(Table 2) Geochemistry of glasses at DSDP Leg 54 Holes

The compositions of 45 natural basalt glasses from nine dredge stations and six Deep Sea Drilling Project Leg 54 sites near 9°N on the East Pacific Rise have been determined by electron microprobe. These comprise 19 distinct chemical groups. Seventeen of these fall in the range of the eastern Pacific tholeiite suite, which is characterized by marked enrichment in FeO*, TiO2, K2O, and P2O5 as CaO, MgO, and Al2O3 all decrease. Based on trace elements, an estimated 50-75 per cent fractionation of plagioclase, clinopyroxene, and olivine is required to produce ferrobasalts from parental olivine tholeiites. Additional chemical variations occur which require source heterogeneities, differences in the degree of melting, different courses of shallow fractionation, or magma mixing to explain. Glass compositions from within the Siqueiros fracture zone are mostly less fractionated than those from the flanks of the Rise, and show chemical differences which require variations in the depth of melting or highpressure fractionation to explain. Some of them could not be parental to East Pacific Rise flank ferrobasalts. Two remaining glass groups, from dredge hauls atop a ridge and a seamount, respectively, have distinctly higher K2O, P2O5, and TiO2 as well as lower CaO/Al2O3 and SiO2 at corresponding values of MgO than the tholeiite suite. These abundances, and whole-rock Y/Zr, Ce/Y, Nb/Zr, and isotopic abundances indicate that these basalts had a deeper, less depleted mantle source than the Rise tholeiite suite. Trace element abundances preclude the "ridge" basalt type from being a hybrid between the "seamount" basalt type and any East Pacific Rise tholeiite so far analyzed. The East Pacific Rise glasses from 9°N compare very closely to glasses dredged and drilled elsewhere on the East Pacific Rise. However, glass compositions from Site 424 on the Galapagos Rift drilled during Leg 54, as well as glasses and basalts dredged from the Galapagos and Costa Rica rifts, indicate that a greater degree of melting prevailed along much of the Galapagos Spreading Center than anywhere along the East Pacific Rise.

Magnetic mineralogy and geochemistry of ODP Holes 137-504B and 140-504B samples

Leg 140 of the Ocean Drilling Program deepened Hole 504B to a total depth of 2000.4 m below seafloor (mbsf), making it the deepest hole drilled into ocean crust. Site 504, south of the Costa Rica Rift, is considered the most important in-situ reference section for the structure of shallow ocean crust. We present the results of studies of magnetic mineralogy and magnetic properties of Hole 504B upper crustal rocks recovered during Legs 137 and 140. Results from this sample set are consistent with those discussed in Pariso et al. (this volume) from Legs 111, 137, and 140. Coercivity (Hc) ranges from 5.3 to 27.7 mT (mean 12 mT), coercivity of remanence (HCR) ranges from 13.3 to 50.6 mT (mean 26 mT), and the ratio HCR/HC ranges from 1.6 to 3.19 (mean 2.13). Saturation magnetization (JS) ranges from 0.03 to 5.94 * 10**-6 Am**2, (mean 2.52 * 10**-6 Am**2), saturation remanence (JR) ranges from 0.01 to 0.58 * 10**-6 Am2 (mean 0.37 * 10**-6 Am**2), and the ratio JR/JS ranges from 0.08 to 0.29 (mean 0.16), consistent with pseudo-single-domain behavior. Natural remanent magnetization (NRM) intensity ranges from 0.029 to 7.18 A/m (mean 2.95 A/m), whereas RM10 intensity varies only from 0.006 to 4.8 A/m and has a mean of only 1.02 A/m. Anhysteretic remanent magnetization (ARM) intensity ranges from 0.04 to 6.0 A/m, with a mean of 2.46 A/m, and isothermal remanent magnetization (IRM) intensity ranges from 0.5 to 1683 A/m, with a mean of 430.7 A/m. Volume susceptibility ranges from 0.0003 to 0.043 SI (mean 0.011 SI). In all samples examined, high-temperature oxidation of primary titanomagnetite has produced lamellae or pods of magnetite and ilmenite. Hydrothermal alteration has further altered the minerals in some samples to a mixture of magnetite, ilmenite, titanite, and a high-titanium mineral (either rutile or anatase). Electron microprobe analyses show that magnetite lamellae are enriched in the trivalent oxides Cr2O3, Al2O3, and V2O5, whereas divalent oxides (MnO and MgO) are concentrated in ilmenite lamellae.

Chemical composition of clay minerals from ODP Leg 168 sites

The exchangeable cation compositions of organic-poor terrigenous sediments containing smectite as primary ion exchanger from a series of holes along ODP Leg 168 transect on the eastern flank of the Juan de Fuca Ridge have been examined as a function of distance from the ridge axis and burial depth. The total cation exchange capacity (CEC) values of the sediments ranged from 2 to 59 meq/100 g, increasing with increases in the wt.% smectite. At the seafloor, the exchangeable cation compositions involving Na, K, Mg, and Ca, expressed in terms of equivalent fraction, are nearly constant regardless of the different transect sites: XNa = 0.21 ± 0.04, XK = 0.08 ± 0.01, XMg = 0.33 ± 0.09, and XCa = 0.38 ± 0.09. The calculated selectivity coefficients of the corresponding quaternary exchange reactions, calculated using porewater data, are in log units -5.45 ± 0.39 for Na, 1.97 ± 0.49 for K, 0.42 ± 0.41 for Mg, and 3.06 ± 0.69 for Ca. The exchangeable cation compositions below the seafloor change systematically with distance from the ridge crest and burial depth, conforming to the trends of the same cations in the porewaters. The selectivities for Na and Mg are roughly constant at temperatures from 2 to 66°C, indicating that the equivalent fractions of these two cations are independent of sediment alteration taking place on the ridge flank. Unlike Na and Mg, the temperature influence is significant for K and Ca, with Ca-selectivity decreases being coupled with increases in K-selectivity. Although potentially related to diagenetic and/or hydrothermal mineral precipitation or recrystallization, no evidence of such alteration was detected by XRD and TEM. In sites where upwelling of hydrothermal fluids from basement is occurring, the K-selectivity of the sediment is appreciably higher than at the other sites and corresponds to the formation of (Fe, Mg) rich smectite and zeolites. Our study indicates that local increases in K-selectivity at hydrothermal sites are caused by the formation of these authigenic minerals.

Geochemistry of low-temperatuer altered basalts of ODP Hole 136-843B

The mineralogy and chemistry of altered basalts and the stable isotopic compositions of secondary vein carbonates were studied in cores from Ocean Drilling Program Hole 843B, located in 95-Ma crust of the Hawaiian Arch. Millimeter- to centimeter-sized dark alteration halos around veins are 5%-15% altered to celadonite and Fe-oxyhydroxides, plus minor saponite and calcite. Adjacent gray host rocks are about 15% altered to saponite and calcite. The dark halos are enriched in H2O+, CO2, FeT, K2O, MnO, and Fe3+/FeT and depleted in SiO2, Al2O3, MgO, and TiO2 relative to gray host rocks. Brown alteration halos occur around veins where veins are more abundant, and are similar to dark halos, but contain more Fe-oxyhydroxides and exhibit greater Fe2O3T contents and higher Fe3+/FeT. Stable isotopic compositions of vein carbonates are consistent with their precipitation from seawater at temperatures of 5°-40°C. Crosscutting relationships of veins and zoned vein and vesicle fillings reveal a sequence of secondary mineral formation and alteration conditions. Celadonite and Fe-oxyhydroxides formed and dark alteration halos developed relatively early, under oxidizing conditions at low temperatures (<50°C). Saponite formed later at lower seawater/rock ratios and under more reducing conditions. Calcite and pyrite formed last in veins and vesicles from more evolved, seawaterderived fluids at temperatures of 5°-40°C. A second stage of celadonite, with compositions distinct from the early celadonite, also occurred relatively late (within the "calcite stage"), and may be related to refracturing of the crust and introduction of less-evolved seawater solutions into the rocks. Trends to higher K2O contents are attributed to alteration, but high K/Ti, Ba, and Zr contents indicate the presence of enriched or transitional MORB. CO2 contents of Pacific ODP cores exhibit a general increase with age suggesting progressive fixation of CO2 as calcite in the crust, but this could be complicated by local heterogeneities in fracturing and calcite formation in the crust.

Geochemistry at DSDP Hole 57-439

Acidic to intermediate volcanic rocks were obtained as boulders, pebbles, and clasts with intercalated matrix sediments near the Japan Trench. A 47.5-meter conglomerate bed unconformably overlies acoustic basement consisting of Upper Cretaceous siltstone and is overlain in turn by massive coarse-sandstone and siltstone beds with many fossil mollusks. The volcanic cobbles and boulders in the conglomerate show pronounced porphyritic texture. Their phenocrysts are plagioclase, hornblende, and biotite; the groundmass consists of plagioclase, K-feldspar, quartz, iron oxide, and altered interstitial glass. The Plagioclase content of these volcanic rocks is very high, whereas iron oxide minerals are rare. The chemical composition of these volcanic rocks was analyzed to determine the rock series. Matrix sediments were also analyzed chemically, and their chemical composition was found to be similar to that of volcanic rocks, except for a lower CaO content. SiO2 content of the volcanic rocks ranges from 60.23 to 73.90, corresponding to that of andesite to rhyolite. All the samples show extremely high Al2O3 content, which reflects the high amounts of modal plagioclase. These volcanic rocks belong to both the calc-alkalic and tholeiitic rock series, and the differentiation trend is controlled by fractional crystallization, mainly of plagioclase, K-feldspar, and hornblende. The assemblage of calc-alkalic and tholeiitic rock series is frequently observed in island arcs and active continental margins. These volcanic rocks are derived from the Oyashio ancient landmass, which is a slightly matured island arc.

Chemical composition and elemental oxide ratios to AI2O3 of bulk solids at DSDP Leg 64 Holes

Analyses of sediments from Leg 64 sites reveal a diverse and in one case unique geochemistry. Sites are characterized by high heat flow along an active, divergent plate boundary, or rapid accumulation of diatom muds, or both. The geochemical trends of Sites 474-476 at the tip of Baja California reflect changes4n the percentages of sedimentary components - particularly biogenous matter and mineralogy - that support interpretations of sedimentary environments inferred to be present since the commencement of subsidence along this young, passive continental margin. The sediments below dolerite sills in Holes 477, 477A, 478, and 481 show major mineralogic and chemical deviations from "average" hemipelagic sediments. The sills appear to have two functions: (1) they allow hydrothermal circulation and metamorphism in a partially closed system by trapping heat and fluids emanating from below, and (2) they expel heated interstitial fluids at the moment of intrusion and mobilize elements, most likely leading to the formation of metalliferous deposits along the surface traces of normal faults in the basin. The hydrothermal system as a whole appears to be localized and ephemeral, as is indicated by the lack of similar geochemical trends and high heat flow at Sites 478 and 481. Site 479 illustrates sedimentation in an oxygen-minimum zone with anoxic sediments and concomitant geochemical trends, especially for MnO. With few exceptions, geochemical trends are remarkably constant with depth, suggesting that Site 479 can serve as an "internal" standard or average sediment against which the magnitude of hydrothermal alteration at the basinal Sites 477, 478, and 481 can be measured.

Ordinary and duplicate analysis from major and trace elements of ODP Holes 146-888B and 168-1027B

Oceanic sediments deposited at high rate close to continents are dominated by terrigenous material. Aside from dilution by biogenic components, their chemical compositions reflect those of nearby continental masses. This study focuses on oceanic sediments coming from the juvenile Canadian Cordillera and highlights systematic differences between detritus deriving from juvenile crust and detritus from old and mature crust. We report major and trace element concentrations for 68 sediments from the northernmost part of the Cascade forearc, drilled at ODP Sites 888 and 1027. The calculated weighted averages for each site can then be used in the future to quantify the contribution of subducted sediments to Cascades volcanism. The two sites have similar compositions but Site 888, located closer to the continent, has higher sandy turbidite contents and displays higher bulk SiO2/Al2O3 with lower bulk Nb/Zr, attributed to the presence of zircons in the coarse sands. Comparison with published data for other oceanic sedimentary piles demonstrates the existence of systematic differences between modern sediments deriving from juvenile terranes (juvenile sediments) and modern sediments derived from mature continental areas (cratonic sediments). The most striking systematic difference is for Th/Nb, Th/U, Nb/U and Th/Rb ratios: juvenile sediments have much lower ratios than cratonic sediments. The small enrichment of Th over Nb in cratonic sediments may be explained by intracrustal magmatic and metamorphic differentiation processes. In contrast, their elevated Th/U and Nb/U ratios (average values of 6.87 and 7.95, respectively) in comparison to juvenile sediments (Th/U ~ 3.09, Nb/U ~ 5.15) suggest extensive U and Rb losses on old cratons. Uranium and Rb losses are attributed to long-term leaching by rain and river water during exposure of the continental crust at the surface. Over geological times, the weathering effects create a slow but systematic increase of Th/U with exposure time.

Mineral and chemical compositions of authigenic carbonates from the northern Deryugin Basin, Sea of Okhotsk

Mineral and chemical compositions of authigenic carbonates are studied by several methods in a sediment core collected in the axial zone of the Deryugin riftogenic basin. Manganese carbonates (kutnahorite, rhodochrosite) associated with manganiferous calcite, manganiferous pyrite, and nontronite are firstly identified in the Sea of Okhotsk. Manganese carbonates in Holocene diatomaceous ooze were presumably formed due to diagenetic transformation of sedimentary manganese hydroxides, organic matter, and biogenic silica, while those found in the underlying turbidites precipitated owing to the intermittent influx of endogenic fluids migrating along sand interbeds.

Geochemistry at DSDP Leg 55 Holes

The tops of the Emperor chain guyots, which were drilled during Leg 55, lie above the carbonate compensation depth (CCD), as well as above the foraminiferal dissolution level, i.e., lysocline. They are therefore the sites of accumulation of pelagic foraminiferal nannofossil ooze, such accumulation having taken place here since the moment of the seamounts' subsidence and the termination of shallow-water carbonate accumulation which was formerly developed on their tops. But the existence of strong bottom currents over the tops and slope scarps limits, and at some places reduces to zero, sedimentation of any pelagic particles. At such areas there are formed thick iron-manganese crusts. The seamounts drilled on Leg 55 are within the northern (Boreal) belt of biogenic silica accumulation, which existed in the northern Pacific throughout the Neogene. This circumstance presupposes a possible enrichment of the relatively fine-grained sediments with biogenic silica - diatoms and radiolarians.

Mineralogy and inorganic geochemistry of sediments at DSDP Leg 65 Holes

During Leg 65, 15 holes were drilled at four sites located on young crust in the mouth of the Gulf of California. Quaternary to upper Pliocene hemipelagic sediments above and interlayered within the young basaltic basement were cored. The influence of hot lava, high temperature gradients, and hydrothermal activity on the mineralogy and geochemistry of the terrigenous sediments near contacts with basalts might therefore be expected. The purpose of the present study was to determine the mineralogy and inorganic geochemistry of these sediments and to analyze the nature and extent of low temperature alteration. To this end we studied the mineralogy and inorganic geochemistry of 75 sediment samples, including those immediately overlying uppermost basalts and those from layers alternating with basalts within the basement. We separated three size fractions - <2 µm (clay), 2-20 µm (intermediate), and >20 µm (coarse) - and applied the following mineralogical determinations: x-ray diffraction (XRD), infrared spectroscopy, transmission and scanning electron microscopy, and optical microscopy (for coarse fractions, using thin sections and smear slides). We calculated the percentages of clay minerals using Biscaye's (1964) method, and used routine wet chemical analyses to determine bulk composition and quantitative spectral analyses for trace elements.

Geochemistry at DSDP Legs 56-57 Holes

About 200 volcanic ash layers were recovered during DSDP Leg 57. The volcanic glass in some of these layers was investigated petrographically and chemically in this study. Volcanic glass is mainly rhyolitic and/or rhyodacitic in chemical composition, and its refractive index ranges from 1.496 to 1.529. Some volcanic ash layers consist of multiple grains of different chemical compositions. All the volcanic glass belongs to the tholeiitic and the calc-alkalic volcanic rock series, in SiO2-(Na2O + K2O) diagram and FeO*/MgO-SiO2 diagram. We correlated successfully three volcanic ash layers from the standpoint of chemical composition and biostratigraphy. Hydration of volcanic glass from Leg 57 is less intense than in other DSDP cores.

Geochemistry and mineralogy of sediments from the Atlantis II Fracture Zone

Thirteen sediment samples, including calcareous ooze, sandy clay, volcanic sand, gravel, and volcanic breccia, from Ocean Drilling Program (ODP) Sites 732B, 734B, 734G and Conrad Cruise 27-9, Station 17, were examined. Contents of major and trace elements were determined using XRF or ICP (on samples <0.5 g). Determinations of rare earth elements (REE) were performed using ICP-MS. Mineralogy was determined using XRD. On the basis of the samples studied, the sediments accumulating in the Atlantis II Fracture Zone are characterized by generally high MgO, Cr, and Ni contents compared with other deep-sea sediments. A variety of sources are reflected in the mineralogy and geochemistry of these sediments. Serpentine, brucite, magnetite, and high MgO, Cr, and Ni contents indicate derivation from ultramafic basement. The occurrence of albite, analcime, primary mafic minerals, and smectite/chlorite in some samples, coupled with high SiO2, Al2O3, TiO2, Fe2O3, V, and Y indicate contribution from basaltic basement. A third major sediment source is characterized as biogenic material and is reflected primarily in the presence of carbonate minerals, and high CaO, Sr, Pb, and Zn in certain samples. Kaolinite, illite, quartz, and some chlorite are most likely derived from continental areas or other parts of the ocean by long-distance sediment transport in surface or other ocean currents. Proportions of source materials in the sediments reflect the thickness of the sediment cover, slope of the seafloor, and the nature of and proximity to basement lithologies. REE values are low compared to other deep-sea sediments and indicate no evidence of hydrothermal activity in the Atlantis II Fracture Zone sediments. This is supported by major- and trace-element data.

Geochemistry of basalts from Serocki Volcano

Basalts collected during drilling and diving programs on Serocki Volcano mostly fall within a limited compositional range, and are moderately evolved, normal MORBs with distinctive high MgO contents (averaging 7.60 wt%) and high A1203 concentrations (averaging 16.14 wt% in whole rock samples). However, samples recovered from within the central crater have lower Ti02 and FeO*/MgO, and higher MgO and Al2O3 concentrations, and are most similar to glasses recovered at Site 649 about 45 km to the north. Comparison of the observed geochemical variations with low-pressure experimental work and other samples from the region suggests that the Serocki Volcano and Site 649 data are compatible with crystal-liquid fractionation involving both olivine and early-stage clinopyroxene, as well as plagioclase, and that the sources may be similar even though Sites 648 and 649 are located in different, but adjacent, spreading cells. Consideration of the stratigraphy and morphology of Serocki Volcano suggests that this feature is more properly described as a megatumulus or lava delta, associated with a steeper, conical peak to the southwest. The evolution of Serocki Volcano involved early construction of a marginal rampart of pillows, followed by doming of this feature and the formation of a perched lava pond. Draining of this pond resulted in collapse and the formation of the central crater.