Geochemistry and minerals at DSDP LEg 58 Holes

Leg 58 successfully recovered basalt at Sites 442, 443, and 444, in the Shikoku Basin, and at Site 446 in the Daito Basin. Only at Site 442 did penetration reach unequivocal oceanic layer 2; at the other sites, only off-axis sills and flows were sampled. Petrographic observations indicate that back-arc basalts from the Shikoku Basin, with the exception of the kaersutite-bearing upper sill at Site 444, are mineralogically similar to basalts being erupted at normal mid-ocean ridges. However, the Shikoku Basin basalts are commonly very vesicular, indicating a high volatile content in the magmas. Site 446 in the Daito Basin penetrated a succession of 23 sills which include both kaersutite-bearing and kaersutite-free basalt varieties. A total of 187 samples from the four sites has been analyzed for major and trace elements using X-ray-fluorescence techniques. Chemically, the basalts from Sites 442 and 443 and the lower sill of Site 444 are subalkaline tholeiites and resemble N-type ocean-ridge basalts found along the East Pacific Rise and at 22° N on the Mid-Atlantic Ridge (MAR), although they are not quite as depleted in certain hygromagmatophile (HYG) elements. They do not show any chemical affinities with island-arc tholeiites. The basalts from Site 446 and from the upper sill at Site 444 show alkaline and tholeiitic tendencies, and are enriched in the more-HYG elements; they chemically resemble enriched or E-type basalts and their differentiates found along sections of the MAR (e.g., 45°N) and on ocean islands (e.g., Iceland and the Azores). Most of the intra-site variation may be attributed to crystal settling within individual massive flows and sills, to high-level fractional crystallization in sub-ridge magma chambers, or, where there is evidence of a long period of magmatic quiescence between units, to batch partial melting. However, the basalts from Sites 442 and 443 and from the lower sill at Site 444 cannot easily be related to those from Site 446 and the upper sill at Site 444, and it is possible that the different basalt types were derived from chemically distinct mantle sources. From comparison of the Leg 58 data with those already available for other intra-oceanic back-arc basins, it appears that the mantle sources giving rise to back-arc-basin basalts are chemically as diverse as those for mid-ocean ridges. In addition, the high vesicularity of the Shikoku Basin basalts supports previous observations that the mantle source of back-arc-basin basalts may be contaminated by a hydrous component from the adjacent subduction zone.

Geochemistry of carbonate cements of ODP Leg 112 samples

The evolution of pore fluids migrating through the forearc basins, continental massif, and accretionary prism of the Peru margin is recorded in the sequence of carbonate cements filling intergranular and fracture porosities. Petrographic, mineralogic, and isotopic analyses were obtained from cemented clastic sediments and tectonic breccias recovered during Leg 112 drilling. Microbial decomposition of the organic-rich upwelling facies occurs during early marine diagenesis, initially by sulfate-reduction mechanisms in the shallow subsurface, succeeded by carbonate reduction at depth. Microcrystalline, authigenic cements formed in the sulfate-reduction zone are 13C-depleted (to -20.1 per mil PDB), and those formed in the carbonate-reduction zone are 13C-enriched (to +19.0 per mil PDB). Calcium-rich dolomites and near-stoichiometric dolomites having uniformly heavy d18O values (+2.7 to +6.6 per mil PDB) are typical organic decomposition products. Quaternary marine dolomites from continental-shelf environments exhibit the strongest sulfate-reduction signatures, suggesting that Pleistocene sea-level fluctuations created a more oxygenated water column, caused periodic winnowing of the sediment floor, and expanded the subsurface penetration of marine sulfate. We have tentatively identified four exotic cement types precipitated from advected fluids and derived from the following diagenetic environments: (1) meteoric recharge, (2) basalt alteration, (3) seafloor venting and (4) hypersaline concentration. Coarsely crystalline, low-magnesium (Lo-Mg) calcite cements having pendant and blocky-spar morphologies, extremely negative d18O values (to -7.5 per mil PDB), and intermediate d13C values (-0.4 per mil to +4.6 per mil PDB) are found in shallow-marine Eocene strata. These cements are evidently products of meteoric diagenesis following subaerial emergence during late Eocene orogenic movements, although the strata have since subsided to greater than 4,000 m below sea level. Lo-Mg calcite cements filling scaly fabrics in the late Miocene accretionary prism sediments are apparently derived from fluids having lowered magnesium/calcium (Mg/Ca) and 18O/16O ratios; such fluids may have reacted with the subducting oceanic crust and ascended through the forearc along shallow-dipping thrust faults. Micritic, high-magnesium (Hi-Mg) calcite cements having extremely depleted d13C values (to -37.3%c PDB), and a benthic fauna of giant clams (Calyptogena sp.) supported by a symbiotic, chemoautotrophic metabolism, provide evidence for venting of methane-charged waters at the seafloor. Enriched d18O values (to +6.6%c PDB) in micritic dolomites from the continental shelf may be derived from hypersaline fluids that were concentrated in restricted lagoons behind an outer-shelf basement ridge, reactivated during late Miocene orogenesis.

Mineral chemistry of basalts at DSDP Leg 55 Holes

Microprobe mineral compositions of olivine, plagioclase, clinopyroxene, chrome spinel, ilmenite, and titanomagnetite are presented for 7 samples from 4 flows of hawaiite and one flow of tholeiitic basalt from Hole 430A at Ojin Seamount, 4 samples from 3 flows of alkalic basalt from Hole 432A at Nintoku Seamount, and 29 samples from 2 flows of alkalic basalt and 24 flows of tholeiitic basalt from Holes 433A, 433B, and 433C at Suiko Seamount. The four hawaiite flows from Hole 430A on Ojin Seamount have nearly identical mineralogy. The plagioclase phenocrysts and calculated equilibrium olivine appear to have crystallized at about 1175°C; the groundmass plagioclase crystallized from about 1135° to 1010°C; and the Fe-Ti oxides equilibrated at temperatures from 1000°C to 720°C under oxygen fugacities of 10**-11 to 10**-17. The single tholeiitic flow contains glomerocrysts of plagioclase (An80 to An65) and clinopyroxene (Wo43En46Fsn to Wo42En45Fs13). The plagioclase phenocrysts give calculated temperatures as high as 1400°C, indicating that they were not equilibrated with a magma having the bulk rock composition. The plagioclase groundmass crystallized at 1120° to 1070°C, and the Fe-Ti oxides equilibrated at 1070° to 930°C under oxygen fugacities of 10**-10 to 10**-12. Using mineral compositions of Hawaiian basalts as a guide, we infer that the hawaiite flows were erupted during the post-caldera alkalic eruptive stage and the tholeiite was erupted during the shield-building or caldera collapse stage. The three alkalic basalt flows from Hole 432A on Nintoku Seamount have similar mineralogy, although Flow Units 1 and 2 contain much more abundant plagioclase phenocrysts. The groundmass plagioclase crystallized at temperatures between 1175° and 1000°C. The olivine and plagioclase phenocrysts do not appear to be in equilibrium with the enclosing magmas. The mineral compositions suggest that these samples are intermediate between alkalic basalt and hawaiite; they probably erupted during the post-caldera alkalic stage of eruption. The two analyzed alkalic basalt flows are the two youngest flows recovered at Holes 433A, 433B, and 433C. Flow Unit 1 contains abundant sector-zoned clinopyroxene, and Flow Unit 2 contains rare kink-banded olivine xenocrysts. The plagioclase phenocrysts yield calculated temperatures of 1440° to 1250°C, indicating that they are probably not cognate. Calculated-equilibrium olivine indicates crystallization of olivine at about 1170°C. The Fe-Ti oxides equilibrated at temperatures of 1140° to 870°C under oxygen fugacities of 10**-9 to 10**-14. The groundmass plagioclase crystallized at temperatures of 1178° to 1035 °C. The mineral compositions indicate that these alkalic basalts erupted during the post-caldera alkalic eruptive stage. The 24 analyzed tholeiitic basalts are subdivided on the basis of phenocryst abundances into olivine tholeiites, plagioclase tholeiites, and tholeiites. The crystallization sequence appears to have been chrome spinel, olivine, plagioclase, and clinopyroxene as phenocryst phases, followed by and overlapping with groundmass crystallization of plagioclase (1180° to 920°C), clinopyroxene, and Fe-Ti oxides (1140° to 670°C). At least three flows contain pigeonite. The mineral compositions indicate that all the samples from Flow Unit 4 downward are tholeiitic basalts, although Flow Unit 64 has mineral compositions transitional to those in alkalic basalts.

Geochemistry and minerals at DSDP Leg 81 Holes

The Leg 81 basalts, drilled either from the margins ("dipping reflectors" sequence: Holes 552, 553A, and 554A) or from the "continental" side (Hole 555) of the Rockall Plateau microcontinent, are strongly light rare-earth element (LREE) depleted oceanic tholeiites. The basalts from the four holes are almost similar. Most of their primary characteristics have been preserved, although they have suffered alteration by seawater. From the petrological and mineralogical points of view, they resemble deep-ocean-floor basalts but show some peculiarities (occurrence of pigeonite and ilmenite as normal components of the groundmass differentiation sequences toward ferrobasalts). Their geochemical characteristics are dominated by their extreme depletion in the most hygromagmaphile elements (Th, Ta, La, and Nb), the concentrations of which are sometimes lower than the corresponding chondritic values. Leg 81 basalts are thus clearly different from continental tholeiites (flood basalts): Possible equivalents in the Thulean Tertiary Magmatic Province include the LREE-depleted tholeiites from the Upper Basaltic Series of the Faeroe Islands and the Preshal Mhor basalt type from the British Tertiary Province.

(Table 1) Compressional-wave and shear-wave velocities and elastic constants from DSDP Legs 69 and 70

Shear-wave and compressional-wave velocities of 26 basalt samples collected at Site 504 during Deep Sea Drilling Project Legs 69 and 70 were measured at elevated confining pressures. The young basalts have higher velocities than average DSDP basalts, because of their lack of alteration. Measurements of sample porosity are combined with laboratory and in situ velocity measurements to yield estimates of total crustal porosity: 13% at the top of Layer 2, and very low porosity below a depth of 2.0 km.

Geochemistry of ODP Leg 115 basalts

Melting-phase relations at high pressures and Sr-Nd isotopic compositions are reported for basalts collected from the western Indian Ocean during Ocean Drilling Program Leg 115. Based on the concentrations of high-field-strength elements, we have subdivided the basalts into eight groups. A tholeiitic primary magma estimated using an olivine maximum fractionation model is representative of depleted lavas. This melt is in equilibrium with lherzolite minerals at 1.3 GPa and 1330°C under dry conditions. Also, an alkaline primary magma, representative of enriched lavas, is not saturated with orthopyroxene under dry conditions, but it is saturated with lherzolite minerals under CO2-saturated conditions at 1.7 GPa and 1350°C. These results imply that the tholeiitic magmas were segregated from mantle diapirs at shallower levels than the alkaline magmas. The highest 143Nd/144Nd value is obtained for the most depleted tholeiitic basalts, and the lowest value corresponds to the enriched alkaline basalt. The Sr isotopes of the basalts range from 0.70378 to 0.70449 and are inversely correlated with the Nd isotopic values. The present experimental and geochemical data suggest that depleted mantle material is underlain by the enriched material in the upper mantle beneath the region.

(Table 1) Bulk and grain density, porosity, and p- and s-wave velocity characteristics of ODP Hole 163-990A sediments

Seismic velocities in rocks are influenced by the properties of the solid, the pore fluid, and the pore space. Cracks dramatically affect seismic velocities in rocks; their influence on the effective elastic moduli of rocks depends on their shape and concentration. Thin cracks (or fractures) substantially lower the moduli of a rock relative to the effect of spherical voids (or vesicles), and lower moduli are reflected by lower P- and S-wave velocities. The objective of this research is to determine the types and concentrations of cracks and their influence on the seismic properties of subaerially erupted basalts drilled from Hole 990A on the Southeast Greenland margin during Ocean Drilling Program Leg 163. Ellipsoidal cracks are used to model the voids in the rocks. The elastic moduli of the solid (grains) are also free parameters in the inverse modeling procedure. The apparent grain moduli reflect a weighted average of the moduli of the constituent minerals (e.g., plagioclase, augite, and clay minerals). The results indicate that (1) there is a strong relationship between P-wave velocity and porosity, suggesting a similarity of pore shape distributions, (2) the distribution of crack types within the massive, central region of aa flows from Hole 990A is independent of total porosity, (3) thin cracks are the first to be effectively sealed by alteration products, and (4) grain densities (an alteration index) and apparent grain moduli of the basalt samples are directly related.

Strontium- and lead-isotope composition of some basalts at DSDP Hole 69-504B

Seventeen whole-rock samples, generally taken at 25- to 50-meter intervals from 5 to 560 meters sub-basement in Deep Sea Drilling Project Hole 504B, were analyzed for 87Sr/86Sr ratios, and rubidium and strontium concentrations. Ten of these samples also were analyzed for Pb-isotope composition. Strontium-isotope ratios for eight samples from the upper 260 meters of the hole range from 0.70287 to 0.70377, with a mean of 0.70320. In the interval 330 to 560 meters, five samples have a restricted range of 0.70259 to 0.70279, with a mean of 0.70266, almost identical to the average value of fresh mid-ocean-ridge basalts. In the interval 260 to 330 meters, approximately intermediate strontium- isotope ratios are found. The higher 87Sr/86Sr ratios in the upper part of the hole can be interpreted in terms of strontium-isotope alteration during basalt-sea-water interaction. Relative to average fresh mid-ocean ridge basalts, the upper 260 meters of basalts are enriched by an average of about 9% in sea-water strontium 87Sr/86Sr = 0.7091). This Sr presumably is located in the smectites, which, as the main secondary minerals throughout the hole, replace olivine and matrix glass and locally fill vesicles (analyzed samples contained no veins). The strontium-isotope data strongly suggest that the integrated flux of sea water through the upper part of the Hole 504B crust has been greater than through the lower part. This is also suggested by (1) the common occurrence of Feoxide- hydroxide minerals as alteration products above 270 meters, but their near absence below 320 meters, (2) the presence of vein calcite above 320 meters, but its near absence below this level, and (3) the occurrence of vein pyrite only below a depth of 270 meters. Sea-water circulation in the lower basalts may have been partly restricted by the greater number of relatively impermeable massive lava flows below 230 meters sub-basement. Although sufficient sea water was present within the lower part of the hole to produce smectitic alteration products, the overall water /rock ratio was low enough to prevent significant modification of strontium-isotope ratios. Lead-isotope ratios of Hole 504B basalts form approximately linear arrays in plots of 208Pb/204Pb and 207Pb/204Pb versus 206Pb/204Pb. The arrays are similar to those reported for basalts from other mid-ocean ridges. There is no trend in Hole 504B lead-isotope ratios with vertical position in the basement. The arrays indicate that the lead-isotope composition of the upper mantle from which the Hole 504B basaltic melts were derived was inhomogeneous.

Chemical and isotopical analsyes of DSDP Hole 34-321 basalts

A blue-green smectite (iron-rich saponite) and green mica (celadonite) are the dominant sheet silicates in veins within the 10.5 m of basalt cored during DSDP Leg 34, Site 32l, in the Nazca plate. Oxygen isotopic analyses of these clays, and associated calcite, indicate a formation temperature of <25°C. Celadonite contains appreciable Fe2O3, K2O and SiO2, intermediate MgO, and very little Al2O3. Celadonite is commonly associated with goethite and hematite, which suggests that this phase formed by precipitation within a dominantly oxygenated environment of components leached from basalt and provided by seawater. A mass balance estimate indicates that celadonite formation can remove no more than 15% of the K annually transported to the oceans by rivers. In contrast, iron-rich saponite containing significant Al2O3 appears to have precipitated from a nonoxidizing, distinctly alkaline fluid containing a high Na/K ratio relative to unmodified seawater. Seawater-basalt interaction at low temperatures, resulting in the formation of celadonite and smectite may explain chemical gradients observed in interstitial waters of sediments overlying basalts.

Geochemistry of ODP Leg 127 igneous rocks

Legs 127 and 128 of the Ocean Drilling Program cored basement samples from two sites in the Yamato Basin (Sites 794 and 797) and one site in the Japan Basin (Site 795) of the Japan Sea. These samples represent sills and lava flows erupted or shallowly intruded in a marine environment during backarc extension and spreading in the middle Miocene. In this paper, we describe the geochemical characteristics of these igneous units using 52 new instrumental neutron activation analyses (INAA), 8 new X-ray fluorescence (XRF) analyses, and previous shipboard XRF analyses. The sills intruded into soft sediment at Sites 794 and 797 were subject to extensive hydrothermal activity, estimated at <230° C under subgreenschist facies conditions, which heavily to totally altered the fine-grained unit margins and moderately to heavily altered the coarse-grained unit interiors. Diagenesis further altered the composition of these igneous bodies and lava flows at Sites 794, 795, and 797, most intensely at unit margins. Our study of two well-sampled units shows that Mg, Ca, Sr, and the large-ion lithophile elements (LILE) mobilized during alteration, and that the concentrations of Y, Yb, and Lu decreased and Ce increased in the most severely altered samples. Nevertheless, our study shows that the rare-earth elements (REE) were relatively immobile in the majority of the samples, even where secondary mixed-layer clays comprised the great majority of the rock. Fresher Yamato Basin samples are compositionally heterogenous tholeiitic basalts and dolerites. At Site 794 in the north-central portion of the basin, Units 1 to 5 (upper basement) comprise mildly light rare-earth element (LREE) enriched basalts and dolerites (chondrite-normalized La/Sm of 1.4-1.8), while the stratigraphically lower Units 6 to 9 are less enriched dolerites with (La/Sm)N of 0.7-1.3. All Site 794 samples lack Nb and Ta depletions and LILE enrichments, lacking a strong subduction-related incompatible element geochemical signature. At Site 797 in the western margin of the basin, two stratigraphically-definable unit groups also occur. The upper nine units are incompatible-element depleted tholeiitic sills and flows with strong depletions of Nb and Ta relative to normal mid-ocean ridge basalt (N-MORB). The lower twelve sills represent LREE-enriched tholeiites (normalized La/Sm ranges from 1.1 to 1.8), with distinctly higher LILE and high field-strength element (HFSE) contents. At Site 795 at the northern margin of the Japan Sea, three eruptive units consist of basaltic andesite to calc-alkaline basalt (normalized La/Sm of 1.1 to 1.5) containing moderate depletions of the HFSE relative to N-MORB. The LILE-depleted nature of these samples precludes their origin in a continental arc, indicating that they more likely erupted within a rifting oceanic arc system. The heterogenous nature of the Japan Sea rocks indicate that they were derived at each site from multiple parental magmas generated from a compositionally heterogenous mantle source. Their chemistry is intermediate in character between arc basalts, MORB, and intraplate basalts, and implies little involvement of continental crust at any point in their genesis. Their flat chondrite-normalized, medium-to-heavy rare earth patterns indicate that the primary magmas which produced them last equilibrated with and segregated from spinel lherzolite at shallow depths (<30 kbar). In strong contrast to their isotopic compositional arrays, subduction-related geochemical signatures are usually poorly defined. No basin-wide temporal or geographic systematics of rock chemistry may be confidently detailed; instead, the data show both intimate (site-specific) and widespread backarc mantle heterogeneity over a narrow (2 Ma or so) range in time, with mantle heterogeneity most closely resembling a "plum-pudding" model.

Mineralogy of southern Kerguelen Plateau sediments

Kaolinite, goethite, minor hematite, and gibbsite were found in fluvial upper Lower Cretaceous basal sediment from the Southern Kerguelen Plateau, Sites 748 and 750, 55°S latitude. This mineral assemblage, derived from the weathering of basalt, indicates near-tropical weathering conditions with high orographic rainfall, at least 100 cm per year. The climate deteriorated by the Turonian or Coniacian, as indicated by the decline in kaolinite content of this sediment. The Upper Cretaceous sediment at Site 748 consists of 200 m of millimeter-laminated, sparsely fossiliferous, wood-bearing glauconitic siltstone and clay stone with siderite concretions deposited on a shelf below wave base. Some graded and cross beds indicate that storms swept over the shelf and reworked the sediment. Overlying this unit is 300 m of intermittently partly silicified, bryozoan-inoceramid-echinoderm-rich glauconitic packstones, grainstones, and wackestones. The dominant clay mineral in both units is identical to the mineral composition of the glauconite pellets: randomly interstratified smectite-mica. The clay fraction has a higher percent of expandable layers than the mineral of the glauconite pellets, and the clay of the underlying subunit has a higher percentage of expandable layers than the clay of the carbonate subunit. Potassium levels mirror these mineral variations, with higher K levels in minerals that have a lower percentage of expandable layers. The decrease in expandability of the mineral in the upper subunit is attributed to diagenesis, the result of higher porosity.

Geochemistry at DSDP Leg 59

Deep Sea Drilling Project Legs 59 and 60 drilled 15 sites along an east-west transect at 18°N from the West Philippine Basin to the Mariana Trench (Fig. 1) in order to study the nature and genesis of the back-arc, marginal basins and the remnant and active arcs of the region. Leg 59 drilled at five sites at the western end of the traverse: Site 447 in the West Philippine Basin; Site 448 on the Palau-Kyushu Ridge; Sites 449 and 450 in the Parece Vela Basin; and Site 451 on the West Mariana Ridge. Penetration into basaltic basement of these sites was 183.5 meters at 447 (8 basalt flows); 623 meters at 448 (46 basalt flows, sills, and dikes and volcaniclastic units); 40.5 meters at 449 (2 basalt flows); 7 meters at 450 (1 basalt intrusion); and 4 meters of basalt breccia at 451 overlain by 861 meters of volcaniclastic sedimentary rocks.

40Ar-39Ar geochronological studies on rocks drilled at DSDP Holes 61-462 and 61-462A

40Ar-39Ar step-heating dating was applied to a basalt from Hole 462 and to basalt and dolerite samples from Hole 462A. Only a basalt sample at Hole 462A yielded a reasonable isochron age, 110 ± 3 million years. The radiometric age is consistent with the fossil record (Cenomanian) in the sediments, into which the basalt sill intruded. However, the age is much less than that of the oceanic basement as deduced from the magnetic anomaly (M-26).

Geochemistry of terrigenous material in deep-sea sediments of the equatorial Pacific

Biological productivity in the modern equatorial Pacific Ocean, a region with high nutrients and low chlorophyll, is currently limited by the micronutrient Fe. In order to test whether Fe was limiting in the past and to identify potential pathways of Fe delivery that could drive Fe fertilization (i.e., dust delivery from eolian inputs vs. Fe supplied by the Equatorial Undercurrent), we chemically isolated the terrigenous material from sediment along a cross-equatorial transect in the central equatorial Pacific at 140°W and at Ocean Drilling Program Site 850 in the eastern equatorial Pacific. We quantified the contribution from each potential Fe-bearing terrigenous source using a suite of chemical- and isotopic discrimination strategies as well as multivariate statistical techniques. We find that the distribution of the terrigenous sources (i.e., Asian loess, South American ash, Papua New Guinea, and ocean island basalt) varies through time, latitude, and climate. Regardless of which method is used to determine accumulation rate, there also is no relationship between flux of any particular Fe source and climate. Moreover, there is no connection between a particular Fe source or pathway (eolian vs. Undercurrent) to total productivity during the Last Glacial Maximum, Pleistocene glacial episodes, and the Miocene "Biogenic Bloom". This would suggest an alternative process, such as an interoceanic reorganization of nutrient inventories, may be responsible for past changes in total export in the open ocean, rather than simply Fe supply from dust and/or Equatorial Undercurrent processes. Additionally, perhaps a change in Fe source or flux is related to a change in a particular component of the total productivity (e.g., the production of organic matter, calcium carbonate, or biogenic opal).