Geochemistry of basement carbonates from ODP Site 801 in the western Pacific Ocean

Many studies argue, based partly on Pb isotopic evidence, that recycled, subducted slabs reside in the mantle source of ocean island basalts (OIB) (Hofmann and White, 1982, doi:10.1016/0012-821X(82)90161-3; Weaver, 1991 doi:10.1016/0012-821X(91)90217-6; Lassiter, and Hauri, 1998, doi:10.1016/S0012-821X(98)00240-4). Such models, however, have remained largely untested against actual subduction zone inputs, due to the scarcity of comprehensive measurements of both radioactive parents (Th and U) and radiogenic daughter (Pb) in altered oceanic crust (AOC). Here, we discuss new, comprehensive measurements of U, Th, and Pb concentrations in the oldest AOC, ODP Site 801, and consider the effect of subducting this crust on the long-term Pb isotope evolution of the mantle. The upper 500 m of AOC at Site 801 shows >4-fold enrichment in U over pristine glass during seafloor alteration, but no net change to Pb or Th. Without subduction zone processing, ancient AOC would evolve to low 208Pb/206Pb compositions unobserved in the modern mantle (Hart and Staudigel, 1989 [Isotopic characterization and identification of recycled components, in: Crust/Mantle Recycling at Convergence Zones, Eds. S.R. Hart, L. Gqlen, NATO ASI Series. Series C: Mathematical and Physical Sciences 258, pp. 15-28, D. Reidel Publishing Company, Dordrecht-Boston, 1989]). Subduction, however, drives U-Th-Pb fractionation as AOC dehydrates in the earth's interior. Pacific arcs define mixing trends requiring 8-fold enrichment in Pb over U in AOC-derived fluid. A mass balance across the Mariana subduction zone shows that 44-75% of Pb but <10% of U is lost from AOC to the arc, and a further 10-23% of Pb and 19-40% of U is lost to the back-arc. Pb is lost shallow and U deep from subducted AOC, which may be a consequence of the stability of phases binding these elements during seafloor alteration: U in carbonate and Pb in sulfides. The upper end of these recycling estimates, which reflect maximum arc and back-arc growth rates, remove enough Pb and U from the slab to enable it to evolve rapidly (<<0.5 Ga) to sources suitable to explain the 208Pb/206Pb isotopic array of OIB, although these conditions fail to simultaneously satisfy the 207Pb/206Pb system. Lower growth rates would require additional U loss (29%) at depths beyond the zones of arc and back-arc magmagenesis, which would decrease upper mantle kappa (232Th/238U) over time, consistent with one solution to the "kappa conundrum" (Elliott et al., 1999, doi:10.1016/S0012-821X(99)00077-1). The net effects of alteration (doubling of l [238U/204Pb]) and subduction (doubling of omega [232Th/204Pb]) are sufficient to create the Pb isotopic signatures of oceanic basalts.

Whole-rock geochemical analyses of serpentinized harzburgites from ODP Site 209-1270

Small-scale shear zones are present in drillcore samples of abyssal peridotites from the Mid-Atlantic ridge at 15°20'N (Ocean Drilling Program Leg 209). The shear zones act as pathways for both evolved melts and hydrothermal fluids. We examined serpentinites directly adjacent to such zones to evaluate chemical changes resulting from melt-rock and fluid-rock interaction and their influence on the mineralogy. Compared to fresh harzburgite and melt-unaffected serpentinites, serpentinites adjacent to melt-bearing veins show a marked enrichment in rare earth elements (REE), strontium and high field strength elements (HFSE) zirconium and niobium. From comparison with published chemical data of variably serpentinized and melt-unaffected harzburgites, one possible interpretation is that interaction with the adjacent melt veins caused the enrichment in HFSE, whereas the REE contents might also be enriched due to hydrothermal processes. Enrichment in alumina during serpentinization is corroborated by reaction path models for interaction of seawater with harzburgite-plagiogranite mixtures. These models explain both increased amounts of alumina in the serpentinizing fluid for increasing amounts of plagiogranitic material mixed with harzburgite, and the absence of brucite from the secondary mineralogy due to elevated silica activity. By destabilizing brucite, nearby melt veins might fundamentally influence the low-temperature alteration behaviour of serpentinites. Although observations and model results are in general agreement, due to absence of any unaltered protolith a quantification of element transport during serpentinization is not straightforward.

Rock magentic investigations of ODP Site 162-983

We report natural remanent magnetization (NRM) directions and geomagnetic paleointensity proxies for part of the Matuyama Chron (0.9-2.2 Ma interval) from two sites located on sediment drifts in the Iceland Basin. At Ocean Drilling Program Sites 983 and 984, mean sedimentation rates in the late Matuyama Chron are 15.9 and 11.5 cm/kyr, respectively. For the older part of the record (>1.2 Ma), oxygen isotope data are too sparse to provide the sole basis for age model construction. The resemblance of the volume susceptibility record and a reference d18O record led us to match the two records to derive the age models. This match, based on Site 983/984 susceptibility, is consistent with available Site 983/984 benthic d18O data. Paleointensity proxies were derived from the slope of the NRM versus anhysteretic remanent magnetization plot for alternating field demagnetization in the 30-60 mT peak field range. Paleointensity lows correspond to polarity reversals at the limits of the Jaramillo, Olduvai, Cobb Mountain, and Réunion Subchrons and to seven excursions in NRM component directions. Magnetic excursions (defined here by virtual geomagnetic polar latitudes crossing the virtual geomagnetic equator) are observed at 932, 1048, 1115, 1190-1215 (Cobb Mountain Subchron), 1255, 1472-1480, 1567-1575 (Gilsa Subchron), and 1977 ka. The results indicate that geomagnetic directional excursions, associated with paleointensity minima, are a characteristic of the Matuyama Chron and probably of polarity chrons in general.

Paleomagnetic and rock magnetic data from IODP Site U1308

Integrated Ocean Drilling Program (IODP) Site U1308 (central North Atlantic) records paleomagnetic directional and relative paleointensity (RPI) variations for the last 1.5 Myr, in 110 m of the sediment sequence at a mean sedimentation rate of 7.3 cm/kyr. A detailed benthic oxygen isotope record was combined with RPI to produce an integrated, high-resolution magneto-isotopic stratigraphy for Site U1308. Apart from the well-known polarity reversals in this interval, the Punaruu excursion is recorded at 1092 ka and the Cobb Mountain Subchron in the 1182-1208 ka interval. The paleointensity proxies are determined as slopes of NRM versus ARM and NRM versus ARMAQ (ARM acquisition) with linear correlation coefficients to monitor the quality of the linear fit. The RPI record for Site U1308 is compared with the three other paleointensity records (one from the Western Equatorial Pacific and two from the North Atlantic) that cover the same time interval and have accompanying oxygen isotope records. The Match protocol of Lisiecki and Lisiecki (2002) is used to optimize the correlation of paleointensity records. Beginning with the original (published) age models for each record, the Match routine is used to optimize the RPI correlations to Site U1308, with checks to ensure compatibility with oxygen isotope records. Squared wavelet coherence (WTC) indicates significant improvement in RPI (and oxygen isotope) correlations after matching each RPI record to Site U1308, particularly for periods > 10 kyr. The level of coherence for the Atlantic RPI records and the lower resolution Pacific record implies synchronous global variability (at scales > 10 kyr) that can be attributed to the axial dipole geomagnetic field.

A 18-years long (1993-2011) snow and meteorological dataset from a mid-altitude mountain site (Col de Porte, France, 1325 altitude)

A quality-controlled snow and meteorological dataset spanning the period 1 August 1993-31 July 2011 is presented, originating from the experimental station Col de Porte (1325 m altitude, Chartreuse range, France). Emphasis is placed on meteorological data relevant to the observation and modelling of the seasonal snowpack. In-situ driving data, at the hourly resolution, consist of measurements of air temperature, relative humidity, windspeed, incoming short-wave and long-wave radiation, precipitation rate partitioned between snow- and rainfall, with a focus on the snow-dominated season. Meteorological data for the three summer months (generally from 10 June to 20 September), when the continuity of the field record is not warranted, are taken from a local meteorological reanalysis (SAFRAN), in order to provide a continuous and consistent gap-free record. Data relevant to snowpack properties are provided at the daily (snow depth, snow water equivalent, runoff and albedo) and hourly (snow depth, albedo, runoff, surface temperature, soil temperature) time resolution. Internal snowpack information is provided from weekly manual snowpit observations (mostly consisting in penetration resistance, snow type, snow temperature and density profiles) and from a hourly record of temperature and height of vertically free ''settling'' disks. This dataset has been partially used in the past to assist in developing snowpack models and is presented here comprehensively for the purpose of multi-year model performance assessment. The data is placed on the PANGAEA repository (doi:10.1594/PANGAEA.774249) as well as on the public ftp server ftp://ftp-cnrm.meteo.fr/pub-cencdp/.

(Table 1) Spacing of diatom abundance index and opal index at ODP Site 175-1084

An important discovery during Ocean Drilling Program Leg 175, when investigating the record of upwelling off Namibia, was the finding of a distinct Late Pliocene diatom maximum spanning the lower half of the Matuyama reversed polarity chron (MDM, Matuyama Diatom Maximum) and centered around 2.6-2.0 Ma. This maximum was observed at all sites off southwestern Africa between 20°S and 30°S, and is most strongly represented in sediments of Site 1084, off Lüderitz, Namibia. The MDM is characterized by high biogenic opal content, high numbers of diatom valves, and a diatom flora rich in Southern Ocean representatives (with Thalassiothrix antarctica forming diatom mats) as well as coastal upwelling components. Before MDM time, diatoms are rare until ca. 3.6 Ma. After the MDM, in the Pleistocene, the composition of the diatom flora points to increased importance of coastal upwelling toward the present, but is accompanied by a general decrease in opal and diatom deposition. Here we present a simple conceptual model as a first step in formalizing a possible forcing mechanism responsible for the record of opal deposition in the upwelling system off Namibia. The model takes into account Southern Ocean oceanography, and a link with deepwater circulation and deepwater nutrient chemistry which, in turn, are coupled to the evolution of North Atlantic Deep Water (NADW). The model proposes that between the MDM and the Mid-Pleistocene climate revolution, opal deposition off Namibia is not directly tied to glacial-interglacial fluctuations (as seen in the global d18O record), but that, instead, a strong deepwater link exists with increased NADW production (as seen in the deepwater d13C record) accounting for higher supply of silicate to the thermocline waters that feed the upwelling process. The opal record of Site 1084 shows affinity to eccentricity on the 400-kyr scale but not for the 100-kyr scale. This points toward long-term geologic processes for delivery of silica to the ocean.

Early Eocene benthic carbon isotope data of ODP Site 208-1263

The early Eocene represents a time of major changes in the global carbon cycle and fluctuations in global temperatures on both short- and long-time scales. These perturbations of the ocean-atmosphere system have been linked to orbital forcing and changes in net organic carbon burial, but accurate age models are required to disentangle the various forcing mechanisms and assess causal relationships. Discrepancies between the employed astrochronological and radioisotopic dating techniques prevent the construction of a robust time frame between ~49 and ~54 Ma. Here we present an astronomically tuned age model for this critical time period based on a new high-resolution benthic d13C record of ODP Site 1263, SE Atlantic. First, we assess three possible tuning options to the stable long-eccentricity cycle (405-kyr), starting from Eocene Thermal Maximum 2 (ETM2, ~54 Ma). Next we compare our record to the existing bulk carbonate d13C record from the equatorial Atlantic (Demerara Rise, ODP Site 1258) to evaluate our three initial age models and compare them with alternative age models previously established for this site. Finally, we refine our preferred age model by expanding our tuning to the 100-kyr eccentricity cycle of the La2010d solution. This solution appears to accurately reflect the long- and short-term eccentricity-related patterns in our benthic d13C record of ODP Site 1263 back to at least 52 Ma and possibly to 54 Ma. Our time scale not only aims to provide a new detailed age model for this period, but it may also serve to enhance our understanding of the response of the climate system to orbital forcing during this super greenhouse period as well as trends in its background state.

Extraterrestrial 3He estimation across the Paleocene-Eocene thermal maximum at ODP Site 208-1266

In the deep-sea, the Paleocene-Eocene Thermal Maximum (PETM) is often marked by clay-rich condensed intervals caused by dissolution of carbonate sediments, capped by a carbonate-rich interval. Constraining the duration of both the dissolution and subsequent cap-carbonate intervals is essential to computing marine carbon fluxes and thus testing hypotheses for the origin of this event. To this end, we provide new high-resolution helium isotope records spanning the Paleocene-Eocene boundary at ODP Site 1266 in the South Atlantic. The extraterrestrial 3He, 3HeET, concentrations replicate trends observed at ODP Site 690 by Farley and Eltgroth (2003, doi:10.1016/S0012-821X(03)00017-7). By assuming a constant flux of 3HeET we constrain relative changes in accumulation rates of sediment across the PETM and construct a new age model for the event. In this new chronology the zero carbonate layer represents 35 kyr, some of which reflects clay produced by dissolution of Paleocene (pre-PETM) sediments. Above this layer, carbonate concentrations increase for ~165 kyr and remain higher than in the latest Paleocene until 234 +48/-34 kyr above the base of the clay. The new chronology indicates that minimum d13C values persisted for a maximum of 134 +27/-19 kyr and the inflection point previously chosen to designate the end of the CIE recovery occurs at 217 +44/-31 kyr. This allocation of time differs from that of the cycle-based age model of Röhl et al. (2007, doi:10.1029/2007GC001784) in that it assigns more time to the clay layer followed by a more gradual recovery of carbonate-rich sedimentation. The new model also suggests a longer sustained d13C excursion followed by a more rapid recovery to pre-PETM d13C values. These differences have important implications for constraining the source(s) of carbon and mechanisms for its subsequent sequestration, favoring models that include a sustained release

Stable isotope record of Cibicidoides wuellerstorfi from Pleistocene sediments of DSDP Site 86-502 in the Caribbean Sea

Variations in the stable isotopic composition of benthic foraminifera from Deep-Sea Drilling Project (DSDP) site 502B in the Caribbean Sea are used to reconstruct Atlantic intermediate water circulation variability over the last 1.2 m.y. Comparison of this record with other North Atlantic benthic isotope records indicates that Atlantic intermediate water circulation was relatively enhanced during glacial maxima when North Atlantic deep water (NADW) production was reduced. However, a simple, compensatory relationship between intermediate and deepwater circulation is not apparent. Geochemical models have shown that such changes in ocean circulation can affect atmospheric CO2 levels by changing vertical nutrient and alkalinity profiles. The Delta delta13C difference between Caribbean site 502B and deep equatorial Pacific site 677 is highly coherent and in phase with ice volume. Like the delta18O record, there is an increase in amplitude (40%) and a large increase in 100 kyr power after 0.7 Ma. The 1.2? Delta delta13C amplitude scales to 70 ppm V in atmospheric CO2 using Boyle's (1986) box model result. The implied increase in CO2 amplitude after 0.7 Ma may suggest a positive feedback role in effecting the higher-amplitude climatic fluctuations which characterize the last 0.7 m.y.

Geochemistry and age models of sediments from the Celtic margin

The sedimentary sections of three cores from the Celtic margin provide high-resolution records of the terrigenous fluxes during the last glacial cycle. A total of 21 14C AMS dates allow us to define age models with a resolution better than 100 yr during critical periods such as Heinrich events 1 and 2. Maximum sedimentary fluxes occurred at the Meriadzek Terrace site during the Last Glacial Maximum (LGM). Detailed X-ray imagery of core MD95-2002 from the Meriadzek Terrace shows no sedimentary structures suggestive of either deposition from high-density turbidity currents or significant erosion. Two paroxysmal terrigenous flux episodes have been identified. The first occurred after the deposition of Heinrich event 2 Canadian ice-rafted debris (IRD) and includes IRD from European sources. We suggest that the second represents an episode of deposition from turbid plumes, which precedes IRD deposition associated with Heinrich event 1. At the end of marine isotopic stage 2 (MIS 2) and the beginning of MIS 1 the highest fluxes are recorded on the Whittard Ridge where they correspond to deposition from turbidity current overflows. Canadian icebergs have rafted debris at the Celtic margin during Heinrich events 1, 2, 4 and 5. The high-resolution records of Heinrich events 1 and 2 show that in both cases the arrival of the Canadian icebergs was preceded by a European ice rafting precursor event, which took place about 1-1.5 kyr before. Two rafting episodes of European IRD also occurred immediately after Heinrich event 2 and just before Heinrich event 1. The terrigenous fluxes recorded in core MD95-2002 during the LGM are the highest reported at hemipelagic sites from the northwestern European margin. The magnitude of the Canadian IRD fluxes at Meriadzek Terrace is similar to those from oceanic sites.

Estimation of sea surface temperatures and salinity of ODP Site 177-1089 (Appendix A)

ODP Site 1089 is optimally located in order to monitor the occurrence of maxima in Agulhas heat and salt spillage from the Indian to the Atlantic Ocean. Radiolarian-based paleotemperature transfer functions allowed to reconstruct the climatic history for the last 450 kyr at this location. A warm sea surface temperature anomaly during Marine Isotope Stage (MIS) 10 was recognized and traced to other oceanic records along the surface branch of the global thermohaline (THC) circulation system, and is particularly marked at locations where a strong interaction between oceanic and atmospheric overturning cells and fronts occurs. This anomaly is absent in the Vostok ice core deuterium, and in oceanic records from the Antarctic Zone. However, it is present in the deuterium excess record from the Vostok ice core, interpreted as reflecting the temperature at the moisture source site for the snow precipitated at Vostok Station. As atmospheric models predict a subtropical Indian source for such moisture, this provides the necessary teleconnection between East Antarctica and ODP Site 1089, as the subtropical Indian is also the source area of the Agulhas Current, the main climate agent at our study location. The presence of the MIS 10 anomaly in the delta13C foraminiferal records from the same core supports its connection to oceanic mechanisms, linking stronger Agulhas spillover intensity to increased productivity in the study area. We suggest, in analogy to modern oceanographic observations, this to be a consequence of a shallow nutricline, induced by eddy mixing and baroclinic tide generation, which are in turn connected to the flow geometry, and intensity, of the Agulhas Current as it flows past the Agulhas Bank. We interpret the intensified inflow of Agulhas Current to the South Atlantic as responding to the switch between lower and higher amplitude in the insolation forcing in the Agulhas Current source area. This would result in higher SSTs in the Cape Basin during the glacial MIS 10, due to the release into the South Atlantic of the heat previously accumulating in the subtropical and equatorial Indian and Pacific Ocean. If our explanation for the MIS 10 anomaly in terms of an insolation variability switch is correct, we might expect that a future Agulhas SSST anomaly event will further delay the onset of next glacial age. In fact, the insolation forcing conditions for the Holocene (the current interglacial) are very similar to those present during MIS 11 (the interglacial preceding MIS 10), as both periods are characterized by a low insolation variability for the Agulhas Current source area. Natural climatic variability will force the Earth system in the same direction as the anthropogenic global warming trend, and will thus lead to even warmer than expected global temperatures in the near future.