Mineral and chemical composition of hydrothermally altered rocks and sediments from the Middle Valley, ODP Leg 139 data

The Middle Valley segment at the northern end of the Juan de Fuca Ridge is a deep extensional rift blanketed with 200-500 m of Pleistocene turbiditic sediment. Sites 857 and 858 were drilled during Ocean Drilling Program Leg 139 to determine whether these two sites were hydrologically linked end members of an active hydrothermal circulation system. Site 858 was placed in an area of active hydrothermal discharge with fluids up to 270°C venting through anhydrite-bearing mounds on top of altered sediment. The shallow basement of fine-grained basalt that underlies the vents at Site 858 is interpreted as a seamount that was subsequently buried by turbidites. Site 857 was placed 1.6 km south of the Site 858 vents in a zone of high heat flow and numerous seismically imaged ridge-parallel faults. Drilling at Site 857 encountered sediments that are increasingly altered with depth and that overlie a series of mafic sills at depths of 460-940 m below sea floor. Sill margins and adjacent baked sediment are highly altered to magnesian chlorite and crosscut with veins filled with quartz, chlorite, sulfides, epidote, and wairakite. The sill interiors vary from slightly altered, with unaltered plagioclase and clinopyroxene in a mesostasis replaced by chlorite, to local zones of intense alteration and brecciation. In these latter zones, the sill interiors are pervasively replaced by chlorite, epidote, quartz, pyrite, titanite, and rare actinolite. The most complete replacement is associated with brecciated horizons with low recovery and slickensides on fracture surfaces, which we interpret as intersections between faults and the sills. Geochemically, the alteration of the sill complex is reflected in significant whole-rock depletions in Ca, Sr, and Na with corresponding enrichments in Mg, Al, and most metals. The latter results from the formation of conspicuous sulfide poikiloblasts. In contrast, metamorphism of the Site 858 seamount includes incomplete albitization of plagioclase phenocrysts and replacement of sparse mafic phenocrysts. Much of the basement alteration at Site 858 is confined to crosscutting veins except for a highly altered and veined horizon at the contact between basaltic basement and the overlying sediment. The sill complex at Site 857 is more highly depleted in 18O (d18O = 2.4 per mil - 4.7 per mil) and more pervasively replaced by secondary minerals relative to the extrusives at Site 858 (d18O = 4.5 per mil - 5.5 per mil). There is no evidence of significant albitization of the plagioclase at Site 857, suggesting high Ca/Na in the pore fluids. Fluid-inclusion data from hydrothermal minerals in altered mafic rocks and veins at Sites 857 and 858 show a consistency of homogenization temperatures, varying from 245 to 270°C, which is within the range of temperatures observed for the fluids venting at Site 858. The consistency of the fluid inclusion temperatures, the lack of albitization within the Site 857 sills, and the apparently low water/rock ratio collectively suggest that the sill complex at Site 857 is in thermal equilibrium and being altered by a highly evolved Ca-rich fluid similar to the fluids now venting at Site 858. The alteration evident in these two deep crustal drillsites is a result of the ongoing hydrothermal circulation and is consistent with downhole logging results, instrumented borehole results, and hydrothermal fluid chemistry. The pervasive alteration of the laterally extensive sill-sediment complex at Site 857 determines the chemistry of the fluids that are venting at Site 858. The limited alteration of the Site 858 lavas suggests that this basement edifice acts as a penetrator or ventilator for the regional hydrothermal reservoir with much of the flow focussed at the highly altered and veined sediment-basalt contact.

Experimental data of CO2, CO3, Omega calcite saturation, pH values, alpha and epsilon fractionation factors, and Dd18O calctite-water

The oxygen isotopic composition (d18O) of calcium carbonate of planktonic calcifying organisms is a key tool for reconstructing both past seawater temperature and salinity. The calibration of paloeceanographic proxies relies in general on empirical relationships derived from field experiments on extant species. Laboratory experiments have more often than not revealed that variables other than the target parameter influence the proxy signal, which makes proxy calibration a challenging task. Understanding these secondary or "vital" effects is crucial for increasing proxy accuracy. We present data from laboratory experiments showing that oxygen isotope fractionation during calcification in the coccolithophore Calcidiscus leptoporus and the calcareous dinoflagellate Thoracosphaera heimii is dependent on carbonate chemistry of seawater in addition to its dependence on temperature. A similar result has previously been reported for planktonic foraminifera, supporting the idea that the [CO3]2- effect on d18O is universal for unicellular calcifying planktonic organisms. The slopes of the d18O/[CO3]2- relationships range between -0.0243 per mil/(µmol/kg) (calcareous dinoflagellate T. heimii) and the previously published -0.0022 per mil/(µmol/kg) (non-symbiotic planktonic foramifera Orbulina universa), while C. leptoporus has a slope of -0.0048 per mil/(µmol/kg). We present a simple conceptual model, based on the contribution of d18O-enriched [HCO3]- to the [CO3]2- pool in the calcifying vesicle, which can explain the [CO3]2- effect on d18O for the different unicellular calcifiers. This approach provides a new insight into biological fractionation in calcifying organisms. The large range in d18O/[CO3]2- slopes should possibly be explored as a means for paleoreconstruction of surface [CO3]2-, particularly through comparison of the response in ecologically similar planktonic organisms.

Geochemistry of Chixulub ejecta in ODP Leg 207 holes

An up to 2-cm thick Chicxulub ejecta deposit marking the Cretaceous-Paleogene (K-Pg) boundary (the "K-T" boundary) was recovered in six holes drilled during ODP Leg 207 (Demerara Rise, tropical western Atlantic). Stunning features of this deposit are its uniformity over an area of 30 km2 and the total absence of bioturbation, allowing documentation of the original sedimentary sequence. High-resolution mineralogical, petrological, elemental, isotopic (Sr-Nd), and rock magnetic data reveal a distinct microstratigraphy and a range of ejecta components. The deposit is normally graded and composed predominantly of rounded, 0.1- to max. 1-mm sized spherules. Spherules are altered to dioctahedral aluminous smectite, though occasionally relict Si-Al-rich hydrated glass is also present, suggesting acidic precursor lithologies. Spherule textures vary from hollow to vesicle-rich to massive; some show in situ collapse, others include distinct Fe-Mg-Ca-Ti-rich melt globules and lath-shaped Al-rich quench crystals. Both altered glass spherules and the clay matrix (Site 1259B) display strongly negative epsilon-Nd (T=65Ma) values (-17) indicating uptake of Nd from contemporaneous ocean water during alteration. Finally, Fe-Mg-rich spherules, shocked quartz and feldspar grains, few lithic clasts, as well as abundant accretionary and porous carbonate clasts are concentrated in the uppermost 0.5-0.7 mm of the deposit. The carbonate clasts display in part very unusual textures, which are interpreted to be of shock-metamorphic origin. The preservation of delicate spherule textures, normal grading with lack of evidence for traction transport, and sub-millimeter scale compositional trends provide evidence for this spherule deposit representing a primary air-fall deposit not affected by significant reworking. The ODP Leg 207 spherule deposit is the first known dual-layer K-Pg boundary in marine settings; it incorporates compositional and stratigraphic aspects of both proximal and distal marine sites. Its stratigraphy strongly resembles the dual-layer K-Pg boundary deposits in the terrestrial Western Interior of North America (although there carbonate phases are not preserved). The occurrence of a dual ejecta layer in these quite different sedimentary environments - separated by several thousands of kilometers - provides additional evidence for an original sedimentary sequence. Therefore, the layered nature of the deposit may document compositional differences between ballistic Chicxulub ejecta forming the majority of the spherule deposit, and material falling out from the vapor (ejecta) plume, which is concentrated in the uppermost part.

(Table 1) Chemical composition of segregations and groundmass seperates of ODP Leg 135 samples

Concentrations of dark-colored, highly vesicular, quench-textured mesostasis occur commonly in volcanic rocks drilled in the Lau Basin during Leg 135. These segregations occur as veins, patches, and vesicle linings in rocks with 49%-54% SiO2. The segregations are depleted in Mg, Ca, Al, Sc, Ni, and Cr and enriched in Ti, Ba, Y, and Zr compared to the groundmass with which they occur. Many of the segregations are unusually enriched in copper. The elemental variations show that the segregations are residual liquids produced by 12%-55% crystallization of plagioclase and clinopyroxene, with minor olivine, opaques, or orthopyroxene from the groundmass melt. The liquids forming the segregations are mobilized and emplaced in earlier formed vesicles during the rapid crystallization of the groundmass. The dominant process in this mobilization and emplacement is volatile exsolution from crystallizing melts constrained by a rigid crystalline framework. This exsolution produces significant overpressures within the late-stage melts; the overpressure drives the residual melts through the walls of the older vesicles, along planes of weakness, and into voids. This mechanism is consistent with the occurrence of bimodal vesicle populations in many of the host lavas.