Geochemistry from DSDP Holes 67-497 and 67-496

Mineralogical identification, glass chemistry, and instrumental neutron activation analyses of Quaternary volcanic ash layers from Leg 67 Holes 496, 497, and 499 are used to correlate the drill holes and on-land sources. We have identified two units at Hole 496 that correspond to the 23,000-yr.-old Pinos Altos ash (Samples 496-3-4, 55-57 cm and 496-3-5, 74-76 cm); the 84,000-yr.-old Los Chocoyos ash corresponds with Sample 496-5-4, 134-146 cm, but this latter correlation is less certain.

Direct visualization of solute locations in laboratory ice samples, links to videos

Many important chemical reactions occur in polar snow, where solutes may be present in several reservoirs, including at the air-ice interface and in liquid-like regions within the ice matrix. Some recent laboratory studies suggest chemical reaction rates may differ in these two reservoirs. While investigations have examined where solutes are found in natural snow and ice, similar research has not identified solute locations in laboratory samples, nor the possible factors controlling solute segregation. To address this, we examined solute locations in ice samples prepared from either aqueous cesium chloride (CsCl) or Rose Bengal solutions that were frozen using several different methods. Samples frozen in a laboratory freezer had the largest liquid-like inclusions and air bubbles, while samples frozen in a custom freeze chamber had somewhat smaller air bubbles and inclusions; in contrast, samples frozen in liquid nitrogen showed much smaller concentrated inclusions and air bubbles, only slightly larger than the resolution limit of our images (~2 µm). Freezing solutions in plastic versus glass vials had significant impacts on the sample structure, perhaps because the poor heat conductivity of plastic vials changes how heat is removed from the sample as it cools. Similarly, the choice of solute had a significant impact on sample structure, with Rose Bengal solutions yielding smaller inclusions and air bubbles compared to CsCl solutions frozen using the same method. Additional experiments using higher-resolution imaging of an ice sample show that CsCl moves in a thermal gradient, supporting the idea that the solutes in ice are present in liquid-like regions. Our work shows that the structure of laboratory ice samples, including the location of solutes, is sensitive to freezing method, sample container, and solute characteristics, requiring careful experimental design and interpretation of results.

Stratigraphic correlation of ODP Site 199-1218 and 199-1219

During Ocean Drilling Program Leg 199 a high-resolution (~1-2 cm/k.y.) biogenic sediment record from the late Paleocene to the early Miocene was recovered, containing an uninterrupted set of geomagnetic chrons as well as a detailed record of calcareous and siliceous biostratigraphic datum events. Shipboard lithologic proxy measurements and shore-based determinations of CaCO3 revealed regular cycles that can be attributed to climatic forcing. Discovering drill sites with well defined magneto- and biostratigraphic records that also show clear lithologic cycles is rare and valuable and creates the opportunity to develop a detailed stratigraphic intersite correlation, providing the basis to study paleoceanographic processes and mass accumulation rates at high resolution. Here we present extensive postcruise work that extends the shipboard composite depth stratigraphy by providing a high-resolution revised meters composite depth (rmcd) scale to compensate for depth distortion within individual cores. The depth-aligned data were then used to generate stacked records of lithologic proxy measurements. Making use of the increased signal-to-noise ratio in the stacked records, we then proceeded to generate a detailed site-to-site correlation between Sites 1218 and 1219 in order to decrease the depth uncertainty for magneto- and biostratigraphic datums. Stacked lithologic proxy records in combination with discrete measurements of CaCO3 were then exploited to calculate high-resolution carbonate concentration curves by regression of the multisensor track data with discrete measurements. By matching correlative features between the cores and wireline logging data, we also rescaled our core rmcd back to in situ depths. Our study identifies lithology-dependent core expansion due to unloading as the mechanism of varying stratigraphic thicknesses between cores.

Radiolarian biostratigraphy and chronology of radiolarian events of ODP Leg 199 sites and EW9709 sediment cores

A generally rich radiolarian fauna ranging in age from Quaternary to early Eocene (Zone RP7) was found at five of the eight sites drilled during Ocean Drilling Program (ODP) Leg 199. Of particular interest are the stratigraphically complete assemblages that range in age from middle Miocene (Zone RN5) to early Eocene (Zone RP7), composites of Sites 1218, 1219, and 1220. At the same sites, multisensor track (MST) data show consistent cycles in gamma ray attenuation density, color, and carbonate content that can be correlated on a submeter scale from the early Miocene to early Eocene. In addition, the magnetic reversal records from these three sites allow construction of an absolute timescale. A series of 305 radiolarian morphologic first and last occurrences and evolutionary transitions for radiolarians were determined and correlated directly with the accompanying MST and paleomagnetic data, resulting in a detailed and accurate dating of events. Since many of the bioevents are found at more than one site, it was also possible to test their reliability within the study area. Twelve new species are described: Calocycletta (Calocycletta) anekathen, Dorcadospyris anastasis, Dorcadospyris copelata, Dorcadospyris cyclacantha, Dorcadospyris ombros, Dorcadospyris scambos, Eucyrtidium mitodes, Theocyrtis careotuberosa, Theocyrtis perpumila, Theocyrtis perysinos, Theocyrtis setanios, and Thyrsocyrtis (Pentalacorys) orthotenes.

Relative abundances of selected radiolarian species in sediments of ODP Leg 199 sites

During Ocean Drilling Program (ODP) Leg 199, sediments were recovered from eight sites in the Central Pacific. Late Oligocene and early Miocene radiolarians are common to abundant and moderately well preserved in Cores 199-1218A-8H through 11H and 199-1219A-5H through 9H. More than 110 radiolarian species were encountered during this study. Of these species, 100 are identifiable forms and the rest are undescribed or unfamiliar forms. This report presents the relative abundances of described forms from the upper Oligocene to lower Miocene sediments.

Radiolarian events in the eastern Equatorial Pacific

The development of an orbitally tuned time scale for the ODP leg 138 sites provides biostratigraphers a very high resolution chronostratigraphic framework. With this framework we are better able to define which of the first and last appearances of species appear to be synchronous. In addition, the geographic distribution of sites provides the means with which the detailed spatial patterns of invasion of new species and the extinction of older species can be mapped. These maps not only provide information on the process of evolution, migration, and extinction, they can also be related to water mass distributions and near-surface circulation of the ocean. Of 39 radiolarian events studied at 11 sites in the eastern equatorial Pacific, 28 were found to have a minimum range in their estimated age that exceeded 0.15 m.y. The temporal pattern of first and last appearances of these diachronous events have coherent spatial patterns that indicate shifts in the areas of high oceanographic gradients over the past 10 Ma. These changes in the locations of high gradient regions suggest that the South Equatorial Current (SEC) was north of its present position prior to approximately 7 Ma. There was a southward shift in the northern boundary of this current between approximately 6 and 7 Ma, and the development of a relatively strong gradient between the northeastern and northwestern sites. Between approximately 3.7 and 3.4 Ma, there was a very slight northward shift in the northern boundary of the SEC and the steep gradients between the northeastern and northwestern sites may have disappeared. This change is thought to be associated with the closing of the Isthmus of Panama. The temporal-spatial patterns of diachronous events younger than 3.4 Ma are consistent with patterns of circulation in the modern ocean.

Stable isotope record and sediment composition of the subantarctic Pacific

Benthic foraminiferal stable carbon isotope records from the South Atlantic show significant declines toward more "Pacific-like" values at ~7 and ~2.7 Ma, and it has been posited that these shifts may mark steps toward increased CO2 sequestration in the deep Southern Ocean as climate cooled over the late Neogene. We generated new stable isotope records from abyssal subantarctic Pacific cores MV0502-4JC and ELT 25-11. The record from MV0502-4JC suggests that the Southern Ocean remained well mixed and free of vertical or interbasinal d13C gradients following the late Miocene carbon shift (LMCS). According to the records from MV0502-4JC and ELT 25-11, however, cold, low d13C bottom waters developed in the Southern Ocean in the late Pliocene and persisted until ~1.7 Ma. These new data suggest that while conditions in the abyssal Southern Ocean following the LMCS were comparable to the present day, sequestration of respired CO2 may have increased in the deepest parts of the Southern Ocean during the late Pliocene, a critical period for the growth and establishment of the Northern Hemisphere ice sheets.

Late Eocene-early Oligocene radiolarian events and abundances in ODP Leg 199 sediments

During Ocean Drilling Program Leg 199, eight sites (Sites 1215-1222) were cored in the Central Pacific. Late Eocene-early Oligocene thick radiolarian-rich biogenic sediments were collected from Holes 1218A, 1219A, and 1220A. This is the first attempt to calibrate the ages of Paleogene radiolarian events using magnetostratigraphy in this region. A total of 107 species and species groups, which are valuable for stratigraphic correlation, are listed with numeric data and figures. Among these three holes, a total of 77 radiolarian events were recognized and their ages were calibrated by correlation with paleomagnetic events recorded in Hole 1220A.