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.

Short-term variations in radiolarian faunal dsitribution in the eastern equatorial Pacific

Two short time intervals centered at 2.3 and 4.7 Ma were studied to investigate short-term variations in surface-ocean processes as indicated by changes in the radiolarian microfossil population. These time intervals represent two different settings of late Neogene climate. The older interval represents a time when tropical circulation between the Pacific and Atlantic oceans was not blocked by the Isthmus of Panama, whereas the younger interval represents a time when Northern Hemisphere glaciation was present but did not display the dominance of the 100,000-yr cycle that characterizes the late Pleistocene. The younger time slice at 2.3 Ma was sampled at all Leg 138 sites except Site 844, where significant reworking was evident. All sites except 844, 853, and 854 were sampled for the older time slice. Samples were taken at 10- to 20-cm intervals at each site and spanned a GRAPE density maximum and minimum. Thus, it was possible to investigate whether the changes in carbonate content (as indicated by GRAPE density) were associated with changes in surface-ocean conditions (indicated by radiolarian assemblage variations). For both time slices, the radiolarian data indicate that intervals of decreased carbonate content are periods of cooler water conditions and possibly enhanced biogenic production. Times of increased carbonate content are associated with inferred warmer oceanographic conditions, as indicated by the dominance of tropical assemblages at 2.3 Ma and tropical and western Pacific assemblages during the time slice centered at 4.8 Ma. However, the spatial patterns of change during each time slice show a distinct difference in the mapped patterns of radiolarian assemblage dominance. The older time slice, representing a period before the closing of the Isthmus of Panama, shows more zonal patterns presumably associated with a more zonal character of equatorial circulation. After the closing of the isthmus, the shifts in faunal patterns between times of high and low carbonates are characterized by shifts in the dominance of the tropical and transitional assemblages, respectively, throughout the region.

(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.

Global compilation of benthic data sets I

Approaches to quantify the organic carbon accumulation on a global scale generally do not consider the small-scale variability of sedimentary and oceanographic boundary conditions along continental margins. In this study, we present a new approach to regionalize the total organic carbon (TOC) content in surface sediments (<5 cm sediment depth). It is based on a compilation of more than 5500 single measurements from various sources. Global TOC distribution was determined by the application of a combined qualitative and quantitative-geostatistical method. Overall, 33 benthic TOC-based provinces were defined and used to process the global distribution pattern of the TOC content in surface sediments in a 1°x1° grid resolution. Regional dependencies of data points within each single province are expressed by modeled semi-variograms. Measured and estimated TOC values show good correlation, emphasizing the reasonable applicability of the method. The accumulation of organic carbon in marine surface sediments is a key parameter in the control of mineralization processes and the material exchange between the sediment and the ocean water. Our approach will help to improve global budgets of nutrient and carbon cycles.

Compilation of planktonic foraminiferal census counts from the Southern Hemisphere Oceans

We present an improved database of planktonic foraminiferal census counts from the Southern Hemisphere Oceans (SHO) from 15°S to 64°S. The SHO database combines 3 existing databases. Using this SHO database, we investigated dissolution biases that might affect faunal census counts. We suggest a depth/[DCO3]2- threshold of ~3800 m/[DCO3]2- = ~-10 to -5 µmol/kg for the Pacific and Indian Oceans, and ~4000 m/[DCO3]2- = ~0 to 10 µmol/kg for the Atlantic Ocean, under which core-top assemblages can be affected by dissolution and are less reliable for paleo-sea surface temperature (SST) reconstructions. We removed all core-tops beyond these thresholds from the SHO database. This database has 598 core-tops and is able to reconstruct past SST variations from 2° to 25.5°C, with a root mean square error of 1.00°C, for annual temperatures. To inspect dissolution affects SST reconstruction quality, we tested the data base with two "leave-one-out" tests, with and without the deep core-tops. We used this database to reconstruct Summer SST (SSST) over the last 20 ka, using the Modern Analog Technique method, on the Southeast Pacific core MD07-3100. This was compared to the SSST reconstructed using the 3 databases used to compile the SHO database. Thus showing that the reconstruction using the SHO database is more reliable, as its dissimilarity values are the lowest. The most important aspect here is the importance of a bias-free, geographic-rich, database. We leave this dataset open-ended to future additions; the new core-tops must be carefully selected, with their chronological frameworks, and evidence of dissolution assessed.

Sediment core-top GDGT data from the Arctic, the North Pacific and the Southern Ocean

TEX86 (TetraEther indeX of tetraethers consisting of 86 carbon atoms) is a sea surface temperature (SST) proxy based on the distribution of archaeal isoprenoid glycerol dialkyl glycerol tetraethers (GDGTs). In this study, we appraise the applicability of TEX86 and TEX86L in subpolar and polar regions using surface sediments. We present TEX86 and TEX86L data from 160 surface sediment samples collected in the Arctic, the Southern Ocean and the North Pacific. Most of the SST estimates derived from both TEX86 and TEX86L are anomalously high in the Arctic, especially in the vicinity of Siberian river mouths and the sea ice margin, plausibly due to additional archaeal contributions linked to terrigenous input. We found unusual GDGT distributions at five sites in the North Pacific. High GDGT-0/crenarchaeol and GDGT-2/crenarchaeol ratios at these sites suggest a substantial contribution of methanogenic and/or methanotrophic archaea to the sedimentary GDGT pool here. Apart from these anomalous findings, TEX86 and TEX86L values in the surface sediments from the Southern Ocean and the North Pacific do usually vary with overlaying SSTs. In these regions, the sedimentary TEX86-SST relationship is similar to the global calibration, and the derived temperature estimates agree well with overlaying annual mean SSTs at the sites. However, there is a systematic offset between the regional TEX86L-SST relationships and the global calibration. At these sites, temperature estimates based on the global TEX86L calibration are closer to summer SSTs than annual mean SSTs. This finding suggests that in these subpolar settings a regional TEX86L calibration may be a more suitable equation for temperature reconstruction than the global calibration.