Major oxides, trace elements and rare earth elements of selected basalt samples at DSDP Hole 83-504B

DSDP Hole 504B is the deepest section drilled into oceanic basement, penetrating through a 571.5-m lava pile and a 209-m transition zone of lavas and dikes into 295 m of a sheeted dike complex. To define the basement composition 194 samples of least altered basalts, representing all lithologic units, were analyzed for their major and 26 trace elements. As is evident from the alteration-sensitive indicators H2O+, CO2, S, K, Mn, Zn, Cu, and the iron oxidation ratio, all rocks recovered are chemically altered to some extent. Downhole variation in these parameters enables us to distinguish five depth-related alteration zones that closely correlate with changes in alteration mineralogy. Alteration in the uppermost basement portion is characterized by pronounced K-uptake, sulfur loss, and iron oxidation and clearly demonstrates low-temperature seawater interaction. A very spectacular type of alteration is confined to the depth range from 910 to 1059 m below seafloor (BSF). Rocks from this basement portion exhibit the lowest iron oxidation, the highest H2O+ contents, and a considerable enrichment in Mn, S, Zn, and Cu. At the top of this zone a stockwork-like sulfide mineralization occurs. The chemical data suggest that this basement portion was at one time within a hydrothermal upflow zone. The steep gradient in alteration chemistry above this zone and the ore precipitation are interpreted as the result of mixing of the upflowing hydrothermal fluids with lower-temperature solutions circulating in the lava pile. Despite the chemical alteration the primary composition and variation of the rocks can be reliably established. All data demonstrate that the pillow lavas and the dikes are remarkably uniform and display almost the same range of variation. A general characteristic of the rocks that classify as olivine tholeiites is their high MgO contents (up to 10.5 wt.%) and their low K abundances (-200 ppm). According to their mg-values, which range from 0.60 to 0.74, most basalts appear to have undergone some high-level crystal fractionation. Despite the overall similarity in composition, there are two major basalt groups that have significantly different abundances and ratios of incompatible elements at similar mg-values. The majority of the basalts from the pillow lava and dike sections are chemically closely related, and most probably represent differentiation products of a common parental magma. They are low in Na2O, TiO2, and P2O5, and very low in the more hygromagmaphile elements. Interdigitated with this basalt group is a very rarely occurring basalt that is higher in Na2O, TiO2, P2O5, much less depleted in hygromagmaphile elements, and similar to normal mid-ocean ridge basalt (MORB). The latter is restricted to Lithologic Units 5 and 36 of the pillow lava section and Lithologic Unit 83 of the dike section. The two basalt groups cannot be related by differentiation processes but have to be regarded as products of two different parental magmas. The compositional uniformity of the majority of the basalts suggests that the magma chamber beneath the Costa Rica Rift reached nearly steady-state conditions. However, the presence of lavas and dikes that crystallized from a different parental magma requires the existence of a separate conduit-magma chamber system for these melts. Occasionally mixing between the two magma types appears to have occurred. The chemical characteristics of the two magma types imply some heterogeneity in the mantle source underlying the Costa Rica Rift. The predominant magma type represents an extremely depleted source, whereas the rare magma type presumably originated from regions of less depleted mantle material (relict or affected by metasomatism).

Stable isotope and trace element geochemistry of carbonate sediments at DSDP Holes 87-577 and 6-47.2

Detailed analyses of well-preserved carbonate samples from across the Cretaceous/Tertiary boundary in Hole 577 have revealed a significant decline in the d13C values of calcareous nannoplankton from the Maestrichtian to the Danian Age accompanied by a substantial reduction in carbonate accumulation rates. Benthic foraminifers, however, do not exhibit a shift in carbon composition similar to that recorded by the calcareous nannoplankton, but actually increase slightly over the same time interval. These results are similar to the earlier findings at two North Pacific Deep Sea Drilling Project locations, Sites 47.2 and 465, and are considered to represent a dramatic decrease in oceanic phytoplankton production associated with the catastrophic Cretaceous/Tertiary boundary extinctions. In addition, the change in carbon composition of calcareous nannoplankton across the Cretaceous/Tertiary boundary at Hole 577 is accompanied by only minor changes in the oxygen isotope trends of both calcareous nannoplankton and benthic foraminifers, suggesting that temperature variations in the North Pacific from the late Maestrichtian to the early Danian Age were insignificant.

Chemistry of interstitial waters of samples from DSDP Leg 25

Interstitial water analyses from sediments collected during Leg 25 of the Deep Sea Drilling Project have revealed that in the southwest Indian Ocean, great chemical activity exists in sediments in various depositional environments. Variable sedimentation rates allow us to set some interesting boundary conditions on chemical and transport processes in these interstitial waters, particularly with regard to the distribution of dissolved sulfate. In terrigenous rapidly deposited sediments, large depletions are observed in magnesium and potassium, whereas relatively small decreases in dissolved calcium occur. In slowly deposited detrital sediments, also, large decreases in potassium and magnesium coincide with very large calcium increases. In truly pelagic sediments, a one to one replacement of magnesium by calcium is observed in the interstitial waters, presumably due to reactions in the basal sediment layers. Biogenous deposits have great influence on dissolved silica (sponge spicules and radiolarians) and on dissolved strontium (carbonate recrystallization). Otherwise, dissolved silica reflects the clay mineralogy and shows variations which seem particularly dependent on the presence or absence of kaolinite. Variable dissolved manganese values reflect reducing conditions and/or availability of manganese in the solid phases for mobilization in reducing sediments.

Rare and trace element analyses from DSDP Holes 31-291 and 31-294 from the Philippine Sea

Metal-rich sediments were found in the West Philippine Basin at DSDP sites 291 (located about 500 km SW of the Philippine Ridge or Central Basin Fault) and 294/295 (located about 580 km NE of the Philippine Ridge). In both cases the metalliferous deposits constitute a layer, probably Eocene in age, resting directly above the basaltic basement at the bottom of the sediment column. The chemistry of the major (including Fe and Mn) and trace elements (including trace metals, rare earth elements, U and Th) suggest a strong similarity of these deposits to metalliferous deposits produced by hydrothermal activity at oceanic spreading centers. Well-crystallized hematite is a major component of the metal-rich deposits at site 294/295. We infer that the Philippine Sea deposits were formed at some spreading center by hydrothermal processes of metallogenesis, similar to processes occurring at oceanic spreading centers. A locus for their formation might have been the Philippine Ridge (Central Basin Fault), probably an extinct spreading center. We conclude that metallogenesis of the type occurring at oceanic spreading centers can take place also in marginal basins. This has implications for the origin of metal deposits found in some ophiolite complexes, such as those in Luzon (Philippines), which may represent fragments of former marginal basins rather than of oceanic lithosphere.

Speciation of metals in bottom sediments from the south Kara Sea and Ob and Yenisei estuarine zones

Speciation of Fe, Mn, Zn, Cu, Co, Ni, Cr, Pb, and Cd was studied in 52 samples of bottom sediments collected during Cruise 49 of the R/V "Dmitry Mendeleev" to the estuaries of the Ob and Yenisei rivers and to the southwest Kara Sea. Immediately after sampling the samples were subjected to on-board consecutive extraction to separate metal species according to their modes of occurrence in the sediments: (1) adsorbed, (2) amorphous Fe-Mn hydroxides and related metals, (3) organic + sulfide, and (4) residual, or lithogenic. Atomic absorption spectroscopy of the extracts was carried out at a stationary laboratory. Distribution of Fe, Zn, Cu, Co, Ni, Cr, Pb, and Cd species is characterized by predominance of lithogenic or geochemically inert modes (70-95% of bulk contents), in which the metals are bound in terrigenous and clastic mineral particles and organic detritus. About half of total Mn amount and 15-30% of Zn and Cu are contained in geochemically mobile modes. Spatiotemporal variations in proportions of the metal species in the surface layer of sediments along sub-meridional sections and through vertical sections of bottom sediment cores testify that Mn and, to a lesser extent, Cu are the most sensitive to changes in sedimentation environment. The role of their geochemically mobile species notably increases under reducing conditions.

Calcium carbonate and trace element composition of ODP Leg 182 sites

An intensive geochemical investigation was conducted on carbonate sediments recovered during Ocean Drilling Program Leg 182. Four trace elements in 635 sediment samples from Sites 1126-1132 on the Great Australian Bight were examined by atomic absorption spectrometry on the acid-soluble fraction. Downhole profiles of these elements exhibit complicated fluctuations throughout the late Eocene to Pleistocene, principally because of the variations in the acid-soluble fraction. The purpose of this study is to present initial results on the geochemical composition of Cenozoic cool-water carbonates as a basis for a future detailed investigation to determine the paleoenvironment of a carbonate-dominated continental margin during the evolution of the Southern Ocean.

Geochemistry of sands and sandstones in ODP Leg 126 sites

During Ocean Drilling Program Leg 126, six sites were cored in a young backarc rift basin and its flanks (rift onset 1.1-3.56 Ma) and in the forearc basin of the Izu-Bonin Arc. In the backarc area, strata are younger than about 4.5 Ma, whereas in the forearc, ages are about 0-31 Ma in sections punctuated by important Miocene unconformities. Bulk chemical analyses of volcaniclastic turbidite sands and sandstones, derived directly from the arc, were obtained from 271 atomic absorption analyses (major elements), 253 XRF analyses (trace elements) and 16 ICP-MS analyses (trace and rare-earth elements). Of the 271 samples, 78 come from the backarc area and the remainder from the forearc. The sands and sandstones reflect the igneous compositions of their sources. Most are formed of materials derived from subalkaline, low-K andesites, and dacites, although compositions range from basalt to rhyolite. Basic and acid andesites are predominant in Oligocene rocks; in contrast, Pliocene-Pleistocene sediments were derived from acid andesitic to rhyolitic sources. The oldest sandstones, estimated to have an age of about 31 Ma, were derived from an arc tholeiitic, not boninitic, source. The 26-31 Ma sandstones furthest to the north, at Sites 787 and 792, have higher relative concentrations of Ti, Zr, and Y than do those at southern Site 793. Data from younger samples indicate that, for more than 30 m.y., the average composition of volcaniclastic sediments and volcanism near Aoga Shima was more basic than to the south, near Sumisu Jima. Using the sandstones as igneous proxies, we conclude that magmas erupted along the arc have become more depleted in light-rare-earth elements (LREE) with time. There was a major change in rare-earth-element (REE) concentrations in the late Oligocene, from essentially flat patterns (normalized La/Yb about 1-1.5) to LREE-depleted patterns (normalized La/Yb about 0.5). At the same time, Zr/Y ratios decreased from about 2-4 to about 1.5-2.5. These changes may reflect a shift in provenance, or changes in the composition of the mantle wedge beneath the arc. In the backarc area, lithic clasts and glass shards of rift-facies basalt are present in sediments as old as 2.35-3.15 Ma. Two samples of mafic sand from the backarc basin have flat REE patterns (normalized La/Yb about 1.0), like some of the <1-Ma rift lavas and unlike pre-rift sand and sandstone samples. These possibly represent the local effects of sedimentary mixing of detritus from arc and backarc eruptions because no evidence from the arc itself exists to suggest a recent change in the REE content of magmas.

Sedimentary facies, clay mineralogy and geochemistry of the Paleogene sediments of ODP Site 105-647

Claystones immediately overlying the early Eocene age ocean-floor basalt, cored at Ocean Drilling Program (ODP) Site 647, underwent hydrothermal and thermal alterations originating from the basalt, which resulted in changes in both the mineralogical and chemical composition of the sediments. Chlorites and higher magnesium and iron concentrations were found in the lowermost sediment sequence. Upcore, changes in the bulk chemical composition of the sediments become smaller, when compensated for variations in the carbonate content originating from biogenic and authigenic components. Chlorite disappears upcore, but still only part of the swelling clay minerals have survived the thermal influence. Thirty meters above the basalt, the clay mineralogy and chemical composition become uniform throughout the Paleogene section. Iron-rich smectites (i.e., nontronitic types), totally dominate the clay mineral assemblage. Biogenic components, responsible for the dominant part of the calcite and cristobalite contents, vary in amount in the upper part, and so do the authigenic carbonate and sulfide contents. Detrital components, such as kaolinite, illite, quartz, and feldspars, make up a very small proportion of the sediment record. The nontronitic smectites are believed to be authigenic, formed by a supply of iron from the continuous formation of ocean-floor basalt in the ridge area that reacted with the detrital and biogenic silicates and alumina silicates.

Geochemistry of secondary carbonates in ODP Leg 115 basalts

This report presents the results of a study of the stable isotopic and chemical composition of secondary carbonate minerals precipitated within basalts at Ocean Drilling Program Sites 707 and 715. At Site 715, the secondary carbonates are all composed of calcite and display a narrow range of carbon and oxygen stable isotope ratios, with values ranging from -2.75 per mil to 1.95 per mil PDB and -0.27 per mil to 2.86 per mil PDB, respectively. Strontium, iron, and manganese values of the samples are generally low. The geochemistry of Site 715 samples indicates that they precipitated from seawater-domi- nated fluids, at low temperatures, as is typical of secondary carbonates from most Deep Sea Drilling Project sites. In contrast, at Site 707, aragonite, siderite, and manganese-rich calcite occur as secondary carbonates in addition to calcite. The carbon isotopes of the Site 707 carbonates of all rock types are depleted in 13C. Values range from -2.79 per mil to -16.43 per mil PDB. Oxygen isotope values do not show a wide variation, ranging from -1.78 per mil to 1.17 per mil. The strontium contents of the samples range from 5200 to 8100 ppm for aragonites, and from 145 to 862 ppm for calcites. Iron and manganese contents are high in calcites and siderites and low in aragonites. Site 707 carbonates precipitated at low temperatures in a fairly closed system, in which basalt-seawater interaction has greatly influenced the chemistry of the pore fluids. The reactions occurring within the system before and in conjunction with secondary carbonate precipita- tion include oxidation of isotopically light methane, derived from fluids circulating within the basalts, and reduction of substantial amounts of iron and manganese oxides from the basalts.

Lead and cadmium in the Weser Estuary and the German Bight: Correlations between bacteria populations, heavy metals and organic carbon

Organic carbon, lead and cadmium contents of 20 sediments were determined and compared with the colony counts of anaerobic heterotrophic, anaerobic nitrogen fixing, chitinoclastic and cellulolytic bacteria. Organic carbon content, which is dependent on the sediment type, was positively correlated with lead and cadmium as well as with colony counts of all 4 physiological groups of bacteria. Even the sediments with the highest concentrations of 251.7 ppm Pb and 3.1 ppm Cd showed no reduction in their colony counts. From 2 different sediment sampIes with lead contents of 140 ppm and 21 ppm lead tolerance of the aerobic heterotrophic bacteria was investigated. However, no significant difference in lead tolerance of the 2 heterotrophic populations was found. Water from 6 stations was analysed for dissolved and particulate organic carbon, lead and cadmium. Dissolved lead concentrations were in the range of 0.2-0.5 µg/l and the particulate lead contents were between 0.05 and 4.3 µg/l. The concentrations of total lead for the stations off-shore were only one order of magnitude from the concentrations of the near-shore stations. The same phenomenon was observed for dissolved cadmium (0.02 - 0.25 µg/l) and particulate cadmium (0.003 - 0.15 µg/I) concentrations. Correlations between dissolved (1.6 - 10.8 mg/I) and particulate organic carbon (0.25 - 1.53 mg/I) with dissolved and particulate lead or cadmium were not found.

Gold and organic carbon in waters from the Bering Sea and the North Pacific

Atomic absorption spectroscopy is used to determine concentration of gold in waters of the Bering Sea and North Pacific. Distributions of gold and organic carbon in colloidal and "dissolved" fractions separated by ultrafiltration through Vladipor filters are determined. Direct evidence of gold association with colloidal matter of sea water is presented and concentrations of gold in various fractions of colloidal solutions are determined. The most important forms of occurrence of colloidal gold prove to be high molecular weight fractions, and the most important form of colloidal organic carbon (Corg) is low molecular fraction. Dissolved forms are important in the balance of gold and Corg. Variations in forms of occurrence of gold and Corg in vertical profiles are described.