chemical reactions and scatter light. We have measured the specific surface area (SSA) of DD at Barrow in March-April 2009. We have also measured its chemical composition in mineral and organic ions, dissolved organic carbon (DOC), aldehydes, H2O2, and the absorption spectra of water-soluble chromophores. Mercury concentrations were also measured in spring 2006, when conditions were similar. The SSA of DD ranges from 79.9 to 223 m**2/kg . The calculated ice surface area in the atmosphere reaches 11000 (±70%) µm**2/cm**3, much higher than the aerosol surface area. However, the impact of DD on the downwelling and upwelling light fluxes in the UV and visible is negligible. The composition of DD is markedly different from that of snow on the surface. Its concentrations in mineral ions are much lower, and its overall composition is acidic. Its concentrations in aldehydes, DOC, H2O2 and mercury are much higher than in surface snows. Our interpretation is that DOC from the oceanic surface microlayer, coming from open leads in the ice off of Barrow, is taken up by DD. Active chemistry in the atmosphere takes place on DD crystal surfaces, explaining its high concentrations in aldehydes and mercury. After deposition, active photochemistry modifies DD composition, as seen from the modifications in its absorption spectra and aldehyde and H2O2 content. This probably leads to the emissions of reactive species to the atmosphere.

Organic matter in bottom sediments of the Northeast Pacific

The book is devoted to study of diagenetic changes of organic matter and mineral part of sediments and interstitial waters of the Pacific Ocean due to physical-chemical and microbiological processes. Microbiological studies deal with different groups of bacteria. Regularities of quantitative distribution and the role of microorganisms in geochemical processes are under consideration. Geochemical studies highlight redox processes of the early stages of sediment diagenesis, alterations of interstitial waters, regularities of variations in chemical composition of iron-manganese nodules.

Phycoerythrin concentration during POLARSTERN cruises ANT-XXIV/4, ANT-XXV/1, and ANT-XXVI/4

Phycobiliproteins are a family of water-soluble pigment proteins that play an important role as accessory or antenna pigments and absorb in the green part of the light spectrum poorly used by chlorophyll a. The phycoerythrins (PEs) are one of four types of phycobiliproteins that are generally distinguished based on their absorption properties. As PEs are water soluble, they are generally not captured with conventional pigment analysis. Here we present a statistical model based on in situ measurements of three transatlantic cruises which allows us to derive relative PE concentration from standardized hyperspectral underwater radiance measurements (Lu). The model relies on Empirical Orthogonal Function (EOF) analysis of Lu spectra and, subsequently, a Generalized Linear Model with measured PE concentrations as the response variable and EOF loadings as predictor variables. The method is used to predict relative PE concentrations throughout the water column and to calculate integrated PE estimates based on those profiles.

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.

Data on multidisciplinary research in the Tajura Rift (Gulf of Aden) during Cruise 7 of R/V Akademik Mstislav Keldysh in winter 1983-1984

In the collective monograph results of geological and geophysical studies in the Tadjura Rift carried out by conventional outboard instruments and from deep/sea manned submersibles "Pisces" in winter 1983-1984 are reported. Main features of rift tectonics, geology, petrology, and geochemistry of basalts from the rift are under consideration. An emphasis is made on lithology, stratigraphy, and geochemistry of bottom sediments. Roles of terrigenous, edafogenic, biogenic, and hydrothermal components in formation of bottom sediments from the rift zone are shown.

Carbohydrates in particulate matter of the Northwest Pacific

Patterns of distribution and variations of group and monosaccharide compositions of carbohydrates in suspended matter of the Pacific Ocean were studied. It is shown that carbohydrate content of surface ocean waters depends on reproduction of organic matter by phytoplankton. Water-insoluble polysaccharides (average 77.9% of total) predominate in composition of carbohydrates in suspended matter. Water-soluble polysaccharides and oligosaccharides were detected in considerably smaller quantities (average 12.4 and 7.3% respectively). Free monosaccharides were not detected. The main sugars in all isolated groups of carbohydrates of suspended matter are hexoses, which account for 90.8% in oligosaccharides, 64.9% in water-soluble polysaccharides, and 69.8% in water-insoluble polysaccharides. Determination of monosaccharide composition of carbohydrates in suspension showed that apparently they basically consist of mixture of reserve and structural polysaccharides (or their residues) of phytoplankton organisms.

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.

Sulphur isotope analyses in the southern ocean and the central Dronning Maud Land, East Antarctica

Sulphur isotope analyses are an important tool for the study of the natural sulphur cycle. On the northern hemisphere such studies of the atmospheric part of the cycle are practically impossible due to the high emission rate of anthropogenic sulphur. Merely in remote areas of the world such as the Antarctic 34S analyses can be used to identify the various sulphur sources (sea spray, biogenic und volcanic sources). We report here results of 34S measurements on sulphates from recent atmospheric precipitations (snow), lake waters, and salt efflorescences sampled in the Schirmacher Oasis and the Gruber Mountains, central Dronning Maud Land, East Antarctica. By plotting the delta 34S of precipitation versus % sea-spray sulphate the isotopic composition of the excess sulphate (which is probably of marine-biogenic origin) is extrapolated to be +4 per mil. Lake water sulphate and atmospheric precipitations have a comparable sulphur isotope composition (about +5 per mil). The analyzed secondary sulphates from the salt efflorescences, mainly gypsum and a few water-soluble sulphatcs (hexahydrite, epsomite, burkeite. and pickeringite), vary in their isotopic composition between about -12 and +8 per mil. This wide scatter is probably due to chemical weathering of primary sulphides having different delta 34S values in the substratum.

Organic matter and sediment properties of samples from site GeoB15105 from the Black Sea

Dissolved organic matter (DOM) in marine sediments is a complex mixture of thousands of individual constituents that participate in biogeochemical reactions and serve as substrates for benthic microbes. Knowledge of the molecular composition of DOM is a prerequisite for a comprehensive understanding of the biogeochemical processes in sediments. In this study, interstitial water DOM was extracted with Rhizon samplers from a sediment core from the Black Sea and compared to the corresponding water-extractable organic matter fraction (<0.4 µm) obtained by Soxhlet extraction, which mobilizes labile particulate organic matter and DOM. After solid phase extraction (SPE) of DOM, samples were analyzed for the molecular composition by Fourier Transform Ion-Cyclotron Resonance Mass Spectrometry (FT-ICR MS) with electrospray ionization in negative ion mode. The average SPE extraction yield of the dissolved organic carbon (DOC) in interstitial water was 63%, whereas less than 30% of the DOC in Soxhlet-extracted organic matter was recovered. Nevertheless, Soxhlet extraction yielded up to 4.35% of the total sedimentary organic carbon, which is more than 30-times the organic carbon content of the interstitial water. While interstitial water DOM consisted primarily of carbon-, hydrogen- and oxygen-bearing compounds, Soxhlet extracts yielded more complex FT-ICR mass spectra with more peaks and higher abundances of nitrogen- and sulfur-bearing compounds. The molecular composition of both sample types was affected by the geochemical conditions in the sediment; elevated concentrations of HS- promoted the early diagenetic sulfurization of organic matter. The Soxhlet extracts from shallow sediment contained specific three- and four-nitrogen-bearing molecular formulas that were also detected in bacterial cell extracts and presumably represent proteinaceous molecules. These compounds decreased with increasing sediment depth while one- and two-nitrogen-bearing molecules increased, resulting in a higher similarity of both sample types in the deep sediment. In summary, Soxhlet extraction of sediments accessed a larger and more complex pool of organic matter than present in interstitial water DOM.

Carbohydrates in waters and sediments

The book is devoted to study of diagenetic changes of organic matter and mineral part of sediments and interstitial waters of the Pacific Ocean due to physical-chemical and microbiological processes. Microbiological studies deal with different groups of bacteria. Regularities of quantitative distribution and the role of microorganisms in geochemical processes are under consideration. Geochemical studies highlight redox processes of the early stages of sediment diagenesis, alterations of interstitial waters, regularities of variations in chemical composition of iron-manganese nodules.

Protein content of Calanus finmarchicus from the North Atlantic collected during Maria S. Merian cruise MSM26 in spring 2013

For the determination of water-soluble protein content of C. finmarchicus of the different stations the Qubit® Protein Assay Kit (Invitrogen) was used. Analysis was performed with extracts of 10 copepods. Working solution was prepared with Qubit® protein reagent and Qubit® protein buffer (1:200). 190 µL working solution was pipetted into each well of a micro plate and 10 µL of sample or Qubit® protein standard (0, 200 and 400 ng/µL) was added. Solutions were mixed and incubated for 15 min at room temperature. Measurements were conducted with a micro plate reader (TriStar LB 941, Berthold Technologies) at 485 nm excitation and 590 nm emission, using the software MikroWin2000 (Berthold Technologies).

Chemical characterization of marine sub-micrometer aerosol particles during the MERIAN cruise MSM18/3 from the Cape Verde island Sao Vicente to Gabun (Atlantic Ocean)

Sub-micron marine aerosol particles (PM1) were collected during the MERIAN cruise MSM 18/3 between 22 June 2011 and 21 July 2011 from the Cape Verde island Sao Vicente to Gabun crossing the tropical Atlantic Ocean and passing equatorial upwelling areas. According to air mass origin and chemical composition of the aerosol particles, three main regimes could be established. Aerosol particles in the first part of the cruise were mainly of marine origin, in the second part was marine and slightly biomass burning influenced (increasing tendency) and in the in last part of the cruise, approaching the African mainland, biomass burning influences became dominant. Generally aerosols were dominated by sulfate (caverage = 1.99 µg/m**3) and ammonium ions (caverage = 0.72 µg/m**3) that are well correlated and slightly increasing along the cruise. High concentrations of water insoluble organic carbon (WISOC) averaging 0.51 µg/m**3 were found probably attributed to the high oceanic productivity in this region. Water soluble organic carbon (WSOC) was strongly increasing along the cruise from concentrations of 0.26 µg/m**3 in the mainly marine influenced part to concentrations up to 3.3 µg/m**3 that are probably caused by biomass burning influences. Major organic constituents were oxalic acid, methansulfonic acid (MSA) and aliphatic amines. MSA concentrations were quite constant along the cruise (caverage = 43 ng/m**3). While aliphatic amines were more abundant in the first mainly marine influenced part with concentrations of about 20 ng/m**3, oxalic acid showed the opposite pattern with average concentrations of 12 ng/m**3 in the marine and 158 ng/m**3 in the biomass burning influenced part. The alpha dicarbonyl compounds glyoxal and methylglyoxal were detected in the aerosol particles in the low ng/m**3 range and followed oxalic acid closely. MSA and aliphatic amines accounted for biogenic marine (secondary) aerosol constituents whereas oxalic acid and the alpha dicarbonyl compounds were believed to result mainly from biomass burning. N-alkane concentrations increased along the cruise from 0.81 to 4.66 ng/m**3, PAHs and hopanes were abundant in the last part of the cruise (caverage of PAHs = 0.13 ng/m**3, caverage of hopanes = 0.19 ng/m**3). Levoglucosan was identified in several samples of the last part of the cruise in concentrations around 2 ng/m**3, pointing to (aged) biomass burning influences. The investigated organic compounds could explain 9.5% of WSOC in the mainly marine influenced part (dominating compounds: aliphatic amines and MSA) and 2.7% of WSOC in the biomass burning influenced part (dominating compound: oxalic acid) of the cruise.