Chemobiostratigraphy of the Cretaceous/Paleocene boundary at ODP Hole 120-750A

An integrated biostratigraphic and stable isotope investigation was conducted on a high-latitude sequence across the Cretaceous/Paleogene (K/P) boundary recovered in Hole 750A in the southern Indian Ocean. The sequence consists of nannofossil chalk and is discontinuous across the boundary; missing is an estimated 0.3-m.y. late Maestrichtian and early Danian interval. Nonetheless, because calcareous nannofossil Zones NP1 and NP2 are well-developed, micropaleontological studies of the sequence have yielded a detailed record of Danian high-latitude microplankton evolution. In addition, stable carbon isotope analyses of planktonic and benthic foraminifer and bulk samples provide a record of late Maestrichtian and early Danian surface- and deep-water carbon isotope variations. Together, the carbon isotope and carbonate accumulation records serve as an index of regional marine net productivity across the boundary. Earliest Danian nannoplankton assemblages consisted mainly of persistent genera that were generally rare or absent in the Upper Cretaceous at Hole 750A. However, by 0.5-0.6 m.y. after the boundary, newly evolving Danian taxa became dominant. The turnover in nannofossil assemblages was accompanied by significant changes in rates of net productivity as gauged by carbon isotope distributions and carbonate accumulation rates. During the period dominated by persistent taxa, net productivity was extremely low, as reflected by the absence of vertical delta13C gradients and reduced carbonate accumulation rates. Later in the Danian, as new species evolved and flourished, vertical delta13C gradients reappeared and carbonate accumulation rates increased, signaling partial recovery of net productivity in this region. The absolute timing and magnitude of late Maestrichtian and early Danian biotic and geochemical changes in the southern Indian Ocean were similar to those recorded in other pelagic K/P boundary sequences from low- and mid-latitude Atlantic and Pacific sites, indicating that these events were ubiquitous.

Assemblages and isotopic signals of modern ostracodes and host waters from Patagonia, Argentine

Ostracode species assemblages and stable oxygen and carbon isotope ratios of living and recent ostracodes, together with delta18O and delta13C_DIC values of host water samples, provide a first data set that characterizes a wide range of modern aquatic environments in the Laguna Cari-Laufquen (41°S, 68 - 69°W) and the Lago Cardiel area (48 - 49°S, 70 - 71°W) in Patagonia, Argentina. This data set will ultimately be used to interpret and calibrate data acquired from lake sediment cores with the goal of reconstructing past climate. Species assemblages and isotope values can be assigned to three groups; (1) springs, seeps and streams, (2) permanent ponds and lakes, and (3) ephemeral ponds and lakes. Springs, seeps and streams are characterized by Darwinula sp., Heterocypris incongruens, Eucypris fontana, Amphicypris nobilis and Ilyocypris ramirezi. Ostracode and water isotope values range between -13 and -5 per mil for oxygen, and between -15 and -3 per mil for carbon. They are the most negative of the entire sample set, reflecting ground water input with little or no evaporative enrichment. Limnocythere patagonica, Eucypris labyrinthica, Limnocythere sp. and Eucypris aff. fontana are typical species of permanent ponds and lakes. Isotope values indicate high degree of evaporation of lake waters relative to feeder springs and streams and range between -7 and +5 per mil for oxygen, and -5 and +4 per mil for carbon. Limnocythere rionegroensis is the dominant species in ephemeral ponds and lakes. These systems display the most enriched isotope values in both ostracodes and host waters, extending from -5 to +7 per mil for oxygen, and from -5 to +6 per mil for carbon. Living ostracodes show a positive offset from equilibrium values of up to 2 per mil for oxygen. Carbon-isotope values are up to 6? more negative than equilibrium values in highly productive pools. Comparison of ostracode and host water isotope signals permits assessment of the life span of the aquatic environments. Valves from dead ostracodes collected from ephemeral ponds and lakes show a wide scatter with each sample providing a snapshot of the seasonal history of the host water. The presence of the stream species Ilyocypris ramirezi and a wide range of ostracode isotope values suggest that ephemeral ponds and lakes are fed by streams during spring run-off and seasonally dry. A temporary character is also indicated by Heterocypris incongruens, a drought-resistant species that occupies most springs and seeps. In addition, Limnocythere rionegroensis has adjusted its reproduction strategies to its environment. Whereas only females were collected in fresh host waters, males were found in ephemeral ponds and lakes with higher solute content. Sexual reproduction seems to be the more successful reproduction strategy in high and variable salinities and seasonal droughts. The temporary character of the aquatic environments shows that the availability of meteoric water controls the life span of host waters and underlines the sensitivity of the area to changes in precipitation.

Radiocarbon, isotope, biogenic, and 230Th measurements for sediment core RC10-196

The subarctic North Pacific Ocean holds a large CO2 reservoir that is currently isolated from the atmosphere by a low-salinity layer. It has recently been hypothesized that the reorganization of these high-CO2 waters may have played a crucial role in the degassing of carbon dioxide to the atmosphere during the last deglaciation. This reorganization would leave some imprint on paleo-productivity records. Here we present 230Th-normalized biogenic fluxes from an intermediate depth sediment core in the Northwest Pacific (RC10-196, 54.7°N, 177.1°E, 1007 m) and place them within the context of a synthesis of previously-published biogenic flux data from 49 deep-sea cores north of 20°N, ranging from 420 to 3968 m water depth. The 230Th-normalized opal, carbonate, and organic carbon fluxes from RC10-196 peak approximately 13,000 calendar years BP during the Bølling/Allerød (B/A) period. Our data synthesis suggests that biogenic fluxes were in general lowest during the last glacial period, increased somewhat in the Northwest Pacific during Heinrich Event 1, and reached a maximum across the entire North Pacific during the B/A period. We evaluate several mechanisms as possible drivers of deglacial change in biogenic fluxes in the North Pacific, including changes in preservation, sediment focusing, sea ice extent, iron inputs, stratification, and circulation shifts initiated in the North Atlantic and North Pacific. Our analysis suggests that while micronutrient sources likely contributed to some of the observed changes, the heterogeneity in timing of glaciogenic retreat and sea level make these mechanisms unlikely causes of region-wide contemporaneous peaks in export production. We argue that paleo-observations are most consistent with ventilation increases in both the North Pacific (during H1) and North Atlantic (during B/A) being the primary drivers of increases in biogenic flux during the deglaciation, as respectively they were likely to bring nutrients to the surface via increased vertical mixing and shoaling of the global thermocline.

Sedimentation rate calculations and isotopic analysis on sediment cores along the IODP Expedition 311 transect

The oceanographic and tectonic conditions of accretionary margins are well-suited for several potential processes governing methane generation, storage and release. To identify the relevant methane evolution pathways in the northern Cascadia accretionary margin, a four-site transect was drilled during Integrated Ocean Drilling Program Expedition 311. The d13C values of methane range from a minimum value of -82.2 per mil on an uplifted ridge of accreted sediment near the deformation front (Site U1326, 1829 mbsl, meters below sea level) to a maximum value of -39.5 per mil at the most landward location within an area of steep canyons near the shelf edge (Site U1329, 946 mbsl). An interpretation based solely on methane isotope values might conclude the 13C-enrichment of methane indicates a transition from microbially- to thermogenically-sourced methane. However, the co-existing CO2 exhibits a similar trend of 13C-enrichment along the transect with values ranging from -22.5 per mil to +25.7 per mil. The magnitude of the carbon isotope separation between methane and CO2 (Ec = 63.8 ± 5.8) is consistent with isotope fractionation during microbially mediated carbonate reduction. These results, in conjunction with a transect-wide gaseous hydrocarbon content composed of > 99.8% (by volume) methane and uniform dDCH4 values (-172 per mil ± 8) that are distinct from thermogenic methane at a seep located 60 km from the Expedition 311 transect, suggest microbial CO2 reduction is the predominant methane source at all investigated sites. The magnitude of the intra-site downhole 13C-enrichment of CO2 within the accreted ridge (Site U1326) and a slope basin nearest the deformation front (Site U1325, 2195 mbsl) is ~ 5 per mil. At the mid-slope site (Site U1327, 1304 mbsl) the downhole 13C-enrichment of the CO2 is ~ 25 per mil and increases to ~ 40 per mil at the near-shelf edge Site U1329. This isotope fractionation pattern is indicative of more extensive diagenetic alteration at sites with greater 13C-enrichment. The magnitude of the 13C-enrichment of CO2 correlates with decreasing sedimentation rates and a diminishing occurrence of stratigraphic gas hydrate. We suggest the decreasing sedimentation rates increase the exposure time of sedimentary organic matter to aerobic and anaerobic degradation, during burial, thereby reducing the availability of metabolizable organic matter available for methane production. This process is reflected in the occurrence and distribution of gas hydrate within the northern Cascadia margin accretionary prism. Our observations are relevant for evaluating methane production and the occurrence of stratigraphic gas hydrate within other convergent margins.

Mid-Wisconsin to Holocene permafrost and landscape dynamics based on a drained lake basin core from the northern Seward Peninsula, Northwest Alaska

Permafrost-related processes drive regional landscape dynamics in the Arctic terrestrial system. A better understanding of past periods indicative of permafrost degradation and aggradation is important for predicting the future response of Arctic landscapes to climate change. Here, we used a multi-proxy approach to analyze a ~4 m long sediment core from a drained thermokarst lake basin on the northern Seward Peninsula in western Arctic Alaska (USA). Sedimentological, biogeochemistical, geochronological, micropaleontological (ostracoda, testate amoeba) and tephra analyses were used to determine the long-term environmental Early-Wisconsin to Holocene history preserved in our core for Central Beringia. Yedoma accumulation dominated throughout the Early to Late-Wisconsin but was interrupted by wetland formation from 44.5 to 41.5 ka BP. The latter was terminated by deposition of 1 m of volcanic tephra, most likely originating from the South Killeak Maar eruption at about 42 ka BP. Yedoma deposition continued until 22.5 ka BP and was followed by a depositional hiatus in the sediment core between 22.5 and 0.23 ka BP. We interpret this hiatus as due to intense thermokarst activity in the areas surrounding the site, which served as a sediment source during the Late-Wisconsin to Holocene climate transition. The lake forming the modern basin on the upland initiated around 0.23 ka BP, which drained catastrophically in spring 2005. The present study emphasizes that Arctic lake systems and periglacial landscapes are highly dynamic and permafrost formation as well as degradation in Central Beringia was controlled by regional to global climate patterns and as well as by local disturbances.

Paleoceanographic data from cores M23414 and PS1243

Variations in the poleward-directed Atlantic heat transfer was investigated over the past 135 ka with special emphasis on the last and present interglacial climate development (Eemian and Holocene). Both interglacials exhibited very similar climatic oscillations during each preceding glacial terminations (deglacial TI and TII). Like TI, also TII has pronounced cold-warm-cold changes akin to events such as H1, Bølling/Allerød, and the Younger Dryas. But unlike TI, the cold events in TII were associated with intermittent southerly invasions of an Atlantic faunal component which underscores quite a different water mass evolution in the Nordic Seas. Within the Eemian interglaciation proper, peak warming intervals were antiphased between the Nordic Seas and North Atlantic. Moreover, inferred temperatures for the Nordic Seas were generally colder in the Eemian than in the Holocene, and vice versa for the North Atlantic. A reduced intensity of Atlantic Ocean heat transfer to the Arctic therefore characterized the Eemian, requiring a reassessment of the actual role of the ocean-atmosphere system behind interglacial, but also, glacial climate changes.

Recent distribution and accumulation of organic carbon on the continental margin west off Spitsbergen

The study compiles the controlling factors for organic matter sedimentation patterns from a suite of organogeochemical parameters in surface sediments off Spitsbergen and direct seabed observations using a Remotely Operated Vehicle (ROV). In addition we assess its storage rates as well as the potential of carbon sinks on the northwestern margin of the Barents Sea with short sediment cores from a selected fjord environment (Storfjord). While sedimentation in the fjords is mainly controlled by river/meltwater discharge and coastal erosion by sea ice/glaciers resulting in high supply of terrigenous organic matter, Atlantic water inflow, and thus enhanced marine organic matter supply, characterizes the environment on the outer shelf and slope. Local deviations from this pattern, particularly on the shelf, are due to erosion and out washing of fine-grained material by bottom currents. Spots dominated by marine productivity close to the island have been found at the outer Isfjord and west off Prins Karls Forland as well as off the Kongsfjord/Krossfjord area and probably reflect local upwelling of nutrient-rich Atlantic water-derived water masses. Accumulation rates of marine organic carbon as well as reconstructed primary productivities decreased since the middle of the last century. Negative correlation of the Isfjord temperature record with reconstructed productivities in the Storfjord could be explained by a reduced annual duration of the marginal ice zone in the area due to global warming. Extremely high accumulation rates of marine organic carbon between 5.4 and 17.2 g/m**2/yr mark the Storfjord area, and probably high-latitude fjord environments in general, as a sink for carbon dioxide.

Stable oxygen and carbon isotope compositions of Campanian grainstones and rudstones

Petrographic descriptions and stable oxygen and carbon isotope compositions of microsamples of Campanian-age sediment gravity-flow deposits from Northeast Providence Channel, Bahamas, indicate deep-marine cementation of shallow-marine skeletal grains that were transported to the channel during the Late Cretaceous. Shallow-marine components are represented by mollusks, especially rudists, and shallow-water benthic foraminifers as well as sparse echinoderm and algal grains. The sole evidence of diagenesis in shallow-marine environments consists of micrite envelopes around skeletal grains. Shallow-marine skeletal grains have mean stable isotope values of -3.1 per mil d18O and +2.6 per mil d13C. The d18O values are consistent with precipitation in equilibrium with warm (20°-30°C), shallow-marine water. Deep-marine components are represented by equant calcite spar cements and rip-up clasts of slope sediments. Spar cements, exhibiting hexagonal morphology with scalenohedral terminations, most commonly occur as thin isopachous linings in the abundant porosity. Deep-marine cements have mean stable isotope values of - 1.1 per mil d18O and +2.7 per mil d13C. Deep-marine cements are 18O-enriched relative to shallow-marine skeletal grains, consistent with precipitation in equilibrium with colder (10°-20°C), deep-marine waters. The cement .source during lithification appears to have been dissolution of aragonite and high-magnesium calcite skeletal grains, which made up part of the transported sediment. Interbedded periplatform ooze remains uncemented, or poorly cemented, probably because of lower permeability. Equant spar cements that occur in gravity-flow deposits recovered from Hole 634A have stable isotope compositions similar to spars in Lower and mid-Cretaceous shallow-water limestones exposed on the Bahama Escarpment, to Campanian-Paleocene deep-marine hardgrounds recovered during DSDP Leg 15 in the Caribbean, and to spars in Aptian-Albian talus deposits at the base of the Campeche Escarpment recovered during DSDP Leg 77.

Tab. 1 Mole % CO2 and 13C values of CO2 at baseline and at the final monitoring event for the eight observation wells

During CO2 storage operations in mature oilfields or saline aquifers it is desirable to trace the movement of injected CO2 for verification and safety purposes. We demonstrate the successful use of carbon isotope abundance ratios for tracing the movement of CO2 injected at the Cardium CO2 Storage Monitoring project in Alberta between 2005 and 2007. Injected CO2 had a d13C value of -4.6±1.1 per mil that was more than 10 per mil higher than the carbon isotope ratios of casing gas CO2 prior to CO2 injection with average d13C values ranging from -15.9 to -23.5 per mil. After commencement of CO2 injection, d13C values of casing gas CO2 increased in all observation wells towards those of the injected CO2 consistent with a two-source end-member mixing model. At four wells located in a NE-SW trend with respect to the injection wells, breakthrough of injected CO2 was registered chemically (>50 mol % CO2) and isotopically 1-6 months after commencement of CO2 injection resulting in cumulative CO2 fluxes exceeding 100000 m**3 during the observation period. At four other wells, casing gas CO2 contents remained below 5 mol % resulting in low cumulative CO2 fluxes (<2000 m**3) throughout the entire observation period, but carbon isotope ratios indicated contributions between <30 and 80% of injected CO2. Therefore, we conclude that monitoring the movement of CO2 in the injection reservoir with geochemical and isotopic techniques is an effective approach to determine plume expansion and to identify potential preferential flow paths provided that the isotopic composition of injected CO2 is constant and distinct from that of baseline CO2.

Geochemical and nannofossil analyses of Cenomanian/Turonian sediments of DSDP Hole 75-530A

One of the key objectives of Deep Sea Drilling Project (DSDP) Leg 75 was to shed light on the underlying causes of Cretaceous oceanic anoxia in the South Atlantic by addressing two major hypotheses: productivity productivity-driven anoxia vs. enhanced ocean stratification leading to preservation of organic matter and black shale deposition. Here we present a detailed geochemical dataset from sediments deposited during the Cenomanian/Turonian (C/T) transition and the global oceanic anoxic event 2 (OAE 2) at DSDP Site 530A, located off-shore Namibia (southeast Angola Basin, north of Walvis Ridge). To characterise the succession of alternating black and green shales at this site and to reconstruct the evolution of their paleoenvironmental setting, we have combined data derived from investigations on bulk organic matter, biomarkers and the inorganic fraction. The location of the C/T boundary itself is biostratigraphically not well constrained due to the carbonate-poor (but organic matter-rich) facies of these sediments. The bulk d13Corg record and compound-specific d13C data, in combination with published as well as new biostratigraphic data, enabled us to locate more precisely the C/T boundary at DSDP Site 530A. The compound-specific d13C record is the first of this kind reported from C/T black shales in the South Atlantic. It is employed for paleoenvironmental reconstructions and chemostratigraphic correlation to other C/T sections in order to discuss the paleoceanographic aspects and implications of the observations at DSDP Site 530A in a broader context, e.g., with regard to the potential trigger mechanisms of OAE 2, global changes in black shale deposition and climate. On a stratigraphic level, an approximation and monitoring of the syndepositional degree of oxygen depletion within the sediments/bottom waters in comparison to the upper water column is achieved by comparing normalised concentrations of redox-sensitive trace elements with the abundance of highly source specific molecular compounds. These biomarkers are derived from photoautotrophic and simultaneously anoxygenic green sulphur bacteria (Chlorobiacea) and are interpreted as paleoindicators for events of photic zone euxinia. In contrast to a number of other OAE 2 sections that are characterised by continuous black shale sequences, DSDP Site 530A represents a highly dynamic setting where newly deposited black shales were repeatedly exposed to conditions of subtle bottom water re-oxidation, presumably leading to their progressive alteration into green shales. The frequent alternation between both facies and the related anoxic to slight oxygenated conditions can be best explained by variations in vertical extent of an oxygen minimum zone in response to changes in a highly productive western continental margin setting driven by upwelling.

Stable oxygen isotope record and Mg/Ca ratios at the Mid-Pleistocene Climate Transition, ODP Site 181-1123

Earth's climate underwent a fundamental change between 1250 and 700 thousand years ago, the Mid-Pleistocene Transition (MPT), when the dominant periodicity of climate cycles changed from 41,000 to 100,000 years in the absence of significant change in orbital forcing. Over this time, an increase occurred in the amplitude of change of deep ocean foraminiferal oxygen isotopic ratios, traditionally interpreted as defining the main rhythm of ice ages although containing large effects of changes in deep-ocean temperature. We have separated the effects of decreasing temperature and increasing global ice volume on oxygen isotope ratios. Our results suggest that the MPT was initiated by an abrupt increase in Antarctic ice volume at 900 ka. We see no evidence of a pattern of gradual cooling but near-freezing temperatures occur at every glacial maximum.