Chemical and Sr isotopic compositions of pore fluids and marine carbonates from ODP Hole 130-807A

The 87Sr/86Sr ratios and Sr concentrations in sediment and pore fluids are used to evaluate the rates of calcite recrystallization at ODP Site 807A on the Ontong Java Plateau, an 800-meter thick section of carbonate ooze and chalk. A numerical model is used to evaluate the pore fluid chemistry and Sr isotopes in an accumulating section. The deduced calcite recrystallization rate is 2% per million years (%/Myr) near the top of the section and decreases systematically in older parts of the section such that the rate is close to 0.1/age (in years). The deduced recrystallization rates have important implications for the interpretation of Ca and Mg concentration profiles in the pore fluids. The effect of calcite recrystallization on pore fluid chemistry is described by the reaction length, L, which varies by element, and depends on the concentration in pore fluid and solid. When L is small compared to the thickness of the sedimentary section, the pore fluid concentration is controlled by equilibrium or steady-state exchange with the solid phase, except within a distance L of the sediment-water interface. When L is large relative to the thickness of sediment, the pore fluid concentration is mostly controlled by the boundary conditions and diffusion. The values of L for Ca, Sr, and Mg are of order 15, 150, and 1500 meters, respectively. L_Sr is derived from isotopic data and modeling, and allows us to infer the values of L_Ca and L_Mg. The small value for L_Ca indicates that pore fluid Ca concentrations, which gradually increase down section, must be equilibrium values that are maintained by solution-precipitation exchange with calcite and do not reflect Ca sources within or below the sediment column. The pore fluid Ca measurements and measured alkalinity allow us to calculate the in situ pH in the pore fluids, which decreases from 7.6 near the sediment-water interface to 7.1+/-0.1 at 400-800 mbsf. While the calculated pH values are in agreement with some of the values measured during ODP Leg 130, most of the measurements are artifacts. The large value for L_Mg indicates that the pore fluid Mg concentrations at 807A are not controlled by calcite-fluid equilibrium but instead are determined by the changing Mg concentration of seawater during deposition, modified by aqueous diffusion in the pore fluids. We use the pore fluid Mg concentration profile at Site 807A to retrieve a global record for seawater Mg over the past 35 Myr, which shows that seawater Mg has increased rapidly over the past 10 Myr, rather than gradually over the past 60 Myr. This observation suggests that the Cenozoic rise in seawater Mg is controlled by continental weathering inputs rather than by exchange with oceanic crust. The relationship determined between reaction rate and age in silicates and carbonates is strikingly similar, which suggests that reaction affinity is not the primary determinant of silicate dissolution rates in nature.

Foraminiferal abundances and preservation in ODP Hole 130-805C

Downcore changes in various carbonate dissolution indexes are documented for Hole 805C for the last 1.2 m.y. These indexes include degree of fragmentation of planktonic foraminifers, percent sand, abundance ratio of species of contrasting solution susceptibilities (Globigerinoides sacculifer vs. Pulleniatina, Globorotalia tumida, and Globorotalia menardii), and the difference in d18O between species of contrasting solution susceptibilities (G. sacculifer vs. Pulleniatina). These preservation indexes have been combined into a single composite dissolution index that corresponds closely to the d18O record. The rate of change of the oxygen isotope signal is also important, with glacial-to-interglacial transitions corresponding to maximum preservation events and vice versa. For information on changing productivity (which is important because an increased supply of organic matter may enhance dissolution by lowering pH upon degradation), we present the abundance of coarse-fraction benthic foraminifers per gram and the ratio between two planktonic foraminiferal species, one of which is strongly associated with equatorial upwelling (Globorotalia tumida vs. Pulleniatina). Our results suggest that productivity plays a subordinate role in determining foraminifer preservation. Furthermore, our results confirm previous observations that associate enhanced preservation events with glacial periods and with glacial-to-interglacial transitions. A correlation between preservation and sedimentation rates of these carbonate-rich sediments could not be established. Notable differences are present between the responses of individual dissolution indexes, indicating that processes other than dissolution determine proxy indexes to varying degrees.

Miocene planktonic foraminifera of ODP Hole 130-806B

We document the waxing and waning of a "proto-warm pool" in the western equatorial Pacific (WEP) based on a study of multi-species planktic foraminiferal isotope ratios and census data spanning the 13.2-5.8 Ma interval at ODP Site 806. We hypothesize that the presence or absence of a proto-warm pool in the WEP, caused by the progressive tectonic constriction of the Indonesian Seaway and modulated by sea level fluctuations, created El Niño/La Niña-like alternations of hydrographic conditions across the equatorial Pacific during the late Miocene. This hypothesis is supported by the general antithetical relationship observed between carbonate productivity and preservation in the western and eastern equatorial Pacific, which we propose is caused by these alternating ocean-climate states. Warming of thermocline and surface waters, as well as a major change in planktic foraminferal assemblages record a two-step phase of proto-warm pool development ~11.6-10 Ma, which coincides with Miocene isotope events Mi5 and Mi6, and sea-level low stands. We suggest that these changes in the biota and structure of the upper water column in the WEP mark the initiation of a more modern equatorial current system, including the development of the Equatorial Undercurrent (EUC), as La Niña-like conditions became established across the tropical Pacific. This situation sustained carbonate and silica productivity in the eastern equatorial Pacific (EEP) at a time when carbonate preservation sharply declined in the Caribbean. Proto-warm pool weakening after ~10 Ma may have contributed to the nadir of a similar "carbonate crash" in the EEP. Cooling of the thermocline and increased abundances of thermocline taxa herald the decay of the proto-warm pool and higher productivity in the WEP, particularly ~ 9.0-8.8 Ma coincident with a major perturbation in tropical nannofossil assemblages. We suggest that this interval of increased productivity records El Niño-like conditions across the tropical Pacific and the initial phase of the widespread "biogenic bloom". Resurgence of a later proto-warm pool in the WEP ~6.5-6.1 Ma may have spurred renewed La Niña-like conditions, which contributed to a strong late phase of the "biogenic bloom" in the EEP.

Paleomagnetic of ODP Hole 130-807C basalts

Characteristic remanent magnetizations derived from detailed thermal and alternating-field demagnetization of basalts recovered at Ocean Drilling Program (ODP) Site 807 on the Ontong Java Plateau reveal constant normal polarity consistent with paleontological ages from overlying sediments, suggesting deposition in early Aptian times at the beginning of the Cretaceous Normal Polarity Superchron (K-N). The paleomagnetic data can be divided into 14 distinct inclination groups, which together define a paleolatitude of 18°S, some 16° shallower than expected from a Pacific apparent polar wander path (APWP) based on nonsedimentary data. The data display a trend in paleomagnetic inclination, showing shallower values with increasing depth. We conclude that this trend is a result of local tectonic tilting during the waning phases of volcanism on the plateau. Hotspot-based plate reconstructions for the Early Cretaceous place the Ontong Java Plateau on the Louisville hotspot, presently located at 51°S, whereas the paleolatitude for Site 807 based on the Pacific APWP is 34°S. Because the nominal mean inclination from Site 807 and values derived from Deep Sea Drilling Project (DSDP) sediments of other sites predict shallower paleolatitudes for the Ontong Java Plateau, values from the Pacific APWP provide lower bounds on true polar wander. Considering mantle plume sources on the southern and northern portions of the plateau (DSDP Site 288 and ODP Site 807, respectively), the Louisville hotspot appears to have moved 9°-17° to the south relative to the spin axis since the Early Cretaceous. This sense of motion is consistent with previous results for the Suiko Seamount (65 Ma) of the Hawaiian-Emperor Chain.

Middle Miocene stable carbon and oxygen isotope record of ODP Holes 130-805B and 130-806B

Bulk carbon isotope records are an effective chemostratigraphic tool for the middle Miocene because of the large and systematic variation in first-order d13C signals. Bulk d13C measurements support the presence of a hiatus at 305 mbsf in Hole 805B (latest middle Miocene), provisionally located while on board ship using biostratigraphic and magnetostratigraphic events. Records at Holes 805B and 806B show the middle Miocene Monterey carbon isotope excursion although the record at Hole 806B is apparently more stratigraphically continuous. Detailed analysis of multispecies foraminiferal carbon isotope records during the middle Miocene ("Monterey excursion") segment at Hole 806B support the assertion that this carbon isotope excursion comprises mainly between-reservoir effects. The benthic d18O data increase after 15.3 Ma, which we suggest corresponds to the mid-Miocene cooling step/ice volume increase of other authors. Planktonic foraminiferal d18O evidence exists for steepening of the thermocline at 17.4 Ma. A second-order d13C excursion superimposed at 13.8 Ma on the first-order Monterey excursion is associated with a second-order negative d18O excursion.

Whole-rock oxygen and carbon isorope record across the Cretaceous/Tertiary boundary in ODP Hole 130-807C

Whole-rock d18O analyses of the Paleogene and Upper Cretaceous succession at Ocean Drilling Program Hole 807C suggest the presence of hiatuses between 876.95 and 894.47 mbsf and between 1138.82 and 1140.94 mbsf. The d13C data show a pronounced positive excursion between 1130 and 1180 mbsf that corresponds to the positive d13C values characteristic of the Paleocene. Despite the stratigraphic breaks in the section, the d18O data show a systematic increase between 1360 mbsf and the hiatus between 876.95 and 894.47 mbsf, which is consistent with previous suggestions of long-term climatic cooling through the Paleogene. The Cretaceous/Tertiary transition is apparently complete in this section and is of remarkable thickness. The expanded nature of this portion of the succession is probably the result of secondary depositional processes. High-resolution sampling across this boundary may reveal detailed structure of the d13C decline associated with the extinctions that mark the termination of the Cretaceous.