Instrument for Analysis of Organic Compounds on Other Planets

The goal of this project is to develop the Instrument for Solvent Extraction and Analysis of Extraterrestrial Bodies using In Situ Resources (ISEE). Specifically, ISEE will extract and characterize organic compounds from regolith which is found on the surface of other planets or asteroids. The techniques this instrument will use are supercritical fluid extraction (SFE) and supercritical fluid chromatography (SFC). ISEE aligns with NASA's goal to expand the frontiers of knowledge, capability, and opportunities in space in addition to supporting NASA's aim to search for life elsewhere by characterizing organic compounds. The outcome of this project will be conceptual designs of 2 components of the ISEE instrument as well as the completion of proof-of-concept extraction experiments to demonstrate the capabilities of SFE. The first conceptual design is a pressure vessel to be used for the extraction of the organic compounds from the regolith. This includes a comparison of different materials, geometry's, and a proposition of how to insert the regolith into the vessel. The second conceptual design identifies commercially available fluid pumps based on the requirements needed to generate supercritical CO2. The proof-of-concept extraction results show the percent mass lost during standard solvent extractions of regolith with organic compounds. This data will be compared to SFE results to demonstrate the capabilities of ISEE's approach

Is native speaker intuition reliable for high-frequency context creation?

This study determined whether native speaker intuition could be relied upon to producecontextual content that mostly fell into what is considered high-frequency vocabulary. Native speakers wrote over 160,000 tokens worth of example sentences for high-frequency multi-word units derived from a corpus. The resulting database was examined to determine whether the content added by the native speakers mostly stayed within the high-frequency realm.Results showed that not only did the vast majority of native speakers\u27 tokens fall into the high-frequency realm, the percentage that fell into the high-frequency realm only dropped by 0.84 percent in comparison to the multi-word units alone despite the large amount of data beingadded. This study highlighted how the intuition of experienced ESL practitioners can be relied upon to produce high-frequency contextual content

Transmission electron microscopy study in-situ of radiation-induced defects in copper at elevated temperatures

Neutrons and high-energy ions incident upon a solid can initiate a displacement collision cascade of lattice atoms resulting in localized regions within the solid containing a high concentration of interstitial and vacancy point defects. These point defects can collapse into various types of dislocation loops and stacking fault tetrahedra (SFT) large enough that their lattice strain fields are visible under diffraction-contrast imaging using a Transmission Electron Microscope (TEM). The basic mechanisms driving the collapse of point defects produced in collision cascades is investigated in situ with TEM for fcc-Cu irradiated with heavy (100 keV Kr) ions at elevated temperature. The isothermal stability of these clusters is also examined in situ. Areal defect yields were observed to decrease abruptly for temperatures greater than 300 C. This decrease in defect yield is attributed to a proportional decrease in the probability of collapse of point defects into clusters. The evolution of the defect density under isothermal conditions appears to be influenced by three different rate processes active in the decline of the total defect density. These rate constants can be attributed to differences in the stability of various types of defect clusters and to different loss mechanisms. Based upon observed stabilities, estimations for the average binding enthalpies of vacancies to SFT are calculated for copper

Nutrient (C, N and P) enrichment induces significant changes in the soil metabolite profile and microbial carbon partitioning

The cycling of soil organic matter (SOM) and carbon (C) within the soil is governed by the presence of key macronutrients, particularly nitrogen (N) and phosphorus (P). The relative ratio of these nutrients has a direct effect on the potential rates of microbial growth and nutrient processing in soil and thus is fundamental to ecosystem functioning. However, the effect of changing soil nutrient stoichiometry on the small organic molecule (i.e., metabolite) composition and cycling by the microbial community remains poorly understood. Here, we aimed to disentangle the effect of stoichiometrically balanced nutrient addition on the soil metabolomic profile and apparent microbial carbon use efficiency (CUE) by adding a labile C source (glucose) in combination with N and/or P. After incorporation of the added glucose into the microbial biomass (48 h), metabolite profiling was undertaken by ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). 494 metabolites were identified across all treatments mainly consisting of lipids (n = 199), amino acids (n = 118) and carbohydrates (n = 43), >97% of which showed significant changes in concentration between at least one treatment. Overall, glucose-C addition generally increased the synthesis of other carbohydrates in soil, while addition of C and N together increased peptide synthesis, indicative of protein formation and turnover. The combination of C and P significantly increased the number of fatty acids synthesised. There was no significant change in the PLFA-derived microbial community structure or microbial biomass following C, N and P addition. Further, N addition led to an increase in glucose-C partitioning into anabolic processes (i.e., increased CUE), suggesting the microbial community was N, but not P limited. Based on the metabolomic profiles observed here, we conclude that inorganic nutrient enrichment causes substantial shifts in both primary and secondary metabolism within the microbial community, leading to changes in resource flow and thus soil functioning, however, the microbial community illustrated significant metabolic flexibility

Infrared Absorption Investigations Confirm the Extraterrestrial Origin of Carbonado-Diamonds

The first complete infrared FTIR absorption spectra for carbonado-diamond confirm the interstellar origin for the most enigmatic diamonds known as carbonado. All previous attempts failed to measure the absorption of carbonado-diamond in the most important IR-range of 1000-1300 cm-1 (10.00-7.69 micro-m.) because of silica inclusions. In our investigation, KBr pellets were made from crushed silica-free carbonado-diamond and thin sections were also prepared. The 100 to 1000 times brighter synchrotron infrared radiation permits a greater spatial resolution. Inclusions and pore spaces were avoided and/or sources of chemical contamination were removed. The FTIR spectra of carbonado-diamond mostly depict the presence of single nitrogen impurities, and hydrogen. The lack of identifiable nitrogen aggregates in the infrared spectra, the presence of features related to hydrocarbon stretch bonds, and the resemblance of the spectra to CVD and presolar diamonds indicate that carbonado-diamonds formed in a hydrogen-rich interstellar environment. This is consistent with carbonado-diamond being sintered and porous, with extremely reduced metals, metal alloys, carbides and nitrides, light carbon isotopes, surfaces with glassy melt-like patinas, deformation lamellae, and a complete absence of primary, terrestrial mineral inclusions. The 2.6-3.8 billion year old fragmented body was of asteroidal proportions

X-ray absorption spectroscopy systematics at the tungsten L-edge

A series of mononuclear six-coordinate tungsten compounds spanning formal oxidation states from 0 to +VI, largely in a ligand environment of inert chloride and/or phosphine, has been interrogated by tungsten L-edge X-ray absorption spectroscopy. The L-edge spectra of this compound set, comprised of [W<sup>0</sup>(PMe<sub>3</sub>)<sub>6</sub>], [W<sup>II</sup>Cl<sub>2</sub>(PMePh<sub>2</sub>)<sub>4</sub>], [W<sup>III</sup>Cl<sub>2</sub>(dppe)<sub>2</sub>][PF<sub>6</sub>] (dppe = 1,2-bis(diphenylphosphino)ethane), [W<sup>IV</sup>Cl<sub>4</sub>(PMePh<sub>2</sub>)<sub>2</sub>], [W<sup>V</sup>(NPh)Cl<sub>3</sub>(PMe<sub>3</sub>)<sub>2</sub>], and [W<sup>VI</sup>Cl<sub>6</sub>] correlate with formal oxidation state and have usefulness as references for the interpretation of the L-edge spectra of tungsten compounds with redox-active ligands and ambiguous electronic structure descriptions. The utility of these spectra arises from the combined correlation of the estimated branching ratio (EBR) of the L<sub>3,2</sub>-edges and the L<sub>1</sub> rising-edge energy with metal Z<sub>eff</sub>, thereby permitting an assessment of effective metal oxidation state. An application of these reference spectra is illustrated by their use as backdrop for the L-edge X-ray absorption spectra of [W<sup>IV</sup>(mdt)<sub>2</sub>(CO)<sub>2</sub>] and [W<sup>IV</sup>(mdt)<sub>2</sub>(CN)<sub>2</sub>]<sup>2–</sup> (mdt<sup>2–</sup> = 1,2-dimethylethene-1,2-dithiolate), which shows that both compounds are effectively W<sup>IV</sup> species. Use of metal L-edge XAS to assess a compound of uncertain formulation requires: 1) Placement of that data within the context of spectra offered by unambiguous calibrant compounds, preferably with the same coordination number and similar metal ligand distances. Such spectra assist in defining upper and/or lower limits for metal Z<sub>eff</sub> in the species of interest; 2) Evaluation of that data in conjunction with information from other physical methods, especially ligand K-edge XAS; 3) Increased care in interpretation if strong π-acceptor ligands, particularly CO, or π-donor ligands are present. The electron-withdrawing/donating nature of these ligand types, combined with relatively short metal-ligand distances, exaggerate the difference between formal oxidation state and metal Z<sub>eff</sub> or, as in the case of [W<sup>IV</sup>(mdt)<sub>2</sub>(CO)<sub>2</sub>], add other subtlety by modulating the redox level of other ligands in the coordination sphere

Photoionization of alkali and alkaline earth atoms: Na and Mg

Determinations of the photoionization cross sections of ground state magnesium atoms and excited state sodium atoms have been made over a wide wavelength range. The ground state measurement in magnesium was performed using synchrotron radiation from the uv ring at the National Synchrotron Light Source. Several autoionizing resonances were observed. The photoionization cross section of excited sodium atoms was determined by irradiating laser-produced Na(3p) with synchrotron light. In both cases, agreement with theory is excellent

Early detection and follow‐up of colorectal neoplasia based on faecal volatile organic compounds

Aim: Early detection and removal of colorectal cancer (CRC) and advanced adenomas (AAs) decreases the incidence of and mortality from the disease. We aimed to evaluate the potential of faecal volatile organic compounds (VOCs) for detection and follow‐up of colorectal adenoma using advanced electronic nose technology. Method: This was a prospective multi‐centre case–control cohort including two district hospitals and one tertiary referral hospital. Patients undergoing colonoscopy were instructed to collect a faecal sample prior to bowel cleansing and were included in the study when CRC, AAs, large adenomas (LAs; 0.5–1.0 cm), small adenomas (SAs; 0.1–0.5 cm) or no endoscopic abnormalities (controls) were observed. Patients undergoing polypectomy and controls were asked for a second sample after 3 months. Faecal VOCs were measured with gas chromatography–ion mobility spectrometry. Random forest, support vector machine, Gaussian process and neural net classification were used to evaluate accuracy. Results: In total, 14 patients with CRC, 64 with AAs, 69 with LAs, 127 with SAs and 227 controls were included. A second sample was collected from 32 polypectomy patients and 32 controls. Faecal VOCs discriminated CRC and adenomas from control [AUC (95% CI): CRC vs control 0.96 (0.89–1); AA vs control 0.96 (0.93–1); LA vs control 0.96 (0.92–0.99); SA vs control 0.96 (0.94–0.99)]. There were no significant differences between CRC and adenoma groups. Patients with adenomas and controls were discriminated prior to polypectomy, whereas 3 months after polypectomy VOC profiles were similar [T0 adenoma vs control 0.98 (0.95–1); T1 adenoma vs control 0.55 (0.40–0.69)]. Conclusions: Faecal VOC profiles may be useful for early detection of CRC and adenomas and the timing of polyp surveillance as polypectomy led to a normalization of the VOC profile

Production of dust by massive stars at high redshift

The large amounts of dust detected in sub-millimeter galaxies and quasars at high redshift pose a challenge to galaxy formation models and theories of cosmic dust formation. At z > 6 only stars of relatively high mass (> 3 Msun) are sufficiently short-lived to be potential stellar sources of dust. This review is devoted to identifying and quantifying the most important stellar channels of rapid dust formation. We ascertain the dust production efficiency of stars in the mass range 3-40 Msun using both observed and theoretical dust yields of evolved massive stars and supernovae (SNe) and provide analytical expressions for the dust production efficiencies in various scenarios. We also address the strong sensitivity of the total dust productivity to the initial mass function. From simple considerations, we find that, in the early Universe, high-mass (> 3 Msun) asymptotic giant branch stars can only be dominant dust producers if SNe generate <~ 3 x 10^-3 Msun of dust whereas SNe prevail if they are more efficient. We address the challenges in inferring dust masses and star-formation rates from observations of high-redshift galaxies. We conclude that significant SN dust production at high redshift is likely required to reproduce current dust mass estimates, possibly coupled with rapid dust grain growth in the interstellar medium.Comment: 72 pages, 9 figures, 5 tables; to be published in The Astronomy and Astrophysics Revie