Results of analyses of fluid inclusions from ODP Site 735B, Leg 118 and 176

Microthermometric and isotopic analyses of fluid inclusions in primitive olivine gabbros, oxide gabbros, and evolved granitic material recovered from Ocean Drilling Program Hole 735B at the Southwest Indian Ridge provide new insights into the evolution of C-O-H-NaCl fluids in the plutonic foundation of the oceanic crust. The variably altered and deformed plutonic rocks span a crustal section of over 1500 m and record a remarkably complex magma-hydrothermal history. Magmatic fluids within this suite followed two chemically distinct paths during cooling through the subsolidus regime: the first path included formation of CO2+CH4+H2O+C fluids with up to 43 mole% CH4; the second path produced hypersaline brines that contain up to 50% NaCl equivalent salinities. Subsequent to devolatilization, respeciation of magmatic CO2, attendant graphite precipitation, and cooling from 800°C to 500°C promoted formation of CH4-enriched fluids. These fluids are characterized by average d13C(CH4) values of -27.1+/-4.3 per mil (N=45) with associated d13C(CO2) compositions ranging from -24.9 per mil to -1.9 per mil (N=39), and average dD values of exsolved vapor of -41+/-12 per mil (N=23). In pods, veins, and lenses of highly fractionated residual material, hypersaline brines formed during condensation and by direct exsolution in the absence of a conjugate vapor phase. Entrapped CO2+CH4+H2O-rich fluids within many oxide-bearing rocks and felsic zones are significantly depleted in 13C (with d13C(CO2) values down to about -25 per mil) and contain CO2 concentrations higher than those predicted by equilibrium devolatilization models. We hypothesize that lower effective pressures in high-temperature shear zones promoted infiltration of highly fractionated melts and compositionally evolved volatiles into focused zones of deformation, significantly weakening the rock strength. In felsic-rich zones, volatile build-up may have driven hydraulic fracturing of gabbroic wall rocks resulting in the formation of magmatic breccias. Comparison of isotopic compositions of fluids in plutonic rocks from 735B, the MARK area of the Mid-Atlantic Ridge, and the Mid-Cayman Rise indicate (1) that the carbon isotope composition of the lower oceanic crust may be far more heterogeneous than previously believed and (2) that carbon-bearing species in the oceanic crust and their distribution at depth are highly variable.

Geochemistry of abyssal oceanic magmas

Massive, nearly holocrystalline dolerites from DSDP Hole 417D contain from 0.5 to 1.5% of granophyric patches composed mainly of Na-plagioclase and quartz. These patches are compositionally similar to other crystalline silicic rocks from oceanic spreading centers and differ from rarer abyssal silicic glasses. Crystalline varieties with SiO2 > 60 wt.% generally have Na/K >10, whereas silicic glasses have Na/K in the range 3-6. While crystal fractionation readily accounts for the Na2O and K2O contents of abyssal silicic glasses, both the 417D granophyres and other crystalline abyssal silicic rocks have much lower K2O than that predicted by any reasonable crystal-liquid fractionation model. We propose that high-temperature vapor phase transport is responsible for removal of potassium during late-stage crystallization of these rocks. This allows for the formation of cogenetic silicic glassy and crystalline rocks with greatly different Na/K ratios. These observations and interpretations lead to a more confident assignment of high Na/K silicic rocks of oceanic and ophiolitic environments to a cogenetic origin with basaltic oceanic crust.

Geochemistry and oxidation state of Lau Basin basalts

The backarc glasses recovered during Ocean Drilling Program Leg 135 are unique among submarine tholeiitic glasses with respect to their oxygen fugacity and sulfur concentrations. Unlike mid-ocean-ridge basalt glasses, fO2 in these samples (inferred from ratios Fe3+/Fe2+) is high and variable, and S variations (90-1140 ppm) are not coupled with FeO concentration. Strong correlations occur between the alkali and alkaline-earth elements and both fO2 (positive correlations) and S concentrations (negative correlations). Correlations between fO2 and various trace elements are strongest for those elements with a known affinity for hydrous fluids (perhaps produced during slab dehydration), suggesting the presence of a hydrous fluid with high fO2 and high alkali and alkaline earth element concentrations in the Lau Basin mantle. Concentrations of S and fO2 are strongly correlated; high fO2 samples are characterized by low S in addition to high alkali and alkaline earth element concentrations. The negative correlations between S and these trace elements are not consistent with incompatible behavior of S during crystallization. Mass balance considerations indicate that the S concentrations cannot result simply from mixing between low-S and high-S sources. Furthermore, there is no relationship between S and other trace elements or isotope ratios that might indicate that the S variations reflect mixing processes. The S variations more likely reflect the fact that when silicate coexists with an S-rich vapor phase the solubility of S in the silicate melt is a function of fO2 and is at a minimum at the fO2 conditions recorded by these glasses. The absence of Fe-sulfides and the high and variable vesicle contents are consistent with the idea that S concentrations reflect silicate-vapor equilibria rather than silicate-sulfide equilibria (as in MORB). The low S contents of some samples, therefore, reflect the high fO2 of the supra-subduction zone environment rather than a low-S source component.

Mercury content and isotopic composition of frost flower, surface snow and brine samples near Barrow, Alaska

Frost flowers are ice crystals that grow on refreezing sea ice leads in Polar Regions by wicking brine from the sea ice surface and accumulating vapor phase condensate. These crystals contain high concentrations of mercury (Hg) and are believed to be a source of reactive halogens, but their role in Hg cycling and impact on the fate of Hg deposited during atmospheric mercury depletion events (AMDEs) are not well understood. We collected frost flowers growing on refreezing sea ice near Barrow, Alaska (U.S.A.) during an AMDE in March 2009 and measured Hg concentrations and Hg stable isotope ratios in these samples to determine the origin of Hg associated with the crystals. We observed decreasing Delta199Hg values in the crystals as they grew from new wet frost flowers (mean Delta199Hg = 0.77 ± 0.13 per mil, 1 s.d.) to older dry frost flowers (mean Delta199Hg = 0.10 ± 0.05 per mil, 1 s.d.). Over the same time period, mean Hg concentrations in these samples increased from 131 ± 6 ng/L (1 s.d.) to 180 ± 28 ng/L (1 s.d.). Coupled with a previous study of Hg isotopic fractionation during AMDEs, these results suggest that Hg initially deposited to the local snowpack was subsequently reemitted during photochemical reduction reactions and ultimately accumulated on the frost flowers. As a result of this process, frost flowers may lead to enhanced local retention of Hg deposited during AMDEs and may increase Hg loading to the Arctic Ocean.

Depth profiles of pore-water and solid-phase constituents, respiration rates and grain size distribution in sediments of the Clarion-Clipperton Fracture Zone

Manganese nodules of the Clarion-Clipperton Fracture Zone (CCFZ) in the NE Pacific Ocean are highly enriched in Ni, Cu, Co, Mo and rare-earth elements, and thus may be the subject of future mining operations. Elucidating the depositional and biogeochemical processes that contribute to nodule formation, as well as the respective redox environment in both, water column and sediment, supports our ability to locate future nodule deposits and evaluates the potential ecological and environmental effects of future deep-sea mining. For these purposes we evaluated the local hydrodynamics and pore-water geochemistry with respect to the nodule coverage at four sites in the eastern CCFZ. Furthermore, we carried out selective leaching experiments at these sites in order to assess the potential mobility of Mn in the solid phase, and compared them with the spatial variations in sedimentation rates. We found that the oxygen penetration depth is 180 - 300 cm at all four sites, while reduction of Mn and NO3- is only significant below the oxygen penetration depth at sites with small or no nodules on the sediment surface. At the site without nodules, potential microbial respiration rates, determined by incubation experiments using 14C-labelled acetate, are slightly higher than at sites with nodules. Leaching experiments showed that surface sediments covered with big or medium-sized nodules are enriched in mobilizable Mn. Our deep oxygen measurements and pore-water data suggest that hydrogenetic and oxic-diagenetic processes control the present-day nodule growth at these sites, since free manganese from deeper sediments is unable to reach the sediment surface. We propose that the observed strong lateral contrasts in nodule size and abundance are sensitive to sedimentation rates, which in turn, are controlled by small-scale variations in seafloor topography and bottom-water current intensity.

Temperature, water level and bathymetry of thermokarst lakes in the continuous permafrost zone of northern Siberia - Lena River Delta, Siberia

Thermokarst lakes are typical features of the northern permafrost ecosystems, and play an important role in the thermal exchange between atmosphere and subsurface. The objective of this study is to describe the main thermal processes of the lakes and to quantify the heat exchange with the underlying sediments. The thermal regimes of five lakes located within the continuous permafrost zone of northern Siberia (Lena River Delta) were investigated using hourly water temperature and water level records covering a 3-year period (2009-2012), together with bathymetric survey data. The lakes included thermokarst lakes located on Holocene river terraces that may be connected to Lena River water during spring flooding, and a thermokarst lake located on deposits of the Pleistocene Ice Complex. Lakes were covered by ice up to 2 m thick that persisted for more than 7 months of the year, from October until about mid-June. Lake-bottom temperatures increased at the start of the ice-covered period due to upward-directed heat flux from the underlying thawed sediment. Prior to ice break-up, solar radiation effectively warmed the water beneath the ice cover and induced convective mixing. Ice break-up started at the beginning of June and lasted until the middle or end of June. Mixing occurred within the entire water column from the start of ice break-up and continued during the ice-free periods, as confirmed by the Wedderburn numbers, a quantitative measure of the balance between wind mixing and stratification that is important for describing the biogeochemical cycles of lakes. The lake thermal regime was modeled numerically using the FLake model. The model demonstrated good agreement with observations with regard to the mean lake temperature, with a good reproduction of the summer stratification during the ice-free period, but poor agreement during the ice-covered period. Modeled sensitivity to lake depth demonstrated that lakes in this climatic zone with mean depths > 5 m develop continuous stratification in summer for at least 1 month. The modeled vertical heat flux across the bottom sediment tends towards an annual mean of zero, with maximum downward fluxes of about 5 W/m**2 in summer and with heat released back into the water column at a rate of less than 1 W/m**2 during the ice-covered period. The lakes are shown to be efficient heat absorbers and effectively distribute the heat through mixing. Monthly bottom water temperatures during the ice-free period range up to 15 °C and are therefore higher than the associated monthly air or ground temperatures in the surrounding frozen permafrost landscape. The investigated lakes remain unfrozen at depth, with mean annual lake-bottom temperatures of between 2.7 and 4 °C.

Processed 2 minutes-averaged continuous VM-ADCP (vessel-mounted Acoustic Doppler Current Profiler) profiles during POLARSTERN cruise ANT-XXVIII/3

This data set was obtained during the R. V. POLARSTERN cruise ANT-XXVIII/3. Current velocities were measured nearly continuously when outside territorial waters along the ship's track with a vessel-mounted TRD Instruments' 153.6-kHz Ocean Surveyor ADCP. The transducers were located 11 m below the water line and were protected against ice floes by an acoustically transparent plastic window. The current measurements were made using a pulse of 2s and vertical bin length of 4 m. The ship's velocity was calculated from position fixes obtained by the Global Positioning System (GPS). Heading, roll and pitch data from the ship's gyro platforms and the navigation data were used to convert the ADCP velocities into earth coordinates. Accuracy of the ADCP velocities mainly depends on the quality of the position fixes and the ship's heading data. Further errors stem from a misalignment of the transducer with the ship's centerline. The ADCP data were processed using the Ocean Surveyor Sputum Interpreter (OSSI) software developed by GEOMAR Helmholtz-Zentrum für Ozeanforschung Kiel. The averaging interval was set to 120 seconds. The reference layer was set to bins 5 to 16 avoiding near surface effects and biases near bin 1. Sampling interval setting: 2s; Number of bins: 80; Bin length: 4m; Pulse length: 4m; Blank beyond transmit length: 4m. Data processing setting: Top reference bin: 5; Bottom reference bin: 16; Average: 120s; Misalignment amplitude: 1.0276 +/- 0.1611, phase: 0.8100 +/- 0.7190. The precision for single ping and 4m cell size reported by TRDI is 0.30m/s. Resulting from the single ping precision and the number of pings (most of the time 36) during 120seconds the velocity accuracy is nearly 0.05m/s. (Velocity accuracy = single ping precision divided by square root of the number of pings).