Chemical, and Sr and Li isotopic composition of pore fluids and sediments from ODP Leg 170 and Leg 205 sites

Pore fluid and sediment chemical and isotopic data were obtained for samples from Ocean Drilling Program (ODP) Leg 205 Sites 1253, 1254, and 1255 in the Costa Rica subduction zone. The chemical and isotopic data reported here were generated in our shore-based laboratories to complement shipboard inorganic geochemical data. Li isotopic analyses were carried out by L.-H. Chan at Louisiana State University (USA). The data reported herein include fluoride, bromide, rubidium, cesium, and barium concentrations; Li and Sr isotopic compositions in pore fluids; and Rb, Cs, and Ba concentrations in representative bulk sediments. The data also include new pore fluid fluoride and bromide concentrations from corresponding ODP Leg 170 Sites 1039, 1040, and 1043. O.M. Saether's Site 1039 and 1040 fluoride concentration data are shown for comparison. Basal sediment fluoride concentrations and Li and Sr isotope ratios at both Sites 1253 and 1039 show reversals that approach modern seawater values. Br/Cl ratios are, however, conservative throughout the sediment section at Sites 1039 and 1253. The observed sharp F and Br concentration maxima, Rb and K concentration minima, the most radiogenic 87Sr/86Sr ratios, and highest 7Li values along the décollement and fracture zone (Sites 1040, 1043, 1254, and 1255) strengthen the evidence obtained during Leg 170 that a deeply sourced fluid, originating from fluid-rock reactions at ~150°C and corresponding to between 10 and 15 km depth, is transporting solutes to the ocean.

Stable chlorine isotopes in pore waters from DSDP Hole 79-546 and ODP Hole 131-808C

Stable Cl isotope ratios, measured in marine pore waters associated with the Barbados and Nankai subduction zones, extend significantly (to ~-8 per mil) the range of d37Cl values reported for natural waters. These relatively large negative values, together with geologic and chemical evidence from Barbados and Nankai and recent laboratory data showing that hydrous silicate minerals (i.e., those with structural OH sites) are enriched up to 7.5 per mil in 37Cl relative to seawater, strongly suggest that the isotopic composition of Cl in pore waters from subduction zones reflects diagenetic and metamorphic dehydration and transformation reactions. These reactions involve clays and/or other hydrous silicate phases at depth in the fluid source regions. Chlorine therefore cannot be considered geochemically conservative in these systems. The uptake of Cl by hydrous phases provides a mechanism by which Cl can be cycled into the mantle through subduction zones. Thus, stable Cl isotopes should help in determining the extent to which Cl and companion excess volatiles like H2O and CO2 cycle between the crust and mantle.

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 isotopic composition of pore fluids and sediments in the Costa Rica subduction zone

Pore fluid and sediment Li concentrations and isotopic ratios provide important insights on the hydrology, sediment contribution to the arc volcanoes and fluid-sediment reactions at the dominantly non-accretionary Costa Rica subduction zone. Ocean Drilling Program Site 1039 in the trench axis provides a reference section of 400 m of the incoming sediments, and Site 1040, situated arcward from the trench, consists of a deformed sedimentary wedge and apron sediments, the décollement, and the partially dewatered underthrust sediment section. At the reference site, pore fluids show important isotopic variations (delta6Li=-21.7 to -37.8 per mil), reflecting the interplay of in situ alteration of volcanic material and ion exchange with clay minerals. In the basal section, a reversal of Li concentration and delta6Li toward seawater values is observed, providing supporting evidence for a lateral seawater flow system in the upper oceanic basement underlying this sediment section. At Site 1040, pore fluid of the lower deformed wedge sediments and within the décollement is enriched in Li and the isotopic compositions are relatively light, suggesting infiltration of a deep-seated fluid. The delta6Li value of -22 per mil of this Li-enriched fluid (261 µM), when compared with the delta6Li value of the subducted sediment section (-11 per mil), suggests that the deep source fluid originates from mineral fluid dehydration and transformation reactions at temperatures of 100 to 150°C, consistent with the temperature range of the up-dip seismogenic zone and of transformation of smectite to illite. The distribution of Li and its isotopes in the underthrust section are similar to those at the reference site, indicating near complete subduction of the incoming sediments and that early dewatering of the underthrust sediments occurs predominantly by lateral flow into the ocean. The hemipelagic clay-rich sediment section of the subducting plate carries most of the Li into this subduction zone, and the pelagic diatomaceous and nannofossil calcareous oozes contain little Li. The Li isotopes of both the clay-rich hemipelagic sediments and of the pelagic oozes are, however, similar, with delta6Li values of -9 to -12 per mil. The observations that (1) the delta6Li values of the underthrust sediments are distinctly lower than that of the mantle, and (2) the lavas of the Costa Rican volcanoes are enriched in Li and 7Li, provide an approximation of the contribution of the subducted sediments to the arc volcanoes. A first order mass balance calculation suggests that approximately half of the Li flux delivered by subducted sediments and altered oceanic crust into the Middle American Trench is recycled to the Costa Rican arc and at most a quarter of sedimentary Li is returned into the ocean through thrust faults, primarily the décollement thrust.

Calcium isotope ratios of pore fluids and solid phase of organic rich sediments

Pore fluid calcium isotope, calcium concentration and strontium concentration data are used to measure the rates of diagenetic dissolution and precipitation of calcite in deep-sea sediments containing abundant clay and organic material. This type of study of deep-sea sediment diagenesis provides unique information about the ultra-slow chemical reactions that occur in natural marine sediments that affect global geochemical cycles and the preservation of paleo-environmental information in carbonate fossils. For this study, calcium isotope ratios (d44/40Ca) of pore fluid calcium from Ocean Drilling Program (ODP) Sites 984 (North Atlantic) and 1082 (off the coast of West Africa) were measured to augment available pore fluid measurements of calcium and strontium concentration. Both study sites have high sedimentation rates and support quantitative sulfate reduction, methanogenesis and anaerobic methane oxidation. The pattern of change of d44/40Ca of pore fluid calcium versus depth at Sites 984 and 1082 differs markedly from that of previously studied deep-sea Sites like 590B and 807, which are composed of nearly pure carbonate sediment. In the 984 and 1082 pore fluids, d44/40Ca remains elevated near seawater values deep in the sediments, rather than shifting rapidly toward the d44/40Ca of carbonate solids. This observation indicates that the rate of calcite dissolution is far lower than at previously studied carbonate-rich sites. The data are fit using a numerical model, as well as more approximate analytical models, to estimate the rates of carbonate dissolution and precipitation and the relationship of these rates to the abundance of clay and organic material. Our models give mutually consistent results and indicate that calcite dissolution rates at Sites 984 and 1082 are roughly two orders of magnitude lower than at previously studied carbonate-rich sites, and the rate correlates with the abundance of clay. Our calculated rates are conservative for these sites (the actual rates could be significantly slower) because other processes that impact the calcium isotope composition of sedimentary pore fluid have not been included. The results provide direct geochemical evidence for the anecdotal observation that the best-preserved carbonate fossils are often found in clay or organic-rich sedimentary horizons. The results also suggest that the presence of clay minerals has a strong passivating effect on the surfaces of biogenic carbonate minerals, slowing dissolution dramatically even in relation to the already-slow rates typical of carbonate-rich sediments.

(Table 1) Geochemical and geothermometry data from fibrous calcite vein fills in the Dabashan Fold Belt, China

Fibrous calcite veins with organic inclusions have been widely considered as indicators of oil and gas generation and migration under overpressure. Abundant fibrous calcite veins containing organic-bearing inclusions occur in faulted Lower Paleozoic through Triassic hydrocarbon source rocks in the Dabashan Foreland Belt (DBF). d13CPDB and d18OPDB values of the fibrous calcite range from - 4.8 to -1.9 to per mil and - 12.8 to - 8.4 per mil respectively, which is lighter than that of associated carbonate host rocks ranging from - 1.7 to + 3.1 per mil and - 8.7 to - 4.5 per mil. A linear relationship between d13CPDB and d18OPDB indicates that the calcite veins were precipitated from a mixture of basinal and surface fluids. The fibrous calcite contains a variety of inclusions, such as solid bitumen, methane bearing all-liquid inclusions, and vapor-liquid aqueous inclusions. Homogenization temperatures of aqueous inclusions range from 140 to 196° with an average of 179°. Salinities of aqueous inclusions average 9.7 wt% NaCl. Independent temperatures from bitumen reflectance and inclusion phase relationships of aqueous and methane inclusions were used to determine fluid pressures. Results indicate high pressures, elevated above typical lithostatic confining pressure, from 150 to 200 MPa. The elevated salinity and high temperature and pressure conditions of the fibrous calcite veins argue against an origin solely from burial overpressure resulting from clay transformation and dehydration reactions. Instead fluid inclusion P-T data and geochemistry results and regional geology indicate abnormally high pressures during fluid migration. These findings indicate that tectonic stress generated fracture and fault fluid pathways and caused migration of organic bearing fluids from the DBF during the Yanshan orogeny.

(Table T1) Fluid inclusions in siltstone and sandstone grains from ODP Hole 210-1276A

Twenty samples of siltstones and sandstones were taken from Ocean Drilling Program Site 1276 during Leg 210 for fluid inclusion studies. With the exception of one sample of vein calcite, all inclusions were in quartz grains. The results of fluid-inclusion petrology and microthermometry indicate the presence of three fluid inclusion types (Types 1, 2, and 3). Type 1 fluid inclusions are two-phase (liquid + vapor) aqueous inclusions, and Type 2 inclusions are monophase fluid inclusions (liquid or vapor). These are common in all samples and are formed either as primary isolated inclusions or as secondary inclusions as trails along annealed fractures in the grain. Type 3 fluid inclusions are three-phase (liquid + vapor + solid) inclusions. Type 3 inclusions are rare and are observed as isolated inclusions or in a cluster with other types (i.e., Types 1 and 2). The predominant population throughout the different units sampled is two-phase (liquid + vapor) aqueous fluid inclusions (i.e., Type 1). The temperature of homogenization (TH) bivariate plots for Type 1 inclusions shows dominance throughout the hole of low- to medium-salinity fluids with minimum trapping temperatures between 150° and 400°C.

Pore water concentrations and solid phase concentrations of sediment cores from the Ligurian continental slope

In October 1979, a period of heavy rainfall along the French Riviera was followed by the collapse of the Ligurian continental slope adjacent to the airport of Nice, France. A body of slope sediments, which was shortly beforehand affected by construction work south of the airport, was mobilized and traveled hundreds of kilometers downslope into the Var submarine canyon and, eventually, into the deep Ligurian basin. As a direct consequence, the construction was destroyed, seafloor cables were torn, and a small tsunami hit Antibes shortly after the failure. Hypotheses regarding the trigger mechanism include (i) vertical loading by construction of an embankment south of the airport, (ii) failure of a layer of sensitive clay within the slope sequence, and (iii) excess pore fluid pressures from charged aquifers in the underground. Over the previous decades, both the sensitive clay layers and the permeable sand and gravel layers were sampled to detect freshened waters. In 2007, the landslide scar and adjacent slopes were revisited for high-resolution seafloor mapping and systematic sampling. Results from half a dozen gravity and push cores in the shallow slope area reveal a limited zone of freshening (i.e. groundwater influence). A 100-250 m wide zone of the margin shows pore water salinities of 5-50% SW concentration and depletion in Cl, SO4, but Cr enrichment, while cores east or west of the landslide scar show regular SW profiles. Most interestingly, the three cores inside the landslide scar hint towards a complex hydrological system with at least two sources for groundwater. The aquifer system also showed strong freshening after a period of several months without significant precipitation. This freshening implies that charged coarse-grained layers represent a permanent threat to the slope's stability, not just after periods of major rainfall such as in October 1979.

Pore water (SO4, CH4, alkalinity, HS-, Ca, Sr, Mg, Ba) and solid phase (Ca, Sr, Mg, Ba) data measured in pockmark sediments of the Northern Congo Fan

This study focuses on the vertical distribution of authigenic carbonates (aragonite and high Mg-calcite) in the form of finely disseminated precipitates as well as massive carbonate concretions present in and above gas hydrate bearing sediments of the Northern Congo Fan. Analyses of Ca, Mg, Sr and Ba in pore water, bulk sediments and authigenic carbonates were carried out on gravity cores taken from three pockmark structures (Hydrate Hole, Black Hole and Worm Hole). In addition, a background core was retrieved from an area not influenced by fluid seepage. Pore water Sr/Ca and Mg/Ca ratios are used to reveal the current depths of carbonate formation as well as the mineralogy of the authigenic precipitates. The Sr/Ca and Mg/Ca ratios of bulk sediments and massive carbonate concretions were applied to infer the presence and depth distribution of authigenic aragonite and high Mg-calcite, based on the approach presented by Bayon et al. [Bayon et al. (2007). Sr/Ca and Mg/Ca ratios in Niger Delta sediments: Implications for authigenic carbonate genesis in cold seep environments. Marine Geology 241(1-4), 93-109, doi:10.1016/j.margeo.2007.03.007]. We show that the approach developed by Bayon et al. (2007) for sediments of cold seeps of the Niger Delta is also suitable to identify the mineralogy of authigenic carbonates in pockmark sediments of the Congo Deep-Sea Fan. We expand this approach by combining interstitial with solid phase Sr/Ca and Mg/Ca ratios, which demonstrate that high Mg-calcite is the predominant authigenic carbonate that currently forms at the sulfate/methane reaction zone (SMRZ). This is the first study which investigates both solid phase and pore water signatures typical for either aragonite or high Mg-calcite precipitation for the same sediment cores and thus is able to identify active and fossil carbonate precipitation events. At all investigated pockmark sites fossil horizons of the SMRZ were deduced from high Mg-calcite located above and below the current depths of the SMRZ. Additionally, aragonite enrichments typical for high seepage rates were detected close to the sediment surface at these sites. However, active precipitation of aragonite as indicated by pore water characteristics only occurs at the Black Hole site. Dissolved and solid phase Ba concentrations were used to estimate the time the SMRZ was fixed at the current depths of the diagenetic barite fronts. The combined pore water and solid phase elemental ratios (Mg/Ca, Sr/Ca) and Ba concentrations allow the reconstruction of past changes in methane seepage at the investigated pockmark sites. At the Hydrate Hole and Worm Hole sites the time of high methane seepage was estimated to have ceased at least 600 yr BP. In contrast, a more recent change from a high flux to a more dormant stage must have occurred at the Black Hole site as evidenced by active aragonite precipitation at the sediment surface and a lack of diagenetic Ba enrichments.

Chemistry of fluid inclusions in rock samples from Dronning Maud Land

Dense, CO2-rich fluid inclusions hosted by plagioclases, An45 to An54, of the O.-v.-Gruber- Anorthosite body, central Dronning Maud Land, East Antarctica, contain varying amounts of small calcite, paragonite and pyrophyllite crystals detected by Raman microspectroscopy. These crystals are reaction products that have formed during cooling of the host and the original CO2-rich H2O-bearing enclosed fluid. Variable amounts of these reaction products illustrates that the reaction did not take place uniformly in all fluid inclusions, possibly due to differences in kinetics as caused by differences in shape and size, or due to compositional variation in the originally trapped fluid. The reaction albite + 2anorthite + 2H2O + 2CO2 = pyrophyllite + paragonite + 2calcite was thermodynamically modelled with consideration of different original fluid compositions. Although free H2O is not detectable in most fluid inclusions, the occurrence of OH-bearing sheet silicates indicates that the original fluid was not pure CO2, but contained significant amounts of H2O. Compared to an actual fluid inclusion it is obvious, that volume estimations of solid phases can be used as a starting point to reverse the retrograde reaction and recalculate the compositional and volumetrical properties of the original fluid. Isochores for an unmodified inclusion can thus be reconstructed, leading to a more realistic estimation of P-T conditions during earlier metamorphic stages or fluid capturing.