Boron isotopes, pH and pCO2 calculation for one Fiji coral specimen Porites (1898-1998), 2012

delta11B results and deduced pH, pCO2 and omega values obtained for a tropical coral specimen Porites collected in 1998 at Yasawa (16°48'S- 177°27'E) on the western side of the Fiji archipelago, location in the north western part of the Pacific Warm Pool. Such Porites specimen grew during the XXth century (1898-1998). Boron isotopes results allowed the reconstruction of surface ocean acidification in the vincinity of Fiji Islands with strong interdecadal influence of the ENSO at regional scale. pHT calculation parameters (Hönisch et al., 2007): a=0 PER MIL; alpha=0.9804; delta11B=39.5 PER MIL; salinity=35.02; pKB from Dickson (1990). pCO2 and omega calculation parameters: TA= 2350 µM; Ca= 10.2 mM; Dickson et al.(2007); Mucci 1983.

Stable oxygen isotopes of calcite veins in ODP Site 146-892

In situ secondary ionization mass spectrometry (SIMS) analyses of oxygen isotopes in authigenic calcite veins were obtained from an active thrust fault system drilled at Ocean Drilling Program (ODP) Site 892 (44°40.4'N, 125°07.1'W) along the Cascadia subduction margin. The average d18OPDB value of all samples is -9.9 per mil and the values are the lowest of any measured in active accretionary prisms. Ranges in individual veins can be as much as 19.6 per mil. There is an isotopic stratigraphy related to the structural stratigraphy. Mean isotope values in the hanging wall, thrust, and footwall are -14.4 per mil, -9.5 per mil, and -5.2 per mil, respectively. Several veins and crosscutting vein sequences show a general trend from lower to higher d18O values over time. Isotopic and textural data indicate several veins formed by a crack-seal mechanism and growth into open fractures. The best explanation for the strong 18O depletions is periodic rapid flow from 2-3 km deeper in the prism. Relatively narrow isotopic ranges for most veins suggest that fluids were derived from a similar source depth for each episode of fluid pulse and calcite crystallization. Structural and mass balance considerations are consistent with a record preserved in the veins of ten to hundreds of thousands of years. The fluid pulses may relate to periodic large earthquake events such as those recognized in the paleoseismicity records from the Cascadia margin.

Osmium isotope record of Late Pleistocene sediments

We report high temporal resolution osmium isotopes records of bulk sediment and sediment leachates from DSDP Site 480 (Gulf of California) over the last 30 ka; from ODP Site 849 (Eastern equatorial Pacific) from the last 200 ka and from ODP Site 1002C (Cariaco Basin) across the 9-17 ka time interval in order to critically evaluate claims of a global 10% shift in the 187Os/188Os of seawater from glacial to interglacial intervals. We use organic-rich continental margin sites and carbonate-rich pelagic sites to isolate the temporal variations of the osmium seawater isotopic composition. Our results reveal that variations in 187Os/188Os fail to correlate with global changes in temperature across glacials/interglacials cycles as previously claimed. Instead, these results indicate differences of a few percent in the measured 187Os/188Os between each oceanic basin. We argue that these differences strongly suggest that seawater is not well homogenized with respect to its Os isotope composition.

Planktonic foraminiferal oxygen isotopes of ODP Site 143-865 samples

Cool tropical sea surface temperatures (SSTs) are reported for warm Paleogene greenhouse climates based on the d18O of planktonic foraminiferal tests. These results are difficult to reconcile with models of greenhouse gas-forced climate. It has been suggested that this "cool tropics paradox" arises from postdepositional alteration of foraminiferal calcite, yielding erroneously high d18O values. Recrystallization of foraminiferal tests is cryptic and difficult to quantify, and the compilation of robust d18O records from moderately altered material remains challenging. Scanning electron microscopy of planktonic foraminiferal chamber-wall cross sections reveals that the basal area of muricae, pustular outgrowths on the chamber walls of species belonging to the genus Morozovella, contain no mural pores and may be less susceptible to postdepositional alteration. We analyzed the d18O in muricae bases of morozovellids from the central Pacific (Ocean Drilling Program Site 865) by ion microprobe using 10 ?m pits with an analytical reproducibility of ±0.34 per mil (2 standard deviations). In situ measurements of d18O in these domains yield consistently lower values than those published for conventional multispecimen analyses. Assuming that the original d18O is largely preserved in the basal areas of muricae, this new d18O record indicates Early Paleogene (~49-56 Ma) tropical SSTs in the central Pacific were 4°-8°C higher than inferred from the previously published d18O record and that SSTs reached at least ~33°C during the Paleocene-Eocene thermal maximum. This study demonstrates the utility of ion microprobe analysis for generating more reliable paleoclimate records from moderately altered foraminiferal tests preserved in deep-sea sediments.

(Table 2) Mineralogy, stable isotopes, and mineral percentages of the carbonate fraction of samples from the South China Sea

Chemoherm carbonates, as well as numerous other types of methane seep carbonates, were discovered in 2004 along the passive margin of the northern South China Sea. Lithologically, the carbonates are micritic containing peloids, clasts and clam fragments. Some are highly brecciated with aragonite layers of varying thicknesses lining fractures and voids. Dissolution and replacement is common. Mineralogically, the carbonates are dominated by high magnesium calcites (HMC) and aragonite. Some HMCs with MgCO3 contents of between 30-38 mol%-extreme-HMC, occur in association with minor amounts of dolomite. All of the carbonates are strongly depleted in d13C, with a range from -35.7 to -57.5 per mil PDB and enriched in d18O (+ 4.0 to + 5.3 per mil PDB). Abundant microbial rods and filaments were recognized within the carbonate matrix as well as aragonite cements, likely fossils of chemosynthetic microbes involved in carbonate formation. The microbial structures are intimately associated with mineral grains. Some carbonate mineral grains resemble microbes. The isotope characteristics, the fabrics, the microbial structure, and the mineralogies are diagnostic of carbonates derived from anaerobic oxidation of methane mediated by microbes. From the succession of HMCs, extreme-HMC, and dolomite in layered tubular carbonates, combined with the presence of microbial structure and diagenetic fabric, we suggest that extreme-HMC may eventually transform into dolomites. Our results add to the worldwide record of seep carbonates and establish for the first time the exact locations and seafloor morphology where such carbonates formed in the South China Sea. Characteristics of the complex fabric demonstrate how seep carbonates may be used as archives recording multiple fluid regimes, dissolution, and early transformation events.

(Table 1) Stabile isotopes at DSDP Leg 55 Holes

Deep sea drilling on four seamounts in the Emperor Seamount chain revealed that Paleogene shallow-water carbonate sediments of the "bryozoan-algal" facies crown the basalt edifices. According to the biofacies model of Schlanger and Konishi (1966, 1975), this bryozoan- algal assemblage suggests that the seamounts formed in cooler, more northerly waters than those presently occupied by the island of Hawaii; i.e., the paleolatitudes of formation were greater than 20 °N. Moving southward toward the youngest member of the seamount chain, a facies gradient indicative of warmer waters was observed. This gradient is interpreted as a reflection of a northward shift in isotherms during the time span in which the seamounts were progressively formed (Savin et al., 1975). On all seamounts, sedimentation at the drilling sites occurred in a high-energy environment with water depths of approximately 20 meters. Early-stage carbonate diagenesis began in the phreatic zone in the presence of meteoric water, but proceeded after subsidence of the seamounts into intermediate sea waters, where the bulk, stable isotopic composition was determined. The subsidence into intermediate waters was rapid, and permitted establishment of an isotopic equilibrium which, like the facies gradient, reflects the northward shift in isotherms during the Paleogene. Calcite and zeolite cements comprise the later-stage diagenesis, and originated from solutions arising from the hydrolysis of the underlying basalt. In conclusion, the results of this study of the shallow-water carbonate sediments are not inconsistent with a paleolatitude of formation for Suiko Seamount (Site 433) of 26.9 ±3.5 °N, as determined by paleomagnetic measurements (Kono, 1980).

(Table 1) Sulfur isotopes, total sulfur, and degree of oxidation of basalt samples from DSDP Hole 69-504B and 70-504B

About 150 basalt samples from Hole 504B, near the Costa Rica Rift were analyzed for sulfur content and sulfur-isotope composition. The basement in Hole 504B can be divided into an upper part, which has oxidative alteration (274.5-550 m below sea floor), and a lower part, which has nonoxidative alteration (550-835 m below sea floor) (the interval from 540 to 585 meters actually is transitional). This division is reflected in both the sulfur content and the sulfurisotope composition. Oxidative alteration of basalts by sea water at low temperatures has resulted in a depletion in sulfur in the upper part of the hole (mostly less than 600 ppm S) as compared to fresh sulfur-saturated oceanic tholeiites (900-1200 ppm S). High amounts of sulfur in the lower part of the hole are a result of precipitation of secondary pyrite under non-oxidative or weakly oxidative conditions from solutions which dissolved igneous sulfides. The average sulfur-isotope composition of the primary igneous sulfides is d34S = -0.01 per mil, which is close to the assumed mantle sulfur composition (d34S = 0 per mil. Pyrite and sulfate sulfur extracted together in a separate preparation step (as "pyrite-sulfate" sulfur) indicate addition of sea-water sulfate to the upper part of the basalts. The d34S of secondary pyrite isolated by hand-picking varies between -8.0 and +5.8 per mil; the "pyrite-sulfate" sulfur (d34S = -4.8 to +10.5 per mil), as well as that of the isolated pyrite, may have originated in the precipitation of pyrite from solutions containing sulfur from the dissolution of igneous sulfides, but addition of sulfur transported by hydrothermal solutions cannot be excluded.

Element contents, sulfur and oxygen isotopes, and molecular biomarkers of phosphatic crust samples from the Chimbote Platform of the shelf off Peru

Authigenic phosphatic laminites enclosed in phosphorite crusts from the shelf off Peru (10°01' S and 10°24' S) consist of carbonate fluorapatite layers, which contain abundant sulfide minerals including pyrite (FeS2) and sphalerite (ZnS). Low d34Spyrite values (average -28.8 per mill) agree with bacterial sulfate reduction and subsequent pyrite formation. Stable sulfur isotopic compositions of sulfate bound in carbonate fluorapatite are lower than that of sulfate from ambient sea water, suggesting bacterial reoxidation of sulfide by sulfide-oxidizing bacteria. The release of phosphorus and subsequent formation of the autochthonous phosphatic laminites are apparently caused by the activity of sulfate-reducing bacteria and associated sulfide-oxidizing bacteria. Following an extraction-phosphorite dissolution-extraction procedure, molecular fossils of sulfate-reducing bacteria (mono-O-alkyl glycerol ethers, di-O-alkyl glycerol ethers, as well as the short-chain branched fatty acids i/ai-C15:0, i/ai-C17:0 and 10MeC16:0) are found to be among the most abundant compounds. The fact that these molecular fossils of sulfate-reducing bacteria are distinctly more abundant after dissolution of the phosphatic laminite reveals that the lipids are tightly bound to the mineral lattice of carbonate fluorapatite. Moreover, compared with the autochthonous laminite, molecular fossils of sulfate-reducing bacteria are: (1) significantly less abundant and (2) not as tightly bound to the mineral lattice in the other, allochthonous facies of the Peruvian crusts consisting of phosphatic coated grains. These observations confirm the importance of sulfate-reducing bacteria in the formation of the phosphatic laminite. Model calculations highlight that organic matter degradation by sulfate-reducing bacteria has the potential to liberate sufficient phosphorus for phosphogenesis.

Iridium contents and microprobe analyses of DSDP Leg 77 samples

Restudy of Deep Sea Drilling Project Sites 536 and 540 in the southeast Gulf of Mexico gives evidence for a giant wave at Cretaceous-Tertiary boundary time. Five units are recognized: (1) Cenomanian limestone underlies a hiatus in which the five highest Cretaceous stages are missing, possibly because of catastrophic K-T erosion. (2) Pebbly mudstone, 45 m thick, represents a submarine landslide possibly of K-T age. (3) Current-bedded sandstone, more than 2.5 m thick, contains anomalous iridium, tektite glass, and shocked quartz; it is interpreted as ejecta from a nearby impact crater, reworked on the deep-sea floor by the resulting tsunami. (4) A 50-cm interval of calcareous mudstone containing small Cretaceous planktic foraminifera and the Ir peak is interpreted as the silt-size fraction of the Cretaceous material suspended by the impact-generated wave. (5) Calcareous mudstone with basal Tertiary forams and the uppermost tail of the Ir anomaly overlies the disturbed interval, dating the impact and wave event as K-T boundary age. Like Beloc in Haiti and Mimbral in Mexico, Sites 536 and 540 are consistent with a large K-T age impact at the nearby Chicxulub crater.

Nd and Pb isotopes in ferromanganese crusts

The intensity of North Atlantic Deep Water (NADW) production has been one of the most important parameters controlling the global thermohaline ocean circulation system and climate. Here we present a new approach to reconstruct the overall strength of NADW export from the North Atlantic to the Southern Ocean over the past 14 Myr applying the deep water Nd and Pb isotope composition as recorded by ferromanganese crusts and nodules. We present the first long-term Nd and Pb isotope time series for deep Southern Ocean water masses, which are compared with previously published time series for NADW from the NW Atlantic Ocean. These data suggest a continuous and strong export of NADW, or a precursor of it, into the Southern Ocean between 14 and 3 Ma. An increasing difference in Nd and Pb isotope compositions between the NW Atlantic and the Southern Ocean over the past 3 Myr gives evidence for a progressive overall reduction of NADW export since the onset of Northern Hemisphere glaciation (NHG). The Nd isotope data allow us to assess at least semiquantitatively that the amount of this reduction has been in the range between 14 and 37% depending on location.

CaCO3, foraminifer fragmentation, benthic carbon isotopes, coarse lithic counts and radiogenic isotopes (Sr, Nd, Pb) of the Pliocene and earliest Pleistocene terrigenous component (3.3-2.4 Ma) of IODP Site 306-U1313

We present Plio-Pleistocene records of sediment color, %CaCO3, foraminifer fragmentation, benthic carbon isotopes (d13C) and radiogenic isotopes (Sr, Nd, Pb) of the terrigenous component from IODP Site U1313, a reoccupation of benchmark subtropical North Atlantic Ocean DSDP Site 607. We show that (inter)glacial cycles in sediment color and %CaCO3 pre-date major northern hemisphere glaciation and are unambiguously and consistently correlated to benthic oxygen isotopes back to 3.3 million years ago (Ma) and intermittently so probably back to the Miocene/Pliocene boundary. We show these lithological cycles to be driven by enhanced glacial fluxes of terrigenous material (eolian dust), not carbonate dissolution (the classic interpretation). Our radiogenic isotope data indicate a North American source for this dust (~3.3-2.4 Ma) in keeping with the interpreted source of terrestrial plant wax-derived biomarkers deposited at Site U1313. Yet our data indicate a mid latitude provenance regardless of (inter)glacial state, a finding that is inconsistent with the biomarker-inferred importance of glaciogenic mechanisms of dust production and transport. Moreover, we find that the relation between the biomarker and lithogenic components of dust accumulation is distinctly non-linear. Both records show a jump in glacial rates of accumulation from Marine Isotope Stage, MIS, G6 (2.72 Ma) onwards but the amplitude of this signal is about 3-8 times greater for biomarkers than for dust and particularly extreme during MIS 100 (2.52 Ma). We conclude that North America shifted abruptly to a distinctly more arid glacial regime from MIS G6, but major shifts in glacial North American vegetation biomes and regional wind fields (exacerbated by the growth of a large Laurentide Ice Sheet during MIS 100) likely explain amplification of this signal in the biomarker records. Our findings are consistent with wetter-than-modern reconstructions of North American continental climate under the warm high CO2 conditions of the Early Pliocene but contrast with most model predictions for the response of the hydrological cycle to anthropogenic warming over the coming 50 years (poleward expansion of the subtropical dry zones).