The bulk composition of Mars Taylor, G. Jeffrey
Chemie der Erde,
12/2013, Letnik:
73, Številka:
4
Journal Article
Recenzirano
An accurate assessment of the bulk chemical composition of Mars is fundamental to understanding planetary accretion, differentiation, mantle evolution, the nature of the igneous parent rocks that ...were altered to produce sediments on Mars, and the initial concentrations of volatiles such as H, Cl and S, important constituents of the Martian surface. This paper reviews the three main approaches that have been used to estimate the bulk chemical composition of Mars: geochemical/cosmochemical, isotopic, and geophysical. The standard model is one developed by Wänke and Dreibus in a series of papers, which is based on compositions of Martian meteorites. Since their groundbreaking work, substantial amounts of data have become available to allow a reassessment of the composition of Mars from elemental data, including tests of the basic assumptions in the geochemical models. The results adjust some of the concentrations in the Wänke–Dreibus model, but in general confirm its accuracy. Bulk silicate Mars has roughly uniform depletion of moderately volatile elements such as K (0.6×CI), and strong depletion of highly volatile elements (e.g., Tl). The highly volatile elements are within uncertainties uniformly depleted at about 0.06 CI abundances. The highly volatile chalcophile elements are likewise roughly uniformly depleted, but with more scatter, with normalized abundances of 0.03 CI. Bulk planetary H2O is much higher than estimated previously: it appears to be slightly less than in Earth, but D/H is similar in Earth and Mars, indicating a common source of water-bearing material in the inner solar system. K/Th ranges from ∼3000 to ∼5000 among the terrestrial planets, a small range compared to CI chondrites (19,000). FeO varies throughout the inner solar system: ∼3wt% in Mercury, 8wt% in Earth and Venus, and 18wt% in Mars. These differences can be produced by varying oxidation conditions, hence do not suggest the terrestrial planets were formed from fundamentally different materials. The broad chemical similarities among the terrestrial planets indicate substantial mixing throughout the inner solar system during planet formation, as suggested by dynamical models.
Pneumothorax can precipitate a life-threatening emergency due to lung collapse and respiratory or circulatory distress. Pneumothorax is typically detected on chest X-ray; however, treatment is ...reliant on timely review of radiographs. Since current imaging volumes may result in long worklists of radiographs awaiting review, an automated method of prioritizing X-rays with pneumothorax may reduce time to treatment. Our objective was to create a large human-annotated dataset of chest X-rays containing pneumothorax and to train deep convolutional networks to screen for potentially emergent moderate or large pneumothorax at the time of image acquisition.
In all, 13,292 frontal chest X-rays (3,107 with pneumothorax) were visually annotated by radiologists. This dataset was used to train and evaluate multiple network architectures. Images showing large- or moderate-sized pneumothorax were considered positive, and those with trace or no pneumothorax were considered negative. Images showing small pneumothorax were excluded from training. Using an internal validation set (n = 1,993), we selected the 2 top-performing models; these models were then evaluated on a held-out internal test set based on area under the receiver operating characteristic curve (AUC), sensitivity, specificity, and positive predictive value (PPV). The final internal test was performed initially on a subset with small pneumothorax excluded (as in training; n = 1,701), then on the full test set (n = 1,990), with small pneumothorax included as positive. External evaluation was performed using the National Institutes of Health (NIH) ChestX-ray14 set, a public dataset labeled for chest pathology based on text reports. All images labeled with pneumothorax were considered positive, because the NIH set does not classify pneumothorax by size. In internal testing, our "high sensitivity model" produced a sensitivity of 0.84 (95% CI 0.78-0.90), specificity of 0.90 (95% CI 0.89-0.92), and AUC of 0.94 for the test subset with small pneumothorax excluded. Our "high specificity model" showed sensitivity of 0.80 (95% CI 0.72-0.86), specificity of 0.97 (95% CI 0.96-0.98), and AUC of 0.96 for this set. PPVs were 0.45 (95% CI 0.39-0.51) and 0.71 (95% CI 0.63-0.77), respectively. Internal testing on the full set showed expected decreased performance (sensitivity 0.55, specificity 0.90, and AUC 0.82 for high sensitivity model and sensitivity 0.45, specificity 0.97, and AUC 0.86 for high specificity model). External testing using the NIH dataset showed some further performance decline (sensitivity 0.28-0.49, specificity 0.85-0.97, and AUC 0.75 for both). Due to labeling differences between internal and external datasets, these findings represent a preliminary step towards external validation.
We trained automated classifiers to detect moderate and large pneumothorax in frontal chest X-rays at high levels of performance on held-out test data. These models may provide a high specificity screening solution to detect moderate or large pneumothorax on images collected when human review might be delayed, such as overnight. They are not intended for unsupervised diagnosis of all pneumothoraces, as many small pneumothoraces (and some larger ones) are not detected by the algorithm. Implementation studies are warranted to develop appropriate, effective clinician alerts for the potentially critical finding of pneumothorax, and to assess their impact on reducing time to treatment.
The advent of digital signal processing (DSP) to optical coherent detection means that more phase estimation options are available, compared to the earlier generation where phase-locked loops (PLLs) ...were invariably deployed in synchronous coherent receivers. Several phase estimation methods are numerically modeled: the maximum a posteriori (MAP) phase estimate, decision directed estimate, power law-Wiener filter estimate and power law-PLL estimate. An asynchronous coherent detection case is also modeled. The phase estimates are evaluated with respect to their tolerance of finite laser linewidth and their suitability for implementation in a parallel digital processor. Laser phase noise causes transmission system performance to be degraded by excess bit errors and cycle slips. The optimal phase estimate is the MAP estimate, and it is also included as a baseline. The power law-Wiener filter phase estimate is found to perform only marginally worse than the MAP estimate. It must be recast using a look-ahead computation to be implemented in a parallel digital processor, and the impact is investigated of the increase in the number of computations required. Differential logical detection is often used to reduce the impact of cycle slip events, and the implications of this operation on the bit error rate are studied. It is found that by choosing the correct FEC scheme differential logical detection does not increase the Q-factor penalty.
Despite the great advances in synthesis and structural determination of atomically precise, thiolate-protected metal nanoclusters, our understanding of the driving forces for their colloidal ...stabilization is very limited. Currently there is a lack of models able to describe the thermodynamic stability of these 'magic-number' colloidal nanoclusters as a function of their atomic-level structural characteristics. Herein, we introduce the thermodynamic stability theory, derived from first principles, which is able to address stability of thiolate-protected metal nanoclusters as a function of the number of metal core atoms and thiolates on the nanocluster shell. Surprisingly, we reveal a fine energy balance between the core cohesive energy and the shell-to-core binding energy that appears to drive nanocluster stabilization. Our theory applies to both charged and neutral systems and captures a large number of experimental observations. Importantly, it opens new avenues for accelerating the discovery of stable, atomically precise, colloidal metal nanoclusters.
Transition-metal complexes are attractive targets for the design of catalysts and functional materials. The behavior of the metal–organic bond, while very tunable for achieving target properties, is ...challenging to predict and necessitates searching a wide and complex space to identify needles in haystacks for target applications. This review will focus on the techniques that make high-throughput search of transition-metal chemical space feasible for the discovery of complexes with desirable properties. The review will cover the development, promise, and limitations of “traditional” computational chemistry (i.e., force field, semiempirical, and density functional theory methods) as it pertains to data generation for inorganic molecular discovery. The review will also discuss the opportunities and limitations in leveraging experimental data sources. We will focus on how advances in statistical modeling, artificial intelligence, multiobjective optimization, and automation accelerate discovery of lead compounds and design rules. The overall objective of this review is to showcase how bringing together advances from diverse areas of computational chemistry and computer science have enabled the rapid uncovering of structure–property relationships in transition-metal chemistry. We aim to highlight how unique considerations in motifs of metal–organic bonding (e.g., variable spin and oxidation state, and bonding strength/nature) set them and their discovery apart from more commonly considered organic molecules. We will also highlight how uncertainty and relative data scarcity in transition-metal chemistry motivate specific developments in machine learning representations, model training, and in computational chemistry. Finally, we will conclude with an outlook of areas of opportunity for the accelerated discovery of transition-metal complexes.
Glioblastoma multiforme (GBM) is the most common and aggressive malignant primary brain tumour in humans and has a very poor prognosis. The existing treatments have had limited success in increasing ...overall survival. Thus, identifying and understanding the key molecule(s) responsible for the malignant phenotype of GBM will yield new potential therapeutic targets. The treatment of brain tumours faces unique challenges, including the presence of the blood brain barrier (BBB), which limits the concentration of drugs that can reach the site of the tumour. Nevertheless, several promising treatments have been shown to cross the BBB and have shown promising pre-clinical results. This review will outline the status of several of these promising targeted therapies.
Purpose
– Mobile applications, or apps, are an increasingly important part of omnichannel retailing. While the adoption and usage of apps for marketing purposes has grown exponentially over the past ...few years, there is little academic research in this area. The purpose of this paper is to examine how the mobile phone platform (Android vs Apple iOS), interest in the app and recency of store visit affect consumers’ likelihood to use the apps for purchasing and information-sharing activities.
Design/methodology/approach
– The paper tests a model by analysing survey data collected from customers of a major US retailer using partial least squares regression.
Findings
– The analysis finds that the level of interest in a retail app is positively related to the consumer's intention to engage in both purchasing and information-sharing activities. In addition, the recency of the consumer's last visit to the retail store has a moderating effect on both types of activities; the more recent the last visit, the larger the effect-size of interest in the app on intention to share information and make a purchase.
Practical implications
– While marketing and advertising managers may have suspected that Apple iOS users are more receptive to retail mobile apps, this study provides empirical support for the proposition. In addition, the moderating effect of recency of visit suggests that in-store promotions may be effective in increasing usage of the retailer's mobile apps.
Originality/value
– This study is among the first in the academic literature to examine predictors of mobile app usage for purchasing and information sharing. It fills a gap in the literature, while at the same time providing actionable information for practitioners.
Abstract
The ESA Rosetta spacecraft followed comet 67P at a close distance for more than 2 yr. In addition, it deployed the lander Philae on to the surface of the comet. The (surface) composition of ...the comet is of great interest to understand the origin and evolution of comets. By combining measurements made on the comet itself and in the coma, we probe the nature of this surface material and compare it to remote sensing observations. We compare data from the double focusing mass spectrometer (DFMS) of the ROSINA experiment on ESA's Rosetta mission and previously published data from the two mass spectrometers COSAC (COmetary Sampling And Composition) and Ptolemy on the lander. The mass spectra of all three instruments show very similar patterns of mainly CHO-bearing molecules that sublimate at temperatures of 275 K. The DFMS data also show a great variety of CH-, CHN-, CHS-, CHO2- and CHNO-bearing saturated and unsaturated species. Methyl isocyanate, propanal and glycol aldehyde suggested by the earlier analysis of the measured COSAC spectrum could not be confirmed. The presence of polyoxymethylene in the Ptolemy spectrum was found to be unlikely. However, the signature of the aromatic compound toluene was identified in DFMS and Ptolemy data. Comparison with remote sensing instruments confirms the complex nature of the organics on the surface of 67P, which is much more diverse than anticipated.
The Kemp elimination (reaction of benzisoxazole with base to give 2-cyanophenolate) is catalyzed in the cavity of a cubic M8L12 coordination cage because of a combination of (i) benzisoxazole ...binding in the cage cavity driven by the hydrophobic effect, and (ii) accumulation of hydroxide ions around the 16+ cage surface driven by ion-pairing. Here we show how reaction of the cavity-bound guest is modified by the presence of other anions which can also accumulate around the cage surface and displace hydroxide, inhibiting catalysis of the cage-based reaction. Addition of chloride or fluoride inhibits the reaction with hydroxide to the extent that a new autocatalytic pathway becomes apparent, resulting in a sigmoidal reaction profile. In this pathway the product 2-cyanophenolate itself accumulates around the cationic cage surface, acting as the base for the next reaction cycle. The affinity of different anions for the cage surface is therefore 2-cyanophenolate (generating autocatalysis) > chloride > fluoride (which both inhibit the reaction with hydroxide but cannot deprotonate the benzisoxazole guest) > hydroxide (default reaction pathway). The presence of this autocatalytic pathway demonstrates that a reaction of a cavity-bound guest can be induced with different anions around the cage surface in a controllable way; this was confirmed by adding different phenolates to the reaction, which accelerate the Kemp elimination to different extents depending on their basicity. This represents a significant step toward the goal of using the cage as a catalyst for bimolecular reactions between a cavity-bound guest and anions accumulated around the surface.
Dependence upon groundwater to meet rising agricultural and domestic water needs is expected to increase substantially across the tropics where, by 2050, over half of the world's population is ...projected to live. Rare, long-term groundwater-level records in the tropics indicate that groundwater recharge occurs disproportionately from heavy rainfalls exceeding a threshold. The ubiquity of this bias in tropical groundwater recharge to intensive precipitation is, however, unknown. By relating available long-term records of stable-isotope ratios of O and H in tropical precipitation (15 sites) to those of local groundwater, we reveal that groundwater recharge in the tropics is near-uniformly (14 15 sites) biased to intensive monthly rainfall, commonly exceeding the ∼70th intensity decile. Our results suggest that the intensification of precipitation brought about by global warming favours groundwater replenishment in the tropics. Nevertheless, the processes that transmit intensive rainfall to groundwater systems and enhance the resilience of tropical groundwater storage in a warming world, remain unclear.
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