Geochemistry of interstitial waters of DSDP Leg 96 sites

Interstitial water studies were done at 9 of the 11 sites visited in the Mississippi Fan and Orca and Pigmy Basins during DSDP Leg 96. High concentrations of sulfate were observed at Mississippi Fan Sites 616, 617, 620, and 623. The maximum sulfate value of 38.8 mM, recorded at Site 617, is the highest ever found in DSDP sediments. Hypersaline interstitial water was observed at Site 618 in Orca Basin. Concentration ratios of salinity to chlorinity and to sodium in interstitial waters are similar to those of Orca Basin bottom water, suggesting that the chemistry of interstitial water is affected by the dissolution of buried salt.

Physico-chemical parameters of sediment core PG1972-1 (09-Tik-03) from a Tundra Lake, Northeastern Siberia

Thermokarst lakes in the Siberian Arctic contain sediment archives that can be used for paleoenvironmental inference. Until now, however, there has been no study from the inner Lena River Delta with a focus on diatoms. The objective of this study was to investigate how the diatom community in a thermokarst lake responded to past limnogeological changes and what specific factors drove variations in the diatom assemblage. We analysed fossil diatom species, organic content, grain-size distribution and elemental composition in a sediment core retrieved in 2009 from a shallow thermokarst lake in the Arga Complex, western Lena River Delta. The core contains a 3,000-year record of sediment accumulation. Shifts in the predominantly benthic and epiphytic diatom species composition parallel changes in sediment characteristics. Paleoenvironmental and limnogeological development, inferred from multiple biological and sedimentological variables, are discussed in the context of four diatom zones, and indicate a strong relation between changes in the diatom assemblage and thermokarst processes. We conclude that limnogeological and thermokarst processes such as lake drainage, rather than direct climate forcing, were the main factors that altered the aquatic ecosystem by influencing, for example, habitat availability, hydrochemistry, and water level.

Composition of hardgrounds and of pore-water parameters in ODP Holes 166-1008 and 166-1009

Mineralogic, petrographic, and geochemical analyses of sediments recovered from two Leg 166 Ocean Drilling Program cores on the western slope of Great Bahama Bank (308 m and 437 m water depth) are used to characterize early marine diagenesis of these shallow-water, periplatform carbonates. The most pronounced diagenetic products are well-lithified intervals found almost exclusively in glacial lowstand deposits and interpreted to have formed at or near the seafloor (i.e., hardgrounds). Hardground cements are composed of high-Mg calcite (~14 mol% MgCO3), and exhibit textures typically associated with seafloor cementation. Geochemically, hardgrounds are characterized by increased d18O and Mg contents and decreased d13C, Sr, and Na contents relative to their less lithified counterparts. Despite being deposited in shallow waters that are supersaturated with the common carbonate minerals, it is clear that these sediments are also undergoing shallow subsurface diagenesis. Calculation of saturation states shows that pore waters become undersaturated with aragonite within the upper 10 m at both sites. Dissolution, and likely recrystallization, of metastable carbonates is manifested by increases in interstitial water Sr and Sr/Ca profiles with depth. We infer that the reduction in mineral saturation states and subsequent dissolution are being driven by the oxidation of organic matter in this Fe-poor carbonate system. Precipitation of burial diagenetic phases is indicated by the down-core appearance of dolomite and corresponding decrease in interstitial water Mg, and the presence of low-Mg calcite cements observed in scanning electron microscope photomicrographs.

Geochemical investigation of ODP Leg 113 sites

Dissolved organic carbon (DOC) was determined in pore water extracted from pelagic and hemipelagic sediments recovered during Leg 113. DOC concentration varied between 1.82 and 13.6 mg C/L which is one to two orders of magnitude less than previously reported for hemipelagic sediments. It is argued that this difference is related to differences in the intensity of degradation of organic matter. As a first approximation it is found that in reducing sediments, the level of DOC is proportional to the intensity of sulfate reduction. It is suggested that DOC is formed by different mechanisms in oxic and reducing environments.

Mineralogy and geochemistry at DSDP Hole 62-465A

Core recovered from Hess Rise contains concentrations of pyrite, marcasite, and barite in the lowermost meter of limestone (Unit II) and in the brecciated upper part of the underlying volcanic basement (Unit HI). Petrographic and chemical data indicate that the sulfide-barite assemblage in the limestone is mainly a product of low-temperature diagenetic processes. The iron-sulfide phases are biogenic and their concentrations mark the diffusion of sea water sulfate through sedimentary horizons containing abundant organic matter and mafic, glassy volcanogenic detritus. There is some evidence, however, that elevated temperatures augmented or intensified the synsedimentary diagenetic process.

High-resolution in situ oxygen microprofiles, porewater and solid phase geochemistry from the Crimean shelf (Black Sea) from Maria S. Merian cruise MSM15/1

The outer western Crimean shelf of the Black Sea is a natural laboratory to investigate effects of stable oxic versus varying hypoxic conditions on seafloor biogeochemical processes and benthic community structure. Bottom-water oxygen concentrations ranged from normoxic (175 µmol O2/L) and hypoxic (< 63 µmol O2/L) or even anoxic/sulfidic conditions within a few kilometers' distance. Variations in oxygen concentrations between 160 and 10 µmol/L even occurred within hours close to the chemocline at 134 m water depth. Total oxygen uptake, including diffusive as well as fauna-mediated oxygen consumption, decreased from 15 mmol/m**2/d on average in the oxic zone, to 7 mmol/m**2/d on average in the hypoxic zone, correlating with changes in macrobenthos composition. Benthic diffusive oxygen uptake rates, comprising respiration of microorganisms and small meiofauna, were similar in oxic and hypoxic zones (on average 4.5 mmol/m**2/d), but declined to 1.3 mmol/m**2/d in bottom waters with oxygen concentrations below 20 µmol/L. Measurements and modeling of porewater profiles indicated that reoxidation of reduced compounds played only a minor role in diffusive oxygen uptake under the different oxygen conditions, leaving the major fraction to aerobic degradation of organic carbon. Remineralization efficiency decreased from nearly 100 % in the oxic zone, to 50 % in the oxic-hypoxic zone, to 10 % in the hypoxic-anoxic zone. Overall, the faunal remineralization rate was more important, but also more influenced by fluctuating oxygen concentrations, than microbial and geochemical oxidation processes.

Geochemistry on manganese deposit from the Median Valley of the Mid-Atlantic Ridge

A manganese oxide crust from an extensive deposit in the median valley of the Mid-Atlantic Ridge was found to be unusually high in manganese (up to 39.4% Mn), low in Fe (as low as 0.01% Fe), low in trace metals and deficient in Th230 and Pa231 with respect to the parent uranium isotopes in the sample. The accumulation rate is 100 mm to 200 mm/10 million year, or 2 orders of magnitude faster than the typical rate for deep-sea ferromanganese deposits. The rapid growth rate and unusual chemistry are consistent with a hydrothermal origin or with a diagenetic origin by manganese remobilized from reduced sediments. Because of the association with an active ridge, geophysical evidence indicative of hydrothermal activity, and a scarcity of sediment in the sampling area, we suggest that a submarine hot spring has created the deposit.

Concentrations of dissolved and particulate manganese in waters of the Southwest Pacific

Concentrations of dissolved and particulate manganese in relation with organic matter in waters of the Southwest Pacific are under consideration.

Interstitial water and sediment chemistry at DSDP Sites 87-582 and 87-584

Two trenches off Japan were explored during DSDP Leg 87. One is the Nankai Trough and the other is the Japan Trench; Site 582 is located on the floor of the former and Site 584 is situated on the deep-sea terrace of the latter. Cores from Site 582 and 584 consist mainly of hemipelagic sediments and diatomaceous silts and mudstone, respectively. In this report we analyze the chemistry of the interstitial water and sediments, as well as the sediment mineralogy. Sulfate reduction is accompanied by the production of secondary pyrite, which is rich in the sediment at both sites. Dissolved Ca concentration is relatively low and changes only slightly at both sites, probably because of the formation of carbonate with high alkalinity. Concentrations of dissolved Mg decrease with depth at Site 584. The dissolved Mg depletion probably results from the formation of Mg-rich carbonate and/or ion exchange and reaction between interstitial water and clay minerals. Higher Si/Al values are due to biogenic opal in the sediments and roughly correlate with higher values of interstitial water SiO2. Increases in dissolved Li concentrations may be related to its release from clay minerals, to advection that results from dewatering, and/or to fluid transport.

Chemistry of interstitial waters and sediments at DSDP Leg 64 Holes

Studies of interstitial waters obtained from DSDP Leg 64 drill sites in the Gulf of California have revealed information both on early diagenetic processes in the sediments resulting from the breakdown of organic matter and on hydrothermal interactions between sediments and hot doleritic sill intrusions into the sediments. In all the sites drilled sulfate reduction occurred as a result of rapid sediment accumulation rates and of relatively high organic carbon contents; in most sites methane production occurred after sulfate depletion. Associated with this methane production are high values of alkalinity and high concentrations of dissolved ammonia, which causes ion exchange processes with the solid phases leading to intermediate maxima in Mg++, K+, Rb+, and Sr++(?). Though this phenomenon is common in Leg 64 drill sites, these concentration reversals had been noticed previously only in Site 262 (Timor Trough) and Site 440 (Japan Trench). Penetrating, hot dolerite sills have led to substantial hydrothermal alteration in sediments at sites drilled in the Guaymas Basin. Site 477 is an active hydrothermal system in which the pore-water chemistry typically shows depletions in sulfate and magnesium and large increases in lithium, potassium, rubidium, calcium, strontium, and chloride. Strontium isotope data also indicate large contributions of volcanic matter and basalt to the pore-water strontium concentrations. At Sites 478 and 481 dolerite sill intrusions have cooled to ambient temperatures but interstitial water concentrations of Li+, Rb+, Sr++ , and Cl- show the gradual decay of a hydrothermal signal that must have been similar to the interstitial water chemistry at Site 477 at the time of sill intrusion. Studies of oxygen isotopes of the interstitial waters at Site 481 indicate positive values of d18O (SMOW) as a result of high-temperature alteration reactions occurring in the sills and the surrounding sediments. A minimum in dissolved chloride at about 100-125 meters sub-bottom at Sites 478, 481, and particularly Site 479 records a possible paleosalinity signal, associated with an event that substantially lowered salinities in the inner parts of the Gulf of California during Quaternary time.

Elemental contents, non-carbonate, fatty acids and alcohols analysis from different Holes of IODP Expedition 310

During IODP Expedition 310 (Tahiti Sea Level), drowned Pleistocene-Holocene barrier-reef terraces were drilled on the slope of the volcanic island. The deglacial reef succession typically consists of a coral framework encrusted by coralline algae and later by microbialites; the latter make up < 80% of the rock volume. Lipid biomarkers were analyzed in order to identify organisms involved in reef-microbialite formation at Tahiti, as the genesis of deglacial microbialites and the conditions favoring their formation are not fully understood. Sterols plus saturated and monounsaturated short-chain fatty acids predominantly derived from both marine primary producers (algae) and bacteria comprise 44 wt% of all lipids on average, whereas long-chain fatty acids and long-chain alcohols derived from higher land plants represent an average of only 24 wt%. Bacterially derived mono-O-alkyl glycerol ethers (MAGEs) and branched fatty acids (10-Me-C16:0; iso- and anteiso-C15:0 and -C17:0) are exceptionally abundant in the microbial carbonates (average, 19 wt%) and represent biomarkers of intermediate-to-high specificity for sulfate-reducing bacteria. Both are relatively enriched in 13C compared to eukaryotic lipids. No lipid biomarkers indicative of cyanobacteria were preserved in the microbialites. The abundances of Al, Si, Fe, Mn, Ba, pyroxene, plagioclase, and magnetite reflect strong terrigenous influx with Tahitian basalt as the major source. Chemical weathering of the basalt most likely elevated nutrient levels in the reefs and this fertilization led to an increase in primary production and organic matter formation, boosting heterotrophic sulfate reduction. Based on the observed biomarker patterns, sulfate-reducing bacteria were apparently involved in the formation of microbialites in the coral reefs off Tahiti during the last deglaciation.

Manganese contents and accumulation rates in reduced bottom sediments of the Sea of Okhotsk

Manganese contents in reduced sediments and accumulation rates were investigated. Their values in sediments of most of cores are background (0.03-0.07 %).Anomalous concentrations (up to 2.5 %) and accumulation rates (up to 60 mg/cm**2/ka) occur near the known region of hydrothermal barite mineralization in the Derugin Basin. High accumulation rates of Mn (>10 mg/cm**2/ka) also occur in Holocene sediments to south-east from the Derugin Basin. It can be assumed that high Mn contents and accumulation rates occur there due to transportation of Mn-rich water from the Derugin Basin in the near-bottom layer under the lower border of the Sea of Okhotsk Intermediate Water. Intensive Mn accumulation is also typical for the South Okhotsk Basin near the Bussol Strait. Mn accumulation rates of glacial sediments of the second oxygen isotope stage are less significant, which is presumed to be caused by paleoceanological reasons.