Stable and radiogenic isotope ratios in pore waters from ODP Leg 127 sites

Interstitial waters from four sites of the Japan Sea (794 to 797) have been analyzed for stable isotopes (delta D, delta11B, delta18O, and delta34S) and 87Sr/86Sr, besides major and minor ions. The isotopic composition is dominated by organic matter degradation, alteration of ash layers and volcaniclastic sands, silica transformation (opal A/CT), and basement alteration. Organic matter degradation and corresponding sulfate reduction leads to 32S depletion and is dependent upon sedimentation rate. The remaining sulfate reservoir is characterized by very "heavy" delta34S ratios, up to +93 ? (rel. CDT = Canyon Diabolo Troilite). "Barite fronts," which may develop in such sediments, should also be characterized by very "heavy" sulfur isotopes. The alteration of volcaniclastic material in the Quaternary sections influences the delta18O (-1.5 ? shift) and delta11B (desorption and later adsorption of "labile"11B). A pronounced positive delta11B anomaly at Site 795 represents the depth range of preferential 10B uptake by alteration products of the ash layers. At Site 796 delta D, delta11B, and 87Sr/86Sr are severely affected by alteration processes of volcaniclastic sands. The opal A/CT transformation may influence the oxygen isotopes and serves as a potential source for B, which is liberated at this interval at Site 795. This positive B anomaly is not reflected in the delta11B profile. Basement alteration processes dominate the sedimentary sequence below the opal A/CT transition, which serves as a chemical and physical boundary. The decreases in delta D and delta18O are probably related to a "paleo ocean water reservoir" situated in the permeable Layer II of the oceanic crust, as is indicated by the positive correlation between these two parameters. Besides Mg, alkalies and delta18O basement rocks also serve as a sink for 11 B (Site 795) and are the source for the Ca and Sr increases, as is documented by the less radiogenic 87Sr/86Sr ratio. 87Sr/86Sr ratios for the lowermost pore waters from Site 795 (0.70529) are comparable to those from volcaniclastic rocks from the "Green Tuff' region (0.704 to 0.706) and oil field brines from the Niigata Oil Field.

Composition and age of ores and bottom sediments accumulated within and near the Rainbow hydrothermal field

Results of direct geological and geochemical observations of the modern Rainbow hydrothermal field (Mid-Atlantic Ridge, 36°14'N; 33°54'W) carried out from the deep-sea manned Mir submersibles during Cruises 41 and 42 of the R/V Akademik Mstislav Keldysh in 1998-1999 and data of laboratory studies of collected samples are under consideration in the paper. The field lacks neovolcanic rocks and the axial part of the rift is filled in with a serpentinite protrusion. In this field there occur metalliferous sediments, as well as active and relict sulfide edifices composed of sulfide minerals; pyrrhotite, chalcopyrite, isocubanite, sphalerite, marcasite, pyrite, bornite, chalcosine, digenite, magnetite, anhydrite, rare troilite, wurtzite, millerite, and pentlandite have been determined. Sulfide ores are characterized by concentric-zoned textures. During in situ measurements during 35 minutes temperature of hydrothermal fluids was varying within a range from 250 to 350°C. Calculated chemical and isotopic composition of hydrothermal fluid shows elevated concentrations of Cl, Ni, Co, CH4, and H2. Values of d34S of H2S range from +2.4 to +3.1 per mil, of d13C of CH4 from -15.2 to -11.2 per mil, and d13C of CO2 from +1.0 to -4.0 per mil. Fluid inclusions are homogenized at temperatures from 140 to 360°C, whereas salinity of the fluid varies from 4.2 to 8.5 wt %. d34S values of sulfides range from +1.3 to +12.5 per mil. 3He/4He ratio in mineral-forming fluid contained in the fluid inclusions from sulfides of the Rainbow field varies from 0.00000374 to 0.0000101. It is shown that hydrothermal activity in the area continues approximately during 100 ka. It is assumed that the fluid and sulfide edifices contain components from the upper mantle. A hypothesis of phase separation of a supercritical fluid that results in formation of brines is proposed. Hydrothermal activity is related to the tectonic, not volcanic, phase of the Mid-Atlantic Ridge evolution.

Boron contents and boron, carbon, and oxygen isotope data for ODP Sites 160-970 and 160-971

Products of two mud volcanoes from the distal part of the Mediterranean Ridge accretionary complex have been investigated regarding their B, C, and O stable isotope signatures. The mud breccias have been divided into mud matrix, lithified clasts, biogenic deposits, and authigenic cements and crusts related to fluid flow and cementation. Isotope geochemistry is used to evaluate the depth of mobilization of each phase in the subduction zone. B contents and isotope ratios of the mud and mud clasts show a general trend of B enrichment and decreasing d11B values with increasing consolidation (i.e., depth). However, the majority of the clast and matrix samples relate to moderate depths of mobilization within the wedge (1-2 km below seafloor). The carbonate cements of most of these clasts as well as the authigenic crusts, however, provide evidence for a deep fluid influence, probably associated with the décollement at 5-6 km depth. This interpretation is supported by d13C ratios of the crust, which indicate precipitation of C from thermogenic methane, and by the d11B ratios of pore-water samples of mud-breccia drill cores. Clams (Vesicomya sp.) living adjacent to fluid vents have d11B and d18O values corresponding to brines known in the area, which acted as the parent solution for shell precipitation. Such brines are most likely Miocene pore waters trapped at deep levels within the backstop to the accretionary prism, probably prior to desiccation of the Mediterranean in the Messinian (6-5 Ma). Combining all results, deep fluid circulation and expulsion are identified as the main processes triggering mud liquefaction and extrusion, whereas brines contribute only locally. Given the high B contents, mud extrusion has to be considered a major backflux mechanism of B into the hydrosphere.

(Table 1) Nutrient concentrations and carbon isotopes of sea ice segments and brine sampled during Nathaniel B. Palmer cruises NBP98-07 and NBP06-08, Ross Sea

We examined controls on the carbon isotopic composition of sea ice brines and organic matter during cruises to the Ross Sea, Antarctica in November/December 1998 and November/December 2006. Brine samples were analyzed for salinity, nutrients, total dissolved inorganic carbon (sum CO2), and the 13C/12C ratio of Sum CO2 (d13C(sum CO2)). Particulate organic matter from sea ice cores was analyzed for percent particulate organic carbon (POC), percent total particulate nitrogen (TPN), and stable carbon isotopic composition (d13C(POC)). Sum CO2 in sea ice brines ranged from 1368 to 7149 µmol/kg, equivalent to 1483 to 2519 µmol/kg when normalized to 34.5 psu salinity (s sum CO2), the average salinity of Ross Sea surface waters. Sea ice primary producers removed up to 34% of the available sum CO2, an amount much higher than the maximum removal observed in sea ice free water. Carbonate precipitation and CO2 degassing may reduce s sum CO2 by a similar amount (e.g., 30%) in the most hypersaline sea ice environments, although brine volumes are low in very cold ice that supports these brines. Brine d13C(sum CO2) ranged from -2.6 to +8.0 per mil while d13C(POC) ranged from -30.5 to -9.2 per mil. Isotopic enrichment of the sum CO2 pool via net community production accounts for some but not all carbon isotopic enrichment of sea ice POC. Comparisons of s sum CO2, d13C(sum CO2), and d13C(POC) within sea ice suggest that epsilon p (the net photosynthetic fractionation factor) for sea ice algae is ~8 per mil smaller than the epsilon p observed for phytoplankton in open water regions of the Ross Sea. These results have implications for modeling of carbon uptake and transformation in the ice-covered ocean and for reconstruction of past sea ice extent based on stable isotopic composition of organic matter in sediment cores.

Sediment and pore water C and N composition of ODP Holes 201-1227A and 201-1230A

This study addresses the problem of diagenetic fractionation of d15N in sedimentary organic matter by constructing isotopic mass balances for the sedimentary nitrogen and pore water ammonium at two Ocean Drilling Program (ODP) sites, 1227 and 1230. At Site 1230, ammonium production flux integrated through the sedimentary column indicates that >60% of organic matter is lost to decomposition. The d15N of pore water ammonium is <0.7 per mil different from that of the sedimentary organic matter, which implies that very little isotopic fractionation is associated with degradation of organic matter at this site. The constant d15N of the solid-phase sedimentary nitrogen through the whole profile supports this conclusion. Atomic C/N ratios (9-12) indicate that organic matter at this site is primarily of marine origin. At Site 1227, the sedimentary organic matter appears to be a mixture of terrestrial and marine components. Ammonium is ~4 heavier than the organic matter. The observed isotopic enrichment of pore water ammonium relative to the sedimentary nitrogen might indicate either the preferential decomposition of isotopically heavier marine fraction of the organic matter, or possibly, a nonsteady-state condition of the ammonium concentration and d15N profiles. Interpretation of the results at Site 1227 is further complicated by the contribution of ammonium with d15N of ~4 per mil that is diffusing upward from Miocene brines.

Geochemistry on interstitial water of 5 sediment profiles from the Persian Gulf

The landward part of the 7 km wide sabkha at Umm Said, SE Qatar, is filled with a stagnant brine virtually saturated with halite. Recent dolomite occurs in the sabkha sediments, the quantity being fully accounted for by the amount of Mg++ ions lost from the interstitial brine. The existence of a reflux system in the seaward parts of the sabkha was established. It was not, however, possible to gi ve any unequivocal demonstration of the effect of this potential system for dolomitization . Although both a reflux mechanism and Recent dolomite formation occur in this tidal flat, the first process has apparently not influenced the second sufficiently to permit the demonstration of reflux dolomitization.

(Table 1) Porewater analysis with respect to gypsum from different ODP holes

The stability of gypsum in marine sediments has been investigated through the calculation of its saturation index at the sediment in situ temperature and pressure, using the entire ODP/IODP porewater composition database (14416 samples recovered from sediments collected during 95 ODP and IODP Legs). Saturation is reached in sediment porewaters of 26 boreholes drilled at 23 different sites, during 12 ODP/IODP Legs. As ocean bottom seawater is largely undersaturated with respect to gypsum, the porewater Ca content or its SO4 concentration, or both, must increase in order to reach equilibrium. At several sites equilibrium is reached either through the presence of evaporitic gypsum layers found in the sedimentary sequence, and/or through a salinity increase due to the presence of evaporitic brines with high concentrations of Ca and SO4. Saturation can also be reached in porewaters of seawater-like salinity (~ 35 per mil), provided sulfate reduction is limited. In this case, saturation is due to the alteration of volcanogenic material which releases large amounts of Ca to the porewaters, where the Ca concentration can reach 55 times its seawater value as for example at ODP Leg 134 site 833. At a few sites, saturation is reached in hydrothermal environments, or as a consequence of the alteration of the basaltic basement. In addition to the well known influence of brines on the formation of gypsum, these results indicate that the alteration of sediments rich in volcanogenic material is a major process leading to gypsum saturation in marine sediment porewaters. Therefore, the presence of gypsum in ancient and recent marine sediments should not be systematically interpreted as due to hypersaline waters, especially if volcanogenic material is present.