(Table T1) Scanning electron microscope (SEM) analyses of IODP Site 321-U1338

The late Miocene to early Pliocene carbonate-rich sediments recovered at Integrated Ocean Drilling Program (IODP) Site U1338 during the Expedition 320/321 Pacific Equatorial Age Transect (PEAT) program contain abundant calcareous nanno- and microfossils. Geochemical proxies from benthic and planktonic foraminiferal and coccolithophore calcite could be very useful at this location; however, good preservation of the calcite is crucial for the proxies to be robust. Here, we evaluate the preservation of specific benthic and planktonic foraminifer species and coccolithophores in fine fraction sediment at Site U1338 using backscattered electron (topography mode) scanning electron microscopy (BSE-TOPO SEM). Both investigated foraminiferal species, Cibicidoides mundulus and Globigerinoides sacculifer, have undergone some alteration. The C. mundulus show minor evidence for dissolution, and only some specimens show evidence of overgrowth. The Gs. sacculifer show definite signs of alteration and exhibit variable preservation, ranging from fair to poor; some specimens show minor overgrowth and internal recrystallization but retain original features such as pores, spine pits, and internal test-wall growth structure, whereas in other specimens the recrystallization and overgrowth disguise many of the original features. Secondary electron and BSE-TOPO SEM images show that coccolith calcite preservation is moderate or moderate to poor. Slight to moderate etching has removed central heterococcolith features, and a small amount of secondary overgrowth is also visible. Energy dispersive spectroscopy analyses indicate that the main sedimentary components of the fine fraction sediment are biogenic CaCO3 and SiO2, with some marine barite. Based on the investigations in this data report, geochemical analyses on benthic foraminifers are unlikely to be affected by preservation, although geochemical analyses on the planktonic foraminifers should be treated cautiously because of the fair to poor and highly variable preservation.

Stable isotope record, opal accumulation rate and geochemistry of middle Miocene sediments of IODP Site 321-U1338

During the middle Miocene, Earth's climate transitioned from a relatively warm phase (Miocene climatic optimum) into a colder mode with re-establishment of permanent ice sheets on Antarctica, thus marking a fundamental step in Cenozoic cooling. Carbon sequestration and atmospheric CO2 drawdown through increased terrestrial and/or marine productivity have been proposed as the main drivers of this fundamental transition. We integrate high-resolution (1-3 k.y.) benthic stable isotope data with XRF-scanner derived biogenic silica and carbonate accumulation estimates in an exceptionally well-preserved sedimentary archive, recovered at Integrated Ocean Drilling Program Site U1338, to reconstruct eastern equatorial Pacific productivity variations and to investigate temporal linkages between high- and low-latitude climate change over the interval 16-13 Ma. Our records show that the climatic optimum (16.8-14.7 Ma) was characterized by high amplitude climate variations, marked by intense perturbations of the carbon cycle. Episodes of peak warmth at (southern hemisphere) insolation maxima coincided with transient shoaling of the carbonate compensation depth and enhanced carbonate dissolution in the deep ocean. A switch to obliquity-paced climate variability after 14.7 Ma concurred with a general improvement in carbonate preservation and the onset of stepwise global cooling, culminating with extensive ice growth over Antarctica at ~13.8 Ma. We find that two massive increases in opal accumulation at ~14.0 and ~13.8 Ma occurred just before and during the final and most prominent cooling step, supporting the hypothesis that enhanced siliceous productivity in the eastern equatorial Pacific contributed to CO2 drawdown.

Raw and normalized X-ray fluorescence (XRF) scannings of IODP Expedition 321, Site U1338

We used X-ray fluorescence (XRF) scanning on Site U1338 sediments from Integrated Ocean Drilling Program Expedition 321 to measure sediment geochemical compositions at 2.5 cm resolution for the 450 m of the Site U1338 spliced sediment column. This spatial resolution is equivalent to ~2 k.y. age sampling in the 0-5 Ma section and ~1 k.y. resolution from 5 to 17 Ma. Here we report the data and describe data acquisition conditions to measure Al, Si, K, Ca, Ti, Fe, Mn, and Ba in the solid phase. We also describe a method to convert the data from volume-based raw XRF scan data to a normalized mass measurement ready for calibration by other geochemical methods. Both the raw and normalized data are reported along the Site U1338 splice.

Sea surface temperatures reconstructed from sediment core U1338

This study presents a new alkenone-derived Sea Surface Temperature (SST) record and d18ONoelaerhabdaceae data of the 2-5 µm carbonate fractions from the IODP site U1338 located in the Eastern Equatorial Pacific (EEP), over the Miocene-Pliocene. Our data and those available from other sites of the same area show the establishment of a cold tongue during the early Pliocene (4.4 - 3.6 Ma). SST and d18ONoelaerhabdaceae time-series indicate periods of significant salinity variations. Comparison with the d18Obenthic curve from sediment cores of the Equatorial Pacific Ocean allow us to distinguish between global changes and local surface salinity variations in the EEP. Ice sheet growth and evaporation-precipitation are then discussed as possible drivers of such changes, as well as the role of Central American and the Indonesian seaway restriction. Our data suggest a shallowing of the thermocline in the EEP, between 6.8 and 6 Ma, and its shoaling between 4.8 and 4.0 Ma, suggesting the appearance of the cold tongue (Steph et al., 2010). The Pliocene climate transition would therefore not be primarily driven by Northern hemisphere glaciation.

Correlation between wet bulk density and carbonate content from IODP Hole 321-U1338A, 321-U1338B and 321-U1338C

Sediment cores collected from the Eastern Equatorial Pacific Ocean display a clear positive second-order relationship between wet bulk density (WBD) and carbonate content. This has long interested the paleoceanography community because detailed Gamma Ray Attenuation Porosity Evaluator (GRAPE) measurements, which approximate WBD, might be used to determine records of carbonate content at very high temporal resolution. Although general causes for the relationship are known, they have not been presented and discussed systematically on the basis of first principles. In this study, we measure the mass and carbonate content of 50 sediment samples with known WBD from Site U1338, before and after rinsing with de-ionized water; we also determine the mass related proportion of coarse (> 63 µm) material. Samples exhibit clear relationships between WBD, carbonate content, mass loss upon rinsing, and grain size. We develop a series of mathematical expressions to describe these relationships, and solve them numerically. As noted by previous workers, the second-order relationship between WBD and carbonate content results from the mixing of biogenic carbonate and biogenic silica, which have different grain densities and different porosities. However, at high carbonate content, a wide range in WBD occurs because samples with greater amounts of coarse carbonate have higher porosity. Moreover compaction impacts carbonate particles more than biogenic silica particles. As such, a single two-component equation cannot be used to determine carbonate content accurately across depth intervals where both the porosity and type of carbonate vary. Instead, the WBD-carbonate relationship is described by an infinite series of curves, each which represents mixing of multiple sediment components with different densities and porosities. Dissolved ions also precipitate from pore space during sample drying, which adds mass to the sediment. Without rinsing samples, simple empirical relationships between WBD and carbonate content are further skewed by salt dilution.

Miocene stable isotope record of IODP Site 320-U1335 and revised stable isotope record of IODP Site 321-U1337

The Miocene Climatic Optimum (MCO; ~16.9 to 14.7 Ma) provides an outstanding opportunity to investigate climate-carbon cycle dynamics during a geologically recent interval of global warmth. We present benthic stable oxygen (d18O) and carbon (d13C) isotope records (5-12 kyr time resolution) spanning the late early to middle Miocene interval (18 to 13 Ma) at Integrated Ocean Drilling Program (IODP) Site U1335 (eastern equatorial Pacific Ocean). The U1335 stable isotope series track the onset and development of the MCO as well as the transitional climatic phase culminating with global cooling and expansion of the East Antarctic ice-sheet at ~13.8 Ma. We integrate these new data with published stable isotope, geomagnetic polarity and X-ray fluorescence (XRF) scanner-derived carbonate records from IODP Sites U1335, U1336, U1337 and U1338 on a consistent, astronomically-tuned timescale. Benthic isotope and XRF scanner-derived CaCO3 records depict prominent 100 kyr variability with 400 kyr cyclicity additionally imprinted on d13C and CaCO3 records, pointing to a tight coupling between the marine carbon cycle and climate variations. Our inter-site comparison further indicates that the lysocline behaved in highly dynamic manner throughout the MCO, with >75% carbonate loss occurring at paleo-depths ranging from ~3.4 to ~4 km in the eastern equatorial Pacific Ocean. Carbonate dissolution maxima coincide with warm phases (d18O minima) and d13C decreases, implying that climate-carbon cycle feedbacks fundamentally differed from the late Pleistocene glacial-interglacial pattern, where dissolution maxima correspond to d13C maxima and d18O minima. Carbonate dissolution cycles during the MCO were, thus, more similar to Paleogene hyperthermal patterns.