Phosphorus components, trace metals and Ba excess of ODP Site 202-1237 sediments

We determined the sedimentary concentrations of phosphorus (P), barium (Ba), manganese (Mn), titanium (Ti), aluminum (Al), and uranium (U) for sediment samples from the southeast Pacific Nazca Ridge, Ocean Drilling Program Site 1237. This unique record extends to 31 Ma over 360 meters composite depth (mcd), recording depositional history as the site progressed eastward over its paleohistory. We sampled with a temporal resolution of ~0.2 m.y. throughout the sequence, equivalent to an average spacing of 1.63 m/sample. Concentrations of sequentially extracted components of P (oxide-associated, authigenic, organic, and detrital) increase toward the modern. Al/Ti ratios indicate that the background detrital source material is consistent with upper continental crust. U enrichment factors (U EFs) generally exceed crustal values and indicate slightly reducing environments. However, authigenic U precipitation can also be influenced by the organic carbon rain rate and may not be solely an indicator of redox conditions. Dramatic changes in Mn EFs at ~162 mcd, from values between 12 and 93 to values <12 after this depth, and a sharp color contact boundary lead us to believe that a paleoredox boundary from an oxygenated to a more reducing depositional environment occurred near this depth. Estimates of biogenic barite concentrations from a total sediment digestion technique (Ba excess) are greater than those from a barite extraction (Ba barite) for selected samples across the entire depth range. Applying a range of Ba/Ti ratios from different source materials to correct for detrital inputs does not change the lack of agreement with Ba barite concentrations. Reactive P (P reactive) concentrations (the sum of oxide-associated, authigenic, and organic P concentrations) increase toward the modern with values typically <12 µmol P/g from the base of our record through ~100 mcd, with a gradual increase to concentrations >15 µmol P/g. Ba excess follows the same general trends as Preactive, with concentrations <14 µmol Ba/g in the lower portion of the record to values >15 µmol Ba/g. Accumulation rate records of these proxies will be needed to infer paleoproductivity. P reactive/Ba excess ratios, an indicator of the relative burial of the nutrient P to organic carbon export, exhibit higher values, similar to modern, from the base of our record through ~180 mcd. The remainder of the record exhibits values lower than modern, indicating that organic carbon export to the sediments was higher relative to nutrient burial.

Stable isotopes measured on Miocene benthic foraminifera from ODP sites 202-1237 and 184-1146

One of the most enigmatic features of Cenozoic long-term climate evolution is the long-lasting positive carbon-isotope excursion or "Monterey Excursion", which started during a period of global warmth after 16.9 Ma and ended at not, vert, similar 13.5 Ma, approximately 400 kyr after major expansion of the Antarctic ice-sheet. We present high-resolution (1-9 kyr) astronomically-tuned climate proxy records in two complete sedimentary successions from the northwestern and southeastern Pacific (ODP Sites 1146 and 1237), which shed new light on the middle Miocene carbon-isotope excursion and associated climatic transition over the interval 17.1-12.7 Ma. We recognize three distinct climate phases with different imprints of orbital variations into the climatic signals (1146 and 1237 d18O, d13C; 1237 XRF Fe, fraction > 63 µm): (1) climate optimum prior to 14.7 Ma characterized by minimum ice volume and prominent 100 and 400 kyr variability, (2) long-term cooling from 14.7 to 13.9 Ma, principally driven by obliquity and culminating with rapid cryosphere expansion and global cooling at the onset of the last and most pronounced d13C increase, (3) "Icehouse" mode after 13.9 Ma with distinct 100 kyr variability and improved ventilation of the deep Pacific. The "Monterey" carbon-isotope excursion (16.9-13.5 Ma) consists overall of nine 400 kyr cycles, which show high coherence with the long eccentricity period. Superposed on these low-frequency oscillations are high-frequency variations (100 kyr), which closely track the amplitude modulation of the short eccentricity period. In contrast to d13C, the d18O signal additionally shows significant power in the 41 kyr band, and the 1.2 Myr amplitude modulation of the obliquity cycle is clearly imprinted in the 1146 d18O signal. Our results suggest that eccentricity was a prime pacemaker of middle Miocene climate evolution through the modulation of long-term carbon budgets and that obliquity-paced changes in high-latitude seasonality favored the transition into the "Icehouse" climate.