Comparison of Experimental vs Theoretical Abundances of ¹³CH₃D and ¹²CH₂D₂ for Isotopically Equilibrated Systems from 1 to 500 °C

Methane is produced and consumed via numerous microbial and chemical reactions in atmospheric, hydrothermal, and magmatic reactions. The stable isotopic composition of methane has been used extensively for decades to constrain the source of methane in the environment. A recently introduced isotopic parameter used to study the formation temperature and formational conditions of methane is the measurement of molecules of methane with multiple rare, heavy isotopes (‘clumped’) such as ¹³CH₃D and ¹²CH₂D₂. In order to place methane clumped-isotope measurements into a thermodynamic reference frame that allows calculations of clumped-isotope based temperatures (geothermometry) and comparison between laboratories, all past studies have calibrated their measurements using a combination of experiment and theory based on the temperature dependence of clumped isotopologue distributions for isotopically equilibrated systems. These have previously been performed at relatively high temperatures (>150˚C). Given that many natural occurrences of methane form below these temperatures, previous calibrations require extrapolation when calculating clumped-isotope based temperatures outside of this calibration range. We provide a new experimental calibration of the relative equilibrium abundances of ¹³CH₃D and ¹²CH₂D₂ from 1–500˚C using a combination of γ-Al₂O₃ and Ni-based catalysts and compare them to new theoretical computations using Path Integral Monte Carlo (PIMC) methods and find 1:1 agreement (within ± 1 standard error) for the observed temperature dependence of clumping between experiment and theory over this range. This demonstrates that measurements, experiments, and theory agree from 1–500°C providing confidence in the overall approaches. Polynomial fits to PIMC computations, which are considered the most rigorous theoretical approach available, are given as follows (valid T ≥ 270 K): ∆¹³CH₃D≅1000×ln(K¹³CH₃D)= 1.47348×10¹⁹/T⁷ - 2.08648×10¹⁷/T⁶ + 1.19810×10¹⁵/T⁵ - 3.54757×10¹²/T⁴ +5.54476×10⁹/T³ – 3.49294×10⁶/T² + 8.89370×10₂/T ∆¹²CH₂D₂≅1000×ln(8/3×K¹²CH₂D₂)= -9.67634×10¹⁵/T⁶ + 1.71917×10¹⁴/T⁵ - 1.24819×10¹²/T⁴ + 4.30283×10⁹/T3 -4.48660×10⁶/T² + 1.86258×10³/T. We additionally compare PIMC computations to those performed utilizing traditional approaches that are the basis of most previous calibrations (Bigeleisen, Mayer, and Urey model, BMU) and discuss the potential sources of error in the BMU model relative to PIMC computations

Basaltic Soil of Gale Crater: Crystalline Component Compared to Martian Basalts and Meteorites

A significant portion of the soil of the Rocknest dune is crystalline and is consistent with derivation from unweathered basalt. Minerals and their compositions are identified by X-ray diffraction (XRD) data from the CheMin instrument on MSL Curiosity. Basalt minerals in the soil include plagioclase, olivine, low- and high-calcium pyroxenes, magnetite, ilmenite, and quartz. The only minerals unlikely to have formed in an unaltered basalt are hematite and anhydrite. The mineral proportions and compositions of the Rocknest soil are nearly identical to those of the Adirondack-class basalts of Gusev Crater, Mars, inferred from their bulk composition as analyzed by the MER Spirit rover

Detecting Nanophase Weathering Products with CheMin: Reference Intensity Ratios of Allophane, Aluminosilicate Gel, and Ferrihydrite

X-ray diffraction (XRD) data collected of the Rocknest samples by the CheMin instrument on Mars Science Laboratory suggest the presence of poorly crystalline or amorphous materials [1], such as nanophase weathering products or volcanic and impact glasses. The identification of the type(s) of X-ray amorphous material at Rocknest is important because it can elucidate past aqueous weathering processes. The presence of volcanic and impact glasses would indicate that little chemical weathering has occurred because glass is highly susceptible to aqueous alteration. The presence of nanophase weathering products, such as allophane, nanophase iron-oxides, and/or palagonite, would indicate incipient chemical weathering. Furthermore, the types of weathering products present could help constrain pH conditions and identify which primary phases altered to form the weathering products. Quantitative analysis of phases from CheMin data is achieved through Reference Intensity Ratios (RIRs) and Rietveld refinement. The RIR of a mineral (or mineraloid) that relates the scattering power of that mineral (typically the most intense diffraction line) to the scattering power of a separate mineral standard such as corundum [2]. RIRs can be calculated from XRD patterns measured in the laboratory by mixing a mineral with a standard in known abundances and comparing diffraction line intensities of the mineral to the standard. X-ray amorphous phases (e.g., nanophase weathering products) have broad scattering signatures rather than sharp diffraction lines. Thus, RIRs of X-ray amorphous materials are calculated by comparing the area under one of these broad scattering signals with the area under a diffraction line in the standard. Here, we measured XRD patterns of nanophase weathering products (allophane, aluminosilicate gel, and ferrihydrite) mixed with a mineral standard (beryl) in the CheMinIV laboratory instrument and calculated their RIRs to help constrain the abundances of these phases in the Rocknest samples

The Amorphous Component in Martian Basaltic Soil in Global Perspective from MSL and MER Missions

The mineralogy instrument CheMin onboard the MSL rover Curiosity analyzed by transmission XRD [1] the <150 microns size fraction of putative global basaltic martian soil from scoops 4 and 5 of the Rocknest aeolian bedform (sol 81-120). Here, we combine chemical (APXS) and mineralogical (Mossbauer; MB) results from the MER rovers with chemical (APXS) and mineralogical (CheMin) results from Curiosity to constrain the relative proportions of amorphous and crystalline components, the bulk chemical composition of those components, and th

Crystal and melt inclusion timescales reveal the evolution of magma migration before eruption

Volatile element concentrations measured in melt inclusions are a key tool used to understand magma migration and degassing, although their original values may be affected by different re-equilibration processes. Additionally, the inclusion-bearing crystals can have a wide range of origins and ages, further complicating the interpretation of magmatic processes. To clarify some of these issues, here we combined olivine diffusion chronometry and melt inclusion data from the 2008 eruption of Llaima volcano (Chile). We found that magma intrusion occurred about 4 years before the eruption at a minimum depth of approximately 8 km. Magma migration and reaction became shallower with time, and about 6 months before the eruption magma reached 3–4 km depth. This can be linked to reported seismicity and ash emissions. Although some ambiguities of interpretation still remain, crystal zoning and melt inclusion studies allow a more complete understanding of magma ascent, degassing, and volcano monitoring data.NRF (Natl Research Foundation, S’pore)MOE (Min. of Education, S’pore)Published versio

Mineralogy and Elemental Composition of Wind Drift Soil at Rocknest, Gale Crater

The Mars Science Laboratory rover Curiosity has been exploring Mars since August 5, 2012, conducting engineering and first-time activities with its mobility system, arm, sample acquisition and processing system (SA/SPaH-CHIMRA) and science instruments. Curiosity spent 54 sols at a location named "Rocknest," collecting and processing five scoops of loose, unconsolidated materials ("soil") acquired from an aeolian bedform (Fig. 1). The Chemistry and Mineralogy (CheMin) instrument analyzed portions of scoops 3, 4, and 5, to obtain the first quantitative mineralogical analysis of Mars soil, and to provide context for Sample Analysis at Mars (SAM) measurements of volatiles, isotopes and possible organic materials

First X-Ray Diffraction Results from Mars Science Laboratory: Mineralogy of Rocknest Aeolian Bedform at Gale Crater

Numerous orbital and landed observations of the martian surface suggest a reasonably uniform martian soil composition, likely as a result of global aeolian mixing [1, 2]. Chemical data for martian soils are abundant [e.g., 2, 3], and phase information has been provided by lander thermal emission and Moessbauer spectroscopic measurements [3, 4, 5, 6]. However, until now no X-ray diffraction (XRD) data were available for martian soil nor has XRD ever been used on another body apart from Earth. XRD is generally considered the most definitive method for determining the crystalline phases in solid samples, and it is the method of choice for determining mineralogy. CheMin s first XRD analysis on Mars coincided with the 100th anniversary of the discovery of X-ray diffraction by von Laue. Curiosity delivered scooped samples of loose, unconsolidated material ("soil") acquired from an aeolian bedform at the Rocknest locality to instruments in the body of the rover (the laboratory). Imaging shows that the soil has a range of particle sizes, of 1-2 mm and smaller, presumably representing contributions from global, regional, and local sources

Confidence Hills Mineralogy and Chemin Results from Base of Mt. Sharp, Pahrump Hills, Gale Crater, Mars

The Mars Science Laboratory (MSL) rover Curiosity recently completed its fourth drill sampling of sediments on Mars. The Confidence Hills (CH) sample was drilled from a rock located in the Pahrump Hills region at the base of Mt. Sharp in Gale Crater. The CheMin X-ray diffractometer completed five nights of analysis on the sample, more than previously executed for a drill sample, and the data have been analyzed using Rietveld refinement and full-pattern fitting to determine quantitative mineralogy. Confidence Hills mineralogy has several important characteristics: 1) abundant hematite and lesser magnetite; 2) a 10 angstrom phyllosilicate; 3) multiple feldspars including plagioclase and alkali feldspar; 4) mafic silicates including forsterite, orthopyroxene, and two types of clinopyroxene (Ca-rich and Ca-poor), consistent with a basaltic source; and 5) minor contributions from sulfur-bearing species including jarosite

Visualisation of Integrated Patient-Centric Data as Pathways: Enhancing Electronic Medical Records in Clinical Practice

Routinely collected data in hospital Electronic Medical Records (EMR) is rich and abundant but often not linked or analysed for purposes other than direct patient care. We have created a methodology to integrate patient-centric data from different EMR systems into clinical pathways that represent the history of all patient interactions with the hospital during the course of a disease and beyond. In this paper, the literature in the area of data visualisation in healthcare is reviewed and a method for visualising the journeys that patients take through care is discussed. Examples of the hidden knowledge that could be discovered using this approach are explored and the main application areas of visualisation tools are identified. This paper also highlights the challenges of collecting and analysing such data and making the visualisations extensively used in the medical domain. This paper starts by presenting the state-of-the-art in visualisation of clinical and other health related data. Then, it describes an example clinical problem and discusses the visualisation tools and techniques created for the utilisation of these data by clinicians and researchers. Finally, we look at the open problems in this area of research and discuss future challenges