(Table 1) Stable isotope records of clathrite and water

Aragonitic clathrites are methane-derived precipitates that are found at sites of massive near-seafloor gas hydrate (clathrate) accumulations at the summit of southern Hydrate Ridge, Cascadia margin. These platy carbonate precipitates form inside or in proximity to gas hydrate, which in our study site currently coexists with a fluid that is highly enriched in dissolved ions as salts are excluded during gas hydrate formation. The clathrites record the preferential incorporation of 18O into the hydrate structure and hence the enrichment of 16O in the surrounding brine. We measured d18O values as high as 2.27 per mil relative to Peedee belemnite that correspond to a fluid composition of -1.18 per mil relative to standard mean ocean water. The same trend can be observed in Ca isotopes. Ongoing clathrite precipitation causes enrichment of the 44Ca in the fluid and hence in the carbonates. Carbon isotopes confirm a methane source for the carbonates. Our triple stable isotope approach that uses the three main components of carbonates (Ca, C, O) provides insight into multiple parameters influencing the isotopic composition of the pore water and hence the isotopic composition of the clathrites. This approach provides a tool to monitor the geochemical processes during clathrate and clathrite formation, thus recording the evolution of the geochemical environment of gas hydrate systems.

Geological investigation of a section at Kulyumbe river in Siberia

An integrated, high-resolution chemostratigraphic (C, O and Sr isotopes) and magnetostratigraphic study through the upper Middle Cambrian - lowermost Ordovician shallow-marine carbonates of the northwestern margin of the Siberian Platform is reported. The interval was analysed at the Kulyumbe section, which is exposed along the Kulyumbe River: an eastern tributary of the Enisej River. It comprises the upper Ust'-Brus, Labaz, Orakta, Kulyumbe, Ujgur, and lower Iltyk formations and includes the Steptoean positive carbon isotopic excursion (SPICE) studied here in detail from upper Cambrian carbonates of the Siberian Platform for the first time. The peak of the excursion, showing d13C positive values as high as +4.6? and least-altered 87Sr/86Sr ratios of 0.70909, is reported herein from the Yurakhian Horizon of the Kulyumbe Formation. The stratigraphic position of the SPICE excursion does not support traditional correlation of the boundary between the Orakta and Labaz formations at Kulyumbe River with its supposedly equivalent level in Australia, Laurentia, South China, and Kazakhstan, where the Glyptagnostus stolidotus and G. reticulatus biozones are known to immediately precede the SPICE excursion and span the Middle-Upper Cambrian boundary. The Cambrian-Ordovician boundary is probably situated in the middle Nyajan Horizon of the Iltyk Formation, in which carbon isotope values show a local maximum below a decrease in the upper part of the Nyajan Horizon, attributed herein to the Tremadocian. A refined magnetic polarity sequence shows that the geomagnetic reversal frequency was very high during the Middle Cambrian at 5-10 reversals per Ma, assuming a total duration of ~10 Ma and up to 100 magnetic intervals in the Middle Cambrian. By contrast, the sequence attributed herein to the Upper Cambrian on chemostratigraphic grounds contains only 10-11 magnetic intervals. Preprint in Open Access hdl:10013/epic.30209.d001

Planktic foraminiferal sieve size specific d13C and d18O values and maximum test diameter from ODP sites 171-1051 and 120-748

Many genera of modern planktic foraminifera are adapted to nutrient-poor (oligotrophic) surface waters by hosting photosynthetic symbionts, but it is unknown how they will respond to future changes in ocean temperature and acidity. Here we show that ca. 40 Ma, some fossil photosymbiont-bearing planktic foraminifera were temporarily 'bleached' of their symbionts coincident with transient global warming during the Middle Eocene Climatic Optimum (MECO). At Ocean Drilling Program (ODP) Sites 748 and 1051 (Southern Ocean and mid-latitude North Atlantic, respectively), the typically positive relationship between the size of photosymbiont-bearing planktic foraminifer tests and their carbon isotope ratios (d13C) was temporarily reduced for ~100 k.y. during the peak of the MECO. At the same time, the typically photosymbiont-bearing planktic foraminifera Acarinina suffered transient reductions in test size and relative abundance, indicating ecological stress. The coincidence of minimum d18O values and reduction in test size-d13C gradients suggests a link between increased sea-surface temperatures and bleaching during the MECO, although changes in pH and nutrient availability may also have played a role. Our findings show that host-photosymbiont interactions are not constant through geological time, with implications for both the evolution of trophic strategies in marine plankton and the reliability of geochemical proxy records generated from symbiont-bearing planktic foraminifera.

Mid-Pleistocene (800-400 ka) records of benthic and planktic foraminfer d18O and d13C, planktic foraminifer based SST, and IRD of IODP Site 306-U1314

Stable carbon and oxygen isotopes from benthic and planktic foraminifers, planktic foraminifer assemblages and ice rafted debris from the North Atlantic Site U1314 (Integrated Ocean Drilling Program Expedition 306) were examined to investigate orbital and millennial-scale climate variability in the North Atlantic and its impact on global circulation focusing on the development of glacial periods during the mid-Pleistocene (ca 800-400 ka). Glacial initiations were characterized by a rapid cooling (6-10 °C in less than 7 kyr) in the mean annual sea surface temperature (SST), increasing benthic d18O values and high benthic d13C values. The continuous increase in benthic d18O suggests a continuous ice sheet growth whereas the positive benthic d13C values indicate that the flow of the Iceland Scotland Overflow water (ISOW) was vigorous. Strong deep water formation in the Norwegian Greenland Sea promoted a high transfer of freshwater from the ocean to the continents. However, low SSTs at Site U1314 suggest a subpolar gyre cooling and freshening that may have reduced deep water formation in the Labrador Sea during glacial initiations. Once the 3.5 per mil threshold in the benthic d18O record was exceeded, ice rafting started and ice sheet growth was punctuated by millennial-scale waning events which returned to the ocean part of the freshwater accumulated on the continents. Ice-rafting events were associated with a rapid reduction in the ISOW (benthic d13C values dropped 0.5-1 per mil) and followed by millennial-scale warmings. The first two millennial-scale warm intervals of each glacial period reached interglacial temperatures and were particularly abrupt (6-10 °C in ~3 kyr). Subsequent millennial-scale warm events were cooler probably because the AMOC was rather reduced as suggested by the low benthic d13C values. These two abrupt warming events that occurred at early glacial periods were also observed in the Antarctic temperature and CO2 records, suggesting a close correlation between both Hemispheres. The comparison of the sea surface proxies with the benthic d18O record (as the Southern sign) indicates the presence of a millennial-scale seesaw pattern similar to that seen during the Last Glacial period.

Occurrence and isotopic composition (d18O, d13C) of benthic foraminifera in sediments from DSDP Leg 72

Changes in the vertical water mass structure of the Vema Channel during the Pliocene have been inferred from benthic foraminiferal assemblages and stable isotopic analyses from three sites of DSDP Leg 72 (South Atlantic). Faunal and isotopic results from Sites 516A and 518 suggest that a major change occurred in deep-water circulation patterns in the late Pliocene near 3.2 Ma. Benthic oxygen isotopic records from Sites 516A and 518 show a characteristic increase in d18O values near 3.2 Ma. This has been documented in numerous Pliocene isotopic records. The magnitude of the oxygen isotopic enrichment near 3.2 Ma appears to increase with water depth from an average enrichment of 0.34 per mil in Site 516A (1313 m) to an average enrichment of 0.58 per mil in Site 518 (3944 m). We suggest that this enrichment resulted partly from a change in deep-water circulation patterns which included a decrease in bottom-water temperatures. Planktonic d18O values near 3.2 Ma show no evidence of an enrichment which would be indicative of an increase in global ice volume. On the contrary, d18O values in Sites 517 and 518 become more depleted near 3.2 Ma, indicating a surface-water warming perhaps due to a change in the strength and/or position of the Brazil Current. An increase in the relative abundance of the benthic foraminifer Nuttalides umbonifera, which is associated with Antarctic Bottom Water (AABW) in the modern ocean, coincides with the benthic 18O enrichment in Site 518. At 3.2 Ma, oxygen and carbon isotopic gradients between Sites 518 (3944 m) and 516A (1313 m) show a marked increase such that Site 518 becomes enriched in 18O and depleted in 13C relative to Site 516A. This enrichment in d18O is interpreted as partly representing a temperature decrease at Site 518; the depletion in d13C indicates a corrosive water mass which is high in metabolic CO2. We suggest that benthic foraminiferal and stable isotopic changes in Site 518 resulted from a pulse-like increase in the formation of AABW near 3.2 Ma. The cause of this circulation event may have been linked to global cooling and/or the final closure of the Central American Seaway.

Age profiles and isotopes d18O and d13C in Globigerina angiporoides and Oridorsalis umbonatus at DSDP Site 90-593 and Holes 12-111, 29-277 and 90-592

The late Eocene through earliest Miocene stable-isotope composition of southwest Pacific microfossils has been examined in a traverse of high-quality sedimentary sequences ranging from subantarctic (DSDP Site 277) through temperate regions (DSDP Sites 592 and 593). Changes in oxygen-isotope values, measured in benthic and planktonic foraminifers, document the Oligocene development and strengthening of latitudinal thermal zonation from water masses with broad temperature gradients during the Eocene to the steeper gradients and more distinct latitudinally distributed surface water-mass belts of the Neogene. The oxygen-isotope records can be divided into three intervals: late Eocene, early Oligocene, and middle to late Oligocene. Each interval represents a successive stage in the evolution of latitudinal thermal gradients between subantarctic and temperate regions in the Southern Hemisphere. During the late Eocene, oxygen-isotope values at subantarctic Site 277 were similar to those at temperate Sites 592 and 593. The isotope values suggest that, although the inferred paleotemperatures at Site 277 are slightly cooler on average than those at the temperate sites, there is no evidence for a major thermal boundary between the regions at this time. All three sites record the well-known oxygen-isotope enrichment of about 1 per mil in both planktonic and benthic foraminifers in close association with the Eocene/Oligocene boundary. In contrast to the earliest Oligocene enrichments in the planktonic and benthic oxygen-isotope composition at Site 277, more northern Sites 592 and 593 exhibit a depletion through the early-middle Oligocene. This documents the beginning of thermal segregation as subantarctic waters cooled relative to those at temperate latitudes. During the Oligocene, this surface-water differentiation continued, as measured by planktonic d18O values. The oxygen-isotope records of the benthic foraminifers also began to diverge in the earliest Oligocene. The most enriched oxygen-isotope values in all records cluster in the middle Oligocene, marked by oscillating episodes of enrichments >0.5 per mil occurring most prominently in the subantarctic record of Site 277. These values can be interpreted as recording either the coldest oceanic temperatures of the Paleogene and/or accumulations of Antarctic ice. After this interval, latitudinal thermal differentiation developed rapidly during the middle Oligocene, especially in the surface waters which actually warmed in temperate areas. If the enriched Oligocene oxygen-isotope values indicate that ice had accumulated, this ice must have disappeared by the early Miocene, when depleted oxygen-isotope values suggest very warm conditions. The data presented in this chapter document the progressive increase of latitudinal temperature gradients from the late Eocene through the late Oligocene. This pattern of increasing isotopic offset between latitudinally distributed southwest Pacific sites is linked to the establishment and strengthening of the Circum-Antarctic Current, previously considered to have developed during the middle to late Oligocene. The intensification of this current system progressively decoupled the warm subtropical gyres from cool polar circulation, in turn leading to increased Antarctic glaciation.

(Table 1) Calcite, siderite, and stable isotopes d13C and d18O at DSDP Hole 93-603B

Diagenesis of the fine-grained, feldspathic sandstones in the Lower Cretaceous submarine fan complex cored in DSDP Hole 603B can be considered to have occurred in three stages: (1) replacement of matrix and framework grains by pyrite, siderite, phillipsite (?), and particularly by ferroan calcite; (2) dissolution of ferroan calcite and feldspars to produce secondary macroporosity; and (3) development of sparse feldspar and quartz overgrowths, and authigenic modification of remnant matrix. Only ferroan calcite is a volumetrically important diagenetic mineral phase (up to 50 vol.%). Matrix in thin sandstone turbidite deposits has been extensively replaced by ferroan calcite. Carbon stable isotope data suggest that organic diagenesis had only a minor influence on calcite precipitation. Oxygen stable isotope data indicate that the minimum average calcite precipitation temperature was 40° C. Preliminary calculations show that steadystate diffusion of Ca+ + from the dissolution of nannoplankton skeletal material in the interbedded pelagic marls to the associated sandstones is a feasible transport mechanism. A thick sandstone unit from 1234-1263 m sub-bottom is extensively replaced by calcite near the upper and lower contacts. Farther into the sand body away from the contacts, the sandstone has good secondary porosity resulting from the dissolution of ferroan calcite that partially replaced matrix and framework grains. The central portion of the thick sand appears to be a channel with high-energy clean sand. We believe that the channel provided a conduit for focused flow of diagenetic compactional fluids responsible for dissolution. Focused flow may be the result of the earlier lithification of the pelagic limestones and thin-bedded sandstones which, then formed vertical permeability barriers. Calcite dissolution has occurred and may still be occurring at temperatures less than 65°C.