Chemical and isotopic compositions and age of carbonates from the Lost City hydrothermal field, Mid-Atlantic Ridge

Two genetically different types of authigenic carbonate mounds are studied: (1) from an active hydrothermal field related to serpentinite protrusions in a zone of intersection of a transform fracture zone with the Mid-Atlantic Ridge, (2) from an active field of methane seepings in the Dnieper canyon of the Black sea. General geochemical conditions, under which authigenic carbonate formation occurs within these two fields, were found. They include: presence of reduced H2S, H2, and CH4 gases at absence of free oxygen; high alkalinity of waters participating in carbonate formation; similarity of textural and structural features of authigenic aragonite, which represents the initial carbonate mineral of the mounds; paragenesis of aragonite with sulfide minerals; close relation of carbonate mounds with communities of sulfate-reducing and methane-oxidizing microorganisms. A new mechanism of formation of hydrothermal authigenic carbonates is suggested. It implies their microbial sulfate reduction over hydrogen from fluid in the subsurface mixing zone of hydrothermal solution and adjacent seawater.

Oxygen, hydrogen, and carbon isotopic compositions in deep sea cherts, porcellanites, and coexisting carbonates from DSDP Legs 2, 3, 6, 7, 11, 14, 16, 17, and 20

Seventy four samples of DSDP recovered cherts of Jurassic to Miocene age from varying locations, and 27 samples of on-land exposed cherts were analyzed for the isotopic composition of their oxygen and hydrogen. These studies were accompanied by mineralogical analyses and some isotopic analyses of the coexisting carbonates. d18O of chert ranges between 27 and 39%. relative to SMOW, d18O of porcellanite - between 30 and 42%. The consistent enrichment of opal-CT in porcellanites in 18O with respect to coexisting microcrystalline quartz in chert is probably a reflection of a different temperature (depth) of diagenesis of the two phases. d18O of deep sea cherts generally decrease with increasing age, indicating an overall cpoling of the ocean bottom during the last 150 m.y. A comparison of this trend with that recorded by benthonic foraminifera (Douglas and Savin, 1975; http://www.deepseadrilling.org/32/volume/dsdp32_15.pdf) indicates the possibility of d18O in deep sea cherts not being frozen in until several tens of millions of years after deposition. Cherts of any Age show a spread of d18O values, increasing diagenesis being reflected in a lowering of d18O. Drusy quartz has the lowest d18O values. On-land exposed cherts are consistently depleted in 18O in comparison to their deep sea time equivalent cherts. Water extracted from deep sea cherts ranges between 0.5 and 1.4 wt %. dD of this water ranges between -78 and -95%. and is not a function of d18O of the cherts (or the temperature of their formation).

Chemical and Sr isotopic compositions of pore fluids and marine carbonates from ODP Hole 130-807A

The 87Sr/86Sr ratios and Sr concentrations in sediment and pore fluids are used to evaluate the rates of calcite recrystallization at ODP Site 807A on the Ontong Java Plateau, an 800-meter thick section of carbonate ooze and chalk. A numerical model is used to evaluate the pore fluid chemistry and Sr isotopes in an accumulating section. The deduced calcite recrystallization rate is 2% per million years (%/Myr) near the top of the section and decreases systematically in older parts of the section such that the rate is close to 0.1/age (in years). The deduced recrystallization rates have important implications for the interpretation of Ca and Mg concentration profiles in the pore fluids. The effect of calcite recrystallization on pore fluid chemistry is described by the reaction length, L, which varies by element, and depends on the concentration in pore fluid and solid. When L is small compared to the thickness of the sedimentary section, the pore fluid concentration is controlled by equilibrium or steady-state exchange with the solid phase, except within a distance L of the sediment-water interface. When L is large relative to the thickness of sediment, the pore fluid concentration is mostly controlled by the boundary conditions and diffusion. The values of L for Ca, Sr, and Mg are of order 15, 150, and 1500 meters, respectively. L_Sr is derived from isotopic data and modeling, and allows us to infer the values of L_Ca and L_Mg. The small value for L_Ca indicates that pore fluid Ca concentrations, which gradually increase down section, must be equilibrium values that are maintained by solution-precipitation exchange with calcite and do not reflect Ca sources within or below the sediment column. The pore fluid Ca measurements and measured alkalinity allow us to calculate the in situ pH in the pore fluids, which decreases from 7.6 near the sediment-water interface to 7.1+/-0.1 at 400-800 mbsf. While the calculated pH values are in agreement with some of the values measured during ODP Leg 130, most of the measurements are artifacts. The large value for L_Mg indicates that the pore fluid Mg concentrations at 807A are not controlled by calcite-fluid equilibrium but instead are determined by the changing Mg concentration of seawater during deposition, modified by aqueous diffusion in the pore fluids. We use the pore fluid Mg concentration profile at Site 807A to retrieve a global record for seawater Mg over the past 35 Myr, which shows that seawater Mg has increased rapidly over the past 10 Myr, rather than gradually over the past 60 Myr. This observation suggests that the Cenozoic rise in seawater Mg is controlled by continental weathering inputs rather than by exchange with oceanic crust. The relationship determined between reaction rate and age in silicates and carbonates is strikingly similar, which suggests that reaction affinity is not the primary determinant of silicate dissolution rates in nature.