The alkali element and boron geochemistry of ODP Site 169-1038 in the Escanaba Trough, East Pacific

A suite of conjugate pore fluid and sediment samples were collected during Leg 169 of the ODP from within the clastic sedimentary sequences which host massive sulphides at Central Hill, Escanaba Trough (ODP Site 1038). We report the alkali element and boron, and Li and B isotope data for these samples. Relative to a reference site (Site 1037) located outside the zone of high heat flow, pore fluids from Site 1038 show a wide variation in Cl (300-800 mM), and have far higher concentrations of Li (up to 6.2 mM), B (up to 9.7 mM), Cs (up to 5.0 mM), and Rb (up to 97 mM). We show that the pore fluids are derived from hydrothermal circulation that has extended into the basement oceanic crust, with input of the alkali elements and B as the rising hydrothermal fluids interact geochemically with the overlying clastic sediments. There is, however, no marked depletion of these elements in the conjugate sediments, suggesting that there has been advective transport of fluids away from the primary hydrothermal reaction site. This is supported by modelling of the Li and B isotope systematics of the pore fluids, which shows that they record extensive formation of secondary minerals during cooling of the fluids from ~350 to ~20ºC. Precipitation of metal-rich sulphides would have occurred prior to the formation of these minerals, thus, the pore fluid Li and B isotope data can place important constraints on the locus of sulphide deposition beneath the seafloor at Escanaba.

Metallic Fluence Monitors and J-value standards

Utilizing the neutron-irradiation parameter J is one of the major uncertainties in 40Ar/39Ar dating. The associated error of the individual J-value for a sample of unknown age depends on the accuracy of the age of the geological standards, the fast-neutron fluence distribution in the reactor and the distances between standards and samples during irradiation. While it is generally assumed that rotating irradiation evens out radial neutron fluence gradients, we observed axial and radial variations of the J-values in sample irradiations in the rotating channels of two reactors. To quantify them, we included three-dimensionally distributed metallic fast- (Ni) and thermal- (Co) neutron fluence monitors in three irradiations and geological age standards in three more. Two irradiations were carried out under Cd-shielding in the FRG1 reactor in Geesthacht, Germany, and four without Cd-shielding in the LVR-15 reactor in Rez, Czech Republic. The 58Ni(nf,p)58Co activation reaction and ?-spectrometry of the 811 keV peak associated with the subsequent decay of 58Co to 58Fe allow to calculate the fast-neutron fluence. The fast-neutron fluences at known positions in the irradiation container correlate with the J-values determined by mass-spectrometric 40Ar/39Ar measurements of the geological age standards. Ra-dial neutron fluence gradients are up to 1.8 %/cm in FRG1 and up to 2.2 %/cm in LVR-15; the corre-sponding axial gradients are up to 5.9 and 2.1 %/cm. We conclude that sample rotation might not al-ways suffice to meet the needs of high-precision dating and gradient monitoring can be crucial.

(Table 1) Chemical compositions of beryllium in sediments and pore waters of ODP Hole 131-808

Studies of Be distributions in subduction zone sediments will help to understand questions regarding the enrichments of cosmogenic Be-10 in arc volcanic rocks. Analyses of Be-10 and Be-9 in sediments of Ocean Drilling Program Site 808, Nankai Trough and Be-9 in porewaters of Site 808 and Sites 671 and 672, Barbados ridge complex, show significant decreases in solid phase Be-10 and large increases of porewater Be-9 at the location of the décollement zone and below or at potential flow conduits. These data imply the potential mobilization of Be during pore fluid expulsion upon sediment burial. Experiments involving reaction between a décollement sediment and a synthetic NaCl-CaCl2 solution at elevated pressure and temperatures were conducted in an attempt to mimic early subduction zone processes. The results demonstrate that Be is mobilized under elevated pressure and temperature with a strong pH dependence. The Be mobilization provides an explanation of Be-10 enrichment in arc volcanic rocks and supports the argument of the importance of the fluid processes in subduction zones at convergent margins.

Photophysiological responses of Southern Ocean phytoplankton to changes in CO2 concentrations: Short-term versus acclimation effects

The present study examines how different pCO2 acclimations affect the CO2- and light-dependence of photophysiological processes and O2 fluxes in four Southern Ocean (SO) key phytoplankton species. We grew Chaetoceros debilis (Cleve), Pseudo-nitzschia subcurvata (Hasle), Fragilariopsis kerguelensis (O'Meara) and Phaeocystis antarctica (Karsten) under low (160 µatm) and high (1000 ?atm) pCO2. The CO2- and light-dependence of fluorescence parameters of photosystem II (PSII) were determined by means of a fluorescence induction relaxation system (FIRe). In all tested species, nonphotochemical quenching (NPQ) is the primary photoprotection strategy in response to short-term exposure to high light or low CO2 concentrations. In C. debilis and P. subcurvata, PSII connectivity (p) and functional absorption cross-sections of PSII in ambient light (sigma PSII') also contributed to photoprotection while changes in re-oxidation times of Qa acceptor (tQa) were more significant in F. kerguelensis. The latter was also the only species being responsive to high acclimation pCO2, as these cells had enhanced relative electron transport rates (rETRs) and sigma PSII' while tQa and p were reduced under short-term exposure to high irradiance. Low CO2-acclimated cells of F. kerguelensis and all pCO2 acclimations of C. debilis and P. subcurvata showed dynamic photoinhibition with increasing irradiance. To test for the role and presence of the Mehler reaction in C. debilis and P. subcurvata, the light-dependence of O2 fluxes was estimated using membrane inlet mass spectrometry (MIMS). Our results show that the Mehler reaction is absent in both species under the tested conditions. We also observed that dark respiration was strongly reduced under high pCO2 in C. debilis while it remained unaltered in P. subcurvata. Our study revealed species-specific differences in the photophysiological responses to pCO2, both on the acclimation as well as the short-term level.

Strontium and boron geochemistry of ODP sites at Hydrate Ridge, eastern Pacific Ocean

ODP Leg 204, which drilled at Hydrate Ridge, provides unique insights into the fluid regime of an accretionary complex and delineates specific sub-seafloor pathways for fluid transport. Compaction and dewatering due to smectite-illite transition increase with distance from the toe of the accretionary prism and bring up fluids from deep within the accretionary complex to sampled depths (<= 600 mbsf). These fluids have a distinctly non-radiogenic strontium isotope signature indicating reaction with the oceanic basement. Boron isotopes are also consistent with a deep fluid source that has been modified by desorption of heavy boron as clay minerals change from smectite to illite. One of three major horizons serves as conduit for the transport of mainly fluid. Our results enable us to evaluate fluid migration pathways that play important roles on massive gas hydrate accumulations and seepage of methane-rich fluids on southern Hydrate Ridge.

Benthic anammox and dentrification rates measured in a slurry incubation experiments at four different stations in the Arabian Sea off Pakistan during the METEOR cruise M74/2 in 2007

Vertical distributions of benthic denitrification and anammox rates within the sediment were estimated from slurry incubation experiments. Rates were used to calculate the contribution of anammox and denitrification to the total N-loss. Briefly, MUC sediment cores were sliced in 2 cm intervals and the sediment was diluted and incubated with degassed bottom water in a gas tight bag. After pre-incubating the bags for 2 h, 15N-labeled substrates were injected into the bags and the slurries were thoroughly mixed. Incubations were performed in the dark at in situ temperatures. The N2 isotope ratio (28N2, 29N2, and 30N2) was determined by gas chromatography-isotopic ratio mass spectrometry (VG Optima, Micromass) and calculated according to Kuypers et al. (2005) and Holtappels et al. (2011), respectively.Furthermore, total organic carbon and nitrogen concentrations were measured of core sediment layers corresponding to those used for rate measurements. Concentrations of organic carbon and nitrogen were determined by combustion/gas chromatography (Carlo Erba NA-1500 CNS analyzer) of dried sediment samples after acidification. The same sediment layer were also used to extract nucleic acids. The concentrations of the DNA in the samples were measured spectrophotometrically with a NanoDrop instrument (Thermo Fisher Scientific Inc.). The biomarker functional gene nirS, encoding the cd1-containing nitrite reductase, for both denitrifiers and marine anammox bacteria were quantified with real-time PCR, using the primers cd3aF/R3cd (5'-GTSAACGTSAAGGARACSGG-3' (Michotey et al., 2000)/5'-GASTTCGGRTGSGTCTTGA-3'; Throback et al., 2004) and Scnir372F/Scnir845R (5'-TGTAGCCAGCATTGTAGCGT-3'/5'-TCAAGCCAGACCCATTTGCT-3'; Lam et al., 2009).

Isotopic composition of carbonates from the Logachev Hydrothermal Field, MAR 14°45'N

We investigate the Logatchev Hydrothermal Field at the Mid-Atlantic Ridge, 14°45' N to constrain the calcium isotope hydrothermal flux into the ocean. During the transformation of seawater to a hydrothermal solution, the Ca concentration of pristine seawater ([Ca]_SW) increases from about 10 mM to about 32 mM in the hydrothermal fluid endmember ([Ca]_HydEnd) and thereby adopts a d44/40Ca_HydEnd of -0.95+/-0.07 per mil relative to seawater (SW) and a 87Sr/86Sr isotope ratio of 0.7034(4). We demonstrate that d44/40Ca_HydEnd is higher than that of the bedrock at the Logatchev field. From mass balance calculations, we deduce a d44/40Ca of -1.17+/-0.04 per mil (SW) for the host-rocks in the reaction zone and -1.45+/-0.05 per mil (SW) for the isotopic composition of the entire hydrothermal cell of the Logatchev field. The values are isotopically lighter than the currently assumed d44/40Ca for Bulk Earth of -0.92+/-0.18 per mil (SW) [Skulan J., DePaolo D. J. and Owens T. L. (1997) Biological control of calcium isotopic abundances in the global calcium cycle. Geochim. Cosmochim. Acta 61,(12) 2505-2510] and challenge previous assumptions of no Ca isotope fractionation between hydrothermal fluid and the oceanic crust [Zhu P. and Macdougall J. D. (1998) Calcium isotopes in the marine environment and the oceanic calcium cycle. Geochim. Cosmochim. Acta 62,(10) 1691-1698; Schmitt A. -D., Chabeaux F. and Stille P. (2003) The calcium riverine and hydrothermal isotopic fluxes and the oceanic calcium mass balance. Earth Planet. Sci. Lett. 6731, 1-16]. Here we propose that Ca isotope fractionation along the fluid flow pathway of the Logatchev field occurs during the precipitation of anhydrite. Two anhydrite samples from the Logatchev Hydrothermal Field show an average fractionation of about D44/40Ca = -0.5 per mil relative to their assumed parental solutions. Ca isotope ratios in aragonites from carbonate veins from ODP drill cores indicate aragonite precipitation directly from seawater at low temperatures with an average d44/40Ca of -1.54+/-0.08 per mil (SW). The relatively large fractionation between the aragonite precipitates and seawater in combination with their frequent abundance in weathered mafic and ultramafic rocks suggest a reconsideration of the marine Ca isotope budget, in particular with regard to ocean crust alteration.

Dissolved organic carbon concentrations, amino sugar concentrations and highly significantly correlating FT-ICR mass peak magnitudes obtained from solid phase extracted marine dissolved organic matter during POLARSTERN cruise ANT-XXV/1

Dissolved organic matter (DOM) was extracted with solid phase extraction (SPE) from 137 water samples from different climate zones and different depths along an Eastern Atlantic Ocean transect. The extracts were analyzed with Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) with electrospray ionization (ESI). D14C analyses were performed on subsamples of the SPE-DOM. In addition, the amount of dissolved organic carbon was determined for all water and SPE-DOM samples as well as the yield of amino sugars for selected samples. Linear correlations were observed between the magnitudes of 43% of the FT-ICR mass peaks and the extract D14C values. Decreasing SPE-DOM D14C values went along with a shift in the molecular composition to higher average masses (m/z) and lower hydrogen/carbon (H/C) ratios. The correlation was used to model the SPE-DOM D14C distribution for all 137 samples. Based on single mass peaks a degradation index was developed to compare the degradation state of marine SPE-DOM samples analyzed with FT-ICR MS. A correlation between D14C, degradation index, DOC values and amino sugar yield supports that SPE-DOM analyzed with FT-ICR MS reflects trends of bulk DOM. A relative mass peak magnitude ratio was used to compare aged SPE-DOM and fresh SPE-DOM regarding single mass peaks. The magnitude ratios show a continuum of different reactivities for the single compounds. Only few of the compounds present in the FT-ICR mass spectra are expected to be highly degraded in the oldest water masses of the Pacific Ocean. All other compounds should persist partly thermohaline circulation. Prokaryotic (bacterial) production, transformation and accumulation of this very stable DOM occurs probably primarily in the upper ocean. This DOM is an important contribution to very old DOM, showing that production and degradation are dynamic processes.

Concentrations and isotopic compositions of low molecular weight hydrocarbons in hydrothermal fluids from ODP Field, Middle Valley, northern Juan de Fuca Ridge

The presence of sedimentary organic matter blanketing midocean ridge crests has a potentially strong impact on metal transport in hydrothermal vent fluids. To constrain the role of organic matter in metal mobility during hydrothermal sediment alteration, we reacted organic-rich diatomaceous ooze from Guaymas Basin, Gulf of California, and organic-poor hemipelagic mud from Middle Valley, northern Juan de Fuca Ridge, with seawater and a Na-Ca-K-Cl fluid of seawater chlorinity, at 275° to 400°C, 350 to 500 bars, and initial fluid: sediment mass ratios ranging from 1.6 to 9.8. Reaction of these fluids with both sediment types released CO2 and high concentrations of ore-forming metals (Fe, Mn, Zn, Pb) to solution. Relatively low concentrations of Cu were observed in solution and likely reflect the reducing conditions that resulted from the presence of sedimentary organic matter. Both the concentrations of CO2 and dissolved metals were lower in fluids reacted with Middle Valley sediment compared with aqueous concentrations in fluids reacted with Guaymas Basin sediment. During alteration of both sediment types, metal concentrations varied strongly as a function of temperature, increasing by up to an order of magnitude over the 75°C range of each experiment. Major element fluid chemistry and observed alteration assemblages suggest that during hydrothermal alteration of organic-lean sediment from Middle Valley a feldspar-quartz-illite mineral assemblage buffered in situ pH. In contrast, data from the experimental alteration of organic-rich Guaymas Basin sediment suggest that a calcite-plagioclase-quartz assemblage regulated in situ pH. Fluid speciation calculations suggest that in situ pH during Guaymas Basin sediment alteration was lower than during alteration of Middle Valley sediment and accounts for the substantially greater metal mobility at a given temperature and pressure during the former experiment. Comparison of our results with the results of basalt alteration experiments indicate that except for Cu, hydrothermal sediment alteration results in equal or greater concentrations of ore-forming metals at a given temperature and pressure. Accordingly, the presence of ore-forming metals in fluids currently venting from sediment-covered hydrothermal systems at concentrations substantially lower than in fluids from bare-rock systems may reflect chemical reequilibration during subsurface cooling within the sediment pile.