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.

Barium in seawater and sediments from the Artic Ocean

As part of ongoing circulation studies in the Arctic, seawater samples for dissolved Ba concentrations were obtained during Sep.-Oct., 1992 at several locations in the Bering Strait, Eastern Chukchi and Southern Beaufort Seas. The results reveal a dynamic rang (10 to 150 nmol/kg) for this element in the Arctic equal to or greater than that in combined Atlantic, Indian and Pacific oceans. Lowest levels are observed in surface waters, with values tending to decrease northwards in the direction of currents generally flowing frorn the Bering Strait along the Alaskan coast. Low surfacc concentrations tend to be accompanied by relatively enriched near bottom levels. On the basis of these spatial distributions, hydrographic observations and a knowledge of its behavior in other marine settings, it appears that Ba can be significantly depleted from surface waters as a result of the highly seasonal biological aclivities over Arctic marginal shelves. Removal at the surface is counteracted to some extent by regeneration at depth or in the sediments and by riverine inputs. The biologically related drawdown is likely to enhance the contrast between 'background' surface Ba levels in the Arctic and waters imprinted by regeneration and/or rivers, These preliminary findings suggest that Ba holds particular promise for tracing river waters and the ventilation of halodine waters hy laterally sinking brines produced during ice formation over the shelves.

Mineralogy and geochemistry of Miocene tuff from ODP Hole 129-802A

Drilling at Ocean Drilling Program Site 802 in the central Mariana Basin, northwest Pacific Ocean, revealed an unexpected 222-m-thick sequence of well-cemented tuff of Miocene age. The deposits are unusual in that their source is presumably an unmapped seamount and they exhibit several peculiar petrological and mineralogical features. The well-developed secondary mineral sequence which includes analcime is rare in such relatively young, unburied deposits, in an area where there is little other evidence of hydrothermal activity. The massive tuff section also contains abundant fissure veins made of a rare silicate carbonate sulfate hydroxide hydrate of calcium, called thaumasite, which has not before been described in deep submarine deposits. The smectite-zeolite-thaumasite paragenesis coincides with the presence of chloride and calcium-enriched interstitial waters. The diagenetic evolution of the deposit appears to have been largely controlled by the depositional mode. The discharges of disaggregated and rejuvenated volcaniclasts seem to have been abrupt and repeated. The Miocene tuff at Site 802 thus provides new insights on the interactions between basaltic glass, biogenic phases, and seawater, in a specific deep-sea environment.

Barium concentrations und stable isotope ratios of late Paleocene deep-sea sediments

Deep-sea sediment Ba* (Ba/Al2O3(sample) * 15% - Ba(aluminosilicate) records show increasing values synchronous with the evolution of the late Paleocene global d13C maximum, reflecting an increase in marine surface primary production and biogenic barite formation at this time. At two oligotrophic locations, Deep Sea Drilling Project (DSDP) Sites 384 and 527 in the North and South Atlantic, respectively, Ba* increases from 160-360 ppm in the early Paleocene to 1100-3000 ppm during the d13C maximum. At equatorial DSDP Site 577, positioned within or near the high-productivity zone, Ba* increases from ~15,500 ppm in the early Paleocene to ~25,400 ppm in conjunction with late Paleocene maximum d13C values. Linear fitted correlation plots of sediment Ba* content versus surface water d13C in all three regions support barite originating in the euphotic zone. The early to late Paleocene relative increase in Ba* illustrates how burial rates of Corg (relative to Al2O3) accelerated by a factor of ~1.8 and ~6.0 in the eutrophic and oligotrophic areas, respectively. A tentative estimate, weighing our result for the entire ocean, suggests that accumulation rates of organic carbon increased by a factor of 2 during the late Paleocene d13C maximum.

Geochemistry of interstitial waters of Lau Backarc Basin sediment samples

Interstitial water samples from Sites 834 through 839, drilled during Ocean Drilling Program Leg 135 in the backarc Lau basin (Southwestern Pacific), have been analyzed for major elements, manganese, copper, strontium, barium, vanadium, and 87Sr/86Sr isotopic composition values. The concentration-depth profiles of the major chemical components show almost straight concentration gradients at all sites, and seem to reflect slight alteration of volcanic material. However, in the lower part of the sedimentary cover, where volcanogenic material is abundant and where diagenetic minerals occur, systematic decreases in calcium, strontium, manganese, copper, and vanadium concentrations are observed. A downwelling flow of bottom seawater, which affected the diagenetic chemical signature of the interstitial water, is probably responsible for the recorded chemical features. This hypothesis is supported by strontium isotope data obtained from interstitial water samples at Site 835. It is also in accordance with data from heat flow and physical properties.

Dissolved chemical elements in river waters of the Wrangel Island

Pioneer information about chemical composition of river waters in the Wrangel Island has been obtained. It is shown that water composition reflects the lithogeochemical specifics of primary rocks and ore mineralization. In contrast to many areas of the Russian Far North river waters of the island are characterized by elevated background value of total mineralization (i.e., total dissolved solids, TDS) (0.3-2 g/l) and specific chemical type (SO4-Ca-Mg). This is related to abundance of Late Carboniferous gypsiferous and dolomitic sequences in the mountainous area of the island. It has also been established that salt composition of some streams is appreciably governed by supergene alterations of sulfide mineralization associated with quartz-carbonate vein systems. They make up natural centers of surface water contamination. Waters in such streams are characterized by low pH values (2.4-5.5), high TDS (up to 6-23 g/l) and SO4-Mg composition. These waters are also marked by anomalously high concentrations of heavy and non-ferrous metals, as well as REE, U, and Th.

Geochemical and biogeochemical parameters of bottom sediments from the area of the Spitsbergen (Svalbard) Archipelago

Quantitative characteristics for rates of diagenetic processes in the upper (0-30 cm) layer of sedimentary deposits in the area of the Spitsbergen (Svalbard) Archipelago (78°-80°N) were obtained by lithologo-geochemical, radioisotope (35S, 14C), and stable isotope (d34S, d13C) studies. It was proved that rates of diagenetic processes in polar deposits at 123-395 m depth affected by the East Spitsbergen ''warm'' current are mostly determined by bioproductivity and are commensurate with rates of processes in shelf deposits of temperate latitudes. High contents of migratory methane (up to 263 ml/dm**3) and isotopically-light organic carbon (Corg, d13C = -30 per mil PDB) were found in the 1 m layer of shelf deposits (at 123 m sea depth) with low bacterial in situ production of methane. It was shown that methane is not utilized in the deposits by the methanotrophic bacterial community and it may be supplied to the water mass and, probably, to the atmosphere.

Water chemistry and sediment age of lake Terrasovoje, Amery Oasis, East Antarctica

The late Quaternary palaeoenvironmental history of the southern Windmill Islands, East Antarctica, has been reconstructed using diatom assemblages from two long, well-dated sediment cores taken in two marine bays. The diatom assemblage of the lowest sediment layers suggests a warm climate with mostly open water conditions during the late Pleistocene. During the following glacial, the Windmill Islands were covered by grounded ice preventing any in situ bioproductivity. Following deglaciation, a sapropel with a well-preserved diatom assemblage was deposited from ~10?500 cal yr BP. Between ~10?500 and ~4000 cal yr BP, total organic carbon (Corg) and total diatom valve concentrations as well as the diatom species composition suggest relatively cool summer temperatures. Hydrological conditions in coastal bays were characterised by combined winter sea-ice and open water conditions. This extensive period of glacial retreat was followed by the Holocene optimum (~4000 to ~1000 cal yr BP), which occurred later in the southern Windmill Islands than in most other Antarctic coastal regions. Diatom assemblages in this period suggest ice-free conditions and meltwater-stratified waters in the marine bays during summer, which is also reflected in high proportions of freshwater diatoms in the sediments. The diatom assemblage in the upper sediments of both cores indicates Neoglacial cooling from ~1000 cal yr BP, which again led to seasonally persistent sea-ice on the bays. The Holocene optimum and cooling trends in the Windmill Islands did not occur contemporaneously with other Antarctic coastal regions, showing that the here presented record reflects partly local environmental conditions rather than global climatic trends.

Geochemistry of fallout tephra from ODP Hole 125-782A

Very rare, halogen-rich andesite melt inclusions (HRA) in bytownitic plagioclase phenocrysts (An89-90) from tephra fallout of the Izu arc volcanic front (Izu VF) provide new insights into the processes of fluid release from slab trenchward to the volcanic front in a cool subduction zone. These HRA are markedly enriched in Cl, F and Li - by factors of up to 8 (Cl, F) and 1.5 (Li) - but indistinguishable with respect to the fluid-mobile large-ion lithophile elements (LILE; K, Sr, Rb, Cs, Ba, Pb, U), rare earths (REE) or high field strength elements (HFSE) from the low-K tholeiitic magmas of the Izu VF. We suggest that the chemical signature of the HRA reflects the presence of a fluid in the mantle source that originated from the serpentinized mantle peridotite above the metacrust. This "wedge serpentinite" presumably formed by fluid infiltration beneath the forearc and was subsequently down-dragged with the slab to arc front depths. The combined evidence from the Izu VF (?110 km above slab) and the outer forearc serpentinite seamounts (~25 to 30 km above slab) suggests that the slab flux of B and Cl is highest beneath the forearc, and decreases with increasing slab depths. In contrast, the slab flux of Li is minor beneath the forearc, but increases with depth. Fluorine may behave similarly to Li, whereas the fluid-mobile LILE appear to be largely retained in the slab trenchward from the Izu VF. Consequently, the chemical signatures of both Izu trench sediments and basaltic rocks appear preserved until arc front depths.

Element and Sr isotope composition of interstitial waters in sediments of ODP Leg 129

Interstitial water samples from Leg 129, Sites 800, 801, and 802 in the Pigafetta and Mariana basins (central western Pacific), have been analyzed for major elements, B, Li, Mn, Sr, and 87Sr/86Sr. At all sites waters show enrichment in Ca and Sr and are depleted in Mg, K, Na, SO4, B, alkalinity, and 87Sr compared to seawater. These changes are related to alteration of basaltic material into secondary smectite and zeolite and recrystallization of biogenic carbonate. Water concentration depth profiles are characterized by breaks due to the presence of barriers to diffusion such as chert layers at Sites 800 and 801 and highly cemented volcanic ash at Site 802. In Site 800, below a chert layer, concentration depth profiles are vertical and reflect slight alteration of volcanic matter, either in situ or in the upper basaltic crust. Release of interlayer water from clay minerals is likely to induce observed Cl depletions. At Site 801, two units act as diffusion barrier and isolate the volcaniclastic sediments from ocean and basement. Diagenetic alteration of volcanic matter generates a chemical signature similar to that at Site 800. Just above the basaltic crust, interstitial waters are less evolved and reflect low alteration of the crust, probably because of the presence in the sediments of layers with low diffusivities. At Site 802, in Miocene tuffs, the chemical evolution generated by diagenetic alteration is extreme (Ca = 130 mmol, 87Sr/86Sr = 0.7042 at 83 meters below seafloor) and is accompanied by an increase of the Cl content (630 mmol) due to water uptake in secondary hydrous phases. Factors that enhance this evolution are a high sediment accumulation rate, high cementation preventing diffusive exchange and the reactive composition of the sediment (basaltic glass). The chemical variation is estimated to result in the alteration of more than 20% of the volcanic matter in a nearly closed system.