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At least 793 records · Page 44

Trace Element Abundances of Olivine-Hosted Melt Inclusions in Shergottites Northwest Africa 7397 and Robert Massif 04262

Olivine-hosted melt inclusions (MIs) may retain trapped parent magma compositions as well as record progressive differentiation while magmas crystallize and ascend towards the surface [1,2 and references therein]. Major element compositions of the MIs, especially Fe and Mg, can be affected by post-entrapment re-equilibration with their host olivine [1,2]. Therefore, Fe/Mg ratio correction is required to obtain MI bulk compositions following equilibrium with their host olivine. Partition coefficients of most of the trace elements in olivine are very low (i.e. DOL/melt<0.001). Thus, ratios of trace elements of olivine-hosted MIs are unlikely to be affected by post-entrapment re-equilibration and no correction is necessary [2]. Hence, tracking trace element behavior in MIs may constrain the composition of the parent magma and its evolution yielding insights on magma differentiation of shergottites. However, analyzing MIs for chemical compositions is a challenging task due to their low abundances and small sizes. Using a highly sensitive and precise micro-beam technique is essential to examine olivine-hosted MIs in order to measure trace element abundances. For this purpose, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is an excellent tool due to its wide range of laser spot sizes (1-150 μm), ability to obtain raster analysis (several mm2) and lower detection limits (0.1 ppb) [3].

Ferdous, J.↗

Tailoring compatibilization potential of maleic anhydride–grafted polypropylene by sequential rheochemical processing of polypropylene and polyamide 66 blends

Reactive compatibilization of immiscible polymer blends using a preferred compatibilizer leaves the following question: How much loading of a compatibilizer is good enough and what maximum properties can be achieved? A good understanding of the process can help solve the reutilization of mixed waste plastics. Here, the reactive compatibilization of polypropylene-graft-maleic anhydride (PP-g-MAH) on polypropylene/polyamide 66 (PP/PA66) blends is quantitatively assessed using thermorheological, microoptical, spectroscopic, and x-ray scattering-based characterization tools. The overall compositions of all PP(60%)/PA66(30%)/PP-g-MAH(10%) blends are kept constant while systematically controlling the degree of the chemical reaction by varying the sequential addition of PP-g-MAH to the melt mixture. The first feeding of PP-g-MAH (x%, 0 ≤ x ≤ 10) is conducted at 280°C and the second feeding of (10–x)% is at 200°C. During the first step, a larger amount of chemical activity is observed up to 4%–6% addition of PP-g-MAH. Furthermore, the constant chemical composition allows a systematic comparison of the compatibilizer-dependent thermal, rheological, morphological, and mechanical properties. With an increased degree of interfacial reaction, the size of dispersed PA66 domains decreases to register improved interfacial adhesion with the PP matrix, yielding enhanced Young's modulus and absolute failure strength of the isotropic matrix.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Distinct Gas-Particle Partitioning and Viscosity Characteristics of Secondary Organic Aerosols Derived from α-Pinene versus Ocimene

Secondary organic aerosols (SOA) have complex, multicomponent composition that controls particle viscosity and gas-particle partitioning, key factors to their atmospheric evolution. This study investigates the chemical composition, volatility and viscosity of SOA formed by ozonolysis of cyclic α-pinene (PSOA) and acyclic ocimene (OSOA) monoterpenes. Using Temperature-Programmed Desorption combined with Direct Analysis in Real-Time ionization and High-Resolution Mass Spectrometry, we determined the molecular composition and saturation mass concentration of individual SOA constituents. These data enabled gas-particle partitioning and viscosity estimates under varied atmospheric conditions. PSOA, composed of higher molecular weight and less oxidized species, shows higher condensability and viscosity under high total organic mass (tOM) loadings. Here, in contrast, OSOA, consisting of more oxidized, lower molecular weight species, exhibits greater sensitivity to tOM, with viscosity increasing significantly upon dilution. Poke-flow experiments support this trend, indicating that OSOA undergoes more dynamic compositional and phase changes during atmospheric aging. These observations reveal distinct dynamic trends in the atmospheric transformations and reactivity of SOA from cyclic and acyclic monoterpenes, with the latter showing greater compositional changes during aging that alter viscosity and diffusion. This highlights the importance of incorporating such dynamic transformations into atmospheric models to improve predictions of SOA atmospheric loadings, lifetimes, and impacts.

cyclic and acyclic monoterpenes↗

Engineering Novosphingobium aromaticivorans to produce cis,cis -muconic acid from biomass aromatics

ABSTRACT The platform chemical cis,cis- muconic acid ( cc MA) provides facile access to a number of monomers used in the synthesis of commercial plastics. It is also a metabolic intermediate in the β-ketoadipic acid pathway of many bacteria and, therefore, a current target for microbial production from abundant renewable resources via metabolic engineering. This study investigates Novosphingobium aromaticivorans DSM12444 as a chassis for the production of cc MA from biomass aromatics. The N. aromaticivorans genome predicts that it encodes a previously uncharacterized protocatechuic acid (PCA) decarboxylase and a catechol 1,2-dioxygenase, which would be necessary for the conversion of aromatic metabolic intermediates to cc MA. This study confirmed the activity of these two enzymes in vitro and compared their activity to ones that have been previously characterized and used in cc MA production. From these results, we generated one strain that is completely derived from native genes and a second that contains genes previously used in microbial engineering synthesis of this compound. Both of these strains exhibited stoichiometric production of cc MA from PCA and produced greater than 100% yield of cc MA from the aromatic monomers that were identified in liquor derived from alkaline pretreated biomass. Our results show that a strain completely derived from native genes and one containing homologs from other hosts are both capable of stoichiometric production of cc MA from biomass aromatics. Overall, this work combines previously unknown aspects of aromatic metabolism in N. aromaticivorans and the genetic tractability of this organism to generate strains that produce cc MA from deconstructed biomass. IMPORTANCE The production of commodity chemicals from renewable resources is an important goal toward increasing the environmental and economic sustainability of industrial processes. The aromatics in plant biomass are an underutilized and abundant renewable resource for the production of valuable chemicals. However, due to the chemical composition of plant biomass, many deconstruction methods generate a heterogeneous mixture of aromatics, thus making it difficult to extract valuable chemicals using current methods. Therefore, recent efforts have focused on harnessing the pathways of microorganisms to convert a diverse set of aromatics into a single product. Novosphingobium aromaticivorans DSM12444 has the native ability to metabolize a wide range of aromatics and, thus, is a potential chassis for conversion of these abundant compounds to commodity chemicals. This study reports on new features of N. aromaticivorans that can be used to produce the commodity chemical cis,cis -muconic acid from renewable and abundant biomass aromatics.

09 BIOMASS FUELS↗

Hydrological control of chemical weathering and rock-carbon fluxes: East River, Colorado

This data package is used in the manuscript entitled “Hydrological control of chemical weathering and rock-carbon fluxes”. The field study was conducted in a lower montane hillslope of the East River watershed, underlain by Mancos Shale, within the lower 140 m section of a transect that extends nearly 1 km to its local peak. The data in this package, in CSV file format, were collected from Fall 2016 to fall 2021, including depth-resolved dynamic water table depths, subsurface water fluxes, solid phase (soil to bedrock) chemical compositions, geochemical properties of porewater and pore-gas, including radio carbon concentrations. The detailed methods of field studies, laboratory chemical analyses, and calculations are described in the Methods section and in the dataset file: Wan_et_al_Methods.pdf. The dataset additionally includes a file-level metadata (flmd.csv) file that lists each file contained in the dataset with associated metadata; and a data dictionary (dd.csv) file that contains column/row headers used throughout the files along with a definition, units, and data type.

54 ENVIRONMENTAL SCIENCES↗

Using multimodal X-ray computed tomography to advance 3D petrography: A non-destructive investigation of olivine inside a carbonaceous chondrite

Rocks form in three dimensions through time and studying them provides information from inside dynamic systems we cannot otherwise observe. Yet how we typically access the interior of the rocks themselves to gain that information may limit our understanding and influence how we reconstruct the processes that formed them. Here, we demonstrate combined non-destructive 3D X-ray imaging techniques that produce quantitative densitometric and crystallographic maps of entire individual grains inside a rock. Olivine grains throughout a sample of the carbonaceous chondrite Northwest Africa (NWA) 11346 were each characterized by size, shape, composition, zoning intensity, and crystallographic orientation. The addition of 3D crystallographic mapping to calibrated 3D densitometric analysis—used to calculate chemical composition—demonstrates a fully non-destructive petrographic method and provides unique insight. For instance, in our case, using crystallographic data to delineate individual grains and then measuring the 3D size, shape, and composition of each distinguishes variably reset relict grains from those later crystallized after a melting event. Intersection in a 2D slice could not have led to this interpretation because the integration of three-dimensional size, rounding, composition, location, and crystallographic orientation measured from each grain forms the key patterns. Multimodal laboratory X-ray imaging has strong potential to advance 3D petrography.

36 MATERIALS SCIENCE↗

Foraging westward for pristine nonmare rocks - Complications for petrogenetic models

New advances are reported concerning an investigation which is being conducted to find and characterize more 'pristine' (compositionally endogenous) lunar rocks. Eleven nonmare samples are characterized petrographically and (except for two clasts that were prohibitively small) by chemical composition. The samples are assessed whether they are pristine on the basis of diagnostic features discussed by Warren and Wasson (1977). Five samples are found to be almost certainly pristine. They include the alkali-rich anorthosite 12073c, the troctolite 14179c, the anorthositic troctolite 14321c1, the troctolitic anorthosite 14321c2, and the anorthositic norite 15565c. Correlations between petrochemistry and longitude are also investigated, taking into account Eu fractionations, Sc-Ti-Sm fractionations, and Ca/Na-Mg/Fe fractionations.

Warren, P. H.↗

Regional aerosol chemistry of the Amazon Basin during the dry season

The distribution and chemical composition of the atmospheric aerosol over the Amazon Basin forest were determined during the 1985 July-August dry season, using data on the aerosol chemical constituent concentration collected during the NASA Global Tropospheric Experiment Amazon Boundary Layer Experiment 2A mission. The results of the analyses suggest that there is a remarkable compositional and spatial homogeneity of the atmospheric aerosol on an extensive regional scale. Particulate organic carbon is the dominant component of the atmospheric aerosol, exhibiting an average concentration of about 740 nmol/cu m in the mixed layer and about 220 nmol/cu m in free tropospheric air. Oxalate and SO4(2-) exhibited the greatest enrichment in the mixed layer, while Cl(-) showed essentially no enrichment. The aerosol in the Amazonian atmosphere is essentially acid-base neutral, primarily as a result of incorporation of NH(+), which is presumably derived from NH3 released by the forest ecosystem.

Talbot, R. W.↗

Deep learning workflow for the inverse design of molecules with specific optoelectronic properties

The inverse design of novel molecules with a desirable optoelectronic property requires consideration of the vast chemical spaces associated with varying chemical composition and molecular size. First principles-based property predictions have become increasingly helpful for assisting the selection of promising candidate chemical species for subsequent experimental validation. However, a brute-force computational screening of the entire chemical space is decidedly impossible. To alleviate the computational burden and accelerate rational molecular design, we here present an iterative deep learning workflow that combines (i) the density-functional tight-binding method for dynamic generation of property training data, (ii) a graph convolutional neural network surrogate model for rapid and reliable predictions of chemical and physical properties, and (iii) a masked language model. As proof of principle, we employ our workflow in the iterative generation of novel molecules with a target energy gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO).

97 MATHEMATICS AND COMPUTING↗

Mars Surveyor Program '01 Mars Environmental Compatibility Assessment wet chemistry lab: a sensor array for chemical analysis of the Martian soil

The Mars Environmental Compatibility Assessment (MECA) instrument was designed, built, and flight qualified for the now canceled MSP (Mars Surveyor Program) '01 Lander. The MECA package consisted of a microscope, electrometer, material patch plates, and a wet chemistry laboratory (WCL). The primary goal of MECA was to analyze the Martian soil (regolith) for possible hazards to future astronauts and to provide a better understanding of Martian regolith geochemistry. The purpose of the WCL was to analyze for a range of soluble ionic chemical species and electrochemical parameters. The heart of the WCL was a sensor array of electrochemically based ion-selective electrodes (ISE). After 20 months storage at -23 degrees C and subsequent extended freeze/thawing cycles, WCL sensors were evaluated to determine both their physical durability and analytical responses. A fractional factorial calibration of the sensors was used to obtain slope, intercept, and all necessary selectivity coefficients simultaneously for selected ISEs. This calibration was used to model five cation and three anion sensors. These data were subsequently used to determine concentrations of several ions in two soil leachate simulants (based on terrestrial seawater and hypothesized Mars brine) and four actual soil samples. The WCL results were compared to simulant and soil samples using ion chromatography and inductively coupled plasma optical emission spectroscopy. The results showed that flight qualification and prolonged low-temperature storage conditions had minimal effects on the sensors. In addition, the analytical optimization method provided quantitative and qualitative data that could be used to accurately identify the chemical composition of the simulants and soils. The WCL has the ability to provide data that can be used to "read" the chemical, geological, and climatic history of Mars, as well as the potential habitability of its regolith.

Non-NASA Center↗

Thermal History of Matrix Forsterite Grains from Murchison Based on High-resolution Tomography

Protoplanetary disks are dust- and gas-rich structures surrounding protostars. Depending on the distance from the protostar, this dust is thermally processed to different degrees and accreted to form bodies of varying chemical compositions. The primordial accretion processes occurring in the early protoplanetary disk such as chondrule formation and metal segregation are not well understood. One way to constrain them is to study the morphology and composition of forsteritic grains from the matrix of carbonaceous chondrites. Here, we present high-resolution ptychographic X-ray nanotomography and multimodal chemical microtomography (X-ray diffraction and X-ray fluorescence) to reveal the early history of forsteritic grains extracted from the matrix of the Murchison CM2.5 chondrite. Here,. the 3D electron density maps revealed, at unprecedented resolution (64 nm), spherical inclusions containing Fe–Ni, very little silica-rich glass and void caps (i.e., volumes where the electron density is consistent with conditions close to vacuum) trapped in forsterite. The presence of the voids along with the overall composition, petrological textures, and shrinkage calculations is consistent with the grains experiencing one or more heating events with peak temperatures close to the melting point of forsterite (~2100 K), and subsequently cooled and contracted, in agreement with chondrule-forming conditions.

58 GEOSCIENCES↗

Insights into Waterflooding in Hydrocarbon-Bearing Nanochannels of Varying Cross Sections from Mesoscopic Multiphase Flow Simulations

Waterflooding is one of the geotechnique used to recover fuel sources from nanoporous geological formations. The scientific understanding of the process that involves the multiphase flow of nanoconfined fluids, however, has lagged, mainly due to the complex nanopore geometries and chemical compositions. To enable benchmarked flow of nanoconfined fluids, the architected geomaterials, such as synthesized mesoporous silica with tunable pore shapes and surface chemical properties, are used for designing and conducting experiments and simulations. This work uses a modified many-body dissipative particle dynamics (mDPD) model with accurately calibrated parameters to perform parametric flow simulations for studying the influences of waterflooding driven power, pore shape, surface roughness, and surface wettability on the multiphase flow in heptane-saturated silica nanochannels. Remarkably, up to 80\% reduction in the effective permeability is found for water-driven heptane flow in a baseline 4.5 nm-wide slit channel, when compared with the Hagen–Poiseuille equation. In the 4.5 nm-wide channels with architected surface roughness, the flow rate is found either higher or lower than the baseline case, depending on the shape and size of cross-sections. High wettability of the solid surface to water is essential for achieving high recovery of heptane, regardless of surface roughness. When the solid surface is less wetting or non-wetting to water, the existence of an optimal waterflooding driven power is found to allow for the highest possible recovery. A detailed analysis on the evolution of the transient water-heptane interface in those nanochannels is presented to elucidate the underlying mechanisms that impact or dictate the multiphase flow behaviors.

58 GEOSCIENCES↗

Solid organic-coated ammonium sulfate particles at high relative humidity in the summertime Arctic atmosphere

The ability of atmospheric aerosols to impact climate through water uptake and cloud formation is fundamentally determined by the size, composition, and phase (liquid, semisolid, or solid) of individual particles. Particle phase is dependent on atmospheric conditions (relative humidity and temperature) and chemical composition and, importantly, solid particles can inhibit the uptake of water and other trace gases, even under humid conditions. Particles composed primarily of ammonium sulfate are presumed to be liquid at the relative humidities (67 to 98%) and temperatures (–2 to 4 °C) of the summertime Arctic. Under these atmospheric conditions, we report the observation of solid organic-coated ammonium sulfate particles representing 30% of particles, by number, in a key size range (<0.2 µm) for cloud activation within marine air masses from the Arctic Ocean at Utqiagvik, AK. The composition and size of the observed particles are consistent with recent Arctic modeling and observational results showing new particle formation and growth from dimethylsulfide oxidation to form sulfuric acid, reaction with ammonia, and condensation of marine biogenic sulfate and highly oxygenated organic molecules. Aqueous sulfate particles typically undergo efflorescence and solidify at relative humidities of less than 34%. Therefore, the observed solid phase is hypothesized to occur from contact efflorescence during collision of a newly formed Aitken mode sulfate particle with an organic-coated ammonium sulfate particle. With declining sea ice in the warming Arctic, this particle source is expected to increase with increasing open water and marine biogenic emissions.

54 ENVIRONMENTAL SCIENCES↗

Geochemistry of Darwin impact glass and target rocks

Results are presented from major and trace element composition analyses of 18 Darwin (Australia) glass samples and seven target rocks from the Darwin crater area. It is found that the chemical composition of the glass samples is in agreement with an origin from terrestrial sediments during an impact. Analyses of the target rocks from the Darwin crater and mixing calculations show that the Darwin glass can be formed from the local target rocks. Evidence is presented for a loss of the volatile elements Ga, Zn, F, and B during the impact event. The elements Na, K, Rb, and Cs show lower abundance in the glass than in the target rocks. This suggests selective volatilization from the impact melt.

Meisel, Thomas↗

Chemical Evolution and the Origin of Life: Bibliography 1975

This bibliography is the sixth annual supplement to the comprehensive bibliography on the same subject which was published in Space Life Sci.We would like to draw attention to a recently published cumulative bibliography on this same subject: Biochemical Origin of Life: Chemistry and Life. Soil and Water and Its Relationship to Origin of Life. MR - Studies of Prebiotic Polypeptides. Energy, Matter, and Life. Prospects for the Future Orientation of Scientific Research. Photochemical Formation of Self Sustaining Coacervates. Photochemical Formation of Self-Sustaining Coacervates. Comparative Study of Abiogenesis of Cysteine and Other Amino Acids Catalyzed by Various Metal Ions. Protein Structure and the Molecular Evolution of Biological Energy Conversion. Origin of Life. Clues from Relations Between Chemical Compositions of Living Organisms and Natural Environments. Shock Synthesis of Amino Acids II.', Origins of Life 6(1-2). Dynamics of the Chemical Evolution of Earth's Primitive Atmosphere. The Mechanisms of Amino Acids Synthesis by High Temperature Shock-Waves. Theory of Chemical Evolution. Physical Foundations of Probability of Biogenesis.

West, Martha W.↗

Optical Properties of Thin Film Molecular Mixtures

Thin films composed of molecular mixtures of metal and dielectric are being considered for use as solar selective coatings for a variety of space power applications. By controlling the degree of molecular mixing, the solar selective coatings can be tailored to have the combined properties of high solar absorptance, alpha, and low infrared emittance, epsilon. On orbit, these combined properties would simultaneously maximize the amount of solar energy captured by the coating and minimize the amount of thermal energy radiated. Mini-satellites equipped with solar collectors coated with these cermet coatings may utilize the captured heat energy to power a heat engine to generate electricity, or to power a thermal bus that directs heat to remote regions of the spacecraft. Early work in this area identified the theoretical boundary conditions needed to operate a Carnot cycle in space, including the need for a solar concentrator, a solar selective coating at the heat inlet of the engine, and a radiator. A solar concentrator that can concentrate sunlight by a factor of 100 is ideal. At lower values, the temperature of the solar absorbing surface becomes too low for efficient heat engine operation, and at higher values, cavity type heat receivers become attractive. In designing the solar selective coating, the wavelength region yielding high solar absorptance must be separated from the wavelength region yielding low infrared emittance by establishing a sharp transition in optical properties. In particular, a sharp transition in reflectance is desired in the infrared to achieve the desired optical performance. For a heat engine operating at 450C, a sharp transition at 1.8 micrometers is desired. The radiator completes the heat flow through the Carnot cycle. Additional work has been done supporting the use of molecular mixtures for terrestrial applications. Sputter deposition provides a means to apply coatings to the tubes that carry a working fluid at the focus of trough-style collectors. Sputtering offers considerable flexibility in coating conditions, including a wide variety of metal and dielectric targets. Coating designs range from simple two or three layer coatings to complex coatings that are purposely graded to be metal-rich at their base and oxide-rich at their surface in order to yield the desired solar selective properties. In these cermet coatings, molecular islands of metal are thought to be embedded in a three dimensional matrix of dielectric. Recent work has identified the use of custom made ion beam sputter deposition targets to produce coatings containing molecular mixtures of metal and dielectric. The targets are cylindrical and the surface consists of a gradually changing composition of metal and dielectric. Rotating the cylinder under the beam during ion beam sputter deposition yields a coating that is a molecular mixture of metal and dielectric, with the composition changing through the thickness of the coating. The optical properties of these coatings are not only dependent on their thickness and chemical composition, but are also dependent on the extent of the through thickness gradient established during deposition. This paper presents a summary of the optical properties of several thin film molecular mixtures designed as solar selective coatings. Optical performance is first identified as a function of wavelength, from the ultraviolet to the visible and infrared. Coating composition, thickness, and gradient from metal to dielectric also play an important role. Additional work for future activities is also identified.

Jaworske, Donald A.↗

Crystal Water on Mars: Insights from the Mars Exploration Rovers

The purpose of this paper is to constrain the total water contents from crystal H2O and OH in several materials analyzed by the Mars Exploration Rovers (MER). Crystal H2O is part of the unit cell and cannot be removed without changing the structure. Minerals that contain only OH in their structures are anhydrous minerals containing hydroxyls, although they are formed as a product of aqueous activity and will decompose with evolution of H2O when heated. The crystal water and OH contents of a bulk material at the MER landing sites can be estimated from mineralogical composition, which is determined by a combination of Fe-mineralogy obtained by the Mossbauer Spectrometer and mineral abundances based upon the chemical composition determined by the Alpha Particle X-ray Spectrometer. Jarosite, along with Ca- and Mg-sulfates, have been suggested as the sulfur-bearing phases in Meridiani Planum outcrop. Models of various hydration states of Fe-, Ca-, and Mg-sulfates and other possible secondary phases suggest that 6 to 22 wt.% of the outcrop may occur as crystal H2O and/or OH (Clark et al., 2005). This estimate of water is consistent with measurements from the Odyssey orbiter, where 7 % H2O-equivalent H was measured down to a depth of approximately 1 m for the region (Feldman et al., 2004).

Ming, D. W.↗