34 research outputs found
Prognostic factors for outcomes after whole-brain irradiation of brain metastases from relatively radioresistant tumors: a retrospective analysis
Overview of the DESI Legacy Imaging Surveys
The DESI Legacy Imaging Surveys (http://legacysurvey.org/) are a combination of three public projects (the Dark Energy Camera Legacy Survey, the Beijing–Arizona Sky Survey, and the Mayall z-band Legacy Survey) that will jointly image ≈14,000 deg2 of the extragalactic sky visible from the northern hemisphere in three optical bands (g, r, and z) using telescopes at the Kitt Peak National Observatory and the Cerro Tololo Inter-American Observatory. The combined survey footprint is split into two contiguous areas by the Galactic plane. The optical imaging is conducted using a unique strategy of dynamically adjusting the exposure times and pointing selection during observing that results in a survey of nearly uniform depth. In addition to calibrated images, the project is delivering a catalog, constructed by using a probabilistic inference-based approach to estimate source shapes and brightnesses. The catalog includes photometry from the grz optical bands and from four mid-infrared bands (at 3.4, 4.6, 12, and 22 μm) observed by the Wide-field Infrared Survey Explorer satellite during its full operational lifetime. The project plans two public data releases each year. All the software used to generate the catalogs is also released with the data. This paper provides an overview of the Legacy Surveys project
Kinetic carbon isotope fractionation links graphite and diamond precipitation to reduced fluid sources
At high temperatures, isotope partitioning is often assumed to proceed under equilibrium and trends in the carbon isotope composition within graphite and diamond are used to deduce the redox state of their fluid source. However, kinetic isotope fractionation modifies fluid- or melt-precipitated mineral compositions when growth rates exceed rates of diffusive mixing. As carbon self-diffusion in graphite and diamond is exceptionally slow, this fractionation should be preserved. We have hence performed time series experiments that precipitate graphitic carbon through progressive oxidization of an initially CH4-dominated fluid. Stearic acid was thermally decomposed at 800 °C and 2 kbar, yielding a reduced COH-fluid together with elemental carbon. Progressive hydrogen loss from the capsule caused CH4 to dissociate with time and elemental carbon to continuously precipitate. The newly formed C0, aggregating in globules, is constantly depleted by -6.5±0.3‰ in 13C relative to the methane, which defines a temperature dependent kinetic graphite-methane 13C/12C fractionation factor. Equilibrium fractionation would instead yield graphite heavier than the methane. In dynamic environments, kinetic isotope fractionation may control the carbon isotope composition of graphite or diamond, and, extended to nitrogen, could explain the positive correlation of δ13C and δ15N sometimes observed in coherent diamond growth zones. 13C enrichment trends in diamonds are then consistent with reduced deep fluids oxidizing upon their rise into the subcontinental lithosphere, methane constituting the main source of carbon.ISSN:0012-821XISSN:1385-013
Experimental carbonatite/graphite carbon isotope fractionation and carbonate/graphite geothermometry
Carbon isotope exchange between carbon-bearing high temperature phases records the carbon (re-) processing in the Earth's interior, where the vast majority of global carbon is stored. Redox reactions between carbonate phases and elemental carbon govern the mobility of carbon, which then can be traced by its isotopes. We determined the carbon isotope fractionation factor between graphite and a Na2CO3-CaCO3 melt at 900–1500 °C and 1 GPa; The failure to isotopically equilibrate preexisting graphite led us to synthesize graphite anew from organic material during the melting of the carbonate mixture. Graphite growth proceeds by (1) decomposition of organic material into globular amorphous carbon, (2) restructuring into nano-crystalline graphite, and (3) recrystallization into hexagonal graphite flakes. Each transition is accompanied by carbon isotope exchange with the carbonate melt. High-temperature (1200–1500 °C) equilibrium isotope fractionation with type (3) graphite can be described by
(temperature T in K). As the experiments do not yield equilibrated bulk graphite at lower temperatures, we combined the ≥1200 °C experimental data with those derived from upper amphibolite and lower granulite facies carbonate-graphite pairs (Kitchen and Valley, 1995; Valley and O'Neil, 1981). This yields the general fractionation function
usable as a geothermometer for solid or liquid carbonate at ≥600 °C.
Similar to previous observations, lower-temperature experiments (≤1100 °C) deviate from equilibrium. By comparing our results to diffusion and growth rates in graphite, we show that at ≤1100 °C carbon diffusion is slower than graphite growth, hence equilibrium surface isotope effects govern isotope fractionation between graphite and carbonate melt and determine the isotopic composition of newly formed graphite. The competition between diffusive isotope exchange and growth rates requires a more careful interpretation of isotope zoning in graphite and diamond.
Based on graphite crystallization rates and bulk isotope equilibration, a minimum diffusivity of Dgraphite = 2 × 10−17 m2s−1 for T > 1150 °C is required. This value is significantly higher than calculated from experimental carbon self-diffusion constants (∼1.6 × 10−29 m2 s−1) but in good agreement with the value calculated for mono-vacancy migration (∼2.8 × 10−16 m2 s−1).ISSN:0016-7037ISSN:1872-953
Intramolecular hydrogen isotope exchange inside silicate melts – The effect of deuterium concentration
Tracing the deep geological water cycle requires knowledge of the hydrogen isotope systematics between and within hydrous materials. For quenched hydrous alkali-silicate melts, hydrogen NMR reveals a distinct heterogeneity in the distribution of stable hydrogen isotopes (D, H) within the silicate tetrahedral network, where deuterons concentrate strongly in network regions that are associated with alkali cations. Previous hydrogen NMR studies performed in the sodium tetrasilicate system (Na2O x 4SiO2, NS4) with a 1:1 D2O/H2O ratio showed on average 1300 ‰ deuterium enrichment in the alkali-associated network, but the effect on varying bulk D2O/H2O ratios on this intramolecular isotope effect remained unconstrained. Experiments in the hydrous sodium tetrasilicate system with 8 wt% bulk water and varying bulk D2O/H2O ratios were performed at 1400 °C and 1.5 GPa. It is found that both hydrogen isotopes preferably partition into the silicate network that is associated with alkali ions. The partitioning is always stronger for the deuterated than for the protonated hydrous species. The relative enrichment of deuterium over protium in the alkali-associated network, i.e., the intramolecular isotope effect, correlates positively with the D2O/H2O bulk ratio of the hydrous NS4 system. Modeled for natural deuterium abundance (D/H near 1.56 × 10−4), a 1.4-fold (c. 340 ‰) deuterium enrichment in the alkali-associated silicate network is predicted. The partitioning model further predicts a positive correlation between the bulk water content of the silicate melt and the intramolecular deuterium partitioning into the alkali-associated silicate network. Such heterogeneities may explain the magnitude and direction of hydrogen isotope fractionation in hydrous silicate melts coexisting with silicate-saturated fluids. As such, this intramolecular isotope effect appears to be an effective mechanism for deuterium separation, particularly in hydrous magmatic settings, such as subduction zones.ISSN:0009-2541ISSN:1872-683
Kinetic carbon isotope fractionation links graphite and diamond precipitation to reduced fluid sources
Experimental carbonatite/graphite carbon isotope fractionation and carbonate/graphite geothermometry
Experimental determination of equilibrium CH4–CO2-CO carbon isotope fractionation factors (300–1200 °C)
Carbon isotope fractionation in the CO2–CO–CH4–C system was investigated at 300–1200 °C at near-atmospheric pressures by thermally decomposing a variety of organic materials in sealed quartz tubes. Measured gas speciations correspond well to the expected range from thermodynamic calculations. We show that chemical and isotopic equilibrium among gas species is obtained when applying a nickel catalyst for CO2/CH4, CH4/CO, and CO2/CO at ≤600 °C or without a catalyzing agent for CO2/CO at ≥800 °C. The experiments define carbon isotope fractionation factors for the CO2/CH4, CO2/CO and CH4/CO pairs as
(i) 103lnαCO2/CH4 = 8.9 (±0.6) ⋅ 105⋅ (1/T2)0.825(±0.005) (200–1200 °C)
(ii) 103lnαCO2/CO = 1.07 (±0.05) ⋅ 106⋅ (1/T2)0.830(±0.003) (300–1200 °C)
(iii) 103lnαCH4/CO = 1.1 (±0.2) ⋅ 103⋅ (1/T2)0.462(±0.001) (300–1200 °C),
which reproduce the experimental values within 0.2‰ for CO2/CH4 and CO2/CO and within 0.12‰ for CH4/CO (T in K, 1σ fit uncertainties in brackets, CO2/CH4 includes the ≤600 °C experimental data of Horita, 2001). Carbon isotope fractionation factors at 1000 °C are still large for CO2/CH4 and CO2/CO (6.6 and 7.5‰ respectively) but only 1.5‰ for CH4/CO. Elemental carbon precipitated through thermal decomposition of the organic starting materials yields δ13C values that depend on the X(O) = O/(O + H) of the organic starting material, i.e. the initial oxidation state of carbon in the organics. We further observe a catalytic effect of the quartz walls on chemical and isotopic exchange in the CO2/CO system, probably due to the activation of the silicate surface by H+ and OH− ions at >650 °C. Our experimental results yield improved calibrations of the CO2/CH4 equilibria and the first experimental calibration of CO2/CO and CH4/CO carbon isotope fractionation. Applications are in the tracing of magmatic hydrothermal gas emissions, in carbon-precipitating COH-fluids, and in monitoring of coal-seam fires, but our results may also be applied for quality control during steel-making processes.ISSN:0012-821XISSN:1385-013
