(Table 1) Oxygen and carbon isotope compositions of altered carbonates from DSDP Hole 6-53 from the western Pacific Ocean

In the lower part of DSDP core 53.0, partly recrystallized carbonate sediments and well recrystallized limestone breccias of Oligo-Miocene age are associated with altered volcanic flows, lithified tuffs, and tuff breccias, suggesting that carbonate alteration was the result of thermal metamorphism. However, the oxygen isotope compositions of these carbonates (-3.4 to +0.6 per mil rel. PDB) are not compatible with recrystallization and isotope exchange with sea water at high temperatures. Evaluating the effects of the composition of the water which exchanged with the carbonates and of carbonate-water isotope exchange in closed systems yields the following approximate maximum temperature of recrystallization: limestone breccias, 100°C; calcite veins rimming breccia clasts, 30°C; and unconsolidated sediments overlying the breccias, 20°C. Therefore, the volcanics at site 53.0 must have been emplaced into the primary carbonate sediments at relatively low temperatures. Subsequent carbonate alteration was probably a consequence of chemical changes in ambient pore waters resulting from the submarine weathering of volcanic material.

Delta 66Zn ratios and age of carbonates from ODP Site 138-849 (Table 1)

The carbonate fraction of sediment core ODP 849, leg 138, located in the eastern equatorial Pacific, mostly consisting of coccoliths, was separated and analyzed for its Zn isotopic composition. The overall variation in Zn isotopic composition, as determined by multiple-collector, magnetic-sector, inductively coupled plasma mass spectrometry, was found to be on the order of 1? (expressed in delta66Zn, where deltaxZn=[(xZn/64Zn)sample/(xZn/64Zn)standard -1]*10**3 and x=66, 67 or 68) over the last 175 ka. The analytical precision was 0.04 per mil and the overall reproducibility was usually better than 0.07 per mil. The Zn isotopic composition signal exhibits several marked peaks and a high-frequency variability. A periodogram of the delta66Zn signal showed two periodicities of 35.2 and 21.2 ka. We suggest that the latter is caused by the precession of the Earth's axis of rotation. The periodogram exhibits a minimum at 41.1 ka, thus showing that the Zn isotopic composition is independent of the obliquity in the eastern equatorial Pacific. The range of delta66Zn values observed for the carbonate fraction of ODP 849 overlaps with the range observed for Fe-Mn nodules in the world's oceans, which suggests that seawater/carbonate Zn isotope fractionation is weak. We therefore assume that most of the Zn isotope variability is a result of the selective entrainment of the light isotopes by organic matter in the surface ocean. The ODP 849 delta66Zn record seems to follow the changes in the insolation cycles. Changes in the late summer/fall equatorial insolation modulate the intensity of the equatorial upwelling, hence the mixing between deep and surface waters. We propose that during decreased summer/fall equatorial insolation, when a steep thermocline can develop (El Niño-like conditions), the surface waters cannot be replenished by deep waters and become depleted in the lighter Zn isotopes by biological activity, thus resulting in the progressive increase of the delta66Zn values of the carbonate shells presumably in equilibrium with surface seawater.

Pore-water chemistry of ODP Sites 124-767 and 124-768

The combination of multiple sediment sources and varying rates of sediment accumulation in the Celebes and Sulu seas have had significant impact on the processes of diagenesis, mineralization, and pore-fluid flow. Isotopic and mass-balance calculations help elucidate the various reactions taking place in these western Pacific basins, where ash alteration and basalt-seawater interactions are superimposed on the effects of sulfate oxidation of organic carbon and biogenic methane and of dolomitization of biogenic carbonates. Based on the shape of the calcium and magnesium depth profiles, two major reactive zones have been identified. The first is located near the zone of sulfate depletion and is characterized by carbonate recrystallization, dolomitization and ash alteration reactions at both Ocean Drilling Program Sites 767 and 768. The second reactive zone corresponds to the bottom of the sedimentary sequence and is characterized by alteration reactions in the basement (Site 767) and in the pyroclastic deposits beneath the sediment column (Site 768).