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.

Geochemistry of pore fluids and bulk solids of ODP Site 195-1200, South Chamorro Seamount

At the South Chamorro Seamount in the Mariana subduction zone, geochemical data of pore fluids recovered from Ocean Drilling Program Leg 195 Site 1200 indicate that these fluids evolved from dehydration of the underthrusting Pacific plate and upwelling of fluids to the surface through serpentinite mud volcanoes as cold springs at their summits. Physical conditions of the fluid source at 27 km were inferred to be at 100°-250°C and 0.8 GPa. The upwelling of fluid is more active near the spring in Holes 1200E and 1200A and becomes less so with increasing distance toward Hole 1200D. These pore fluids are depleted in Cl and Br, enriched in F (except in Hole 1200D) and B (up to 3500 µM), have low 11B (16-21), and have lower than seawater Br/Cl ratios. The mixing ratios between seawater and pore fluids is calculated to be ~2:1 at shallow depth. The F, Cl, and Br concentrations, together with B concentrations and B isotope ratios in the serpentinized igneous rocks and serpentine muds that include ultramafic clasts from Holes 1200A, 1200B, 1200D, 1200E, and 1200F, support the conclusion that the fluids involved in serpentinization originated from great depths; the dehydration of sediments and altered basalt at the top of the subducting Pacific plate released Cl, H2O, and B with enriched 10B. Calculation from B concentrations and upwelling rates indicate that B is efficiently recycled through this nonaccretionary subduction zone, as through others, and may contribute the critical missing B of the oceanic cycle.

Lithium sources in pore fluids of Peru slope

High Li concentrations, up to a maximum of 1155 µM are observed in the pore fluids of the Peru convergent margin slope sediments. At Ocean Drilling Program Sites 683 and 685 (ca. 9°S), the Li concentration depth gradients are twice as steep as at Site 682 and 688 (ca. 11°S). Within the sediments, the most important Li sources are from aluminosilicate minerals. Biogenic opal-A contains little Li and thus dilutes the Li concentration of the bulk sediments. The sediment compositions and the thermal regimes are similar at 9° and 11°S, suggesting there is an additional, non-sedimentary source for the observed high Li concentrations in the northern pore fluids. At 9°S, the 87Sr/86Sr ratios reach a maximum value of 0.709958. The observed radiogenic 87Sr/86Sr values in the pore fluids support the suggestion that the additional Li may derive from exchange reactions with underlying continental crust. The high concentrations of Li at 11°S may derive from basalt alteration at moderate to high temperatures, as suggested by the non-radiogenic 87Sr/86Sr ratios in these pore fluids, which reach a minimum value of 0.707218. Based on (1) Li concentrations in the pore fluids in slope sediments from Peru and several other margins, and (2) an approximate estimate of fluid flux from continental margins into the ocean, continental margins provide an estimated 1 to 3 * 10**10 moles Li/yr to the ocean. This source of oceanic Li, which has not been considered previously, is of the same order of magnitude as some estimates of hydrothermal and river Li fluxes and may have important consequences for the oceanic Li isotope budget. The sink is unknown for this newly discovered and possibly large Li source, but it may be more pervasive low-temperature alteration of oceanic basement than previously estimated, or burial of mineral phases, such as authigenic clay minerals, or metal oxyhydroxides which may be Li-rich.

Bromine and iodine concentrations in sediments and pore fluids of ODP Leg 112

At the Peruvian convergent margin, two distinct pore fluid regimes are recognized from differences in their Cl- concentrations. The slope pore fluids are characterized by low Cl- concentrations, but elevated Br- and I- concentrations due to biogenic production. The shelf pore fluids exhibit elevated Cl- and Br- concentrations due to diffusive mixing with an evaporitic brine. In the slope pore fluids, the Br-, I-, and NH4+ concentrations are elevated following bacterial decomposition of organic matter, but the I- concentrations are in excess of those expected based on mass balance calculations using NH4+ and Br- concentrations. The slope sediment organic matter, which is enriched in iodine from oxidationreduction processes at the oxygenated sediment-water interface, is responsible for this enrichment. The increases in dissolved I- and the I- enrichments relative to NH4+ and Br- correlate well with sedimentation rates because of differential trapping following regeneration. The pore-fluid I-/Br- ratios suggest that membrane ion fiitration is not a major cause of the decreases in Cl- concentrations. Other possible sources for low Cl- water, including meteoric water, clathrate dissociation, and/or mineral dehydration reactions, imply that the diluting component of the slope low-Cl- fluids has flowed at least 1 km through the sediment. The low bottom-water oxygenation in the shelf is responsible for the low (if any) enrichment of iodine in the shelf sediments. Fluctuations in bottom-water oxygen concentrations in the past, however, may be responsible for the observed variations in the sediment I/Br ratios. Comparison of Na+/Cl- and Br-/Cl- molar ratios in the pore fluids shows that the shelf high-Cl- fluid formed from mixing with a brine that formed from seawater concentrated by twelve to nineteen times and probably was modified by halite dissolution. This dense brine, located below the sediment sections drilled, appears to have flowed a distance >500 km through the sediment.