Geochemistry of sediments from the Eastern Cape Basin

Sediment cores retrieved in the Benguela coastal upwelling system off Namibia show very distinct enrichments of solid phase barium at the sulfate/methane transition (SMT). These barium peaks represent diagenetic barite (BaSO4) fronts which form by the reaction of upwardly diffusing barium with interstitial sulfate. Calculated times needed to produce these barium enrichments indicate a formation time of about 14,000 yr. Barium spikes a few meters below the SMT were observed at one of the investigated sites (GeoB 8455). Although this sulfate-depleted zone is undersaturated with respect to barite, the dominant mineral phase of these buried barium enrichments was identified as barite by scanning electron microscopy (SEM). This is the first study which reports the occurrence/preservation of pronounced barite enrichments in sulfate-depleted sediments buried a few meters below the SMT. At site GeoB 8455 high concentrations of dissolved barium in pore water as well as barium in the solid phase were observed. Modeling the measured barium concentrations at site GeoB 8455 applying the numerical model CoTReM reveals that the dissolution rate of barite directly below the SMT is about one order of magnitude higher than at the barium enrichments deeper in the sediment core. This indicates that the dissolution of barite at these deeper buried fronts must be retarded. Thus, the occurrence of the enrichments in solid phase barium at site GeoB 8455 could be explained by decreased dissolution rates of barite due to the changes in the concentration of barite in the sediment, as well as changes in the saturation state of fluids. Furthermore, the alteration of barite into witherite (BaCO3) via the transient phase barium sulfide could lead to the preservation of a former barite front as BaCO3. The calculations and modeling indicate that a relocation of the barite front to a shallower depth occurred between the last glacial maxium (LGM) and the Pleistocene/Holocene transition. We suggest that an upward shift of the SMT occurred at that time, most likely as a result of an increase in the methanogenesis rates due to the burial of high amounts of organic matter below the SMT.

Chemical compositions of rocks and minerals from an underwater volcano of the Kuril deep-sea basin

Mineralogy and geochemistry of low-temperature hydrothermal manifestations occurring on the surface of basalts and in their cracks within a submarine volcano in the north-eastern part of the Kuril deep-sea basin have been studied. The following order of isolation of mineral phases has been found out: Fe-rich sulphides (pyrite) - Fe-rich layered silicates (hydromica of celadonite-nontronite type) - amorphous silica (opal) - Fe-oxyhydroxides (goethite) - Mn-oxyhydroxides (vernadite). Sulphide mineralization is of the phenocryst-stockwork type. Finding of pure barite fragments does not exclude presence of hydrothermal exhalations (smokers) on this volcanic structure.

Isotope compositions and mineralogy of carbonates and barites from sediments of the Deryugin Basin (Sea of Okhotsk)

Results of studies of mineralogy, geochemistry, and isotope parameters (d13C, d34S, d180, and 87Sr/86Sr) of carbonates and barites from sediments of the Deryugin Basin in the Sea of Okhotsk are presented. Diagenetic nature of carbonates and barites formed due to prolonged activity of cold seeps acting along a fracture zone and supplying methane- and barium saturated fluids is determined. Any signs for hydrothermal activity were not observed.

Geochemistry of microtektites from Victoria Land Transantarctic Mountains

We extended the petrographic and geochemical dataset for the recently discovered Transantarctic Mountain microtektites in order to check our previous claim that they are related to the Australasian strewn field. Based on color and composition, the 465 microtektites so far identified include two groups of transparent glass spheres less than ca. 800 µm in diameter: the most abundant pale-yellow, or normal, microtektites, and the rare pale-green, or high-Mg, microtektites. The major element composition of normal microtektites determined through electron microprobe analysis is characterized by high contents of silica (SiO2 = 71.5 ± 3.6 (1 sigma) wt%) and alumina (Al2O3 = 15.5 ± 2.2 (1 sigma) wt%), low total alkali element contents (0.50-1.85 wt%), and MgO abundances <6 wt%. The high-Mg microtektites have a distinctly higher MgO content >10 wt%. Transantarctic Mountain microtektites contain rare silica-rich (up to 93 wt% SiO2) glassy inclusions similar to those found in two Australasian microtektites analyzed here for comparison. These inclusions are interpreted as partially digested, lechatelierite-like inclusions typically found in tektites and microtektites. The major and trace element (by laser ablation - inductively coupled plasma - mass spectrometry) abundance pattern of the Transantarctic Mountain microtektites matches the average upper continental crust composition for most elements. Major deviations include a strong to moderate depletion in volatile elements including Pb, Zn, Na, K, Rb, Sr and Cs, as a likely result of severe volatile loss during the high temperature melting and vaporization of crustal target rocks. The normal and high-Mg Transantarctic Mountain microtektites have compositions similar to the most volatile-poor normal and high-Mg Australasian microtektites reported in the literature. Their very low H2O and B contents (by secondary ion mass spectrometry) of 85 ± 58 (1 sigma) ?g/g and 0.53 ± 0.21 ?g/g, respectively, evidence the extreme volatile loss characteristically observed in tektites. The Sr and Nd isotopic compositions of multigrain samples of Transantarctic Mountain microtektites are 87Sr/86Sr ~ 0.71629 and 143Nd/144Nd ~ 0.51209, and fall into the Australasian tektite compositional field. The Nd model age calculated with respect to the chondritic uniform reservoir (CHUR) is TNdCHUR ~ 1.1 Ga, indicating a Meso-Proterozoic crustal source rock, as was derived for Australasian tektites as well. Coupled with the Quaternary age from the literature, the extended dataset presented in this work strengthens our previous conclusion that Transantarctic Mountain microtektites represent a major southward extension of the Australasian tektite/microtektite strewn field. Furthermore, the significant depletion in volatile elements (i.e., Pb, B, Na, K, Zn, Rb, Sr and Cs) of both normal and high-Mg Transantarctic Mountain microtektites relative to the Australasian ones provide us with further confirmation of a possible relationship between high temperature-time regimes in the microtektite-forming process and ejection distance.

(Table 1, page 661) Average composition of fossil nodules from three localities studied in the Transdanubian Central Mountains of Hungary

Fossil manganese nodules and encrustations from seamount' and basin' localities in the Transdanubian Central Mountains of Hungary are lithologically, mineralogically and chemically similar to some modern marine ferromanganese oxide deposits, and show no evidence of postdepositional changes other than cementation. Five groups of deposits were encountered: Fe/Mn nodules, encrusted shells, pavements, stains, and Fe oxide encrusted intraclasts, the first three of which are specific to the 'seamount' environment and the last to the basins'. Optical and electron microprobe investigation of the samples shows them to exhibit many similarities with modern ferromanganese oxide deposits, and that many of the nodules are surrounded by a halo of dispersed ferromanganese oxides, strongly suggesting that they continued to accrete metals through the pore waters of unlithified sediments for a period after burial. By contrast, pavements which appear to have grown on hardgrounds at the sea floor show little or no evidence of derivation of metals from underlying sediments. Geochemical investigations on the deposits show the seamount' varieties to be closer in composition to most modern nodules and crusts than the basin' varieties, and that the latter are essentially manganese and trace-element-poor ferruginous deposits. Nevertheless, all can be more or less compositionally equated with modern ferromanganese oxide deposits forming in marginal Atlantic environments, which would be in accord with the proposed depositional environment of the Transdanubian Central Mountains based on other evidence.

(Table 3) Barium barite and excess comparison, accumulation rates and productivity from surface sediments

Since Dymond et al. (1992, doi:10.1029/92PA00181) proposed the paleoproductivity algorithm based on "Bio-Ba", which relies on a strong correlation between Ba and organic carbon fluxes in sediment traps, this proxy has been applied in many paleoproductivity studies. Barite, the main carrier of particulate barium in the water column and the phase associated with carbon export, has also been suggested as a reliable paleoproductivity proxy in some locations. We demonstrate that Ba(excess) (total barium minus the fraction associated with terrigenous material) frequently overestimates Ba(barite) (barium associated with the mineral barite), most likely due to the inclusion of barium from phases other than barite and terrigenous silicates (e.g., carbonate, organic matter, opal, Fe-Mn oxides, and hydroxides). A comparison between overlying oceanic carbon export and carbon export derived from Ba(excess) shows that the Dymond et al. (1992) algorithm frequently underestimates carbon export but is still a useful carbon export indicator if all caveats are considered before the algorithm is applied. Ba(barite) accumulation rates from a wide range of core top sediments from different oceanic settings are highly correlated to surface ocean 14C and Chlorophyll a measurements of primary production. This relationship varies by ocean basin, but with the application of the appropriate f ratio to 14C and Chlorophyll a primary production estimates, the plot of Ba(barite) accumulation and carbon export for the equatorial Pacific, Atlantic, and Southern Ocean converges to a global relationship that can be used to reconstruct paleo carbon export.

Chemical composition of hydrothermal carbonates and barites from the Deryugin Basin, Sea of Okhotsk

Data on hydrothermal activity in the Deryugin Basin (Sea of Okhotsk) are reviewed. Barites and carbonates found in sediment cores sampled at feet of hydrothermal mounds were subdivided into recycled and authigenic types. Recycled minerals were represented by crystals and aggregations of travertine-like barite and fragments of barite and carbonate tubes. Authigenic formations included: (1) carbonate nodules; (2) barite micronodules; (3) transparent colorless barite that generated numerous small nests and filled cavities in sediments; (4) yellow barite formed thin (0.5 mm) veins; and (5) white barite cemented small aggregations of coarse-grained sediments. A detailed examination of formation processes of authigenic minerals in the bottom sediment cores allowed to conclude that, there, hydrothermal activity is still going on today. This was confirmed by high methane concentration in near-bottom water above a field of hydrothermal barite minerals.

Barite accumulation rates throughout Pliocene-Pleistocene in Eastern Equatorial Pacific at ODP Site 138-849

Export production is an important component of the carbon cycle, modulating the climate system by transferring CO2 from the atmosphere to the deep ocean via the biological pump. Here we use barite accumulation rates to reconstruct export production in the eastern equatorial Pacific over the past 4.3 Ma. We find that export production fluctuated considerably on multiple time scales. Export production was on average higher (51 g C/m**2/yr) during the Pliocene than the Pleistocene (40 g C/m**2/yr), decreasing between 3 and 1 Ma (from more than 60 to 20 g C/m**2/yr) followed by an increase over the last million years. These trends likely reflect basin-scale changes in nutrient inventory and ocean circulation. Our record reveals decoupling between export production and temperatures on these long (million years) time scale. On orbital time scales, export production was generally higher during cold periods (glacial maxima) between 4.3 and 1.1 Ma. This could be due to stronger wind stress and higher upwelling rates during glacial periods. A shift in the timing of maximum export production to deglaciations is seen in the last ~1.1 million years. Results from this study suggest that, in the eastern equatorial Pacific, mechanisms that affect nutrient supply and/or ecosystem structure and in turn carbon export on orbital time scales differ from those operating on longer time scales and that processes linking export production and climate-modulated oceanic conditions changed about 1.1 million years ago. These observations should be accounted for in climate models to ensure better predictions of future climate change.

Description of manganese nodules and crust collected from the Hakurei Maru Cruise GH76-1, January-March, 1976, in the Central Pacific Basin

This report of the GH76-1 cruise mainly includes the results of the on-board observations in the survey area of the medial-eastern part of Central Pacific Basin (5 degree -10 degree N, 170 degree -175 degree W) and partly of analytical work at the on-shore laboratory. In addition, the results of some on-board optical and geophysical works along the tracks of Japan-Ogasawara-survey area-Hawaii, are described in appendices. The GH76-1 cruise of the R/V Hakurei-maru was carried out from the 10th January to the 9th March, 1976 as the second phase field work of the Geological Survey of Japan five-year research program of study on the manganese nodule deposits of the Central Pacific Basin and also as a part of the National Research Institute for Pollution and Resources research program of technological study on the exploitation of deep sea mineral resources. The GSJ research program (F.Y. 1974-F.Y. 1978) aims at providing basic information on the manganese nodule distribution and their origin on the deep sea floor of the Central Pacific Basin bounded by the Marshall Ridge to the west, the Christmas Ridge to the east, and the Mid-Pacific Mountains to the north. The first phase of investigation was carried out during the GH74-5 cruise in the eastern part of the area (6 degree -10 degree 30'W, 164 degree 30'-171 degree 30'N)(Mizuno and Chujo, eds., 1975), and the present second phase covered an areas of 5 degree square, just west of the GH74-5 area.