Strontium chemistry of anhydrite from DSDP/ODP Hole 504B

A unique record of the chemical evolution of seawater during hydrothermal recharge into oceanic crust is preserved by anhydrite from the volcanic sequences and sheeted dike complex in ODP Hole 504B. Chemical and isotopic analyses 87Sr/86Sr, delta18O, delta34S of anhydrite constrain the changing composition of fluids due to reaction with basalt. There is a general trend of decreasing 87Sr/86Sr of anhydrite, corresponding to the minor incorporation of basaltic strontium with depth in the volcanic rocks. 87Sr/86Sr ratios decrease rapidly with depth in the dikes to values identical to host basalt (0.7029). Sr/Ca ratios (<0.1 mmol/mol) suggest that recharge fluids have very low Sr concentrations and fluids evolve by first precipitating Sr-bearing phases before extensive exchange of Sr with the host basalt. There is a background trend of decreasing sulfate delta18O with depth from +12-13? in the lower volcanics to +7? in the lower sheeted dikes recording an increase in recharge fluid temperature from c. 150° to c. 250°C, and confirming the presence of sulfate in hydrothermal fluids at elevated temperatures. From the amount of anhydrite recovered from Hole 504B and the amount of seawater sulfur that has been reduced to sulfide, a minimum seawater recharge flux can be calculated. This value is 4-25 times lower than estimates of high-temperature fluid fluxes based on either thermal constraints or global chemical budgets and suggests that there is significant deficit of seawater-derived sulfur in the oceanic crust. Only a minor proportion of the seawater that percolates into the crust near the axis is heated to high temperatures and exits as black smoker-type fluids. A significant proportion of the axial heat loss must be advected at 200-250°C by sulfate-bearing hydrothermal solutions that egress diffusely from the crust. These fluids penetrate into the dikes and exchange both heat and chemical tracers without the extensive clogging of porosity by anhydrite precipitation, which would halt hydrothermal circulation for any reasonable fluid flux. The heating of the major proportion of hydrothermal fluids to only moderate temperatures (c. 250°C) reconciles estimates of hydrothermal fluxes derived from thermal models and global geochemical budgets. The flux of hydrothermal sulfate would be of a magnitude similar to the riverine input, and oxygen-isotopic exchange at 200-250°C between dissolved sulfate and recharge fluids during hydrothermal circulation provides a mechanism to continuously buffer seawater sulfate oxygen to the light isotopic composition observed.

Physical properties and elastic constants of ODP Holes 137-504B and 140-504B upper crustal rocks

Seismic velocities have been measured at confining pressures of 100 MPa and 600 MPa for sheeted dike samples recovered during Ocean Drilling Program Legs 137 and 140. The compressional- and shear-wave velocities show an increase with depth at Hole 504B, which is in sharp contrast to the atmospheric pressure velocity measurements performed as part of the shipboard analyses. Rocks exposed to different types of alteration and fracture patterns show distinct changes in their physical properties. The seismic reflectors observed on the vertical seismic profile (VSP) experiment performed during Leg 111 may have been caused by low velocity zones resulting from alteration. The amount of fracturing and hydrothermal alteration in several zones also may have contributed to the acoustic impedance contrast necessary to produce the E5 reflector. Poisson's ratios calculated from laboratory velocity measurements show several low values at depths ranging from 1600 mbsf to 2000 mbsf, which tends to follow similar trends obtained from previous oceanic refraction experiments. A comparison of physical properties between samples recovered from Hole 504B and ophiolite studies in the Bay of Islands and Oman shows a good correlation with the Bay of Islands but significant differences from the measurements performed in the Oman complex.

Oxygen and carbon isotopes of planktic foraminifera and ageprofile datum description at DSDP Hole 69-504

A detailed oxygen isotope record (resolution: about 2500 years) has been obtained for the Pleistocene sediments at Hole 504. Preliminary measurements made deeper in the section suggest that at least the upper Pliocene section is also amenable to detailed stable isotope work. The record for the middle Pleistocene resembles that obtained previously from piston cores in the western equatorial Pacific, although the superior resolution of this high-accumulation-rate site reveals a greater amplitude of isotope variation than previously observed. The record for the lower Pleistocene reveals variation that is both greater in amplitude and higher in frequency than apparent from previously analyzed piston cores. The site provides the best material recovered to date for the study of the evolution of climatic variability during the past few million years.

Magnetic properties of basalts at DSDP Hole 83-504B

We have studied the magnetic properties of 22 samples from DSDP Leg 83 to determine the origin of remanence and its relationship to such problems as the tectonic and chemical evolution of the section, the depth of the magnetized layer, and the applicability of magnetic properties of ophiolites to the marine crust. The magnitude of natural remanence has fairly typical values in the uppermost part of the section, falls two to three orders of magnitude in the transition zone, and returns to values slightly less than the upper part in the dike complex. This behavior reflects, for the most part, variations in the amount of magnetic minerals present. Directional behavior is highly variable throughout the section and often shows complexity even on the level of a single sample. Curie temperature measurements and preliminary opaque petrography indicate that the remanence is chemical in origin and probably involves a resetting of the original thermal remanent magnetization (TRM) direction. Selective destructive demagnetization of four breccia samples shows that the remanence of the clasts was acquired prior to consolidation and did not change significantly thereafter. There are also indications that some of the remanence may be carried by secondary magnetic phases. A comparison of these samples with comparable ophiolite rocks is equivocal, with similarities in remanence characteristics but differences in magnetic mineralogy. As for magnetic anomalies, the transition zone is too weakly magnetized to contribute significantly. The available data on the dike complex are inconclusive and their contribution is still open to debate.

Mechanical behavior of ODP Hole 137-504B basalts

Core samples of basalt collected from Hole 504B during Leg 137 were investigated regarding their mechanical behavior. The rock samples were measured for hardness, compression strength, and modulus of elasticity. Abrasion loss of weight and Shore sclerometer methods were used for determining hardness. Static and dynamic methods were used for calculating modulus of elasticity. Test results were compared with shipboard measurements of ultrasonic velocity and dry-bulk density. Test results were interpreted statistically to provide data not only on mechanical behavior changes of the rock but also on the precision of the methods used.

Platinum group elements and geochemistry of altered oceanic crust of ODP Hole 140-504B

Primary chemical heterogeneity in the sheeted dike complex in Deep Sea Drilling Project Hole 504B makes these rocks unsuitable for conventional mass balance calculations in determining element mobility associated with hydrothermal alteration. Due to the original heterogeneity and variable degrees of fractionation in the dikes, an appropriate reference sample on which calculations can be based is difficult to find. Therefore, the use of incompatible element ratios is developed to evaluate geochemical changes during alteration(s). For example, on a Zr/Yb-La/Yb plot, scatter along a straight line suggests tapping of a variably depleted mantle source and deviation from the line suggests element mobility (gain or loss). Using this method, our data indicates that the hydrothermal evolution of the sheeted dike complex was accompanied by significant loss of Cu, Zn, and Ti and some loss of La. The sheeted dike complex has low platinum group element (PGE) concentrations and steep PGE patterns, typical of mid-ocean ridge basalts (MORBs) on the global scale. We propose that the unusual PGE patterns of MORBs cannot be entirely generated by a partial melting and sulfide segregation model; instead, these patterns in part must have been inherited from their mantle source. The Au data show no evidence for mobilization during hydrothermal alteration of the dikes.

Magnetic properties and heavy metals at DSDP Hole 83-504B

We report measurements of magnetic intensity, inclination, initial susceptibility, Koenigsberger's ratio, saturation magnetization, and Curie temperatures of 68 basalt samples from the Leg 83 section of Hole 504B. As in the upper part of the hole, reversely magnetized units predominate. Intensities of natural remanent magnetization vary widely, but the range of variation is an order of magnitude less than in the upper part of the hole. This and the other properties measured indicate that the magnetic characteristics of basalts from Hole 504B have been strongly affected by hydrothermal alteration, particularly in the deeper, Leg 83 section. The alteration states of the magnetic samples were studies using Xray diffraction, electron microprobe, X-ray fluorescence, and ion coupled plasma. Our results suggest three alteration zones in Hole 504B: a low-temperature zone (274.5-890 m) and two high-temperature zones (890-1050 m and 1050- 1350 m), differing in the number of veins observed in the samples and presumably differing in the volumes of hydrothermal fluids which reacted with the basalts.

Geochemistry of minerals in medium-grained diabase from ODP Holes 137-504B and 140-504B

Samples recovered from Hole 504B during Leg 140 include a number of medium-grained, holocrystalline diabases that appear to represent the cores of thick dikes. The plagioclase and pyroxene in these samples occur in a variety of crystal morphologies. Plagioclase occurs as phenocrysts, microphenocrysts, elongate crystals, skeletal crystals, and branching radial clusters. Pyroxene occurs as phenocrysts, microphenocrysts, ophitic crystals, and poikilitic crystals. Plagioclase compositions became progressively poorer in anorthite and MgO and progressively richer in FeO as crystallization proceeded, while the average grain volume decreased and the aspect ratio of individual grains increased. Pyroxene compositions are largely independent of crystal morphology. The diabase dikes recovered from Hole 504B during Leg 140 appear to have crystallized in situ. Crystal compositions and morphologies are consistent with a rapid cooling rate and solidification times for individual dikes on the order of hours or days. The crystallization rate and nucleation rate of plagioclase lagged behind the cooling rate so that the degree of undercooling progressively increased as crystallization proceeded. Plagioclase crystal morphologies indicate much greater degrees of supersaturation than do pyroxene or olivine crystal morphologies. The 504B diabase magmas appear to have been emplaced with abundant preexisting pyroxene and olivine nuclei, but with few preexisting plagioclase nuclei. The suppression of plagioclase nucleation and crystallization relative to that of pyroxene and olivine could provide a mechanism by which the actual fractionation assemblage is more pyroxene-rich and plagioclase-poor than that predicted from thermodynamic models, or that observed in isothermal crystallization experiments.

Geochemistry, isotopes, trace elements and fluid inclusion geothermometry at DSDP Hole 83-504B

Stockwork-like metal sulfide mineralizations were found at 910-928 m below seafloor (BSF) in the pillow/dike transition zone of Hole 504B. This is the same interval where most physical properties of the 5.9-m.y.-old crust of the Costa Rica Rift change from those characteristic of Layer 2B to those of Layer 2C. The pillow lavas, breccias, and veins of the stockwork-like zone were studied by transmitted and reflected light microscopy, X-ray diffraction, and electron microprobe analysis. Bulk rock oxygen isotopic analyses as well as isolated mineral oxygen and sulfur isotopic analyses and fluid inclusion measurements were carried out. A complex alteration history was reconstructed that includes three generations of fissures, each followed by precipitation of characteristic hydrothermal mineral parageneses: (1) Minor and local deposition of quartz occurred on fissure walls; adjacent wall rocks were silicified, followed by formation of chlorite and minor pyrite I in the veins, whereas albite, sphene, chlorite and chlorite-expandable clay mixtures, actinolite, and pyrite replaced igneous phases in the host rocks. The hydrothermal fluids responsible for this first stage were probably partially reacted seawater, and their temperatures were at least 200-250° C. (2) Fissures filled during the first stage were reopened and new cracks formed. They were filled with quartz, minor chlorite and chlorite-expandable clay mixtures, traces of epidote, common pyrite, sphalerite, chalcopyrite, and minor galena. During the second stage, hydrothermal fluids were relatively evolved metal- and Si-rich solutions whose temperatures ranged from 230 to 340° C. The fluctuating chemical composition and temperature of the solutions produced a complex depositional sequence of sulfides in the veins: chalcopyrite I, ± Fe-rich sphalerite, chalcopyrite II ("disease"), Fe-poor sphalerite, chalcopyrite III, galena, and pyrite II. (3) During the last stage, zeolites and Mg-poor calcite filled up the remaining spaces and newly formed cracks and replaced the host rock plagioclase. Analcite and stilbite were first to form in veins, possibly at temperatures below 200°C; analcite and earlier quartz were replaced by laumontite at 250°C, whereas calcite formation temperature ranged from 135 to 220°C. The last stage hydrothermal fluids were depleted in Mg and enriched in Ca and 18O compared to seawater and contained a mantle carbon component. This complex alteration history paralleling a complex mineral paragenesis can be interpreted as the result of a relatively long-term evolution of a hydrothermal system with superimposed shorter term fluctuations in solution temperature and composition. Hydrothermal activity probably began close to the axis of the Costa Rica Rift with the overall cooling of the system and multiple fracturing stages due to movement of the crust away from the axis and/or cooling of a magmatic heat source.