Late Eocene-earliest Miocene Sr isotopic reference section of DSDP Site 73-522

We present a revised calibration of Sr isotopes to the geomagnetic polarity timescale (GPTS) using closely spaced (~0.15 m.y. resolution) samples from the classic uppermost Eocene through lowermost Miocene section at Site 522, eastern South Atlantic. The Sr isotopic data are fit with two linear segments with a sharp change in slope at circa 27.5 Ma from 0.000038/m.y. (27.5 to 34.4 Ma) to 0.000051/m.y. (23.8 to 27.5 Ma). Regression analysis indicates that stratigraphic resolution ranges from ±1 m.y. (for one analysis) to ±0.6 m.y. (for three analyses) for the younger interval and ±1.2 m.y. (for one analysis) to ±0.7 m.y. (for three analyses) for the older interval, representing an increase in resolution from previous studies of ±1-2 m.y. The paleoceanographic significance of this change in slope is unclear. It occurs during an interval of intermittent Antarctic glaciation, between the Oi2a and Oi2b glaciations. The subsequent interval from circa 27 to 24 Ma appears to be an interval of minimal glaciation. Thus this observation does not support previous suggestions that increases in rates of Sr isotopic change are directly associated with the frequency of Antarctic glaciations. Rather, the increase in slope may be related to increased weathering associated with the "mid-Oligocene" glaciation.

Coral oxygen isotope and Sr/Ca data from the Northern Gulf of Aqaba (Red Sea)

The last interglacial period (about 125,000 years ago) is thought to have been at least as warm as the present climate (Kukla et al., 2002, doi:10.1006/qres.2001.2316). Owing to changes in the Earth's orbit around the Sun, it is thought that insolation in the Northern Hemisphere varied more strongly than today on seasonal timescales (Berger, 1987, doi:10.1175/1520-0469(1978)035<2362:LTVODI>2.0.CO;2), which would have led to corresponding changes in the seasonal temperature cycle (Montoya et al., 2000, doi:10.1175/1520-0442(2000)013<1057:CSFKBW>2.0.CO;2). Here we present seasonally resolved proxy records using corals from the northernmost Red Sea, which record climate during the last interglacial period, the late Holocene epoch and the present. We find an increased seasonality in the temperature recorded in the last interglacial coral. Today, climate in the northern Red Sea is sensitive to the North Atlantic Oscillation (Felis et al., 2000 doi:10.1029/1999PA000477; Rimbu et al., 2001, doi:10.1029/2001GL013083), a climate oscillation that strongly influences winter temperatures and precipitation in the North Atlantic region. From our coral records and simulations with a coupled atmosphere-ocean circulation model, we conclude that a tendency towards the high-index state of the North Atlantic Oscillation during the last interglacial period, which is consistent with European proxy records (Zagwijn, 1996, doi:10.1016/0277-3791(96)00011-X; Aalbersberg and Litt, 1998, doi:10.1002/(SICI)1099-1417(1998090)13:5<367::AID-JQS400>3.0.CO;2-I; Klotz et al., 2003, doi:10.1016/S0921-8181(02)00222-9), contributed to the larger amplitude of the seasonal cycle in the Middle East.

Oxygen isotopes and Sr/Ca ratios of fossil corals from Bonaire

Explanations for the demise of the Classic Maya civilization on the Yucatán Peninsula during the Terminal Classic Period (TCP; CE 750-1050) are controversial. Multiyear droughts are one likely cause, but the role of the Caribbean Sea, the dominant moisture source for Mesoamerica, remains largely unknown. Here we present bimonthly resolved snapshots of reconstructed sea surface temperature (SST) and salinity (SSS) variability in the southern Caribbean from precisely dated fossil corals. Our fossil coral results from Bonaire indicate strong interannual to decadal SST and SSS variability in the southern Caribbean Sea during the TCP with multiyear extremes of high SSS and high SST that coincide with droughts on the Yucatán Peninsula. The results are best explained by changed Caribbean SST gradients affecting the Caribbean low-level atmospheric jet with consequences for Mesoamerican precipitation, possibly linked to changes in Atlantic Meridional Overturning Circulation strength. Our findings provide a new perspective on the anomalous hydrological changes on the Yucatán Peninsula during the TCP that complement the often-suggested southward displacement of the Intertropical Convergence Zone. We advocate for a strong role of ocean-atmosphere interactions in the Caribbean Sea related to the multiyear variations in Caribbean Sea surface conditions as an important driver of the spatially complex pattern of hydrological anomalies during the TCP.

Alkali contents, Sr isotope and U-Th-Pb data for ocean crust vein minerals from DSDP Holes 27-261, 61-462A, and 72-516F

Cation exchange experiments (ammonium acetate and cation resin) on celadonite-smectite vein minerals from three DSDP holes demonstrate selective removal of common Sr relative to Rb and radiogenic Sr. This technique increases the Rb/Sr ratio by factors of 2.3 to 22 without significantly altering the age of the minerals, allowing easier and more precise dating of such vein minerals. The ages determined by this technique (Site 261 - 121.4+/-1.6 m.y.; Site 462A - 105.1+/-2.8 m.y.; Site 516F - 69.9+/-2.4 m.y.) are 34, 54 and 18 m.y. younger, respectively, than the age of crust formation at the site; in the case of site 462A, the young age is clearly related to off-ridge emplacement of a massive sill/flow complex. At the other sites, either the hydrothermal circulation systems persisted longer than for normal crust (10-15 m.y.), or were reactivated by off-ridge igneous activity. Celadonites show U and Pb contents and Pb isotopic compositions little changed from their basalt precursors, while Th contents are significantly lower. Celadonites thus have unusually high alkali/U,Th ratios and low Th/U ratios. If this celadonite alteration signature is significantly imprinted on oceanic crust as a whole, it will lead to very distinctive Pb isotope signatures for any hot spot magmas which contain a component of aged subducted recycled oceanic crust. Initial Sr isotope ratios of ocean crust vein minerals (smectite, celadonite, zeolite, calcite) are intermediate between primary basalt values and contemporary sea water values and indicate formation under seawaterdominated systems with effective water/rock ratios of 20-200.

Element and Sr isotope composition of interstitial waters in sediments of ODP Leg 129

Interstitial water samples from Leg 129, Sites 800, 801, and 802 in the Pigafetta and Mariana basins (central western Pacific), have been analyzed for major elements, B, Li, Mn, Sr, and 87Sr/86Sr. At all sites waters show enrichment in Ca and Sr and are depleted in Mg, K, Na, SO4, B, alkalinity, and 87Sr compared to seawater. These changes are related to alteration of basaltic material into secondary smectite and zeolite and recrystallization of biogenic carbonate. Water concentration depth profiles are characterized by breaks due to the presence of barriers to diffusion such as chert layers at Sites 800 and 801 and highly cemented volcanic ash at Site 802. In Site 800, below a chert layer, concentration depth profiles are vertical and reflect slight alteration of volcanic matter, either in situ or in the upper basaltic crust. Release of interlayer water from clay minerals is likely to induce observed Cl depletions. At Site 801, two units act as diffusion barrier and isolate the volcaniclastic sediments from ocean and basement. Diagenetic alteration of volcanic matter generates a chemical signature similar to that at Site 800. Just above the basaltic crust, interstitial waters are less evolved and reflect low alteration of the crust, probably because of the presence in the sediments of layers with low diffusivities. At Site 802, in Miocene tuffs, the chemical evolution generated by diagenetic alteration is extreme (Ca = 130 mmol, 87Sr/86Sr = 0.7042 at 83 meters below seafloor) and is accompanied by an increase of the Cl content (630 mmol) due to water uptake in secondary hydrous phases. Factors that enhance this evolution are a high sediment accumulation rate, high cementation preventing diffusive exchange and the reactive composition of the sediment (basaltic glass). The chemical variation is estimated to result in the alteration of more than 20% of the volcanic matter in a nearly closed system.

Sr-Nd isotopic analyses of sand-sized sediment from the San Francisco Bay coastal system

A diverse suite of geochemical tracers, including 87Sr/86Sr and 143Nd/144Nd isotope ratios, the rare earth elements (REEs), and select trace elements were used to determine sand-sized sediment provenance and transport pathways within the San Francisco Bay coastal system. This study complements a large interdisciplinary effort (Barnard et al., 2012) that seeks to better understand recent geomorphic change in a highly urbanized and dynamic estuarine-coastal setting. Sand-sized sediment provenance in this geologically complex system is important to estuarine resource managers and was assessed by examining the geographic distribution of this suite of geochemical tracers from the primary sources (fluvial and rock) throughout the bay, adjacent coast, and beaches. Due to their intrinsic geochemical nature, 143Nd/144Nd isotopic ratios provide the most resolved picture of where sediment in this system is likely sourced and how it moves through this estuarine system into the Pacific Ocean. For example, Nd isotopes confirm that the predominant source of sand-sized sediment to Suisun Bay, San Pablo Bay, and Central Bay is the Sierra Nevada Batholith via the Sacramento River, with lesser contributions from the Napa and San Joaquin Rivers. Isotopic ratios also reveal hot-spots of local sediment accumulation, such as the basalt and chert deposits around the Golden Gate Bridge and the high magnetite deposits of Ocean Beach. Sand-sized sediment that exits San Francisco Bay accumulates on the ebb-tidal delta and is in part conveyed southward by long-shore currents. Broadly, the geochemical tracers reveal a complex story of multiple sediment sources, dynamic intra-bay sediment mixing and reworking, and eventual dilution and transport by energetic marine processes. Combined geochemical results provide information on sediment movement into and through San Francisco Bay and further our understanding of how sustained anthropogenic activities which limit sediment inputs to the system (e.g., dike and dam construction) as well as those which directly remove sediments from within the Bay, such as aggregate mining and dredging, can have long-lasting effects.

40-year long monthly-resolved Sr/Ca record from 2.35 ka Bonaire coral, sample BON-6-A

We present a 40-year long monthly resolved Sr/Ca record from a fossil Diploria strigosa coral from Bonaire (Southern Caribbean Sea) dated with U/Th at 2.35 ka before present (BP). Secondary modifiers of this sea surface temperature (SST) proxy in annually-banded corals such as diagenetic alteration of the skeleton and skeletal growth-rate are investigated. Extensive diagenetic investigations reveal that this fossil coral skeleton is pristine which is further supported by clear annual cycles in the coral Sr/Ca record. No significant correlation between annual growth rate and Sr/Ca is observed, suggesting that the Sr/Ca record is not affected by coral growth. Therefore, we conclude that the observed interannual Sr/Ca variability was influenced by ambient SST variability. Spectral analysis of the annual mean Sr/Ca record reveals a dominant frequency centred at 6-7 years that is not associated with changes of the annual growth rate. The first monthly resolved coral Sr/Ca record from the Southern Caribbean Sea for preindustrial time suggests that fossil corals from Bonaire are suitable tools for reconstructing past SST variability. Coastal deposits on Bonaire provide abundant fossil D. strigosa colonies of Holocene age that can be accurately dated and used to reconstruct climate variability. Comparisons of long monthly resolved Sr/Ca records from multiple fossil corals will provide a mean to estimate seasonality and interannual to interdecadal SST variability of the Southern Caribbean Sea during the Holocene.