Stable isotope (delta C-13 and delta O-18) records of bulk marine sediment carry information on past carbon cycling and oceanography, but origins and interpretations remain uncertain because such signals represent mixtures of different biogenic components, each with potential offsets from primary parameters. Studies of Neogene sediment from the eastern equatorial Pacific (EEP) exemplify this issue, because stable isotope records of bulk sediment and foraminifera at different sites exhibit similarities and differences in absolute value that somehow relate to depositional age. Here we measure delta C-13 and delta O-18 of bulk carbonate, two fine-grained fractions (<63 and <20 mu m), mixed-species planktic and benthic foraminifera, and foraminifera fragments from sediments deposited over four time intervals within the last 7 Ma at ODP Site 851. These data are compared to published delta C-13 and delta O-18 records of multiple single-species planktic foraminifera from the same site and benthic foraminifera from an adjacent site. Bulk sediment delta C-13 and delta O-18 records represent a mixed signal dominated by reticulofenestrid coccolith calcite but modified by variable amounts of different foraminifera. Similarities and differences between stable isotope records result from temporal changes in water chemistry and temperature, depths of calcite precipitation, and vital effects that impact fractionation of various biogenic components. The remarkable correlation of bulk stable isotope records within the EEP suggests that several factors change collectively over time across a broad oceanographic region. Ideally, multiple stable isotope records coupled with other proxy measurements might lead to an internally consistent paleoceanographic perspective of the EEP since the late Miocene.

Sediments deposited along continental margins of the Arctic Ocean presumably host large amounts of methane (CH4) in gas hydrates. Here we apply numerical simulations to assess the potential of gas hydrate dissociation and methane release from the East Siberian slope over the next 100 years. Simulations are based on a hypothesized bottom water warming of 3 degrees C, and an assumed starting distribution of gas hydrate. The simulation results show that gas hydrate dissociation in these sediments is relatively slow, and that CH4 fluxes toward the seafloor are limited by low sediment permeability. The latter is true even when sediment fractures are permitted to form in response to overpressure in pore space. With an initial gas hydrate distribution dictated by present-day pressure and temperature conditions, nominally 0.35 Gt of CH4 are released from the East Siberian slope during the first 100 years of the simulation. However, this CH4 discharge becomes significantly smaller (approximate to 0.05 Gt) if glacial sea level changes in the Arctic Ocean are considered. This is because a lower sea level during the last glacial maximum (LGM) must result in depleted gas hydrate abundance within the most sensitive region of the modern gas hydrate stability zone. Even if all released CH4 reached the atmosphere, the amount coming from East Siberian slopes would be trivial compared to present-day atmospheric CH4 inputs from other sources.

A marked switch in the abundance of the planktic foraminiferal genera Morozovella and Acarinina occurred at low-latitude sites near the start of the Early Eocene Climatic Optimum (EECO), a multi-million-year interval when Earth surface temperatures reached their Cenozoic maximum. Stable carbon and oxygen isotope data of bulk sediment are presented from across the EECO at two locations: Possagno in northeast Italy and Deep Sea Drilling Project (DSDP) Site 577 in the northwest Pacific. Relative abundances of plank tic foraminifera are presented from these two locations, as well as from Ocean Drilling Program (ODP) Site 1051 in the northwest Atlantic. All three sections have good strati graphic markers, and the delta C-13 records at each section can be correlated amongst each other and to delta C-13 records at other locations across the globe. These records show that a series of negative carbon isotope excursions (CIEs) occurred before, during and across the EECO, which is defined here as the interval between the J event and the base of Discoaster sublodoensis. Significant though ephemeral modifications in planktic foraminiferal assemblages coincide with some of the short-term CIEs, which were marked by increases in the relative abundance ofAcarinina, similar to what happened across established hyperthermal events in Tethyan settings prior to the EECO. Most crucially, a temporal link exists between the onset of the EECO, carbon cycle changes during this time and the decline in Morozovella. Possible causes are mani- fold and may include temperature effects on photosymbiont-bearing planktic foraminifera and changes in ocean chemistry.

To improve the understanding and utility of bulk carbonate stable carbon and oxygen isotope measurements, we examine sediment from cores in the eastern equatorial Pacific that span the last 8Ma. We measured C-13 and O-18 in 791 samples from Integrated Ocean Drilling Program Site U1338 and Deep Sea Drilling Project Site 573, both located close to the Pacific equator. In 100 samples, we measured C-13 and O-18 on isolated <63 mu m and <38 mu m fractions, which concentrates calcareous nannofossil carbonate and progressively excludes foraminiferal carbonate. Bulk carbonate C-13 and O-18 records are similar to published records from other sites drilled near the equator and seem to reflect mixed layer conditions, albeit with some important caveats involving the precipitation of calcite by coccolithophores. The comparatively lower C-13 and O-18 of the <63 mu m and <38 mu m fractions in sediments younger than 4.4Ma is attributed to an increase in deep-dwelling planktic foraminifera material in bulk carbonate, shifting the bulk isotopic signals toward higher values. Bulk carbonate C-13 is similar over 2500km along the Pacific equator, suggesting covarying concentrations and C-13 of dissolved inorganic carbon within surface waters since 8Ma. Greater bulk sediment C-13 and O-18, higher sedimentation rates, and low content of coarse material suggest intensified wind-driven upwelling and enhanced primary productivity along the Pacific equator between 8.0 and 4.4Ma, although a full understanding of bulk carbonate records will require extensive future work.

Major variations in global carbon cycling occurred between 62 and 48 Ma, and these very likely related to changes in the total carbon inventory of the ocean-atmosphere system. Based on carbon cycle theory, variations in the mass of the ocean carbon should be reflected in contemporaneous global ocean carbonate accumulation on the seafloor and, thereby, the depth of the calcite compensation depth (CCD). To better constrain the cause and magnitude of these changes, the community needs early Paleogene carbon isotope and carbonate accumulation records from widely separated deep-sea sediment sections, especially including the Indian Ocean. Several CCD reconstructions for this time interval have been generated using scientific drill sites in the Atlantic and Pacific oceans; however, corresponding information from the Indian Ocean has been extremely limited. To assess the depth of the CCD and the potential for renewed scientific drilling of Paleogene sequences in the Indian Ocean, we examine lithologic, nannofossil, carbon isotope, and carbonate content records for late Paleocene - early Eocene sediments recovered at three sites spanning Ninetyeast Ridge: Deep Sea Drilling Project (DSDP) Sites 213 (deep, east), 214 (shallow, central), and 215 (deep, west). The disturbed, discontinuous sediment sections are not ideal, because they were recovered in single holes using rotary coring methods, but remain the best Paleogene sediments available from the central Indian Ocean. The delta C-13 records at Sites 213 and 215 are similar to those generated at several locations in the Atlantic and Pacific, including the prominent high in delta C-13 across the Paleocene carbon isotope maximum (PCIM) at Site 215, and the prominent low in delta C-13 across the early Eocene Climatic Optimum (EECO) at both Site 213 and Site 215. The Paleocene-Eocene thermal maximum (PETM) and the K/X event are found at Site 213 but not at Site 215, presumably because of coring gaps. Carbonate content at both Sites 213 and 215 drops to < 5% shortly after the first occurrence of Discoaster lodoensis and the early Eocene rise in delta C-13 (similar to 52 Ma). This reflects a rapid shoaling of the CCD, and likely a major decrease in the net flux of C-13-depleted carbon to the ocean. Our results support ideas that major changes in net fluxes of organic carbon to and from the exogenic carbon cycle occurred during the early Paleogene. Moreover, we conclude that excellent early Paleogene carbonate accumulation records might be recovered from the central Indian Ocean with future scientific drilling.

Gas hydrate and free gas accumulation in heterogeneous marine sediment is simulated using a two-dimensional (2-D) numerical model that accounts for mass transfer over geological timescales. The model extends a previously documented one-dimensional (1-D) model such that lateral variations in permeability (k) become important. Various simulations quantitatively demonstrate how focused fluid flow through high-permeability zones affects local hydrate accumulation and saturation. Simulations that approximate a vertical fracture network isolated in a lower permeability shale (k(fracture) >>k(shale)) show that focused fluid flow through the gas hydrate stability zone (GHSZ) produces higher saturations of gas hydrate (25-70%) and free gas (30-60%) within the fracture network compared to surrounding shale. Simulations with a dipping, high-permeability sand layer also result in elevated saturations of gas hydrate (60%) and free gas (40%) within the sand because of focused fluid flow through the GHSZ. Increased fluid flux, a deep methane source, or both together increase the effect of flow focusing upon hydrate and free gas distribution and enhance hydrate and free gas concentrations along the high-permeability zones. Permeability anisotropy, with a vertical to horizontal permeability ratio on the order of 10(-2), enhances transport of methane-charged fluid to high-permeability conduits. As a result, gas hydrate concentrations are enhanced within these high-permeability zones. The dip angle of these high-permeability structures affects hydrate distribution because the vertical component of fluid flux dominates focusing effects. Hydrate and free gas saturations can be characterized by a local Peclet number (localized, vertical, focused, and advective flux relative to diffusion) relative to the methane solubility gradient, somewhat analogous to such characterization in 1-D systems. Even in lithologically complex systems, local hydrate and free gas saturations might be characterized by basic parameters (local flux and diffusivity).

Deep Sea Drilling Project Site 577 on Shatsky Rise (North Pacific Ocean) recovered a series of cores at three holes that contain calcareous nannofossil ooze of latest Cretaceous (late Maastrichtian) through early Eocene age. Several important records have been generated using samples from these cores, but the stratigraphy has remained outdated and confusing. Here we revise the stratigraphy at Site 577. This includes refining several age datums, realigning cores in the depth domain, and placing all stratigraphic markers on a current time scale. The work provides a template for appropriately bringing latest Cretaceous and Paleogene data sets at old drill sites into current paleoceanographic literature for this time interval. While the Paleocene Eocene Thermal Maximum (PETM) lies within core gaps at Holes 577* and 577A, the sedimentary record at the site holds other important events and remains crucially relevant to understanding changes in oceanographic conditions from the latest Cretaceous through early Paleogene.

Sediment cores collected from the Eastern Equatorial Pacific Ocean display a clear positive second-order relationship between wet bulk density (WED) and carbonate content. This has long interested the paleoceanography community because detailed Gamma Ray Attenuation Porosity Evaluator (GRAPE) measurements, which approximate WBD, might be used to determine records of carbonate content at very high temporal resolution. Although general causes for the relationship are known, they have not been presented and discussed systematically on the basis of first principles. In this study, we measure the mass and carbonate content of 50 sediment samples with known WBD from Site U1338, before and after rinsing with de-ionized water; we also determine the mass related proportion of coarse (>63 mu m) material. Samples exhibit clear relationships between WBD, carbonate content, mass loss upon rinsing, and grain size. We develop a series of mathematical expressions to describe these relationships, and solve them numerically. As noted by previous workers, the second-order relationship between WBD and carbonate content results from the mixing of biogenic carbonate and biogenic silica, which have different grain densities and different porosities. However, at high carbonate content, a wide range in WBD occurs because samples with greater amounts of coarse carbonate have higher porosity. Moreover compaction impacts carbonate particles more than biogenic silica particles. As such, a single two-component equation cannot be used to determine carbonate content accurately across depth intervals where both the porosity and type of carbonate vary. Instead, the WBD-carbonate relationship is described by an infinite series of curves, each which represents mixing of multiple sediment components with different densities and porosities. Dissolved ions also precipitate from pore space during sample drying, which adds mass to the sediment. Without rinsing samples, simple empirical relationships between WBD and carbonate content are further skewed by salt dilution.

The late Paleocene to the early Eocene (∼58–52 Ma) was marked by significant changes in global climate and carbon cycling. The evidence for these changes includes stable isotope records that reveal prominent decreases in δ¹⁸O and δ¹³C, suggesting a rise in Earth's surface temperature (∼4°C) and a drop in net carbon output from the ocean and atmosphere. Concurrently, deep-sea carbonate records at several sites indicate a deepening of the calcite compensation depth (CCD). Here we investigate possible causes (e.g., increased volcanic degassing or decreased net organic burial) for these observations, but from a new perspective. The basic model employed is a modified version of GEOCARB III. However, we have coupled this well-known geochemical model to LOSCAR (Long-term Ocean-atmosphere Sediment CArbon cycle Reservoir model), which enables simulation of seawater carbonate chemistry, the CCD, and ocean δ¹³C. We have also added a capacitor, in this case represented by gas hydrates, that can store and release¹³C-depleted carbon to and from the shallow geosphere over millions of years. We further consider accurate input data (e.g., δ¹³C of carbonate) on a currently accepted timescale that spans an interval much longer than the perturbation. Several different scenarios are investigated with the goal of consistency amongst inferred changes in temperature, the CCD, and surface ocean and deep ocean δ¹³C. The results strongly suggest that a decrease in net organic carbon burial drove carbon cycle changes during the late Paleocene and early Eocene, although an increase in volcanic activity might have contributed. Importantly, a drop in net organic carbon burial may represent increased oxidation of previously deposited organic carbon, such as stored in peat or gas hydrates. The model successfully recreates trends in Earth surface warming, as inferred from δ¹⁸O records, the CCD, and δ¹³C. At the moment, however, our coupled modeling effort cannot reproduce the magnitude of change in all these records collectively. Similar problems have arisen in simulations of short-term hyperthermal events during the early Paleogene (Paleocene-Eocene Thermal Maximum), suggesting one or more basic issues with data interpretation or geochemical modeling remain.

The late Paleocene to early Eocene was marked by major changes in Earth surface temperature and carbon cycling. This included at least two, and probably more, geologically brief (<200-k.yr.) intervals of extreme warming, the Paleocene-Eocene thermal maximum (PETM) and the Eocene thermal maximum-2 (ETM-2). The long-term rise in warmth and short-term hyperthermal events have been linked to massive injections of C-13-depleted carbon into the ocean-atmosphere system and intense global climate change. However, the causes, environmental impact, and relationships remain uncertain because detailed and coupled proxy records do not extend across the entire interval of interest; we are still recognizing the exact character of the hyperthermals and developing models to explain their occurrence. Here we present lithologic and carbon isotope records for a 200-m-thick sequence of latest Paleocene-earliest Eocene upper slope limestone exposed along Mead Stream, New Zealand. New carbon isotope and lithologic analyses combined with previous work on this expanded section shows that the PETM and ETM-2, the suspected H-2, I-1, I-2, and K/X hyperthermals, and several other horizons are marked by pronounced negative carbon isotope excursions and clay-rich horizons. Generally, the late Paleocene-early Eocene lithologic and delta C-13 records at Mead Stream are similar to records recovered from deep-sea sites, with an important exception: lows in delta C-13 and carbonate content consistently span intervals of relatively high sedimentation (terrigenous dilution) rather than intervals of relatively low sedimentation (carbonate dissolution). These findings indicate that, over similar to 6 m.yr., there was a series of short-term climate perturbations, each characterized by massive input of carbon and greater continental weathering. The suspected link involves global warming, elevated greenhouse-gas concentrations, and enhanced seasonal precipitation.