30 million years of Permian volcanism recorded in the Choiyoi igneous province (W Argentina) and their source for younger ash fall deposits in the Paraná Basin: SHRIMP U–Pb zircon geochronology evidence

We present four SHRIMP U–Pb zircon ages for the Choiyoi igneous province from the San Rafael Block, central–western Argentina. Dated samples come from the Yacimiento Los Reyunos Formation (281.4 ± 2.5 Ma) of the Cochicó Group (Lower Choiyoi section: andesitic breccias, dacitic to rhyolitic ignimbrites and continental conglomerates), Agua de los Burros Formation (264.8 ± 2.3 Ma and 264.5 ± 3.0 Ma) and Cerro Carrizalito Formation (251.9 ± 2.7 Ma Upper Choiyoi section: rhyolitic ignimbrites and pyroclastic flows) spanning the entire Permian succession of the Choiyoi igneous province. A single zircon from the El Imperial Formation, that is overlain unconformably by the Choiyoi succession, yielded an early Permian age (297.2 ± 5.3 Ma), while the main detrital zircon population indicated an Ordovician age (453.7 ± 8.1 Ma). The new data establishes a more precise Permian age (Artinskian–Lopingian) for the section studied spanning 30 Ma of volcanic activity. Volcanological observations for the Choiyoi succession support the occurrence of explosive eruptions of plinian to ultraplinian magnitudes, capable of injecting enormous volumes of tephra in the troposphere–stratosphere. The new SHRIMP ages indicate contemporaneity between the Choyoi succession and the upper part of the Paraná Basin late Paleozoic section, from the Irati up to the Rio do Rasto formations, encompassing about 24 Ma. Geochemical data show a general congruence in compositional and tectonic settings between the volcanics and Paraná Basin Permian ash fall derived layers of bentonites. Thickness and granulometry of ash fall layers broadly fit into the depletion curve versus distance from the remote source vent of ultraplinian eruptions. Thus, we consider that the Choiyoi igneous province was the source of ash fall deposits in the upper Permian section of the Paraná Basin. Data presented here allow a more consistent correlation between tectono-volcanic Permian events along the paleo-Pacific margin of southwestern Gondwana and the geological evolution of neighboring Paleozoic foreland basins in South America and Africa.     

Gas hydrate characterization and grain-scale imaging of recovered cores from the Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope

Using cryogenic scanning electron microscopy (CSEM), powder X-ray diffraction, and gas chromatography methods, we investigated the physical states, grain characteristics, gas composition, and methane isotopic composition of two gas-hydrate-bearing sections of core recovered from the BPXA-DOE-USGS Mount Elbert Gas Hydrate Stratigraphic Test Well situated on the Alaska North Slope. The well was continuously cored from 606.5 m to 760.1 m depth, and sections investigated here were retrieved from 619.9 m and 661.0 m depth. X-ray analysis and imaging of the sediment phase in both sections shows it consists of a predominantly fine-grained and well-sorted quartz sand with lesser amounts of feldspar, muscovite, and minor clays. Cryogenic SEM shows the gas-hydrate phase forming primarily as a pore-filling material between the sediment grains at approximately 70-75% saturation, and more sporadically as thin veins typically several tens of microns in diameter. Pore throat diameters vary, but commonly range 20-120 microns. Gas chromatography analyses of the hydrate-forming gas show that it is comprised of mainly methane (>99.9%), indicating that the gas hydrate is structure I. Here we report on the distribution and articulation of the gas-hydrate phase within the cores, the grain morphology of the hydrate, the composition of the sediment host, and the composition of the hydrate-forming gas.     

The influence of light on nitrogen cycling and the primary nitrite maximum in a seasonally stratified sea

In the seasonally stratified Gulf of Aqaba Red Sea, both release by phytoplankton and oxidation by nitrifying microbes contributed to the formation of a primary nitrite maximum (PNM) over different seasons and depths in the water column. In the winter and during the days immediately following spring stratification, formation was strongly correlated (R² = 0.99) with decreasing irradiance and chlorophyll, suggesting that incomplete reduction by light limited phytoplankton was a major source of . However, as stratification progressed, continued to be generated below the euphotic depth by microbial oxidation, likely due to differential photoinhibition of and oxidizing populations. Natural abundance stable nitrogen isotope analyses revealed a decoupling of the δ¹⁵N and δ¹⁸O in the combined and pool, suggesting that assimilation and nitrification were co-occurring in surface waters. As stratification progressed, the δ¹⁵N of particulate N below the euphotic depth increased from −5‰ to up to +20‰.N uptake rates were also influenced by light; based on ¹⁵N tracer experiments, assimilation of , , and urea was more rapid in the light (434 ± 24, 94 ± 17, and 1194 ± 48 nmol N L⁻¹ day⁻¹ respectively) than in the dark (58 ± 14, 29 ± 14, and 476 ± 31 nmol N L⁻¹ day⁻¹ respectively). Dark assimilation was 314 ± 31 nmol N L⁻¹ day⁻¹, while light assimilation was much faster, resulting in complete consumption of the ¹⁵N spike in less than 7 h from spike addition. The overall rate of coupled urea mineralization and oxidation (14.1 ± 7.6 nmol N L⁻¹ day⁻¹) was similar to that of oxidation alone (16.4 ± 8.1 nmol N L⁻¹ day⁻¹), suggesting that mineralization of labile dissolved organic N compounds like urea was not a rate limiting step for nitrification. Our results suggest that assimilation and nitrification compete for and that N transformation rates throughout the water column are influenced by light over diel and seasonal cycles, allowing phytoplankton and nitrifying microbes to contribute jointly to PNM formation. We identify important factors that influence the N cycle throughout the year, including light intensity, substrate availability, and microbial community structure. These processes could be relevant to other regions worldwide where seasonal variability in mixing depth and stratification influence the contributions of phytoplankton and non-photosynthetic microbes to the N cycle.     

Estimation of extreme slamming pressures using the non-uniform Fourier phase distributions of a design loads generator

Slamming pressures are predicted using a nonlinear ship motion program whose input is an ensemble of short wave trains tailored to produce a large, linear pitch response. These short wave trains are calculated via a design methodology that first creates short time series containing a specified, large ship response and then back-calculates the incident wave trains using linear systems theory. The background simulations and theory used to create these short time series are presented here. Monte Carlo simulation of moderately rare events of a random process indicate the random Fourier component phase PDFs are non-uniform, non-identically distributed, and dependent on the rarity of the target event. These PDFs are modeled using a single parameter, Modified Gaussian distribution and used to generate design time series with a given expected value at a specific time. To predict rare events without resorting to Monte Carlo simulation, the parameters of the Modified Gaussian distributions are calculated via characteristic function comparison. The characteristic functions compare a target PDF calculated from extreme value theory to a PDF based on a discrete Fourier representation of the stochastic process with non-uniform component phases. The comparison to extreme value theory helps to quantify the risk associated with rare events.     

Orbital forcing recorded in subtidal cycles from a Lower Miocene siliciclastic–carbonate ramp system (Central Italy)

Metre-scale siliciclastic–carbonate cycles are the basic depositional motif of the lower Miocene Guadagnolo Formation outcropping in the central Apennines. The mechanisms which formed the mixed-lithology cycles are still a matter of debate. The mixed siliciclastic–carbonate system discussed in this paper provides a new case study to illustrate the role of orbital forcing in controlling the facies evolution and cyclic stacking of small-scale sequences deposited on the outer sector of a ramp. Two sections are discussed that display mixed siliciclastics and carbonates arranged in upward-shallowing cycles. Each cycle shows an upward decrease in the terrigenous input and a parallel increase in benthic fauna. Time-series analyses indicate the cyclic carbonate-terrigenous pattern to be largely controlled by orbital forcing in the Milankovitch frequency band. Coupling of climate change and sea-level fluctuations in tune with orbital cycles are proposed as driving mechanisms.     

Alkali and halogen chemistry in volcanic gases on Io

We use chemical equilibrium calculations to model the speciation of alkalis and halogens in volcanic gases emitted on Io. The calculations cover wide temperature (500-2000 K) and pressure (10⁻⁶ to 10⁺¹ bars) ranges, which overlap the nominal conditions at Pele (T=1760 K, P=0.01 bars). About 230 compounds of 11 elements (O, S, Li, Na, K, Rb, Cs, F, Cl, Br, I) are considered. The elemental abundances for O, S, Na, K, and Cl are based upon observations. CI chondritic elemental abundances relative to sulfur are used for the other alkalis and halogens (as yet unobserved on Io). We predict the major alkali species in Pele-like volcanic gases and the percentage distribution of each alkali are LiCl (73%), LiF (27%); NaCl (81%), Na (16%), NaF (3%); KCl (91%), K (5%), KF (4%); RbCl (93%), Rb (4%), RbF (3%); CsCl (92%), CsF (6%), Cs (2%). Likewise the major halogen species and the percentage distribution of each halogen are NaF (88%), KF (10%), LiF (2%); NaCl (89%), KCl (11%); NaBr (89%), KBr (10%), Br (1%); NaI (61%), I (30%), KI (9%). We predict the major halogen condensates and their condensation temperatures at P=0.01 bar are NaF (1115 K), LiF (970 K); NaCl (1050 K), KCl (950 K); KBr (750 K), RbBr (730 K), CsBr (645 K); and solid I₂ (200 K). We also model disequilibrium chemistry of the alkalis and halogens in the volcanic plume. Based on this work and our prior modeling for Na, K, and Cl in a volcanic plume, we predict the major loss processes for the alkali halide gases are photolysis and/or condensation onto grains. Their estimated photochemical lifetimes range from a few minutes for alkali iodides to a few hours for alkali fluorides. Condensation is apparently the only loss process for elemental iodine. On the basis of elemental abundances and photochemical lifetimes, we recommend searching for gaseous KCl, NaF, LiF, LiCl, RbF, RbCl, CsF, and CsCl around volcanic vents during eruptions. Based on abundance considerations and observations of brown dwarfs we also recommend a search of Io's extended atmosphere and the Io plasma torus for neutral and ionized Li, Cs, Rb, and F.     

Outgassing of ordinary chondritic material and some of its implications for the chemistry of asteroids, planets, and satellites

We used chemical equilibrium calculations to model thermal outgassing of ordinary chondritic material as a function of temperature, pressure, and bulk composition and use our results to discuss outgassing on asteroids and the early Earth. The calculations include ∼1000 solids and gases of the elements Al, C, Ca, Cl, Co, Cr, F, Fe, H, K, Mg, Mn, N, Na, Ni, O, P, S, Si, and Ti. The major outgassed volatiles from ordinary chondritic material are CH₄, H₂, H₂O, N₂, and NH₃ (the latter at conditions where hydrous minerals form). Contrary to widely held assumptions, CO is never the major C-bearing gas during ordinary chondrite metamorphism. The calculated oxygen fugacity (partial pressure) of ordinary chondritic material is close to that of the quartz-fayalite-iron (QFI) buffer. Our results are insensitive to variable total pressure, variable volatile element abundances, and kinetic inhibition of C and N dissolution in Fe metal. Our results predict that Earth's early atmosphere contained CH₄, H₂, H₂O, N₂, and NH₃; similar to that used in Miller—Urey synthesis of organic compounds.     

Heavy metal frost on Venus

Chemical equilibrium calculations of volatile metal geochemistry on Venus show that high dielectric constant compounds of lead and bismuth such as PbS (galena), Bi₂S₃ (bismuthite) or Pb-Bi sulfosalts condense in the venusian highlands and may be responsible for the low radar emissivities observed by Magellan and Pioneer Venus. Our calculations also show that elemental tellurium is unstable on Venus' surface and will not condense below 46.6 km. This is over 30 km higher than Maxwell Montes, the highest point on Venus' surface. Elemental analyses of Venus' highlands surface by laser induced breakdown spectroscopy (LIBS) and/or X-ray fluorescence (XRF) can verify the identity of the heavy metal frost on Venus. The Pb-Pb age of Venus could be determined by mass spectrometric measurements of the Pb²⁰⁷/Pb²⁰⁴ and Pb²⁰⁶/Pb²⁰⁴ isotopic ratios in Pb-bearing frosts. All of these measurements are technologically feasible now.