(Table A1) CaCO3 contents and Sr/Ca ratios in ODP Leg 130, 138 and 154

Strontium/calcium (Sr/Ca) ratios in bulk and foraminiferal calcite have been used to constrain the history of Sr/Ca in the oceans and to evaluate calcite diagenetic alteration. However bulk Sr/Ca records also may be influenced by differences in Sr uptake and/or in the diagenetic susceptibility of different calcium carbonate sedimentary components. We present data on the sediment size fraction and calcium carbonate distribution in bulk samples, Sr/Ca in a range of sedimentary size components, and Sr/Ca in bulk sediments. Ocean Drilling Program samples from sites on Ontong Java Plateau and Ceara Rise (in the western equatorial Pacific and Atlantic, respectively) and from sites in the eastern equatorial Pacific were selected to represent progressive stages in the diagenetic pathway from the sea floor through a range of burial depths equivalent to sediment ages of ~5.6, ~9.4, and ~37.1 Ma. Samples were subdivided by size to produce a unique data set of size-specific Sr/Ca ratios. Fine fraction (<45 ?m) Sr/Ca ratios are higher than those of all corresponding coarse fractions, indicating that fine nannofossil-dominated calcite has a Sr partition coefficient 1.3-1.5 times greater than that of coarse foraminifera-dominated calcite. Thus, absolute values of bulk Sr/Ca in contemporaneous samples reflect, in part, the ratio of fine to coarse calcite sedimentary components. Sr/Ca values in fine and coarse components also behave differently in their response to pre-burial dissolution and to recrystallization at depth. Coarse size components are sensitive to bottom water carbonate ion undersaturation, and they lose original Sr/Ca differences among contemporary samples over not, vert, similar10 my. In contrast, fine components recrystallize faster in more deeply buried samples. Interpretation of the historical Sr/Ca record is complicated by post-depositional diagenetic artifacts, and thus our data do not provide clear evidence of specific temporal changes in oceanic Sr/Ca ratios over the past 10 million years. This paper represents the first systematic attempt to examine trends in calcite Sr/Ca as a function of sediment size fraction and age.

(Table 3) Relative depth and age, CaCO3, d18O, d13C and Sr/Ca analysis from ODP Leg 130, 154 and 138

Interpretations of calcite strontium/calcium records in terms of ocean history and calcite diagenesis require distinguishing the effects on deep-sea calcite sediments of changes in ocean chemistry, of different mixes of calcite-depositing organisms as sediment contributors through time and space, and of the loss of Sr during diagenetic calcite recrystallization. In this paper Sr/Ca and d18O values of bulk calcium carbonate sediments are used to estimate the relative extent of calcite recrystallization in samples from four time points (core tops, 5.6, 9.4, and 37.1 Ma) at eight Ocean Drilling Program sites in the equatorial Atlantic (Ceara Rise) and equatorial Pacific (Ontong Java Plateau and two eastern equatorial Pacific sites). The possibility that site-to-site differences in calcite Sr/Ca at a given time point originated from temporal variations in ocean chemistry was eliminated by careful age control of samples for each time point, with sample ages differing by less than the oceanic residence times of Sr and Ca. The Sr/Ca and d18O values of 5.6- and 9.4-Ma samples from the less-carbonate-rich eastern equatorial Pacific sites and Ceara Rise Site 929 appear to be less diagenetically altered than the Sr/Ca and d18O values of contemporaneous samples from the more carbonate-rich sites. It is evident from these data that both Sr/Ca and d18O in bulk calcite have been diagenetically altered in some samples 5.6 Ma and older. These data indicate that noncarbonate sedimentary components, like clay and biogenic silica, have partially suppressed recrystallization at the lower carbonate sites. Sr/Ca data from the less altered, carbonate-poor sites indicate higher oceanic Sr/Ca relative to today at 5.6 and 9.4 Ma.

Accumulation rates of bulk sediment and total organic carbon for Ontong Java Plateau sediments

Organic geochemical investigations were performed on sediments of Leg 130 to reconstruct the depositional environment of the Ontong Java Plateau. The Miocene to Quaternary sediments collected during the drilling campaign are characterized by extremely low organic carbon contents. As indicated by C/N ratios and Rock-Eval data, most of the organic matter is probably of marine origin. Based on mass-accumulation rates of organic carbon, the paleoproductivity for the Miocene-Pliocene and the late Pliocene-Pleistocene time intervals as well as the modern surface-water production were estimated. The productivity values of the surface sediments (25-59 gC/m2/yr) reflect the various influences of the equatorial upwelling cell on the different sites. The accumulation rates of organic carbon are generally low; however, they show a distinct increase at 8 Ma and a decrease at 2 Ma.

The Fohsella chronocline in middle Miocene sediments from the Ontong Java Plateau, Pacific Ocean

Micropaleontologists have traditionally recognized the mid-Miocene Fohsella lineage as a flagship for phyletic gradualism within the planktic foraminifera. However, study of a deep-sea record from the western equatorial Pacific (ODP Site 806) reveals that coiling ratios within this clade suddenly (<5 kyr) shift after a prolonged, ancestral state of near randomness (~50%) to a transient phase (13.42-13.43 Ma) of dextral dominance (~75%) immediately following the first common occurrence of keeled fohsellids. This brief period of dextral dominance was abruptly (<5 kyr) succeeded by an irreversible change to sinistral dominance (~96%). Fohsellid abundances decline markedly through the interval in which the sinistral preference is established. The shift to sinistrality (13.42 Ma) predated the deepening of fohsellid depth ecology by ~240-488 kyr, indicating that these two events were unrelated. This view is supported by a lack of delta 18O evidence for depth-habitat differences between the two chiral forms, which refutes the notion that sinistral fohsellids were "pre-adapted" for ensuing hydrographic change because they occupied a deeper depth habitat than their dextral counterparts. Planktic foraminiferal assemblages become strongly oligotrophic in character through the interval in which the fohsellid delta 18O increase is recorded, indicating that the migration to deeper depths was fostered by an expansion of the mixed layer in the western equatorial Pacific. Salient aspects of this brief, but conspicuous faunal change are a marked increase in the abundance of symbiont-bearing globigerinoidids, a concomitant collapse of local Jenkinsella mayeri/siakensis populations, and reduced fohsellid abundances. The rapid and permanent nature of the Fohsella sinistral shift provides a distinct, unequivocal datum that may prove useful for correlating mid-Miocene sections throughout the Caribbean Sea and tropical regions in the western sectors of the Pacific and Atlantic. The coiling ratio changes that occurred during the evolution of the Fohsella chronocline probably reflect changing population dynamics between cryptic genotypes with different coiling preferences.

Lower to middle Miocene calcareous nannofossil events from the Ontong Java Plateau

Uppermost Oligocene through middle Miocene calcareous nannofossil events that were considered potentially useful from a biostratigraphic point of view have been investigated from Ocean Drilling Program Sites 806 and 807 in the western equatorial Pacific Ocean. Comparisons have been made to the corresponding events from other equatorial regions and the mid-latitude North Atlantic. In terms of biostratigraphic reliability, defined by the ability of the pertinent species to provide distinctive marker events and synchroneity over geographic distance, the investigated events can be classified into four general categories: The good markers: last occurrence (LO) Sphenolithus ciperoensis, first occurrence (FO) S. delphix, LO S. delphix, FO S. belemnos, LO S. belemnos, FO S. heteromorphus, termination acme (TA) Discoaster deflandrei, and LO Sphenolithus heteromorphus. The poor markers: LO Helicosphaera recta, TA Cyclicargolithus abisectus, LO Triquetrorhabdulus carinatus, and FO Calcidiscus macintyrei. Ecologically controlled markers with regional value: LO Dictyococcites bisectus, LO Helicosphaera ampliaperta, FO Reticulofenestra pseudoumbilica, LO Cyclicargolithus floridanus, and LO Coronocyclus nitescens. The low abundance markers: FO Discoaster druggii, gradational form of Sphenoliths dissimilis/Sphenolithus belemnos, FO Triquetrorhabdulus rugosus, and FO T. rioensis.

Age-depth correlations for Ontong Java Plateau sites

We used well logs, in some cases combined with shipboard physical properties measurements to make more complete profiles and to correlate between sites on the Ontong Java Plateau. By comparing sediment bulk density, velocity, and resistivity logs from adjacent holes at the same site, we showed that even subtle features of the well logs are reproducible and are caused by variations in sedimentation. With only minor amounts of biostratigraphic information, we could readily correlate these sedimentary features across the entire top of the Ontong Java Plateau, demonstrating that for most of the Neogene the top of the plateau is a single sedimentary province. We found it more difficult, but still possible, to correlate in detail sites from the top of the plateau to those drilled on the flanks. The pattern of sedimentation rate variation down the flank of the plateau cannot be interpreted as simply controlled by dissolution. Site 805, in particular, oscillates between accumulating sediment at roughly the same rate as cores on top of the Ontong Java Plateau, and accumulating sediment as slowly as Site 803, 200 m deeper in the water column. These oscillations do not match earlier reconstructions of central Pacific carbonate compensation depth variations.

Radioisotopes and He accumulation in deep sea sediments of the Ontong Java Plateau

The accumulation of extraterrestrial 3He, a tracer for interplanetary dust particles (IDPs), in sediments from the Ontong Java Plateau (OJP; western equatorial Pacific Ocean) has been shown previously to exhibit a regular cyclicity during the late Pleistocene, with a period of ~100 ka. Those results have been interpreted to reflect periodic variability in the global accretion of IDPs that, in turn, has been linked to changes in the inclination of Earth's orbit with respect to the invariable plane of the solar system. Here we show that the accumulation in OJP sediments of authigenic 230Th, produced by radioactive decay of 234U in seawater, exhibits a 100-ka cyclicity similar in phase and amplitude to that evident in the 3He record. We interpret the similar patterns of 230Th and 3He accumulation to reflect a common origin within the ocean-climate system. Comparing spatial and temporal patterns of sediment accumulation against regional patterns of biological productivity and against the well-established pattern of CaCO3 dissolution in the deep Pacific Ocean leads to the further conclusion that a common 100-ka cycle in accumulation of biogenic, authigenic and extraterrestrial constituents in OJP sediments reflects the influence of climate-related changes in sediment focusing, rather than changes in the rate of production or supply of sedimentary constituents.

Neogene calcareous nannofossil abundances and biostratigraphy of the Ontong Java Plateau

A total of 35 calcareous nannofossil datums were found in the Neogene sediments recovered at five sites (Sites 803-807) on the Ontong Java Plateau in the equatorial Pacific during Ocean Drilling Program Leg 130. Among them, 12 datums in the Pleistocene-upper Pliocene sequences were correlated with magnetostratigraphy. Pliocene and Miocene calcareous nannofossil assemblages in 289 samples obtained from Holes 804C, 805B, 805C, and 806B were studied. Reticulofenestra coccolith size distribution patterns in these Pliocene-Miocene sediments were also revealed through the present investigation.

The evolutionary history of size variation of planktic foraminiferal assemblages in the Cenozoic

The iterative evolutionary radiation of planktic foraminifers is a well-documented macroevolutionary process. Here we document the accompanying size changes in entire planktic foraminiferal assemblages for the past 70 My and their relationship to paleoenvironmental changes. After the size decrease at the Cretaceous/Paleogene (K/P) boundary, high latitude assemblages remained consistently small. Size evolution in low latitudes can be divided into three major phases: the first is characterized by dwarfs (65-42 Ma), the second shows moderate size fluctuations (42-14 Ma), and in the third phase, planktic foraminifers have grown to the unprecedented sizes observed today. Our analyses of size variability with paleoproxy records indicate that periods of size increase coincided with phases of global cooling (Eocene and Neogene). These periods were characterized by enhanced latitudinal and vertical temperature gradients in the oceans and high diversity (polytaxy). In the Paleocene and during the Oligocene, the observed (minor) size changes of the largely low-diversity (oligotaxic) assemblages seem to correlate with productivity changes. However, polytaxy per se was not responsible for larger test sizes.

Foraminifera abundances and biostratigraphy of Cenozoic sediments from the Ontong Java Plateau

The Ontong Java Plateau in the western equatorial Pacific contains a deposition record of biserial planktonic foraminifers concentrated in the Paleogene, in which frequencies up to 67% of the planktonic foraminifers are reported, and in the late Neogene, in which a maximum frequency of 48% is reported. Biserial planktonic foraminifers are rare or absent in the latest Oligocene and early Miocene, an interval characterized by warm bottom water and low temperature gradients. These conditions supported a surface assemblage rather than the biserial planktonic foraminifers, whose Neogene species inhabited the oxygen minimum at intermediate depths in the upper water column. Biserial planktonic foraminifers tend to be of high frequency during high sea stands and low frequency during low sea level, presumably in response to the strengthening or weakening of the oxygen minimum. Species extinction and evolution events occur during low sea stands in the Neogene and sometimes correspond to strong reflection horizons of the plateau's seismic stratigraphy. The biserial species are useful biostratigraphic indexes in the plateau section. The last occurrence (LO) of Streptochilus martini corresponds with the Eocene/Oligocene boundary; S. subglobigerum without Neogloboquadrina acostaensis indicates Zone N15; S. latum occurs from the middle of Zone N16 to near the top of Zone N17; S. globigerum ranges from near the top of Zone N17 to the middle of Zone N19/N20; and the S. globulosum continuous range begins just before the first left-to-right coiling change of Pulleniatina, but the species becomes rare in the Pleistocene section.

(Table 3) Li concentrations and isotopic compositions in foraminiferal shells, carbonate sediments, and associated pore waters from ODP Sites 131-806 and 138-851

An improved procedure for lithium isotope analysis using Li3PO4 as the ion source has been investigated for application to geological samples. The 7Li/6Li ratio is measured using double rhenium filament thermal ionization mass spectrometry in which isotopic fractionation is minimized at high temperatures. The method produces a stable, high intensity Li+ ion beam that allows measurement of nanogram quantities of lithium. This results in a reduction in sample size of up to 1000 times relative to that required for the established Li2BO2+ method while maintaining a comparable precision of better than 1? (1 sigma). Replicate analyses of the NBS L-SVEC Li2CO3 standard yielded a mean value of 12.1047+/-0.0043 (n=21), which is close to the reported absolute value of 12.02+/-0.03. Intercalibration with a wide range of geological samples shows excellent agreement between the Li3PO4 and Li2BO2+ techniques. Replicate analyses of seawater and a fresh submarine basalt display high precision results that agree with previous measurements. Taking advantage of the high ionization efficiency of the phosphate ion source, we have made the first measurements of the lithium concentration (by isotope dilution) and isotopic composition of calcareous foraminiferal tests and other marine carbonates. Preliminary results indicate that substantial lithium exchange occurs between carbonate sediments and their interstitial waters. In addition, a possible link between lithium paleoceanography and paleoclimate during the last 1000 ky may be derived from planktonic foraminiferal tests. This highly sensitive technique can be applied in the examination of low lithium reservoirs and thereby provide insight into some fundamental aspects of lithium geochemistry.

Pacific Neogene carbonate accumulation rates

I have compiled CaCO3 mass accumulation rates (MARs) for the period 0-25 Ma for 144 Deep Sea Drilling Project and Ocean Drilling Program drill sites in the Pacific in order to investigate the history of CaCO3 burial in the world's largest ocean basin. This is the first synthesis of data since the beginning of the Ocean Drilling Program. Sedimentation rates, CaCO3 contents, and bulk density were estimated for 0.5 Myr time intervals from 0 to 14 Ma and for 1 Myr time intervals from 14 to 25 Ma using mostly data from Initial Reports volumes. There is surprisingly little coherence between CaCO3 MAR time series from different Pacific regions, although regional patterns exist. A transition from high to low CaCO3 MAR from 23-20 Ma is the only event common to the entire Pacific Ocean. This event is found worldwide. The most likely cause of lowered pelagic carbonate burial is a rising sea-level trend in the early Miocene. The central and eastern equatorial Pacific is the only region with adequate drill site coverage to study carbonate compensation depth (CCD) changes in detail for the entire Neogene. The latitude-dependent decrease in CaCO3 production away from the equator is an important defining factor of the regional CCD, which shallows away from the equatorial region. Examination of latitudinal transects across the equatorial region is a useful way to separate the effects of changes in carbonate production ('productivity') from changes in bottom water chemistry ('dissolution') upon carbonate burial.

Revised Cenozoic hiatus database

The differential effects of climate change, sea level, and water mass circulation on deposition/erosion of marine sediments can be constrained from the distribution of unconformities in the world's oceans. I identified temporal and depth patterns of hiatuses ("hiatus events") from a large and chronologically well constrained stratigraphic database of deep-sea sediments. The Paleogene is characterized by few, several million year long hiatuses. The most significant Cenozoic hiatus event spans most of the Paleocene. The Neogene is characterized by short, frequent hiatus events nearly synchronous in shallow and deep water sediments. Epoch boundaries are characterized by peaks in deep water hiatuses possibly caused by an increased circulation of corrosive bottom water and sediment dissolution. The Plio-Pleistocene is characterized by a gradual decrease in the frequency of hiatuses. Future studies will focus on the regional significance of the hiatus events and their possible causes.