Ann G. Dunlea

Dust, volcanic ash, and the evolution of the South Pacific Gyre through the Cenozoic

We examine the 0–100 Ma paleoceanographic record retained in pelagic clay from the South Pacific Gyre (SPG) by analyzing 47 major, trace, and rare earth elements in bulk sediment in 206 samples from seven sites drilled during Integrated Ocean Drilling Program Expedition 329. We use multivariate statistical analyses (Q-mode factor analysis and multiple linear regression) of the geochemical data to construct a model of bulk pelagic clay composition and mass accumulation rates (MAR) of six end-members, (post-Archean average Australian shale, rhyolite, basalt, Fe-Mn-oxyhydroxides, apatite, and excess Si). Integrating the results with Co-based age models at Sites U1365, U1366, U1369, and U1370, we link changes in MAR of these components to global oceanographic, terrestrial, and climatic transformations through the Cenozoic. Our results track the spatial extent (thousands of kilometers) of dust deposition in the SPG during the aridification of Australia. Dispersed ash is a significant component of the pelagic clay, often comprising >50% by mass, and records episodes of Southern Hemisphere volcanism. Because both are transported by wind, the correlation of dust and ash MAR depends on the sites latitude and suggests meridional shifts in the position of atmospheric circulation cells. The hydrothermal MARs provide evidence for rapid deposition from the Osbourn Trough spreading ridge before it went extinct. Excess Si MARs show that the abrupt increase in siliceous productivity observed at Site U1371 also extended at least as far north as Sites U1369 and U1370, suggesting large-scale reorganizations of oceanic Si distributions ~10–8 Ma in the southern SPG.

Glacial-interglacial changes in central tropical Pacific surface seawater property gradients

Much uncertainty exists about the state of the oceanic and atmospheric circulation in the tropical Pacific over the last glacial cycle. Studies have been hampered by the fact that sediment cores suitable for study were concentrated in the western and eastern parts of the tropical Pacific, with little information from the central tropical Pacific. Here we present information from a suite of sediment cores collected from the Line Islands Ridge in the central tropical Pacific, which show sedimentation rates and stratigraphies suitable for paleoceanographic investigations. Based on the radiocarbon and oxygen isotope measurements on the planktonic foraminifera Globigerinoides ruber, we construct preliminary age models for selected cores and show that the gradient in the oxygen isotope ratio of G. ruber between the equator and 8°N is enhanced during glacial stages relative to interglacial stages. This stronger gradient could reflect enhanced equatorial cooling (perhaps reflecting a stronger Walker circulation) or an enhanced salinity gradient (perhaps reflecting increased rainfall in the central tropical Pacific).

Cobalt‐based age models of pelagic clay in the South Pacific Gyre

Dating pelagic clay can be a challenge due to its slow sedimentation rate, post-depositional alteration, and lack of biogenic deposition. Co-based dating techniques have the potential to create age models in pelagic clay under the assumption that the flux of non-detrital Co to the seafloor is spatially and temporally constant, resulting in the non-detrital Co concentrations being inversely proportional to sedimentation rate. We apply a Co-based method to the pelagic clay sequences from Sites U1365, U1366, U1369, and U1370 drilled during Integrated Ocean Drilling Program (IODP) Expedition 329 in the South Pacific Gyre. We distinguished non-detrital Co from detrital Co using multivariate statistical partitioning techniques. We found that the non-detrital flux of Co at Site U1370 is approximately twice as high than at the other sites, implying that the non-detrital Co flux is not regionally constant. This regional variation reflects the heterogeneous distribution of Co in the water column, as is observed in the present day. We present an improved approach to Co-based age modeling throughout the South Pacific Gyre and determine that the Co-based method can effectively date oxygenated pelagic clay deposited in the distal open-ocean, but is less reliable for deposition closer to continents. When extending the method to geologically old sediment, it is important to consider the paleolocation of a given site to ensure these conditions are met. This article is protected by copyright. All rights reserved.

Quantifying K, U, and Th contents of marine sediments using shipboard natural gamma radiation spectra measured on DV JOIDES Resolution

During International Ocean Discovery Program (IODP) expeditions, shipboard-generated data provide the first insights into the cored sequences. The natural gamma radiation (NGR) of the recovered material, for example, is routinely measured on the ocean drilling research vessel DV JOIDES Resolution. At present, only total NGR counts are readily available as shipboard data, although full NGR spectra (counts as a function of gamma-ray energy level) are produced and archived. These spectra contain unexploited information, as one can estimate the sedimentary contents of potassium (K), thorium (Th), and uranium (U) from the characteristic gamma-ray energies of isotopes in the ^(40)K, ^(232)Th, and ^(238)U radioactive decay series. Dunlea et al. [2013] quantified K, Th and U contents in sediment from the South Pacific Gyre by integrating counts over specific energy levels of the NGR spectrum. However, the algorithm used in their study is unavailable to the wider scientific community due to commercial proprietary reasons. Here, we present a new MATLAB algorithm for the quantification of NGR spectra that is transparent and accessible to future NGR users. We demonstrate the algorithms performance by comparing its results to shore-based inductively coupled plasma-mass spectrometry (ICP-MS), inductively coupled plasma-emission spectrometry (ICP-ES), and quantitative wavelength-dispersive X-ray fluorescence (XRF) analyses. Samples for these comparisons come from eleven sites (U1341, U1343, U1366-U1369, U1414, U1428-U1430, U1463) cored in two oceans during five expeditions. In short, our algorithm rapidly produces detailed high-quality information on sediment properties during IODP expeditions at no extra cost.

Hydrogen Utilization Potential in Subsurface Sediments.

Subsurface microbial communities undertake many terminal electron-accepting processes, often simultaneously. Using a tritium-based assay, we measured the potential hydrogen oxidation catalyzed by hydrogenase enzymes in several subsurface sedimentary environments (Lake Van, Barents Sea, Equatorial Pacific, and Gulf of Mexico) with different predominant electron-acceptors. Hydrogenases constitute a diverse family of enzymes expressed by microorganisms that utilize molecular hydrogen as a metabolic substrate, product, or intermediate. The assay reveals the potential for utilizing molecular hydrogen and allows qualitative detection of microbial activity irrespective of the predominant electron-accepting process. Because the method only requires samples frozen immediately after recovery, the assay can be used for identifying microbial activity in subsurface ecosystems without the need to preserve live material. We measured potential hydrogen oxidation rates in all samples from multiple depths at several sites that collectively span a wide range of environmental conditions and biogeochemical zones. Potential activity normalized to total cell abundance ranges over five orders of magnitude and varies, dependent upon the predominant terminal electron acceptor. Lowest per-cell potential rates characterize the zone of nitrate reduction and highest per-cell potential rates occur in the methanogenic zone. Possible reasons for this relationship to predominant electron acceptor include (i) increasing importance of fermentation in successively deeper biogeochemical zones and (ii) adaptation of H2ases to successively higher concentrations of H2 in successively deeper zones.

Radiolytic Hydrogen Production in the Subseafloor Basaltic Aquifer

Hydrogen (H2) is produced in geological settings by dissociation of water due to radiation from radioactive decay of naturally occurring uranium (238U, 235U), thorium (232Th) and potassium (40K). To quantify the potential significance of radiolytic H2 as an electron donor for microbes within the South Pacific subseafloor basaltic aquifer, we use radionuclide concentrations of 43 basalt samples from IODP Expedition 329 to calculate radiolytic H2 production rates in basement fractures. The samples are from three sites with very different basement ages and a wide range of alteration types. U, Th, and K concentrations vary by up to an order of magnitude from sample to sample at each site. Comparison of our samples to each other and to the results of previous studies of unaltered East Pacific Rise basalt suggests that significant variations in radionuclide concentrations are due to differences in initial (unaltered basalt) concentrations (which can vary between eruptive events) and post-emplacement alteration. However, there is no clear relationship between alteration type and calculated radiolytic yields. Local maxima in U, Th, and K produce hotspots of H2 production, causing calculated radiolytic rates to differ by up to a factor of 80 from sample to sample. Fracture width also greatly influences H2 production, where microfractures are hotspots for radiolytic H2 production. For example, H2 production rates normalized to water volume are 190 times higher in 1 μm wide fractures than in fractures that are 10 cm wide. To assess the importance of water radiolysis for microbial communities in subseafloor basaltic aquifers, we compare electron transfer rates from radiolysis to rates from iron oxidation in subseafloor basalt. Radiolysis appears likely to be a more important electron donor source than iron oxidation in old (>10 Ma) basement basalt. Radiolytic H2 production in the volume of water adjacent to a square cm of the most radioactive SPG basalt may support as many as 1500 cells.

Optimization of end‐members used in multiple linear regression geochemical mixing models

Tracking marine sediment provenance (e.g., of dust, ash, hydrothermal material, etc.) provides insight into contemporary ocean processes and helps construct paleoceanographic records. In a simple system with only a few end-members that can be easily quantified by a unique chemical or isotopic signal, chemical ratios and normative calculations can help quantify the flux of sediment from the few sources. In a more complex system (e.g., each element comes from multiple sources), more sophisticated mixing models are required. MATLAB codes published in Pisias et al. (2013) solidified the foundation for application of a constrained least square (CLS) multiple linear regression technique that can use many elements and several end-members in a mixing model. However, rigorous sensitivity testing to check the robustness of the CLS model is time- and labor intensive. MATLAB codes provided in this paper reduce the time and labor involved and facilitate finding a robust and stable CLS model. By quickly comparing the goodness of fit between thousands of different end member combinations, users are able to identify trends in the results that reveal the CLS solution uniqueness and the end-member composition precision required for a good fit. Users can also rapidly check that they have the appropriate number and type of end-members in their model. In the end, these codes improve the users confidence that the final CLS model(s) they select are the most reliable solutions. These advantages are demonstrated by application of the codes in two case studies of well-studied datasets (Nazca Plate, South Pacific Gyre). This article is protected by copyright. All rights reserved.