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At least 217 records · Page 12

Synthesis, Structure, Characterization, and Decomposition of Nickel Dithiocarbamates: Effect of Precursor Structure and Processing Conditions on Solid-State Products

Single-crystal X-ray structures of four nickel dithiocarbamate complexes, the homoleptic mixed-organic bis-dithiocarbamates Ni[S2CN(isopropyl)(benzyl)]2, Ni[S2CN(ethyl)(n-butyl)]2, and Ni[S2CN(phenyl)(benzyl)]2, as well as the heteroleptic mixed-ligand complex NiCl[P(phenyl)3][(S2CN(phenyl)(benzyl)], were determined. Synthetic, spectroscopic, structural, thermal, and sulfide materials studies are discussed in light of prior literature. The spectroscopic results are routine. A slightly distorted square-planar nickel coordination environment was observed for all four complexes. The organic residues adopt conformations to minimize steric interactions. Steric effects also may determine puckering, if any, about the nickel and nitrogen atoms, both of which are planar or nearly so. A trans-influence affects the Ni-S bond distances. Nitrogen atoms interact with the CS2 carbons with a bond order of about 1.5, and the other substituents on nitrogen display transoid conformations. There are no strong intermolecular interactions, consistent with prior observations of the volatility of nickel dithiocarbamate complexes. Thermogravimetric analysis of the homoleptic species under inert atmosphere is consistent with production of 1:1 nickel sulfide phases. Thermolysis of nickel dithiocarbamates under flowing nitrogen produced hexagonal or -NiS as the major phase; thermolysis under flowing forming gas produced millerite (-NiS) at 300 C, godlevskite (Ni9S8) at 325 and 350 C, and heazlewoodite (Ni3S2) at 400 and 450 C. Failure to exclude oxygen results in production of nickel oxide. Nickel sulfide phases produced seem to be primarily influenced by processing conditions, in agreement with prior literature. Nickel dithiocarbamate complexes demonstrate significant promise to serve as single-source precursors to nickel sulfides, a quite interesting family of materials with numerous potential applications.

microscopy↗

Bessel Tube to Capture Lunar Volatiles

Current arts to create linear motion or acceleration of fine particles and molecules into devices such as mass spectrometers and vacuum pumps rely on the pressure difference created by a pinhole or mechanical processes. However, in an environment of vacuum, these approaches do not create such a pressure differential to drive and move fine particles and molecules. In some cases, electrostatic or magnetic processes may work to create the desired motion. A cylindrical harmonic of electric field, which is widely used in electron accelerators, offers a unique capability to capture and induce a linear motion of molecules and particles when electrically charged. Generally, lunar volatiles are electrostatically charged. The idea to capture and collect the lunar volatiles by creating a drift axis of motion using a cylindrical harmonic field has led to the development of a device concept, called a Bessel Tube. The Bessel Tube concept ingests fine particles, gaseous atoms, and gaseous molecules and guides them along an extraction tube for collection, separation, and analysis. The Bessel Tube concept for lunar volatile collection is discussed.

Bessel Tube↗

Development of a sparging technique for volatile emissions from potato (Solanum tuberosum)

Accumulation of volatile emissions from plants grown in tightly closed growth chambers may have allelopathic or phytotoxic properties. Whole air analysis of a closed chamber includes both biotic and abiotic volatile emissions. A method for characterization and quantification of biogenic emissions solely from plantlets was developed to investigate this complex mixture of volatile organic compounds. Volatile organic compounds from potato (Solanum tuberosum L. cv. Norland) were isolated, separated and identified using an in-line configuration consisting of a purge and trap concentrator with sparging vessels coupled to a GC/MS system. Analyses identified plant volatile compounds: transcaryophyllene, alpha-humulene, thiobismethane, hexanal, cis-3-hexen-1-ol, and cis-3-hexenyl acetate.

Berdis, Elizabeth↗

A Chemical Containment Model for the General Purpose Work Station

Contamination control is a critical safety requirement imposed on experiments flying on board the Spacelab. The General Purpose Work Station, a Spacelab support facility used for life sciences space flight experiments, is designed to remove volatile compounds from its internal airpath and thereby minimize contamination of the Spacelab. This is accomplished through the use of a large, multi-stage filter known as the Trace Contaminant Control System. Many experiments planned for the Spacelab require the use of toxic, volatile fixatives in order to preserve specimens prior to postflight analysis. The NASA-Ames Research Center SLS-2 payload, in particular, necessitated the use of several toxic, volatile compounds in order to accomplish the many inflight experiment objectives of this mission. A model was developed based on earlier theories and calculations which provides conservative predictions of the resultant concentrations of these compounds given various spill scenarios. This paper describes the development and application of this model.

Flippen, Alexis A.↗

Trade can buffer climate-induced risks and volatilities in crop supply

Climate change is intensifying the frequency and severity of extreme events, posing challenges to food security. Corn, a staple crop for billions, is particularly vulnerable to heat stress, a primary driver of yield variability. While many studies have examined climate impact on average corn yields, little attention has been given to the climate impact on production volatility. This study investigates the future volatility and risks associated with global corn supply under climate change, evaluating the potential benefits of two key adaptation strategies: irrigation and market integration. A statistical model is employed to estimate corn yield response to heat stress and utilize NEX-GDDP-CMIP6 climate data to project future production volatility and risks of substantial yield losses. Three metrics are introduced to quantify these risks: Sigma (σ), the standard deviation of year-on-year yield change, which reflects overall yield volatility; Rho (ρ), the risk of substantial loss, defined as the probability of yield falling below a critical threshold; and Beta (β), a relative risk coefficient that captures the volatility of a region's corn production compared to the globally integrated market. The analysis reveals a concerning trend of increasing year-on-year yield volatility (σ) across most regions and climate models. This volatility increase is significant for key corn-producing regions like Brazil and the United States. While irrigated corn production exhibits a smaller rise in volatility, suggesting irrigation as a potential buffer against climate change impacts, it is not a sustainable option as it can cause groundwater depletion. On the other hand, global market integration reduces overall volatility and market risks significantly with less sustainability concerns. Furthermore, these findings highlight the importance of a multidimensional approach to adaptation in the food sector. While irrigation can benefit individual farmers, promoting global market integration offers a broader solution for fostering resilience and sustainability across the entire food system.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Overview of NASA's RESOURCE (Resource Exploration and Science of OUR Cosmic Environment) Project

The RESOURCE(Resource Exploration and Science of OUR Cosmic Environment) project is supported by NASA’s SSERVI (Solar System Exploration Research Virtual Institute) and is led by Principal Investigator (PI) Dr. Jennifer L. Heldmann and Deputy PIs Dr. Matthew Deans and Dr. Alexander Sehlke at NASA Ames Research Center. RESOURCE is focused on enabling In Situ Resource Utilization (ISRU) near the sites of robotic and/or human missions to enable sustainable and affordable exploration of the Moon and near-Earth objects (NEOs). This year RESOURCE has supported the development of a summary of the current state of knowledge regarding lunar polar volatiles as well as a comprehensive catalog and analysis of NEOs. RESOURCE is developing advanced mission capabilities to enable rapid, collaborative operations for lunar resource exploration missions. Hardware testing has been conducted to evaluate potential contaminants released during lunar polar regolith heating. Volatiles and particulates are the two sources of contamination that will affect the requirements of a water cleanup system, and RESOURCE research has identified the requirement for filtration prior to electrolysis for ISRU. RESOURCE also supports development of next-generation planetary drilling systems with integrated instrumentation within the drill. RESOURCE is also deeply committed to sustained efforts to engage educators, students, and broadening participation among under represented groups, and has partnered with Howard University in Washington, DC to foster minoritized students’ interest in STEAMD (science, technology, engineering, arts, math, design) careers through direct and virtual experiences with NASA Subject Matter Experts.

Jennifer L Heldmann↗

El Chichon - Composition of plume gases and particles

Aircraft measurements were made of trace gases, atmospheric particles, and condensed acid volatiles in the plume of El Chichon volcano, Chiapas, Mexico, in November 1982. Hydrogen sulfide was the primary gaseous sulfur species in the plume at the time of collection. Concentrations of 28 elements were determined by neutron activation analysis of particulate material from the plume. The volatile elements sulfur, chlorine, arsenic, selenium, bromine, antimony, iodine, tungsten, and mercury were enriched relative to bulk pyroclastic material by factors of 60 to 20,000. Arsenic, antimony, and selenium were associated predominantly with small (not greater than 3 micrometer) particles. Calcium and sodium were present almost exclusively on larger particles and aluminum and manganese were bimodally distributed. Ashladen particulate material injected into the stratosphere during the early violent eruptions was enriched by factors of 10 to 30 relative to ash in some of the same elements observed in the quiescent plume.

Kotra, J. P.↗

Assessing the drivers of Isoprene SOA: laboratory studies, field observations and modeling (Final Technical Report)

This report describes the research results and products stemming from the funding award DE-SC0018221. The main goals of this project were to develop a quantitative understanding of the factors driving secondary organic aerosol (SOA) formation from biogenic volatile organic compounds, namely isoprene and monoterpenes, using a combination of laboratory measurements, field data analysis, and modeling. Specifically, we aimed to: 1) develop an observationally constrained volatility distribution of trace gases produced from the oxidation of biogenic hydrocarbons that can explain the formation of SOA from in situ observations made during DOE ASR/ARM field campaigns such as HI-SCALE and BAECC 2) use new and existing (e.g. DOE ASR funded SOAFFEE experiments) laboratory chamber experiments to develop detailed parameterizations of isoprene-derived epxoy diol (IEPOX) reactive uptake, including product branching, product volatility, and solubility constants, as well as SOA formation generally from the formation of highly oxygenated organic molecules (HOM) formed from isoprene and monoterpene photo-oxidation that can be directly incorporated into models. 3) collaborate with PNNL modeling teams to incorporate new parameterizations into detailed box models, such as MOSAIC, and regional or Earth System models such as WRF.

54 ENVIRONMENTAL SCIENCES↗

Evolved Gas Analyses of Mudstones from the Vera Rubin Ridge

The Sample Analysis at Mars (SAM) instrument suite on the Mars Science Laboratory (MSL) rover has been essential in understanding volatile-bearing phases in Gale Crater materials. SAM’s evolved gas analysis mass spectrometry (EGA-MS) has detected H2O, CO2, O2, H2, SO2, H2S, HCl, NO, and other trace gases, including organic fragments, in many samples. The identity and evolution temperature of evolved gases can support CheMin instrument mineral detection and place constraints on trace volatile-bearing phases or phases difficult to characterize with X-ray diffraction (e.g., amorphous phases). For the past ~500 sols, MSL has been exploring the Vera Rubin Ridge (VRR), which exhibits a striking hematite signature in orbital remote sensing data, in order to understand the depositional and diagenetic history recorded in the rocks and how it relates to the underlying Murray Formation. Four rock samples were drilled, one from the Blunts Point Member (Duluth, DU), one from the Pettegrrove Point Member (Stoer, ST), and two from the Jura Member. The Jura Member displays differences in color, summarized as grey and red, and a key goal was to constrain the cause of this color difference and the associated implications for depositional or post-depositional conditions. To investigate, a grey (Highfield, HF) and a red (Rock Hall, RH) Jura sample were drilled. Here we will give an overview of results from SAM EGA-MS analyses of VRR materials, with some comparisons to analyses of samples of the underlying Murray.

McAdam, A. C.↗

Characterization of microbial and chemical composition of shuttle wet waste with permanent gas and volatile organic compound analyses

Solid-waste treatment in space for Advanced Life Support, ALS, applications requires that the material can be safely processed and stored in a confined environment. Many solid-wastes are not stable because they are wet (40-90% moisture) and contain levels of soluble organic compounds that can contribute to the growth of undesirable microorganisms with concomitant production of noxious odors. In the absence of integrated Advanced Life Support systems on orbit, permanent gas, trace volatile organic and microbiological analyses were performed on crew refuse returned from the volume F "wet" trash of three consecutive Shuttle missions (STS-105, 109, and 110). These analyses were designed to characterize the short-term biological stability of the material and assess potential crew risks resulting from microbial decay processes during storage. Waste samples were collected post-orbiter landing and sorted into packaging material, food waste, toilet waste, and bulk liquid fractions deposited during flight in the volume F container. Aerobic and anaerobic microbial loads were determined in each fraction by cultivation on R2A and by acridine orange direct count (AODC). Dry and ash weights were performed to determine both water and organic content of the materials. Experiments to determine the aerobic and anaerobic biostability of refuse stored for varying periods of time were performed by on-line monitoring of CO2 and laboratory analysis for production of hydrogen sulfide and methane. Volatile organic compounds and permanent gases were analyzed using EPA Method TO15 by USEPA et al. [EPA Method TO15, The Determination of Volatile Organic Compounds (VOCs) in Ambient Air using SUMMA, Passivated Canister Sampling and Gas Chromatographic Analysis,1999] with gas chromatography/mass spectrometry and by gas chromatography with selective detectors. These baseline measures of waste stream content, labile organics, and microbial load in the volume F Shuttle trash provide data for waste subsystem analysis and atmospheric management within the ALS Project. Published by Elsevier Ltd on behalf of COSPAR.

NASA Center KSC↗

Origin of Chlorobenzene Detected by the Curiosity Rover in Yellowknife Bay: Evidence for Martian Organics in the Sheepbed Mudstone

The Sample Analysis at Mars (SAM) instrument on the Curiosity rover is designed to determine the inventory of organic and inorganic volatiles thermally evolved from solid samples using a combination of evolved gas analysis (EGA), gas chromatography mass spectrometry (GCMS), and tunable laser spectroscopy. Here we discuss the SAM EGA and GCMS measurements of volatiles released from the Sheepbed mudstone. We focus primarily on the elevated CBZ detections at CB and laboratory analog experiments conducted to help determine if CBZ is derived from primarily terrestrial, martian, or a combination of sources. Here we discuss the SAM EGA and GCMS measurements of volatiles released from the Sheepbed mudstone. We focus primarily on the elevated CBZ detections at CB and laboratory analog experiments conducted to help determine if CBZ is derived from primarily terrestrial, martian, or a combination of sources.

Glavin, D.↗

Volatile Detections in Gale Crater Sediment and Sedimentary Rock: Results from the Mars Science Laboratory's Sample Analysis at Mars Instrument

This chapter discusses the detection of evolved gases from Gale crater sedimentary rock and eolian sediment by the Mars Science Laboratory rover's Sample Analysis at Mars (SAM) instrument. An overview is presented of the SAM instrument along with summary of key results from previous evolved gas analyses conducted at the Viking and Phoenix landing sites. The SAM measurements of evolved water, sulfur dioxide, carbon dioxide, carbon monoxide, oxygen, and nitrous oxide from Gale crater samples are presented. The phases responsible for the evolved gas detections and the implications for their presence are then evaluated. The water deuterium to hydrogen (D/H) ratio is discussed in context of understanding the degree of water loss from Mars. In the introduction of this book, we briefly explored the history of the exploration of Mars, where we discussed a major shift in the scientific thinking and public perception of the nature of the surface of Mars as new missions explored the Red Planet. The first observations of the surface sparked speculations of Mars being inhabited by intelligent beings, inspiring fantasy, science fiction, and, of course, further exploration. The turn came when Mariner 4 returned images of a lunar-like landscape, a monotonous basaltic world with many impact craters but no water, and therefore no prospects for life to find a habitable niche. The authors of the chapters of this book show how different our understanding of Mars is today from the historical Mariner 4 perspective!

Sutter, Brad↗

H-chondrites - Trace element clues to their origin

RNAA is used to determine the abundances of 20 trace elements in four H4, two H3, two H5, and two H6 chondrites from the British Museum, as a contribution to a multiple-method study of these objects. The results are presented in tables and graphs and analyzed in terms of the inhomogeneity of the parent bodies and the depletion of volatiles in the higher petrologic types. Features observed include siderophile depletion in H3 chondrites; systematic variation of siderophile abundance pattern with petrologic type; volatile depletion as a primary feature; mineralogy consistent with accretion at 420-500 K; and the factor-analysis groupings siderophiles (Os, Re, Ir, Ni, Pd, Au, and Ge), volatiles (Ag, Br, In, Cd, Bi, and Tl), and alkalis (Rb and Cs).

Morgan, J. W.↗

Microwave spectra of some volatile organic compounds

A computer-controlled microwave (MRR) spectrometer was used to catalog reference spectra for chemical analysis. Tables of absorption frequency, peak absorption intensity, and integrated intensity are included for 26 volatile organic compounds, all but one of which contain oxygen.

White, W. F.↗

Vapor-Phase Heteroatom Incorporation into Semiconductive Molecular-Scale Magic-Size Clusters

Magic-size metal chalcogenide clusters of molecular size exhibit well-defined structure and unique properties that might be further expanded with the incorporation or substitution of a second metal. Here, we report the postmodification of magic-size clusters synthesized in polymer thin films via exposure to volatile metal organic precursors commonly utilized for atomic layer deposition. Exposure of In 6 S 6 (CH 3 ) 6 clusters to dimethylcadmium results in exposure-dependent incorporation of Cd 2+ , which extends the optical absorbance of the clusters into the visible spectrum. The mechanism for Cd 2+ incorporation is consistent with Cd 2+ replacement of In 3+ that includes methyl ligand removal to maintain charge neutrality. Even for clusters embedded in a polymer matrix, ligand loss leads to sintering and transformation into larger nanoscale aggregates with zinc blende-type structure. The extent of Cd incorporation can be modulated by varying the process temperature and volatile metal organic exposure as well as the choice of volatile metal organic precursor. A computational thermodynamic analysis of heteroatom incorporation for several metals and chemistries reveals that both the stability of the substituted cluster and the favorability of reaction byproducts jointly determine the favorability of cation incorporation.

atomic layer deposition↗

Solid-Sorbent Air Sampler

Portable unit takes eight 24-hour samples. Volatile organic compounds in air collected for analysis by portable, self-contained sampling apparatus. Sampled air drawn through sorbent material, commercial porous polymer of 2, 3-diphenyl-p-phenylene oxide. High-boiling-point organic compounds adsorbed onto polymer, while low-boiling-point organics pass through and returned to atmosphere. Sampler includes eight sample tubes filled with polymeric sorbent. Organic compounds in atmosphere absorbed when air pumped through sorbent. Designed for checking air in spacecraft, sampler adaptable to other applications as leak detection, gas-mixture analysis, and ambient-air monitoring.

Galen, T. J.↗