Chemical composition of ODP Leg 138 sediments

A major oceanographic event preserved in the Cocos plate sedimentary column survived subduction and is recorded in the changing composition of Nicaraguan magmas. A uranium increase in these magmas since the latest Miocene (after 7 Ma) resulted from the 'carbonate crash' at 10 Ma and the ensuing high organic carbon burial in the sediments. The response of the arc to this paleoceanographic event requires near steady-state sediment recycling at this margin since 20 Ma. This relative stability in sediment subduction invites one of the first attempts to balance sedimentary input and arc output across a subduction zone. Calculations based on Th indicate that as much as 75% of the sedimentary column was subducted beneath the arc. The Nicaraguan margin is one of the few places to observe such strong links between the oceans and the solid earth.

Lithology of ODP Leg 138 holes

During Leg 138, we measured reflectance spectra in the visible and near-infrared bands (455-945 nm) every few centimeters on split core surfaces from eastern tropical Pacific Ocean sediments. Here, we evaluate predictions of the content of biogenic calcite, biogenic opal, and nonbiogenic sediments from the reflectance spectra. For Sites 844 through 847, which contain a significant nonbiogenic component, reflectance spectra yielded a useful proxy for the percentages of CaCO3 over a wide range of values from nearly 0% to 100%, with root-mean-square (RMS) errors of about 9%. Direct estimates of "nonbiogenic" sediment percentages, approximated by 100 - (CaCO3 + opal), were reasonably successful (RMS error of 10%), however, were incorrect in some intervals. This suggests that mineralogy of the nonbiogenic material changes through time and that further subdivision of this component will be needed for useful estimation from reflectance. For percentages of biogenic opal, calibration equations appear to work well (RMS error of 6%) at concentrations of less than 30%, but for higher opal concentrations, reflectance equations often underestimate the true contents of opal. Improvements in multiparameter lithologic estimates from reflectance spectra may come from (1) expanding the wavelengths measured to better capture unique mineral reflectance bands, and (2) adding the ability to measure diffuse, rather than directional, reflectance to minimize the effects of surface roughness.

(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.

Barite accumulation rates throughout Pliocene-Pleistocene in Eastern Equatorial Pacific at ODP Site 138-849

Export production is an important component of the carbon cycle, modulating the climate system by transferring CO2 from the atmosphere to the deep ocean via the biological pump. Here we use barite accumulation rates to reconstruct export production in the eastern equatorial Pacific over the past 4.3 Ma. We find that export production fluctuated considerably on multiple time scales. Export production was on average higher (51 g C/m**2/yr) during the Pliocene than the Pleistocene (40 g C/m**2/yr), decreasing between 3 and 1 Ma (from more than 60 to 20 g C/m**2/yr) followed by an increase over the last million years. These trends likely reflect basin-scale changes in nutrient inventory and ocean circulation. Our record reveals decoupling between export production and temperatures on these long (million years) time scale. On orbital time scales, export production was generally higher during cold periods (glacial maxima) between 4.3 and 1.1 Ma. This could be due to stronger wind stress and higher upwelling rates during glacial periods. A shift in the timing of maximum export production to deglaciations is seen in the last ~1.1 million years. Results from this study suggest that, in the eastern equatorial Pacific, mechanisms that affect nutrient supply and/or ecosystem structure and in turn carbon export on orbital time scales differ from those operating on longer time scales and that processes linking export production and climate-modulated oceanic conditions changed about 1.1 million years ago. These observations should be accounted for in climate models to ensure better predictions of future climate change.