Chemistry of interstitial waters of ODP Leg 112 samples

Two distinct hydrogeochemical regimes currently dominate the Peruvian continental margin. One, in shallower water (150-450 m) shelf to upper-slope regions, is characterized by interstitial waters with strong positive chloride gradients with depth. The maximum measured value of 1043 mM chloride at Site 680 at ITS corresponds to a degree of seawater evaporation of ~2 times. Major ion chemistry and strontioum isotopic composition of the interstitial waters suggest that a subsurface brine that has a marine origin and is of pre-early Miocene "age," profoundly influences the chemistry and diagenesis of this shelf environment. Site 684 at ~9°S must be closest to the source of this brine, which becomes diluted with seawater and/or interstitial water as it flows southward toward Site 686 at ~13?S (and probably beyond) at a rate of approximately 3 to 4 cm/yr, since early Miocene time. The other regime, in deep water (3000-5000 m) middle to lower-slope regions, is characterized by interstitial waters with steep negative and nonsteady-state chloride gradients with depth. The minimum measured value of 454 mM chloride, at Site 683 at ITS, corresponds to ~20% dilution of seawater chloride The most probably sources of these low-chloride fluids are gas hydrate dissociation and mineral (particularly clay) dehydration reactions. Fluid advection is consistent with (1) the extent of dilution shown in the chloride profiles, (2) the striking nonsteady-state depth profiles of chlorides at Sites 683 and 688 and of 87Sr/86Sr ratios at Site 685, and (3) the temperatures resulting from an average geothermal gradient of 50°C/km and required for clay mineral dehydration reactions. Strontium isotope data reveal two separate fluid regimes in this slope region: a more northerly one at Sites 683 and 685 that is influenced by fluids with a radiogenic continental strontium signature, and a southerly one at Sites 682 and 688 that is influenced by fluids with a nonradiogenic oceanic signatures. Stratigraphically controlled fluid migration seems to prevail in this margin. Because of its special tectonic setting, Site 679 at ITS is geochemically distinct. The interstitial waters are characterized by seawater chloride concentrations to -200 mbsf and deeper by a significantly lower chloride concentration of about two-thirds of the value in seawater, suggesting mixing with a meteoric water source. Regardless of the hydrogeochemical regime, the chemistry and isotopic compositions of the interstitial waters at all sites are markedly modified by diagenesis, particularly by calcite and dolomite crystallization.

Occurrence and chemistry of microtektites of ODP Site 121-758

The Toba lake event, the Australasian microtektite event, and the Cretaceous/Paleogene boundary were analyzed on the basis of foraminifers, carbonate content, trace elements, and spherules (microtektites). The Toba ash event, recovered in Hole 758C, may have had minor influences on the foraminiferal populations. The Australasian tektite event has probably some influence on foraminiferal ecology, because the larger specimens become scarce just above the microtektite layer. Microtektites recovered from Hole 758B closely resemble spherules recovered from several Cretaceous/Paleogene boundary localities in North America. The Cretaceous/Paleogene spherules, however, are usually larger and are completely altered to goyazite in the terrestrial environment and to smectite in a marine environment. The Cretaceous/Paleogene boundary of Hole 752B does not show obvious anomalous trace-element concentrations, and iridium concentrations are below our detection limits. The trace-element pattern is dominated by the alternation of chalk with volcanic ash layers above the Cretaceous/Paleogene boundary.

Chemistry of altered basaltic glass shards and zeolites of volcaniclastic sediments from ODP Hole 157-953C

Trace element concentrations of altered basaltic glass shards (layer silicates) and zeolites in volcaniclastic sediments drilled in the volcanic apron northeast of Gran Canaria during Ocean Drilling Program (ODP) leg 157 document variable element mobilities during low-temperature alteration processes in a marine environment. Clay minerals (saponite, montmorillonite, smectite) replacing volcanic glass particles are enriched in transition metals and rare earth elements (REE). The degree of retention of REE within the alteration products of the basaltic glass is correlated with the field strength of the cations. The high field-strength elements are preferentially retained or enriched in the alteration products by sorption through clay minerals. Most trace elements are enriched in a boundary layer close to the interface mineral-altered glass. This boundary layer has a key function for the physico-chemical conditions of the subsequent alteration process by providing a large reactive surface and by lowering the fluid permeability. The release of most elements is buffered by incorporation into secondary precipitates (sodium-rich zeolites, phillipsite, Fe- and Mn-oxides) as shown by calculated distribution coefficients between altered glasses and authigenic minerals. Chemical fluxes change from an open to a closed system behavior during prograde low-temperature alteration of volcaniclastic sediments with no significant trace metal flux from the sediment to the water column.

Organic chemistry of sediments of the Peru margin

Organic-carbon-rich anoxic sediments from the continental shelf (Site 680) and the lower continental slope (Site 688) off Peru were studied to determine factors controlling the accumulation of reduced sulfur. High concentrations of organic matter in diatomaceous muds, its thermal immaturity, and the presence of abundant hydrogen-containing organic compounds lead to the conclusion that organic matter is not limiting for reduced sulfur formation. Rather, high degrees of iron pyritization at Site 680 limit pyrite accumulation in sediments from this shelf site. The low degree of iron pyritization and nearly complete reduction of dissolved sulfate at Site 688 suggest that a lack of interstitial sulfate is limiting pyrite formation there. Although factors that limit the formation of sedimentary iron sulfide are different at each site, the resulting average reduced-sulfur concentrations are remarkably similar (0.85 wt.% at Site 680 and 0.86 wt.% at Site 688). Carbon to sulfur (C/S) ratios are higher in samples containing in excess of 3 wt.% organic carbon than the average of 2.8 in normal marine sediments and have been primarily influenced by variations in organic matter concentrations.

Chemistry of hydrothermal clasy and sulfides of ODP Site 106-649

Several meters of unconsolidated hydrothermal sediment were recovered from the Snake Pit hydrothermal field during ODP Leg 106. Polymetallic sulfides comprise most of the sediment with minor fragments of massive sulfide, organic debris, clay minerals, and fresh glass shards. Trace element and Sr-isotope contents of hydrothermal clays and sulfides from Holes 649B and 649G indicate that these minerals precipitated from a mixed hydrothermal fluid-seawater solution. Evaluation of the REE mineral data and the Snake Pit hydrothermal fluids shows that the REE distribution coefficients between the hydrothermal fluids and clay-sulfide mixes range from 100-500. This indicates that hydrothermal fluids originating in the root-zone of the Snake Pit hydrothermal system may be modified by the precipitation of hydrothermal minerals, either in the shallow subsurface or within chimney structures. Contrasting REE profiles of clay-sulfide aggregates and massive sulfides from Holes 649B and 649G may be accounted for by spatial and/or temporal variations in redox conditions in the plumbing system.

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.

Chemistry of peridotites from ODP Hole 109-670A

Two types of serpentinized peridotites from Hole 670A of Leg 109 were studied in detail. A small piece of relatively unaltered sample, 109-670A-9R-1, #3 (22-24 cm), is olivine websterite characterized by aluminous chromian spinel with Cr/(Cr + Al) ratio of about 0.2. The other minerals have compositions essentially identical with those in more commonly observed serpentinized harzburgite like 109-670A-9R-01, #12 (94-97 cm). The occurrence of pyroxene-rich peridotite with normal harzburgite suggests that small scale heterogeneity in modal compositions exists in the upper mantle beneath the Mid-Atlantic Ridge. Low Cr/Al ratios of spinel and pyroxenes of those peridotites indicate that they are relatively less refractory among peridotites ever recovered from the oceanic region. Textures and the estimated equilibration temperatures indicate that peridotites recovered from Hole 670A are recrystallized and reequilibrated at subsolidus temperature. The occurrence of serpentinized peridotites from the rift valley of the active mid-oceanic ridge may suggest that they represent direct exposure of upwelling mantle materials rather than serpentine diapirs.