Calcium isotope ratios from marine barite and carbonate over Paleocene-Eocene Boundary (ODP Sites 1212 and 1221)

Carbonates are invaluable archives of the past, and have been used extensively to reconstruct paleoclimate and paleoceanographic conditions over geologic time scales. Such archives are susceptible to diagenetic alteration via dissolution, recrystallization and secondary precipitation, particularly during ocean acidification events when intense dissolution can occur. Despite the importance of diagenesis on proxy fidelity, the effects of diagenesis on the calcium isotopic composition (d44Ca) of carbonates are unclear. Accordingly, bulk carbonate d44Ca was measured at high resolution in two Pacific deep sea sediment cores (ODP Sites 1212 and 1221) with considerably different dissolution histories over the Paleocene-Eocene Thermal Maximum (PETM, ~55 Ma). The d44Ca of marine barite was also measured at the deeper Site 1221, which experienced severe carbonate dissolution during the PETM. Large (~0.8 per mil) variations in bulk carbonate d44Ca occur in the deeper site near the peak carbon isotope excursion, and are correlated with a large drop in carbonate weight percent. Such an effect is seen in neither the 1221 barite record nor the bulk carbonate record at the shallower, less dissolved Site 1212. We contend that ocean chemical changes associated with the abrupt and massive carbon release into the ocean-atmosphere system and subsequent ocean acidification at the PETM affected the bulk carbonate d44Ca record via diagenesis in the sedimentary column. Such changes are considerable, and need to be taken into account when interpreting and modeling Ca isotope data over extreme climatic events associated with ocean chemical evolution.

Neogene radiolarian datum levels in the equatorial Indian and Pacific Oceans

Fifty radiolarian events of early Pleistocene and Neogene age were identified in an E-W transect of equatorial DSDP sites, extending from the Gulf of Panama to the western Pacific and eastern Indian Oceans. Our objective was to document the degree of synchroneity or time-transgressiveness of stratigraphically-useful datum levels from this geologic time interval. We restricted our study to low latitudes within which morphological variations of individual taxa are minimal, the total assemblage diversity remains high, and stratigraphic continuity is well-documented by an independent set of criteria. Each of the five sites chosen (503, 573, 289/586, 214) was calibrated to an "absolute" time scale, using a multiple of planktonic foraminiferal, nannofossil, and diatom datum levels which have been independently correlated to the paleomagnetic polarity time scale in piston core material. With these correlations we have assigned "absolute" ages to each radiolarian event, with a precision of 0.1-0.2 m.y. and an accuracy of 0.2-0.4 m.y. On this basis we have classified each of the events as either: (a) synchronous (range of ages <0.4 m.y.); (b) time-transgressive (i.e., range of ages >1.0 m.y.); and (c) not resolvable (range of ages 0.4-1.0 m.y.). Our results show that, among the synchronous datum levels, a large majority (15 out of 19) are last occurrences. Among those events which are clearly time-transgressive, most are first appearances (10 out of 13). In many instances taxa appear to evolve first in the Indian Ocean, and subsequently in the western and eastern Pacific Ocean. This pattern is particularly unexpected in view of the strong east-to-west zonal flow in equatorial latitudes. Three of the time-transgressive events have been used to define zonal boundaries: the first appearances of Spongaster pentas, Diartus hughesi, and D. petterssoni. Our results suggest that biostratigraphic non-synchroneity may be substantial (i.e., greater than 1 m.y.) within a given latitudinal zone; one would expect this effect to be even more pronounced across oceanographic and climatic gradients. We anticipate that the extent of diachroneity may be comparable for diatom, foraminiferal, and nannofossil datum levels as well. If this proves true, global "time scales" may need to be re-formulated on the basis of a smaller number of demonstrably synchronous events.

Mössbauer study at DSDP Hole 95-612

57Fe Mössbauer spectra of 15 oceanic sediment samples collected from Site 612 (Deep Sea Drilling Project Leg 95) were recorded. These spectra showed that most of the iron in the sediments was present as high-spin, paramagnetic Fe2+ and Fe3+. The ferrous iron was mainly distributed in terrigenous clays and biogenic carbonates. The variation of the Mössbauer parameters for Fe2+ with sub-bottom depth suggests that the main Fe2+-bearing component changed with geologic time. The amount of iron in each iron-bearing phase as estimated from the corresponding peak areas in the spectra also changed with depth. These variations in the Mössbauer parameters and peak areas are correlated with lithologic changes in the sediment column.

Massic magnetic susceptibility and CaCO3 content at the P. ohmi and T. hugii zones from the Rio Argos X.Ag-1 section, southeastern Spain

An orbital floating time scale of the Hauterivian-Barremian transition (Early Cretaceous) is proposed using high-resolution magnetic susceptibility measurements. Orbital tuning was performed on the Río Argos section (southeast Spain), the candidate for a Global boundary Stratotype Section and Point (GSSP) for the Hauterivian-Barremian transition. Spectral analyses of MS variations, coupled with the frequency ratio method, allow the recognition of precession, obliquity and eccentricity frequency bands. Orbitally-tuned magnetic susceptibility provides minimum durations for ammonite biozones. The durations of well-constrained ammonite zones are assessed at 0.78 myr for Pseudothurmannia ohmi (Late Hauterivian) and 0.57 myr for Taveraidiscus hugii (Early Barremian). These results are consistent with previous estimates from the other reference section (Angles, southeast France) and tend to show that the Río Argos section displays a complete succession for this time interval. They differ significantly from those proposed in the Geologic Time Scale 2008 and may help to improve the next compilation. The Faraoni Oceanic Anoxic Event, a key Early Cretaceous oceanographic perturbation occurring at the P. ohmi/P. catulloi subzone boundary has a duration estimated at 0.10-0.15 myr, which is similar to previous assessments.

(Table 19, page 199) Minor constituents of one of the San Clemente iron concretions and its metallic core

The chemical and mineralogical composition of pelagic sediments from the East Pacific Ocean has been determined with the aim of defining the ultimate sources and the mechanisms of formation of the solid phases. The distribution of elements between sea-water, the pore solution and the various solid components of the sediments permits interpretations of the variations in time and space of the gross chemical composition of pelagic clays. For example, manganese, present in sea-water in a divalent form, is apparently oxidized at the sediment-water interface to tetravalent species which subsequently become a part of the group of ferromanganese oxide minerals which are found in the marine environment. It is suggested the rate of manganese accumulation in sediments is some function of the length of time the sediment surface is in contact with sea-water. The contribution of chemical species from the different geospheres is considered. The quantitative importance of pelagic clays in the major sedimentary cycle is studied on the basis of the distribution of the weathered igneous rock products between continental and pelagic deposits and sea-water. These analyses of a wide variety of pelagic clays allow a reformulation of the geochemical balance and it is concluded that pelagic clays account for approximately 13 per cent of the total mass of sediments produced over geologic time.

Middle Eocene Fe and Ca counts, Ca/Fe ratios, revised splices and astronomical age models form different Sites of IODP Exp342

Accurate age models are a tool of utmost important in paleoclimatology. Constraining the rate and pace of past climate change are at the core of paleoclimate research, as such knowledge is crucial to our understanding of the climate system. Indeed, it allows for the disentanglement of the various drivers of climate change. The scarcity of highly resolved sedimentary records from the middle Eocene (Bartonian - Lutetian Stages; 47.8 - 37.8 Ma) has led to the existence of the "Eocene astronomical time scale gap" and hindered the establishment of a comprehensive astronomical time scale (ATS) for the entire Cenozoic. Sediments from the Newfoundland Ridge drilled during Integrated Ocean Drilling Program (IODP) Expedition 342 span the Eocene gap at an unprecedented stratigraphic resolution with carbonate bearing sediments. Moreover, these sediments exhibit cyclic lithological changes that allow for an astronomical calibration of geologic time. In this study, we use the dominant obliquity imprint in XRF-derived calcium-iron ratio series (Ca/Fe) from three sites drilled during IODP Expedition 342 (U1408, U1409, U1410) to construct a floating astrochronology. We then anchor this chronology to numerical geological time by tuning 173-kyr cycles in the amplitude modulation pattern of obliquity to an astronomical solution. This study is one of the first to use the 173-kyr obliquity amplitude cycle for astrochronologic purposes, as previous studies primarily use the 405-kyr long eccentricity cycle as a tuning target to calibrate the Paleogene geologic time scale. We demonstrate that the 173-kyr cycles in obliquity's amplitude are stable between 40 and 50 Ma, which means that one can use the 173-kyr cycle for astrochronologic calibration in the Eocene. Our tuning provides new age estimates for magnetochron reversals C18n.1n - C21r and a stratigraphic framework for key sites from Expedition 342 for the Eocene. Some disagreements emerge when we compare our tuning for the interval between C19r and C20r with previous tuning attempts from the South Atlantic. We therefore present a revision of the original astronomical interpretations for the latter records, so that the various astrochronologic age models for the middle Eocene in the North- and South-Atlantic are consistent.

Compilation of organic carbon distribution and sedimentology in the surface sediments on the continental margin offshore southwestern Africa

In this study we demonstrate the relevance of lateral particle transport in nepheloid layers for organic carbon (OC) accumulation and burial across high-productive continental margins. We present geochemical data from surface sediments and suspended particles in the bottom nepheloid layer (BNL) from the most productive coastal upwelling area of the modern ocean, the Benguela upwelling system offshore southwest Africa. Interpretation of depositional patterns and comparison of downslope trends in OC content, organic matter composition, and 14C age between suspended particles and surface sediments indicate that lateral particle transport is the primary mechanism controlling supply and burial of OC. We propose that effective seaward particle transport primarily along the BNL is a key process that promotes and maintains local high sedimentation rates, ultimately causing high preservation of OC in a depocenter on the upper slope offshore Namibia. As lateral transport efficiently displaces areas of enhanced OC burial from maximum production at highly productive continental margins, vertical particle flux models do not sufficiently explain the relationship between primary production and shallow-marine OC burial. On geologic time scales, the widest distribution and strongest intensity of lateral particle transport is expected during periods of rapid sea-level change. At times in the geologic past, widespread downslope lateral transport of OC thus may have been a primary driver of enhanced OC burial at deeper continental slopes and abyssal basins.

Amino acid racemization for several DSDP samples (Table 1)

Kinetic parameters for the epimerization of isoleucine in multispecific foraminiferal asemblages were used to establish the effects of burial depth and the geothermal gradient on the extent of reaction. It was observed that with a little as thirty meters of burial in a normal thermal regime there were differences between the extent of epimerization measured and that which would have been predicted for thermal equilibrium with bottom water temperatures. As would be expected, these differences are greatest when the heat flow (the geothermal gradient) and/or the sedimentation rates are highest. These effects were observed in most of the DSDP samples studied, and have been used to estimate the average heat flux since the time of sample deposition. Occasional anomalous effects were observed which could not be related to past or present heat flux. These were determined to be due to such geologic occurrences as slumping and reworking or to recent sample contamination. Other problems emerged related to bottom water temperatures including changes over geologic time which are unknown and could not be deduced. Thus, the presence of epimerization anomalies in DSDP cores as noted above limits the effectiveness of amino acid geochronology in such cores, unless these anomalies can be recognized as ab initio.