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.

Isotope composition of sulfur, oxygen and carbon in Black Sea sediments

Inversion of isotopic composition in the SO4(2-)-H2S system is shown to be universal in Neoeuxine sediments and an explanation of its occurrence is proposed. Change in isotopic composition of sulfate sulfur in Black Sea waters over last 10-15 thousand years is reconstructed. Periods of alteration between aerobic and anaerobic situations are identified, the beginning of entry of Mediterranean waters into the basin is dated, presence of authigenic carbonates in sediments of the sea is established and amounts are determined. Methane generation from carbon dioxide is shown to have been replaced by its generation from acetate in the paleo-Black Sea period.

Mineral composition and geochemistry of sediments from ODP Leg 127 sites

The lithostratigraphy of Neogene hemipelagic sediments recovered from the Japan Sea during Leg 127 was revised to improve intersite consistency and to remove confusion stemming from diagenetic modification of the lithology through the opal-A to opal-CT transformation. Special emphasis was put on the presence and nature of dark-light cycles in revising the lithostratigraphy. Mineral composition analysis was conducted for samples from Sites 794, 795, and 797. In addition, major element chemical composition analysis was conducted for these same sample sets from Site 794. The result of mineral composition analysis suggests that the detrital component, which consists of such minerals as quartz, plagioclase, illite, and kaolinite plus chlorite, is diluted to various degrees by biogenic silica (opal-A) and its diagenetic equivalents (opal-CT and quartz). Smectite, on the other hand, may be a diagenetic or hydrothermal alteration product of volcanic material, although more study is necessary to confirm its origin. As a whole, vertical variation in the sediment composition is consistent with the revised lithostratigraphy and helps to characterize the redefined lithologic units quantitatively.

Isotopic composition of diagenetic silica and associated pore waters of Japan Sea sediments

Over a broad region of the eastern Japan Sea, Neogene opaline diatomaceous sediments alter with depth to hard porcellanites and cherts composed of opal-CT and quartz. We examined the oxygen isotopic compositions of these diagenetic silica minerals at four widely spaced sites occupied during ODP Leg 127 in order to investigate the thermal history of the region. Formation temperatures computed from these isotopic data range from 22° to 68°C for opal-CT and from 44° to 92°C for diagenetic quartz, quite similar to temperature ranges estimated from the extrapolated modern gradients, 36°-43°C and 49°-64°C, respectively. At each site the isotopic temperature values cluster near the extrapolated ambient sediment temperatures. As a first approximation, the similarities suggest that the positions of the silica transformations in the basin are controlled by the present thermal regime. In detail, isotopic and ambient temperatures differ. If these differences are real, then they reflect variations in the thermal histories at these sites. At Sites 794 and 797 in the Yamato Basin, isotopic temperatures and gradients computed from these data are lower than or comparable to ambient temperatures and gradients. We suggest that the silica zones have roughly equilibrated with the modern gradients at these localities. At Site 795 in the Japan Basin, isotopic temperatures are also lower than ambient sediment temperatures at comparable depths, but the gradient computed from the isotopic temperatures is higher than the present measured gradient. For both scenarios to hold, the silica zones must have formed under initially high gradients during the early post-rift period at this locality. These zones were then rapidly buried and have yet to equilibrate with the modern lower gradient. At Site 796 on Okushiri Ridge, isotopic temperatures exceed present temperatures as expected for an area of recent uplift. The gradient computed from our isotopic data and the thickness of the opal-CT zone indicate a higher gradient than at present at this site, apparently reflecting higher heat fluxes during the early post-rift period or recent frictional heating from nearby reverse fault activity.