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.

Pore water chemistry of sediment core GeoB15101-7 and water chemistry of CTD casts GeoB15101-1 and GeoB15101-6

Submarine brine lakes feature sharp and persistent concentration gradients between seawater and brine, though these should be smoothed out by free diffusion in open ocean settings. The anoxic Urania basin of the Eastern Mediterranean contains an ultra sulfidic, hypersaline brine of Messinian origin above a thick layer of suspended sediments. With a dual modeling approach we reconstruct its contemporary stratification by geochemical solute transport fundamentals, and show that thermal convection is required to maintain mixing in the brine and mud layer. The origin of the Urania basin stratification was dated to 1650 years before present, which may be linked to a major earthquake in the region. The persistence of the chemoclines may be key to the development of diverse and specialized microbial communities. Ongoing thermal convection in the fluid mud layer may have important, yet unresolved consequences for sedimentological and geochemical processes, also in similar environments.

Pore-water chemistry of ODP sites 111-677 and 111-678

Sites 677 and 678 were drilled on ODP Leg 111 to test hypotheses about the nature and pattern of hydrothermal circulation on a mid-ocean ridge flank. Together with earlier results from DSDP Site 501/504 and several heatflow and piston coring surveys covering a 100-km**2 area surrounding the three drill sites, they confirm that hydrothermal circulation persists in this 5.9-m.y.-old crust, both in basement and through the overlying sediments (Langseth et al., 1988, doi:10.2973/odp.proc.ir.111.102.1988). Profiles of sediment pore-water composition with depth at the three drill sites show both vertical and horizontal gradients. The shapes of the profiles and their variation from one site to another result from a combination of vertical and horizontal diffusion, convection, and reaction in the sediments and basement. Chemical species that are highly reactive in the siliceous-calcareous biogenic sediments include bicarbonate (alkalinity), ammonium, sulfate, manganese, calcium, strontium, lithium, silica, and possibly potassium. Reactions include bacterial sulfate reduction, mobilization of Mn2+, precipitation of CaCO3, and recrystallization of calcareous and siliceous oozes to chalk, limestone, and chert. Species with profiles more affected by reaction in basaltic basement than in the sediments include Mg, Ca, Na, K, and oxygen isotopes. Reaction in basement at 60?C and at higher temperatures has produced a highly altered basement formation water that is uniform in composition over distances of several kilometers. As inferred from the composition of the basal sediment pore water at the three sites, this uniformity extends from up flow zone to downflow zone in basement and the sediments. It exists in spite of large variations in heat flow and depth to basement, apparently as a result of homogenization by hydrothermal circulation in basement. Profiles for chlorinity, Na, Mg, and other species in the sediment pore waters confirm that Site 678, drilled on a localized heatflow high identified by Langseth et al. (1988), is a site of long-lived upwelling of warm water from basement through the sediments at velocities of 1 to 2 mm/yr. The upflow through the anomalously thin sediments is apparently localized above an uplifted fault block in basement. This site and other similar sites in the survey area give rise to lateral diffusion and possibly flow through the sediments, which produces lateral gradients in sediment pore-water composition at sites such as 501/504. The complementary pore-water profiles at the low-heatflow Site 677 2 km to the south indicate that downflow is occurring through the sediments there, at comparable rates of 1 to 2 mm/yr.

Sediment and pore water chemistry and physical oceanography of samples obtained during Baltic Sea research cruises

Sediment samples from approximately 40 stations in the Western, middle and eastern Baltic Sea were investigated for manganese and iron content. In a series of interstitial water samples and numerous deep and surface water samples, the manganese content was likewise determined. A strong enrichment of these elements in the basin sediments was shown. In many instances, several percent manganese were present. As a maximum value, 13% was found in a 1 mm thick layer. Furthermore, a distinct decrease in manganese content with increasing sediment depth was shown in the upper 10 to 20 cm of the Sediment at almost all stations. Both phenomena may be explained by the release of manganese from the Sediment through diffusion. In the flat parts of the Baltic and those parts having good bottom water circulation, this diffusion progresses especially vigorously as a result of a steep gradient of the Mn++ concentration in the interstitial water-deep water interface. The manganese which hereby passes into the water overlying the bottom (manganese contents between 10 and 100 y Mn/l were determined in numerous deep water samples) is partly reprecipitated on the Sediment surface, and partly carried by currents into the deeper basins where it is finallv deposited. It is bound there as a manganese-rich mixed carbonate, the composition of which can be proved chemically and by x-ray methods. Iron is likewise of higher content in the basinal sediments, however, the extent of its enrichment is far less since it is less soluble than manganese under the reducing conditions in the sediments. The fine bands of manganese- and iron-rich layers in the basin sediments may likewise be explained as a result of diffusion.

Diffusion transport of water in basalts

Studying diffusive transport in porous rocks is of fundamental importance in understanding a variety of geochemical processes including: element transfer, primary mineral dissolution kinetics and precipitation of secondary phases. Here we report new findings on the relationship between diffusive transport and textural characteristics of the pore systems on the example of mid-oceanic ridge basalts having different degree of alteration but very similar bulk pore volume. Diffusion processes in porous basalts were studied in situ using H2O -> D2O exchange experiments. The effective diffusion coefficients of water molecules increase systematically from 5.05*10**-11 to 1.19*10**-10 m**2/s for fresh and moderately altered basalts and from 2.40*10**-11 to 6.72*10**-11 m**2/s for completely altered basalt as temperature increases from 5 to 50 °C. The activation energy of the diffusion process increases from 12.29 ± 0.71 kJ/mol for fresh and moderately altered basalts to 14.3 ± 1.33 kJ/mol for completely altered basalt. The results indicate that neither the bulk porosity nor the degree of alteration can be used as proxies for the efficiency of element transport during MORB-water interaction. The formation of secondary phases that replace primary minerals and fill the pore space in the rock leads to the formation of tiny pores and phases with large specific surface area. These factors might have a dominant control on the transport properties of altered basaltic rocks.

Rare earth and trace elements in igneous and metamorphic minerals of oceanic gabbros from the Mid-Atlantic Ridge

SIMS analyses have been carried out on clinopyroxenes, plagioclases and amphiboles of six gabbroic samples from Holes 921-924 of the Ocean Drilling Program Leg 153 sited in the MARK area of the Mid-Atlantic Ridge at the ridge-transform intersection, to investigate the rare earth, trace and volatile element distribution in the lower ocean crust during igneous crystallization and higher grade metamorphic conditions. The metagabbros underwent granulite to subgreenschist facies conditions through three main tectono-metamorphic phases: (1) ductile regime (750 < T < 1000 °C and P = 0.3 GPa); (2) transitional regime (600 < T < 700 °C and P = 0.2 GPa); (3) brittle regime (350 < T < 600 °C and P < 0.2 GPa). Igneous clinopyroxenes show Cl-chondrite normalized patterns depleted in LREE, and nearly flat for HREE. The rare earth and trace element distributions in igneous clinopyroxenes and plagioclases indicate that these minerals act as REE reservoirs, and comprise the main contribution to the overall rock content. The abundances in igneous minerals reflect the degree of fractionation of the parent liquids. In metamorphic clinopyroxenes recrystallized in anhydrous assemblages, the REE and trace elements patterns mimic those of the primary ones. Conversely, clinopyroxerie re-equilibrated in amphibolebearing assemblages shows a significant increase in REE, Ti, Zr, Y and V, a negative Eu anomaly, and slight decreases in Sr and Ba. An overall increase of REE and some trace elements is evident in hydrous assemblages, with preferential partitioning in the amphibole. It shows high Ti (18196-22844 ppm), LREE depleted patterns and LaN/SmN = 0.10-0.33, LaN/YbN = 0.10-0.30. Amphiboles from granoblastic assemblages show homogeneous patterns with no or a positive anomaly for TiN and negative anomalies for SrN and ZrN. Volatiles in amphibole are low, with Cl/F < 1; H2O% is significantly lower than the stoichiometric ratio (1.33-1.53%). The composition of the clinopyroxene and amphibole recrystallized in low-strain domains records evidence of incomplete re-equilibration, and element diffusion and partitioning is in part controlled by the textural site. The possible origins of the fluids involved in the metamorphic recrystallization are discussed: (1) remobilization from igneous amphibole; (2) exsolution from evolved melts; (3) introduction of seawater-derived fluids modified in rock-dominated systems; (4) injection of highly evolved hydrous melts during the metamorphic process.