Chemical and isotope compositions of interstitial water in sediments from Mediterranean basin at DSDP Sites 42-372 and 42-374

The Br/Cl, Li/Cl and B/Cl ratios and boron isotope compositions of hypersaline pore fluids from DSDP Sites 372 and 374 were measured in an attempt to evaluate the origin of the brines. In Site 374 the relationships between the Cl concentrations (up to 5000 mM) and Br/Cl (~0.012), Na/Cl (as low as 0.1), B/Cl (0.0025), and d11B values (43-55?) of the deep pore water between 380 and 405 mbsf, located within the Messinian sediments, reflect remnants of ~65-fold evaporated sea water. The original evaporated sea water was modified by: (1) dilution with overlying or less saline water by about 30%; and (2) slight dissolution of NaCl evaporites. The variations in d11B show a continuous increase in d11B values with depth in Site 374, up to 66.7? at a depth of 300 mbsf (Upper Pliocene marl sediments). The conspicuous 11B enrichment trend is consistent with elemental boron depletion, which was calculated from the expected boron concentrations of evaporated sea water with corresponding Br/Cl and Na/Cl ratios. Li/Cl variations also show a depletion of Li relative to evaporated sea water. The apparent depletions of B and Li, as well as the 11B enrichment, reflect uptake of these elements by clay minerals at low water/sediment ratios.

Chemical composition of zoobenthos and bottom sediments from the gas-hydrate seep area near the Paramushir Island, Kuril Island arc

Bioaccumulation of metals by zoobenthos was investigated during cruise 11A of R/V Akademik Mstislav Keldysh in the vicinity of a gas-hydrate seep off Paramushir Island in the Sea of Okhotsk. Atomic absorption studies of concentrations of Al, Fe, Mn, Ni, Cu and Zn in zoobenthos (polychaetes, bivalves, ophiurans and echinoderms) collected from depths of 700-800 m indicated that their concentrations in individuals near the seep were not significantly different from those in individuals from other communities. Obtained results indicate that sea urchins and holothurians (non-sorting bottom-feeders) can separate mineral fraction of ingested bottom material.

Chemical composition of bulk sediments from ODP Hole 199-1215A

Elemental concentrations were determined on 21 samples from Hole 1215A to evaluate the influence of hydrothermal sources on bulk sediment composition. Rare earth element (REE) concentrations were also determined on 10 of these samples. Concentration profiles and REE patterns are consistent with a strong hydrothermal influence on sediment composition at the base of Hole 1215A.

Chemical and strontium isotopic compositions of interstitial waters from sediments of ODP Site 135-841

The depth variations in the major chemical components dissolved in interstitial waters from the Tonga margin (ODP Site 841) are much more pronounced than those usually observed in deep-sea sediments. The extensive alteration of volcanic Miocene sediments to secondary minerals such as analcime, clays, and thaumasite forms a CaCl2-rich brine. The brine results from a high exchange of Ca to Na, K, and Mg and an increase in Cl concentrations due to removal of H2O from the fluid during the authigenesis of hydrous minerals. The formation of thaumasite could have partly controlled the concentration of dissolved SO4, HCO3, and Ca in the Miocene sediments. The strontium isotopic signature of the interstitial water suggests that alteration of the volcanic Miocene sediments occurred a long time after sedimentation. A transient diffusion model indicates that molecular diffusion was not prevented by lithologic barriers and that the formation of secondary minerals in the Miocene sediment occurred over a short period of time (e.g.,sediments.

Contents of rare earth and other chemical elements in Fe-Mn micronodules, nodules, and bottom sediments from the Clarion-Clipperton ore province in the Pacific Ocean

Processes governing the formation of rare earth element (REE) composition are under consideration for ferromanganese deposits (nodules, separate parts of nodules, and micronodules of different size fractions) within the Clarion-Clipperton ore province in the Pacific Ocean. It is shown that ferromanganese oxyhydroxide deposits with different chemical compositions can be produced in sediments under similar sedimentation conditions. In areas with high bioproductivity size of micronodules has positive correlation with Mn content and Mn/Fe and P/Fe ratios and negative correlation with Fe, P, REE, and Ce anomaly. Behavior of REE in micronodules from sediments within bioproductive zones is related to increase of influence of diagenetic processes in sediments as a response to the growth of size of micronodules. Distinctions in chemical composition of micronodules and nodules are related to their interaction with associated sediments. Micronodules grow in sediments using hydrogenous ferromanganese oxyhydroxides. As they grow, micronodules are enriched in labile fraction of sediments reworked during diagenesis. Sources of material of ferromanganese nodules are governed by their formation at the water bottom interface. Their upper part is formed by direct settling of iron oxyhydroxides from bottom water, whereas the lower part is accumulated due to diagenetic processes in sediments. Differences of REE compositions in ferromanganese deposits are caused by the reduction of manganese during diagenesis and its separation from iron. Iron oxyhydroxides form a sorption complex due to sorption of phosphate-ion from bottom and pore waters. Sorption of phosphate-ion results in additional sorption of REE.

Contents of major and noble chemical elements in phosphorites and bottom sediments

Ag and Au are typically concentrated in phosphorites; they genetically related to organic matter of bottom sediments that extract these elements from seawater or interstitial water. Consequently, the phosphorites inherit Ag and Au from host sediments that are not always enriched in them. In contrast to other organic-rich sediments, analyzed sample of recent diatom ooze from the Namibian shelf is not enriched in Ag and Au, although some sediments from this region are enriched in Au. In addition to authigenic Au, allochthonous Au associated with quartz grains and micrograins can also be present in shelf phosphorites. This was observed in oceanic phosphorites of various types. Anomalous Au and Fe contents recorded in one seamount phosphorite sample can be related to extraction of Au and nonferrous metals by ferromanganese hydroxides from seawater. This process can serve as one of major mechanisms of Au supply to ferromanganese crusts on seamounts. Phosphorites and sediments are enriched in Ru simultaneously with U. Author's data show that U content varies from 17 (seamount phosphorite) to 887 ppm (Pleistocene phosphorite nodule from the Namibian shelf). This is probably caused by different types of behavior of light and heavy PGEs in the marine environment.

Chemical and Sr isotopic compositions of 3 step leachates and residues of bulk samples, zeolites, and smectites from Lower Miocene sediments at ODP Site 166-1007

Massive clinoptilolite authigenesis was observed at about 1105 meters below sea floor (mbsf) in lower Miocene wellcompacted carbonate periplatform sediments from the Great Bahama Bank [Ocean Drilling Program, ODP Leg 166, Site 1007]. The diagenetic assemblage comprises abundant zeolite crystallized within foraminifer tests and sedimentary matrix, as well as Mg smectites. In carbonate-rich deposits, the formation of the zeolite requires a supply of silica. Thus, the objective of the study is to determine the origin of the silica supply, its diagenetic evolution, and consequently the related implications on interpretation of the sedimentary record, in terms of local or global paleoceanographic change. For lack of evidence for any volcaniclastic input or traces of Si-enriched deep fluids circulation, an in situ biogenic source of silica is validated by isotopic data and chemical modeling for the formation of such secondary minerals in shallow-water carbonate sequences. Geochemical and strontium isotopic data clearly establish the marine signature of the diagenetic zeolite, as well as its contemporaneous formation with the carbonate deposition (Sr model ages of 19.6-23.2 Ma). The test of saturation for the pore fluids specifies the equilibrium state of the present mineralogical assemblage. Seawater-rock modeling specifies that clinoptilolite precipitates from the dissolution of biogenic silica, which reacts with clay minerals. The amount of silica (opal-A) involved in the reaction has to be significant enough, at least 10 wt.%, to account for the observed content of clinoptilolite occurring at the most zeolite-rich level. Modeling also shows that the observed amount of clinoptilolite (~19%) reflects an in situ and short-term reaction due to the high reactivity of primary biogenic silica (opal-A) until its complete depletion. The episodic occurrence of these well-lithified zeolite-rich levels is consistent with the occurrence of seismic reflectors, particularly the P2 seismic sequence boundary located at 1115 mbsf depth and dated as 23.2 Ma. The age range of most zeolitic sedimentary levels (biostratigraphic ages of 21.5-22 Ma) correlates well with that of the early Miocene glaciation Mi-1 and Mi-1a global events. Thus, the clinoptilolite occurrence in the shallow carbonate platform environment far from volcanogenic supply, or in other sensitive marine areas, is potentially a significant new proxy for paleoproductivity and oceanic global events, such as the Miocene events, which are usually recognized in deep-sea pelagic sediments and high latitude deposits.

Chemical and isotope compositions of bottom sediments from ODP Leg 168, Eastern Flank of the Juan de Fuca Ridge

Ten sites were drilled in the eastern flank of the Juan de Fuca Ridge (North East Pacific) along a 100 km-long east-west transect during Leg ODP 168. This study focuses on the mineralogical and chemical study of sediments that overly basaltic basement through which seawater circulates. Silicate authigenesis was observed in the sediment layer just above basement at sites located more than 30 km from the ridge axis. This sediment alteration is particularly abundant at ODP Sites 1031 and 1029 where authigenic formation of Fe-Mg rich smectite and zeolite and the dissolution of biogenic calcite are observed. Comparison of the distribution of the alteration in the basal sediment collected along this transect suggests that diffusional transport of aqueous solutes from the basement into the overlying sediment cannot produce the mineralogical and chemical changes in the basal sediments at Sites 1031 located on a basement topographic high, and at Site 1029 located at about 50 km from the ridge axis on a buried basement area. Vertical advection of basement fluid though the sediment section is required to produce this alteration. These processes are still active at Site 1031, based on systematic variations in pore-water profiles and temperatures obtained from stable isotopic data on calcium carbonates and the nature of authigenic minerals. At Site 1029, there is no present-day advection of basement fluids though the sediment section, suggesting that this is a relic site for fluid flow.