Methane, helium isotope and hydrogen data from the Nibelungen hydrothermal area, Mid Atlantic Ridge

Hydrothermal emission of mantle helium appears to be directly related to magma production rate, but other processes can generate methane and hydrogen on mid-ocean ridges. In an on-going effort to characterize these processes in the South Atlantic, the flux and distribution of these gases were investigated in the vicinity of a powerful black smoker recently discovered at 8°17.9' S, 13°30.4' W. The vent lies on the shoulder of an oblique offset in the Mid-Atlantic Ridge and discharges high concentrations of methane and hydrogen. Measurements during expeditions in 2004 and 2006 show that the ratio of CH4 to 3He in the neutrally buoyant plume is quite high, 4 x 10**8. The CTD stations were accompanied by velocity measurements with lowered acoustic Doppler current profilers (LADCP), and from these data we estimate the methane transport to have been 0.5 mol/sec in a WSW-trending plume that seems to develop during the ebb tidal phase. This transport is an order of magnitude greater than the source of CH4 calculated from its concentration in the vent fluid and the rise height of the plume. From this range of methane fluxes, the source of 3He is estimated to be between 0.14 and 1.2 nmol/sec. In either case, the 3He source is significantly lower than expected from the spreading rate of the Mid-Atlantic Ridge. From the inventory of methane in the rift valley adjacent to the vent, it appears that the average specific rate of oxidation is 2.6 to 23/yr, corresponding to a turnover time between 140 and 16 days. Vertical profiles of methane in the surrounding region often exhibited Gaussian-like distributions, and the variances appear to increase with distance from the vent. Using a Gaussian plume model, we obtained a range of vertical eddy diffusivities between 0.009 and 0.08 m2m2/sec. These high values may be due to tidally driven internal waves across the promontory on which the vent is located.

Concentration of hydrogen sulfide in waters of the Black Sea in the layer of its coexistence with oxygen

About 100 parallel determinations of hydrogen sulfide by the volumetric and photometric methods were made in the layer of coexistence of oxygen with hydrogen sulfide (C layer). Thiosulfates were determined simultaneously. Regardless of locations of the stations, determinations by two methods coincided for the entire range of depths of occurrence of the C layer upper boundary. Within the C layer hydrogen sulfide readings obtained by these two independent methods agreed; thiosulfates were not found by direct measurements. Difference in the readings appears at the lower boundary of the C layer and below it, accompanied by appearance of thiosulfates. It is therefore concluded that it is correct to determine the upper boundary of the C layer by the iodometric method and to use concentration of hydrogen sulfide obtained by this method in the C layer to calculate rate of chemical oxidation of hydrogen sulfide in quasistationary processes.

Solid phase analysis of sediment core GeoB9309-1 from the Zambezi (or Mozambique) deep-sea fan

The Zambezi deep-sea fan, the largest of its kind along the east African continental margin, is poorly studied to date, despite its potential to record marine and terrestrial climate signals in the southwest Indian Ocean. Therefore, gravity core GeoB 9309-1, retrieved from 1219 m water depth, was investigated for various geophysical (magnetic susceptibility, porosity, colour reflectance) and geochemical (pore water and sediment geochemistry, Fe and P speciation) properties. Onboard and onshore data documented a sulphate/methane transition (SMT) zone at ~ 450-530 cm sediment depth, where the simultaneous consumption of pore water sulphate and methane liberates hydrogen sulphide and bi-carbonate into the pore space. This leads to characteristic changes in the sediment and pore water chemistry, as the reduction of primary Fe (oxyhydr)oxides, the precipitation of Fe sulphides, and the mobilization of Fe (oxyhydr)oxide-bound P. These chemical processes also lead to a marked decrease in magnetic susceptibility. Below the SMT, we find a reduction of porosity, possibly due to pore space cementation by authigenic minerals. Formation of the observed geochemical, magnetic and mineralogical patterns requires a fixation of the SMT at this distinct sediment depth for a considerable time-which we calculated to be ~ 10 000 years assuming steady-state conditions-following a period of rapid upward migration towards this interval. We postulate that the worldwide sea-level rise at the last glacial/interglacial transition (~ 10 000 years B.P.) most probably caused the fixation of the SMT at its present position, through drastically reduced sediment delivery to the deep-sea fan. In addition, we report an internal redistribution of P occurring around the SMT, closely linked to the (de)coupling of sedimentary Fe and P, and leaving a characteristic pattern in the solid P record. By phosphate re-adsorption onto Fe (oxyhydr)oxides above, and formation of authigenic P minerals (e.g. vivianite) below the SMT, deep-sea fan deposits may potentially act as long-term sinks for P.

Chemical composition of sediment core GeoB12309-5 from the northern Arabian Sea, its pore water profile and age depth relationship as well as CTD data obtained during cruise M74/3

The Arabian Sea off the Pakistan continental margin is characterized by one of the world's largest oxygen minimum zones (OMZ). The lithology and geochemistry of a 5.3 m long gravity core retrieved from the lower boundary of the modern OMZ (956 m water depth) were used to identify late Holocene changes in oceanographic conditions and the vertical extent of the OMZ. While the lower part of the core (535 - 465 cm, 5.04 - 4.45 cal kyr BP, Unit 3) is strongly bioturbated indicating oxic bottom water conditions, the upper part of the core (284 - 0 cm, 2.87 cal kyr BP to present, Unit 1) shows distinct and well-preserved lamination, suggesting anoxic bottom waters. The transitional interval from 465 to 284 cm (4.45 - 2.87 cal kyr BP, Unit 2) contains relicts of lamination which are in part intensely bioturbated. These fluctuations in bioturbation intensity suggest repetitive changes between anoxic and oxic/suboxic bottom-water conditions between 4.45 - 2.87 cal kyr BP. Barium excess (Baex) and total organic carbon (TOC) contents do not explain whether the increased TOC contents found in Unit 1 are the result of better preservation due to low BWO concentrations or if the decreased BWO concentration is a result of increased productivity. Changes in salinity and temperature of the outflowing water from the Red Sea during the Holocene influenced the water column stratification and probably affected the depth of the lower boundary of the OMZ in the northern Arabian Sea. Even if we cannot prove certain scenarios, we propose that the observed downward shift of the lower boundary of the OMZ was also impacted by a weakened Somali Current and a reduced transport of oxygen-rich Indian Central Water into the Arabian Sea, both as a response to decreased summer insolation and the continuous southward shift of the Intertropical Convergence Zone during the late Holocene.

Compilation of 231Protactinium/230 Thorium excess ratios in various surface sediment samples from the South Atlantic

In large areas of the world's oceans, there is a relationship between the mass flux of particulate matter and the unsupported 231Pa/230Th (xs231Pa/xs230Th) activity ratio of recent sediments. This observation forms the basis for using the xs231Pa/xs230Th ratio as a proxy for past changes in export productivity. However, a simple relationship between xs231Pa/xs 230Th ratio and particle flux requires that the water residence time in an ocean basin is far in excess of the scavenging residence time of 231Pa, and that the composition of sinking particles maintains a strong preference for the adsorption of 230Th over 231Pa with a constant 230Th/231Pa fractionation factor (F). The best correlation between xs231Pa/xs230Th ratio and mass flux is found in the Pacific Ocean. In the Atlantic, the contrast in the xs231Pa/xs230Th ratios between open ocean (low flux regions) and ocean margins (high flux regions) is much less pronounced due to the shorter residence time of deep water, resulting in less effective boundary scavenging of 231Pa. In the Southern Ocean, south of the Polar Front, there is no more a simple relationship between xs231Pa/xs230Th and particle flux. This is a result of a southward decrease in F, probably reflecting the increased opal content of sinking particles. Opal does not fractionate 231Pa and 230Th significantly. This lack of fractionation results in high xs231Pa/xs230Th ratios in opal-dominated regions, even in areas of very low particle fluxes such as the Weddell Sea. The xs231Pa/xs230Th ratio can therefore only be used as a paleoproductivity proxy if, in the time interval of interest, changes in the basin ventilation rate and differential scavenging of both radionuclides due to changes in the chemical composition of particulate matter can be excluded.

Oxygen and hydrogen isotopes at DSDP Leg 65 Holes

In order to provide information on the degree of alteration of the very young basaltic basement drilled on Leg 65 in the mouth of the Gulf of California, we have measured the oxygen isotopic composition of whole rocks and mineral separates. Considerable data already exist for older ocean crust, in particular for the deep holes drilled in the Atlantic Ocean on Deep Sea Drilling Project (DSDP) Legs 37, 45, 46, and 51-53. These data indicate that in all of these holes, which include crust as young as 3.5 m.y. old, a significant amount of alteration has taken place as the result of low-temperature interaction between basalt and seawater (cf. Muehlenbachs, 1977, 1980; Hoernes et al., 1978; Friedrichsen and Hoernes, 1980). It is therefore of interest to determine whether Leg 65 crust, which is only 0.5 to 1.5 m.y. old, has experienced a similar degree of alteration.