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.

Physical oceanography and current meter measurements on the Gulf of Lion continental margin between June 1993 and July 1996

Nine hydrographic cruises were performed on the Gulf of Lion continental margin between June 1993 and July 1996. These observations are analysed to quantify the fluxes of particulate matter and organic carbon transported along the slope by the Northern Current and to characterise their seasonal variability. Concentration of particulate matter and organic carbon are derived from light-transmission data and water sample analyses. The circulation is estimated from the geostrophic current field. The uncertainty on the transport estimate, related to the error on the prediction of particle concentrations from light-transmission data and the error on velocities, is assessed. The particulate matter inflow entering the Gulf of Lion off Marseille is comparable to the Rhône River input and varies seasonally with a maximum transport between autumn and spring. These modifications result from variations of the water flux rather than variations of the particulate matter concentration. Residual transports of particulate matter and organic carbon across the entire Gulf of Lion are calculated for two cruises enclosing the domain that were performed in February 1995 and July 1996. The particulate matter budgets indicate a larger export from the shelf to deep ocean in February 1995 (110 ± 20 kg/s) than in July 1996 (25 ± 18 kg/s). Likewise, the mean particulate organic carbon export is 12.8 ± 0.5 kg/s in February 1995 and 0.8 ± 0.2 kg/s in July 1996. This winter increase is due to larger allochthonous and autochthonous inputs and also to enhanced shelf-slope exchange processes, in particular the cascading of cold water from the shelf. The export of particulate matter by the horizontal currents is moreover two orders of magnitude larger than the vertical particulate fluxes measured at the same time with sediment traps on the continental slope.

Sulphate concentrations and sulphur isotopic composition in pore fluids from ODP Leg 168 sites

A numerical model of sulfate reduction and isotopic fractionation has been applied to pore fluid SO4**2- and d34S data from four sites drilled during Ocean Drilling Program (ODP) Leg 168 in the Cascadia Basin at 48°N, where basement temperatures reach up to 62°C. There is a source of sulfate both at the top and the bottom of the sediment column due to the presence of basement fluid flow, which promotes bacterial sulfate reduction below the sulfate minimum zone at elevated temperatures. Pore fluid d34S data show the highest values (135 per mil) yet found in the marine environment. The bacterial sulfur isotopic fractionation factor, a, is severely underestimated if the pore fluids of anoxic marine sediments are assumed to be closed systems and Rayleigh fractionation plots yield erroneous values for a by as much as 15 per mil in diffusive and advective pore fluid regimes. Model results are consistent with a = 1.077+/-0.007 with no temperature effect over the range 1.8 to 62°C and no effect of sulfate reduction rate over the range 2 to 10 pmol/ccm/day. The reason for this large isotopic fractionation is unknown, but one difference with previous studies is the very low sulfate reduction rates recorded, about two orders of magnitude lower than literature values that are in the range of µmol/ccm/day to tens of nmol/ccm/day. In general, the greatest 34S depletions are associated with the lowest sulfate reduction rates and vice versa, and it is possible that such extreme fractionation is a characteristic of open systems with low sulfate reduction rates.

Permeable coral reef sediment dissolution driven by elevated pCO2 and pore water advection

Ocean acidification (OA) is expected to drive the transition of coral reef ecosystems from net calcium carbonate (CaCO3) precipitating to net dissolving within the next century. Although permeable sediments represent the largest reservoir of CaCO3 in coral reefs, the dissolution of shallow CaCO3 sands under future pCO2 levels has not been measured under natural conditions. In situ, advective chamber incubations under elevated pCO2 (~800 µatm) shifted the sediments from net precipitating to net dissolving. Pore water advection more than doubled dissolution rates (1.10 g CaCO3/m**2/day) when compared to diffusive conditions (0.42 g CaCO3/m**2 /day). Sediment dissolution could reduce net ecosystem calcification rates of the Heron Island lagoon by 8% within the next century, which is equivalent to a 25% reduction in the global average calcification rate of coral lagoons. The dissolution of CaCO3 sediments needs to be taken into account in order to address how OA will impact the net accretion of coral reefs under future predicted increases in CO2.

(Table 1) Isotopic and geochemical parameters of gas phase from underground fluids of the Baikal rift and its framing

Results of studying isotopic composition of helium in underground fluids of the Baikal-Mongolian region during the last quarter of XX century are summarized. Determinations of 3He/4He ratio in 139 samples of gas phase from fluids, collected at 104 points of the Baikal rift zone and adjacent structures are given. 3He/4He values lie within the range from 1x10**-8 (typical for crustal radiogenic helium) to 1.1x10**-5 (close to typical MORB reservoir). Repeated sampling in some points during more than 20 years showed stability of helium isotopic composition in time in each of them at any level of 3He/4He values. There is no systematic differences of 3He/4He in samples from surface water sources and deeper intervals of boreholes in the same areas. Universal relationship between isotopic composition of helium and general composition of gas phase is absent either, but the minimum 3He/4He values occurred in methane gas of hydrocarbon deposits, whereas in nitrogen and carbon dioxide gases of helium composition varied (in the latter maximum 3He/4He values have been measured). According to N2/Ar_atm ratio nitrogen gases are atmospheric. In carbonic gas fN2/fNe ratio indicates presence of excessive (non-atmogenic) nitrogen, but the attitude CO2/3He differs from one in MORB. Comparison of helium isotopic composition with its concentration and composition of the main components of gas phase from fluids shows that it is formed under influence of fractionation of components with different solubility in the gas-water system and generation/consumption of reactive gases in the crust. Structural and tectonic elements of the region differ from the spectrum of 3He/4He values. At the pre-Riphean Siberian Platform the mean 3He/4He = (3.6+/-0.9)x10**- 8 is very close to radiogenic one. In the Paleozoic crust of Khangay 3He/4He = (16.3+/-4.6)x10**-8, and the most probable estimate is (12.3+/-2.9)x10**-8. In structures of the eastern flank of the Baikal rift zone (Khentei, Dauria) affected by the Mz-Kz activization 3He/4He values range from 4.4x10**-8 to 2.14x10**-6 (average 0.94x10**-6). Distribution of 3He/4He values across the strike of the Baikal rift zone indicates advective heat transfer from the mantle not only in the rift zone, but also much further to the east. In fluids of the Baikal rift zone range of 3He/4He values is the widest: from 4x10**-8 to 1.1x10**-5. Their variations along the strike of the rift zone are clearly patterned, namely, decrease of 3He/4He values in both directions from the Tunka depression. Accompanied by decrease in density of conductive heat flow and in size of rift basins, this trend indicates decrease in intensity of advective heat transfer from the mantle to peripheral segments of the rift zone. Comparing this trend with data on other continental rift zones and mid-ocean ridges leads to the conclusion about fundamental differences in mechanisms of interaction between the crust and the mantle in these environments.

Noble gases sampled from three cruises in the eastern tropical Atlantic

Oceanic upwelling velocities are too small to be measured directly. Deviations of the He-3/He-4 ratio in the mixed layer from solubility equilibrium provide an indirect means to infer vertical velocities at the base of the mixed layer. This method is applied to the Mauritanian upwelling region for data from three cruises in summer 2006 and winter 2007 and 2008. Diapycnal mixing coefficients are estimated from microstructure measurements, reaching from 10**-3 m**2/s over the shelf break to 10**-5 m**2/s in the open ocean. The resulting upwelling velocities in the onshore region (upto 50 km from the 50 m isobath) are of the order of 2 x 10**-5 m/s}, in agreement with Ekman theory. Further offshore, in some cases the vertical velocities inferred from the helium isotope disequilibrium exceed the values derived from the wind stress curl by one order of magnitude. The Mauritanian coastal area as part of the Canary Current upwelling system belongs to the most productive ocean regions in the world. Nutrient fluxes into the mixed layer (both advective and diffusive) are equivalent to a net community production of about 1 g C/d, and associated heat fluxes vary between 183 +/- 62 W/m**2 in summer and 97 +/- 25 W/m**2 in winter. Regarding the flux into the mixed layer, the contribution of diffusion and advection are of similar magnitude for both heat and nutrients. The upwelling, however, provides the supply of cold and nutrient rich water from below. The large offshore vertical velocities inferred from the helium method are associated with nutrient fluxes of the same order as for the onshore region, and may be responsible for observed patches of high productivity in that area. The offshore heat fluxes due to upwelling and diapycnal mixing are smaller than 70 W/m**2 for all cruises.