B-isotope and Mg/Ca ratios of planktonic foraminifera from ODP Hole 108-668B and esimates of salinity, alkalinity and pCO2 (Table 1)

Knowledge of past atmospheric pCO2 is important for evaluating the role of greenhouse gases in climate forcing. Ice core records show the tight correlation between climate change and pCO2, but records are limited to the past ~900 kyr. We present surface ocean pH and pCO2 data, reconstructed from boron isotopes in planktonic foraminifera over two full glacial cycles (0-140 and 300-420 kyr). The data co-vary strongly with the Vostok pCO2-record and demonstrate that the coupling between surface ocean chemistry and the atmosphere is recorded in marine archives, allowing for quantitative estimation of atmospheric pCO2 beyond the reach of ice cores.

Carbon, boron and oxygen isotope ratios of sediments from the Moresby Seamount

We report results from boron, carbon and oxygen stable isotope analyses of faulted and veined rocks recovered by scientific ocean drilling during ODP Leg 180 in the western Woodlark Basin, off Papua New Guinea. In this area of active continental extension, crustal break-up and incipient seafloor spreading, a shallow-dipping, seismically active detachment fault accommodates strain, defining a zone of mylonites and cataclasites, vein formation and fluid infiltration. Syntectonic microstructures and vein-fill mineralogy suggest frictional heating during slip during extension and exhumation of Moresby Seamount. Low carbon and oxygen isotope ratios of calcite veins indicate precipitation from hydrothermal fluids (delta13C PDB down to -17?; delta18O PDB down to -22?) formed by both dehydration and decarbonation. Boron contents are low (<7 ppm), indicating high-grade metamorphic source rock for the fluids. Some of the delta11B signatures (17-35?; parent solutions to calcite vein fills) are low when compared to deep-seated waters in other tectonic environments, likely reflecting preferential loss of 11B during low-grade metamorphism at depth. Pervasive devolatilization and flux of CO2-rich fluids are evident from similar vein cement geochemistry in the detachment fault zone and splays further updip. Multiple rupture-and-healing history of the veins suggests that precipitation may be an important player in fluid pressure evolution and, hence, seismogenic fault movement.

Alkenone and boron based Oligocene pCO2 records

The Pliocene period is the most recent time when the Earth was globally significantly (~3°C) warmer than today. However, the existing pCO2 data for the Pliocene are sparse and there is little agreement between the various techniques used to reconstruct palaeo-pCO2. Moreover, the temporal resolution of the published records does not allow a robust assessment of the role of declining pCO2 in the intensification of the Northern Hemisphere Glaciation (INHG) and a direct comparison to other proxy records are lacking. For the first time, we use a combination of foraminiferal (delta11B) and organic biomarker (alkenone-derived carbon isotopes) proxies to determine the concentration of atmospheric CO2 over the past 5 Ma. Both proxy records show that during the warm Pliocene pCO2 was between 330 and 400 ppm, i.e. similar to today. The decrease to values similar to pre-industrial times (275-285 ppm) occurred between 3.2 Ma and 2.8 Ma - coincident with the INHG and affirming the link between global climate, the cryosphere and pCO2.

Stable isotopes and element concentrations of samples from the Wadi Bih, United Arab Emirates

Ocean acidification triggered by Siberian Trap volcanism was a possible kill mechanism for the Permo-Triassic Boundary mass extinction, but direct evidence for an acidification event is lacking. We present a high-resolution seawater pH record across this interval, using boron isotope data combined with a quantitative modeling approach. In the latest Permian, increased ocean alkalinity primed the Earth system with a low level of atmospheric CO2 and a high ocean buffering capacity. The first phase of extinction was coincident with a slow injection of carbon into the atmosphere, and ocean pH remained stable. During the second extinction pulse, however, a rapid and large injection of carbon caused an abrupt acidification event that drove the preferential loss of heavily calcified marine biota.

Stable oxygen isotope record and age determination of sediments from the North Atlantic Ocean

Sea surface temperature and salinity estimates reconstructed using planktonic foraminiferal abundance and delta18O records from core SU90-03 (40°N, 32°W, 2475 m water depth) reveal large climatic fluctuations linked to major instabilities in Northern Hemisphere ice sheets over the last 150 000 years. Episodes of enhanced ice rafted detritus (IRD) input were accompanied by discrete temperature minima, representing coolings of between 4 and 8°C, and reductions in surface salinity of up to 2.5-3.5 per mil. Several additional cooling episodes of a similar magnitude were documented during intervals of low IRD input that appear to be synchronous, within the limits of dating, with ice rafting events spatially confined to higher latitudes. Accelerator mass spectrometer 14C dates for Heinrich events (H1 - 14.2 ka, H2 - 21.4 ka, H3 - 26.7 ka, H4 - 34.8 ka, H5 - 47.2 ka) obtained from core SU90-03 agree well with other published age estimates and suggest a contemporaneous pattern of climate change throughout the North Atlantic during the last glacial period. This interpretation is supported by a comparison of IRD and palaeotemperature records from DSDP site 609 and core SU90-03, which clearly shows that the major climatic fluctuations identified at high latitudes were transmitted toward the subtropics. However, 14C dates suggest that ice rafting episodes may be diachronous to some extent. The northward migration of the polar front after the H1 event at 40°N in the mid-Atlantic occurred at 14 ka, approximately 500 years earlier than along the Portuguese margin, where the southerly advection of polar waters persisted within eastern boundary current system.

The alkali element and boron geochemistry of ODP Site 169-1038 in the Escanaba Trough, East Pacific

A suite of conjugate pore fluid and sediment samples were collected during Leg 169 of the ODP from within the clastic sedimentary sequences which host massive sulphides at Central Hill, Escanaba Trough (ODP Site 1038). We report the alkali element and boron, and Li and B isotope data for these samples. Relative to a reference site (Site 1037) located outside the zone of high heat flow, pore fluids from Site 1038 show a wide variation in Cl (300-800 mM), and have far higher concentrations of Li (up to 6.2 mM), B (up to 9.7 mM), Cs (up to 5.0 mM), and Rb (up to 97 mM). We show that the pore fluids are derived from hydrothermal circulation that has extended into the basement oceanic crust, with input of the alkali elements and B as the rising hydrothermal fluids interact geochemically with the overlying clastic sediments. There is, however, no marked depletion of these elements in the conjugate sediments, suggesting that there has been advective transport of fluids away from the primary hydrothermal reaction site. This is supported by modelling of the Li and B isotope systematics of the pore fluids, which shows that they record extensive formation of secondary minerals during cooling of the fluids from ~350 to ~20ºC. Precipitation of metal-rich sulphides would have occurred prior to the formation of these minerals, thus, the pore fluid Li and B isotope data can place important constraints on the locus of sulphide deposition beneath the seafloor at Escanaba.

Table 1: Technetium-99 in seawater in the West Spitsbergen Current and adjacent areas, sorted from east to west

99Tc levels were measured in seawater samples collected between 2000 and 2002 in the West Spitsbergen Current (WSC) and along the western coast of Svalbard or Spitzbergen and compared with available oceanographic 3-D modelling results for the late 1990s. Additional data from related regions are also presented in order to support the data interpretation. The seawater in the Arctic fjord Kongsfjorden on the western coast of Svalbard is influenced by the WSC, as shown by the 99Tc levels in surface water. By means of the WSC, 99Tc reaches the Eastern Fram Strait, where one branch of the WSC turns west into the East Greenland Current (EGC), and another branch continues northwards into the Arctic Ocean. Surface seawater collected in the central part of the WSC during a cruise on board the R/V "Polarstern" in the summer of 2000, showed higher levels of 99Tc than samples measured in Kongsfjorden in the spring of 2000. However, all levels measured in surface water are of the same order of magnitude. Data from sampling of deeper water in the WSC and EGC provide information pertaining to the lateral distribution of 99Tc. In all vertical profiling surveys (conducted in spring and summer), the highest levels of 99Tc were found in surface water. Comparison with oceanographic 3-D modelling indicates both significant seasonal variations in the lateral stratification of the WSC and variations with depth over shorter vertical distances. This information can be applied in sampling strategies, environmental monitoring, long-range transport of pollutants and physical oceanography.

Pollen record and dating of sediment core GIK16776-1 off Liberia

Based on pollen analysis of a sediment core from the Atlantic Ocean off Liberia the West African vegetation history for the last 400 ka is reconstructed. During the cold oxygen isotope stages 12, 10, 8, 6, 4, 3 and 2 an arid climate is indicated, resulting in a southward shifting of the southern border of the savanna. Late Pleistocene glacial stages were more arid than during the Middle Pleistocene. A persistence of the rain forest in the area, even during the glacial stages, is recorded. This suggests a glacial refuge of rain forest situated in the Guinean mountains. Afromontane forests with Podocarpus occurred in the Guinean mountains from the stages 12 to 2 and disappeared after. The tree expanded from higher to lower elevations twice in the warm oxygen isotope stage 11 (pollen subzones 11d, 11b) and at least twice during the warm stage 5 (pollen subzones 5d, 5a), indicating a relative cool but humid climate for these periods.

Boron isotopes, trace elements and pH calculation for Norwegian deep sea coral specimen Madrepora o. (1968-2007), 2012

d11B and trace results obtained for a deep sea coral specimen Madrepora oculata collected from the Norwegian Sea (67°N, 9°E, 340 m) during the RV Polarstern ARK/II/Ia cruise (2007). Such coral specimen grew during the last four decades (1968-2007) and geochemical results highligh a seawater pH decrease with an order of magnitude in good agreement with an ocean acidification rate today known. This pH record is strongly impacted by inter-decadal change of ocean dynamic (NAO) and productivity. pHT calculation parameters (Hönisch et al., 2007): a=5; a=0.9804, d11B=39.5 PER MIL, Li/Mg temperature, salinity=35.1, pKB from Dickson (1990).

Boron contents and boron, carbon, and oxygen isotope data for ODP Sites 160-970 and 160-971

Products of two mud volcanoes from the distal part of the Mediterranean Ridge accretionary complex have been investigated regarding their B, C, and O stable isotope signatures. The mud breccias have been divided into mud matrix, lithified clasts, biogenic deposits, and authigenic cements and crusts related to fluid flow and cementation. Isotope geochemistry is used to evaluate the depth of mobilization of each phase in the subduction zone. B contents and isotope ratios of the mud and mud clasts show a general trend of B enrichment and decreasing d11B values with increasing consolidation (i.e., depth). However, the majority of the clast and matrix samples relate to moderate depths of mobilization within the wedge (1-2 km below seafloor). The carbonate cements of most of these clasts as well as the authigenic crusts, however, provide evidence for a deep fluid influence, probably associated with the décollement at 5-6 km depth. This interpretation is supported by d13C ratios of the crust, which indicate precipitation of C from thermogenic methane, and by the d11B ratios of pore-water samples of mud-breccia drill cores. Clams (Vesicomya sp.) living adjacent to fluid vents have d11B and d18O values corresponding to brines known in the area, which acted as the parent solution for shell precipitation. Such brines are most likely Miocene pore waters trapped at deep levels within the backstop to the accretionary prism, probably prior to desiccation of the Mediterranean in the Messinian (6-5 Ma). Combining all results, deep fluid circulation and expulsion are identified as the main processes triggering mud liquefaction and extrusion, whereas brines contribute only locally. Given the high B contents, mud extrusion has to be considered a major backflux mechanism of B into the hydrosphere.

Orbital-resolution Pliocene-Pleistocene simulations of CO2, sea level, global temperature and benthic d18O, and d11B-based proxy-CO2 data

During the past five million yrs, benthic d18O records indicate a large range of climates, from warmer than today during the Pliocene Warm Period to considerably colder during glacials. Antarctic ice cores have revealed Pleistocene glacial-interglacial CO2 variability of 60-100 ppm, while sea level fluctuations of typically 125 m are documented by proxy data. However, in the pre-ice core period, CO2 and sea level proxy data are scarce and there is disagreement between different proxies and different records of the same proxy. This hampers comprehensive understanding of the long-term relations between CO2, sea level and climate. Here, we drive a coupled climate-ice sheet model over the past five million years, inversely forced by a stacked benthic d18O record. We obtain continuous simulations of benthic d18O, sea level and CO2 that are mutually consistent. Our model shows CO2 concentrations of 300 to 470 ppm during the Early Pliocene. Furthermore, we simulate strong CO2 variability during the Pliocene and Early Pleistocene. These features are broadly supported by existing and new d11B-based proxy CO2 data, but less by alkenone-based records. The simulated concentrations and variations therein are larger than expected from global mean temperature changes. Our findings thus suggest a smaller Earth System Sensitivity than previously thought. This is explained by a more restricted role of land ice variability in the Pliocene. The largest uncertainty in our simulation arises from the mass balance formulation of East Antarctica, which governs the variability in sea level, but only modestly affects the modeled CO2 concentrations.

Boron, carbonate carbon and oxygen isotope analyses of samples from the Yangtze Platform (China), Congo craton (Namibia), and Karatau microcontinent (Kazakhstan) of the Marinoan glaciation

Boron isotope patterns preserved in cap carbonates deposited in the aftermath of the younger Cryogenian (Marinoan, ca. 635 Ma) glaciation confirm a temporary ocean acidification event on the continental margin of the southern Congo craton, Namibia. To test the significance of this acidification event and reconstruct Earth's global seawater pH states at the Cryogenian-Ediacaran transition, we present a new boron isotope data set recorded in cap carbonates deposited on the Yangtze Platform in south China and on the Karatau microcontinent in Kazakhstan. Our compiled d11B data reveal similar ocean pH patterns for all investigated cratons and confirm the presence of a global and synchronous ocean acidification event during the Marinoan deglacial period, compatible with elevated postglacial pCO2 concentrations. Differences in the details of the ocean acidification event point to regional distinctions in the buffering capacity of Ediacaran seawater.