Isotopic composition of interstitial fluids in sediment at DSDP Sites 87-582 and 87-583

The isotopic compositions of dissolved CO2 and CH4 in sediments of the Nankai Trough indicate that CH4 is formed during early diagenesis by microbial reduction of CO2. At the shallowest sampled depths, the CO2 dissolved in the pore water is unusually enriched in 12C (d13C = -35.2 per mil), indicating contribution of CO2 from oxidation of CH4. The most intense microbiological activity appears to be confined to the uppermost 50 m of sediment, based on relative lack of change in the isotopic compositions below this depth. Gas hydrate probably is not present at these localities (Sites 582, 583) because of CH4 concentrations that are insufficient to saturate the pore water with respect to gas hydrate stability.

Geochemistry and physics on sediment cores from the Peru Basin

We studied preservation/dissolution cycles and paleoproductivity in eight sediment cores from the Peru Basin south of the highly productive surface waters of the eastern equatorial Pacific. Stratigraphy is based on stable oxygen isotopes and on combined magnetostratigraphy and biostratigraphy. Sediment cores which span the last 8 m.y., were retrieved during cruise 79 with RV SONNE close to the carbonate compensation depth (CCD). In general, sediments show Pacific-type carbonate cycles. We interpret a pronounced carbonate peak between 6 and 7 Ma as the result of a western and northern extension of the highly productive Peru Current. Decreased carbonate contents from the late Miocene to the late Pliocene might be associated with a slow contraction of the latitudinal extent of the high-productivity belt north of the study areas. During the Pliocene, carbonate variations showed 400 kyr cycles indicating the growth and decay of ice sheets, which should have been associated with pulsations of the Antarctic ice cap. An abrupt collapse of the carbonate system occurred at 2.4 Ma. Higher frequency variations of the carbonate record indicate the major increase of the northern hemisphere glaciation. During the Quaternary, carbonate fluxes are high during glacials and low during interglacials. Large amplitude variations with long broad minima and maxima, associated with small migrations of the lysocline and the CCD (< 200 m), are indicative of the preservation/dissolution history in the Peru Basin. During the early Pleistocene, climatic forcing by the 41 kyr obliquity cycle is not observed in the carbonate record. During the last 800 kyr, variability in the carbonate record was dominated by the 100 kyr eccentricity cycle. Fluxes of biogenic material (calcium carbonate, organic carbon, opal, and barium) were greatest during glacials, which imply higher productivity and export production of the Peru Current during cold climatic periods. Dissolution was greatest during interglacials as inferred from the relatively poor preservation of planktonic foraminifera and from the low accumulation rate of carbonate. After the Mid-Brunhes Event (400 ka), we observe a plateaulike shift to enhanced dissolution and to intensified productivity.

Characterization of diagenetic fluids at ODP Site 103-639

Site 639, drilled during Leg 103 of the Ocean Drilling Program, penetrated an Upper Jurassic to Lower Cretaceous carbonate platform on a tilted fault block along the Galicia margin off the northwest Iberian Peninsula. The carbonate platform is composed primarily of a sequence of dolomite overlying limestone. Samples were analyzed for mineral chemistry, stable isotope geochemistry, fluid inclusion microthermometry, and volatile contents and by dolomite pyrolysis mass spectrometry for trace sulfate minerals. The dolomite recovered from the Galicia margin at Site 639 formed during shallow burial from sulfate-bearing, hypersaline brines at slightly elevated temperatures. The light oxygen isotopic signatures of the dolomite are interpreted as the result of the evaporative loop and slightly elevated temperatures during dolomite formation or from reequilibration at higher temperatures during deeper burial. The hypersalinity is interpreted to be associated with a nearby, shallow restricted basin that formed during rifting of the Iberian margin from Newfoundland. The dolomitization of the platform is therefore a by-product of the rifting.

Isotopic composition of interstitial fluids and origin of methane at DSDP Leg 84 Holes

CH4 and CO2 species in pore fluids from slope sediments off Guatemala show extreme 13C-enrichment (d13C of -41 and +38 per mil, respectively) compared with the typical degree of 13C-enrichment in pore fluids of DSDP sediments (d13C of - 60 and + 10 per mil). These unusual isotopic compositions are believed to result from microbial decomposition of organic matter, and possibly from additional isotopic fractionation associated with the formation of gas hydrates. In addition to the isotopic fractionation displayed by CH4 and CO2, the pore water exhibits a systematic increase in d18O with decrease in chlorinity. As against seawater d18O values of 0 and chlorinity of 19 per mil, the water collected from decomposed gas hydrate from Hole 570 had a d18O of + 3.0 per mil and chlorinity of 9.5 per mil. The isotopic compositions of pore-fluid constituents change gradually with depth in Hole 568 and discontinuously with depth in Hole 570.

Chemistry and age determination of basement fluids from Juan de Fuca Ridge

The geochemical implications of thermally driven flow of seawater through oceanic crust on the mid-ocean ridge flank have been examined on a well-studied 80 km transect across the eastern flank of the Juan de Fuca Ridge at 48°N, using porewater and basement fluid samples obtained on ODP Leg 168. Fluid flow is recognised by near-basement reversals in porewater concentration gradients from altered values in the sediment section to seawater-like values in basaltic basement. In general, the basement fluids become more geochemically evolved with distance from the ridge and broadly follow basement temperature which ranges from not, vert, similar16° to 63°C. Although thermal effects of advective heat exchange are only seen within 20 km east of where basement is exposed near the ridge crest, chemical reactivity extends to all sites. Seawater passing through oceanic crust has reacted with basement rocks leading to increases in Ca2+ and decreases in alkalinity, Mg2+, Na+, K+, SO42- and delta18O. Sr isotope exchange between seawater and oceanic crust off axis is unequivocally demonstrated with endmember 87Sr/86Sr ~ 0.707. Evidence of more evolved fluids is seen at sites where rapid upwelling of fluids through sediments occurs. Chlorinities of the basement fluids are consistent with post-glacial seawater and thus a short residence time in the crust. Rates of lateral flow have been by estimated by modelling porewater sulphate gradients, using Cl as a glacial chronometer, and from radiocarbon dating of basal fluids. All three methods reveal fluid flow with 14C ages less than 10,000 yr and particle velocities of ~1-5 m/yr, in agreement with thermally constrained volumetric flow rates through a ~600 m thick permeable layer of ~10% porosity. Delta(element)/Delta(heat) extraction ratios are similar to values for ridge-crest hydrothermal systems.

Geochemical and isotopic composition of pore fluids of ODP Hole 131-808C

At the Western Nankai Trough subduction zone at ODP Site 808, chemical concentration and isotopic ratio depth profiles of D, O, Sr, and He do not support fluid flow along the décollement nor at the frontal thrust. They do, however, support continuous or periodic lateral fluid flow: (1) at the base of the Shikoku Basin volcanic-rich sediment member, situated ~140 m above the décollement, and particularly (2) below the décollement. The latter must have been rather vigorous, as it was capable of transporting clay minerals over great distances. The fluid at ~140 m above the décollement is characterized by lower than seawater concentrations of Cl- (>=18% seawater dilution). It is 18O-rich and D-poor and has a non-radiogenic, oceanic, or volcanic arc Sr isotopic signature. It originates from "volcanic" clay diagenesis. The fluid below the décollement has also less Cl- than seawater (>20% dilution), is more enriched in 18O and depleted in D than fluid, but its Sr isotopic signature is radiogenic, continentalterrigenous. The source of this fluid is located arcward, is deep-seated, where illitization of the subducted clay minerals, a mixture of terrigenous and volcanic clays, occurs. The 3He/4He ratio below the décollement points to an ~25% mantle contribution. The nature of the physical and chemical discontinuities across the décollement suggests it is overpressured and is forming a leaky "dynamic seal" for fluid flow. In contrast with the situation at Barbados and Peru, where the major tectonic features are mineralized, here, although the complex is extremely fractured and faulted, mineralized macroscopic veins, fractures, and faults are absent. Instead, mineralized microstructures are widespread, indicating a diffuse mode of dewatering.

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.

Sulfur isotope composition of pore fluids at ODP Sites 128-798 and 128-799

Micro-crystalline barites recovered by deep-sea drilling from Site 684 on the Peru margin and Site 799 in the Japan Sea are highly enriched in the heavy sulfur isotope relative to seawater ( d34S up to +84?). This isotopic composition is consistent with remobilization of biogenic barite triggered by sulfate reduction, and subsequent reprecipitation as a diagenetic barite front. The high levels of barium sulfate in these deposits (10-50%) cannot be explained by a diffusive transport model in sediments experiencing a constant rate of sedimentation. When sedimentation rates change radically, the barite front will remain at a given depth interval leading to large accumulations of barium sulfate. Such conditions may have generated the barite deposits at Site 799. At Site 684, on the other hand, there is evidence that the barite deposits are a result of the tectonically-driven advection of sulfate-bearing fluids through the sediment column.

Iodine and boron concentrations in pore fluids, ultramafic clasts and interstitial serpentinite mud of ODP Hole 125-779A and Site 195-1200

Iodine and boron were analyzed in pore fluids, serpentinized ultramafic clasts, and the serpentinized mud matrix of the South Chamorro Seamount mud volcano (Ocean Drilling Program Leg 195 Site 1200) to determine the distribution of these elements in deep forearc settings. Similar analyses of clasts and muds from the Conical Seamount mud volcano (Leg 125 Site 779) were also carried out. Interstitial pore fluids are enriched in boron and iodine without appreciable change in chloride concentration relative to seawater. Both the ultramafic clasts and the associated serpentinized mud present the highest documented iodine concentrations for all types of nonsedimentary rocks (6.3-101.7 µmol/kg). Such high iodine concentrations, if commonplace in marine forearc settings, may constitute a significant, previously unknown reservoir of iodine. This serpentinized forearc mantle reservoir may potentially contribute to the total crustal iodine budget and provide a mechanism for its recycling at convergent plate margins. Both clasts and mud show concurrent enrichments in boron and iodine, and the similarity in pore fluid profiles also suggests that these two incompatible, fluid-mobile elements behave similarly at convergent plate margins.