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 algorithm's 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, and 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.

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.

Water radiolysis continuously produces H2 and oxidized chemicals in wet sediment and rock. Radiolytic H2 has been identified as the primary electron donor (food) for microorganisms in continental aquifers kilometers below Earth’s surface. Radiolytic products may also be significant for sustaining life in subseafloor sediment and subsurface environments of other planets. However, the extent to which most subsurface ecosystems rely on radiolytic products has been poorly constrained, due to incomplete understanding of radiolytic chemical yields in natural environments. Here we show that all common marine sediment types catalyse radiolytic H2 production, amplifying yields by up to 27X relative to pure water. In electron equivalents, the global rate of radiolytic H2 production in marine sediment appears to be 1-2% of the global organic flux to the seafloor. However, most organic matter is consumed at or near the seafloor, whereas radiolytic H2 is produced at all sediment depths. Comparison of radiolytic H2 consumption rates to organic oxidation rates suggests that water radiolysis is the principal source of biologically accessible energy for microbial communities in marine sediment older than a few million years. Where water permeates similarly catalytic material on other worlds, life may also be sustained by water radiolysis.

We reconstruct the provenance of aluminosilicate sediment deposited in Ulleung Basin, Japan Sea, over the last 12 Ma at Site U1430 drilled during Integrated Ocean Drilling Program Expedition 346. Using multivariate partitioning techniques (Q-mode factor analysis, multiple linear regressions) applied to the major, trace and rare earth element composition of the bulk sediment, we identify and quantify four aluminosilicate components (Taklimakan, Gobi, Chinese Loess and Korean Peninsula), and model their mass accumulation rates. Each of these end-members, or materials from these regions, were present in the top-performing models in all tests. Material from the Taklimakan Desert (50–60 % of aluminosilicate contribution) is the most abundant end-member through time, while Chinese Loess and Gobi Desert components increase in contribution and flux in the Plio-Pleistocene. A Korean Peninsula component is lowest in abundance when present, and its occurrence reflects the opening of the Tsushima Strait at c. 3 Ma. Variation in dust source regions appears to track step-wise Asian aridification influenced by Cenozoic global cooling and periods of uplift of the Tibetan Plateau. During early stages of the evolution of the East Asian Monsoon, the Taklimakan Desert was the major source of dust to the Pacific. Continued uplift of the Tibetan Plateau may have influenced the increase in aeolian supply from the Gobi Desert and Chinese Loess Plateau into the Pleistocene. Consistent with existing records from the Pacific Ocean, these observations of aeolian fluxes provide more detail and specificity regarding the evolution of different Asian source regions through the latest Cenozoic.

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We examine the paleoceanographic record over the last ∼400 kyr derived from major, trace, and rare earth elements in bulk sediment from two sites in the East China Sea drilled during Integrated Ocean Drilling Program Expedition 346. We use multivariate statistical partitioning techniques (Q‐mode factor analysis, multiple linear regression) to identify and quantify five crustal source components (Upper Continental Crust (UCC), Luochuan Loess, Xiashu Loess, Southern Japanese Islands, Kyushu Volcanics), and model their mass accumulation rates (MARs). UCC (35–79% of terrigenous contribution) and Luochuan Loess (16–55% contribution) are the most abundant end‐members through time, while Xiashu Loess, Southern Japanese Islands, and Kyushu Volcanics (1–22% contribution) are the lowest in abundance when present. Cycles in UCC and Luochuan Loess MARs may indicate continental and loess‐like material transported by major rivers into the Okinawa Trough. Increases in sea level and grain size proxy (e.g., SiO2/Al2O3) are coincident with increased flux of Southern Japanese Islands, indicating localized sediment supply from Japan. Increases in total terrigenous MAR precede minimum relative sea levels by several thousand years and may indicate remobilization of continental shelf material. Changes in the relative contribution of these end‐members are decoupled from total MAR, indicating compositional changes in the sediment are distinct from accumulation rate changes but may be linked to variations in sea level, riverine and eolian fluxes, and shelf‐bypass processes over glacial‐interglacials, complicating accurate monsoon reconstructions from fluvial dominated sediment.

Obtaining quantitative chemical information using laser-induced breakdown spectroscopy is challenging due to the variability in the bulk composition of geological materials. Chemical matrix effects caused by this variability produce changes in the peak area that are not proportional to the changes in minor element concentration. Therefore the use of univariate calibrations to predict trace element concentrations in geological samples is plagued by a high degree of uncertainty. This work evaluated the accuracy of univariate minor element predictions as a function of the composition of the major element matrices of the samples and examined the factors that limit the prediction accuracy of univariate calibrations. Five different sample matrices were doped with 10-85 000 ppm Cr, Mn, Ni, Zn, and Co and then independently measured in 175 mixtures by X-ray fluorescence, inductively coupled plasma atomic emission spectrometry, and laser-induced breakdown spectroscopy, the latter at three different laser energies (1.9, 2.8, and 3.7 mJ). Univariate prediction models for minor element concentrations were created using varying combinations of dopants, matrices, normalization/no normalization, and energy density; the model accuracies were evaluated using root mean square prediction errors and leave-one-out cross-validation. The results showed the superiority of using normalization for predictions of minor elements when the predicted sample and those in the training set had matrices with similar SiO contents. Normalization also mitigates differences in spectra arising from laser/sample coupling effects and the use of different energy densities. Prediction of minor elements in matrices that are dissimilar to those in the training set can increase the uncertainty of prediction by an order of magnitude. Overall, the quality of a univariate calibration is primarily determined by the availability of a persistent, measurable peak with a favorable transition probability that has little to no interference from neighboring peaks in the spectra of both the unknown and those used to train it.

To produce thin p+ layers in n-Si substrates, low-energy B+ ions have been implanted into amorphous layers formed by the prior implantation of Si+ ions. Thermal annealing results in recrystallization of the amorphous material by solid-phase epitaxy. After annealing, the B depth profile determined by secondary ion mass spectrometry is close to the calculated profile, transmission electron microscopy shows that the implanted layer is of good crystal quality, and sheet-resistivity measurements show that electrical activation is complete. Diodes with p+/n junctions ∼0.25 μm deep produced by the dual implantation technique show excellent I-V characteristics, with reverse leakage current densities ∼5 and 16 nA/cm2 at −1 and −5 V, respectively. P-channel metal-oxide-semiconductor field-effect transistors fabricated using the dual implantation technique exhibit superior electrical characteristics compared to similar devices fabricated using the conventional single B implant process.