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At least 361 records · Page 20

The Effect of Transport and Circulation Differences on Stratospheric Ozone Recovery in Two 35-year Three-dimensional Simulations

The NASA Global Modeling Initiative (GMI) has completed two 35-year simulations with WMO future baseline boundary conditions that simulate increasing N2O and CH4 emissions and decreasing organic chlorine and bromine emissions. Simulations were done with the GMI offline chemistry and transport model using 1) 1 year of winds from the Finite-Volume General Circulation Model (FV-GCM), repeated for the 35 years, and 2) 1 year of winds from the Finite-Volume Data Assimilation System (FV-DAS), repeated for 35-years. The simulations have full stratospheric chemistry. To understand differences in simulated ozone recoveries, basic transport and circulation differences between these models are evaluated. The distribution of mean age of stratospheric air in the FV-GCM run agrees well with observations in the lower stratosphere but the FV-DAS ages are generally too low. This implies circulation and mixing differences that will affect the distributions of other trace species such as CH4, NO, and the organic halogens, all of which are responding to changing boundary conditions and are involved in ozone loss. Realism of model transport is evaluated, with particular attention given to regions and seasons where ozone recovery is expected. Preliminary results indicate increasing ozone trends in the lowermost stratosphere in summer and in the Antarctic and Arctic lower stratosphere in winter and spring.

Bhartia, P. K.↗

Laboratory Studies of Extraterrestrial Ices and PAHs: Making an Astrobiological Silk Purse Out of An Interstellar Sow's Ear

Tremendous strides have been made in our understanding of interstellar material over the past twenty years thanks to significant, parallel developments in observational astronomy and laboratory astrophysics. Today, the composition of dust in the ISM is reasonably well constrained to cold, micron-sized particles of various refractory materials. Shrouded within the protective confines of cold, opaque molecular clouds--the birthplace of stars and planets--these particles secrete mantles of mixed molecular lees whose major components are also well constrained. Finally, amidst the molecular inventory of these ice mantles are likely to be found polycyclic aromatic hydrocarbons (PAHs), whose telltale infrared signature I is now recognized throughout the Universe. However, of what significance is this scenario to the origin of life in our solar system--or any other? The major components of the icy materials observed in interstellar clouds and in our own solar system are uniformly quite simple. In addition, despite the fact that PAHs likely represent the single largest molecular reservoir of organic carbon in evolving planetary systems, they are not what would be considered "biogenic" molecules. Although interesting from a chemical and astrophysical standpoint, in the absence of a mechanism by which these materials can be transformed into more biochemically significant structures, they are of little Astrobiological significance. In this talk, we will begin with a brief review of the nature and abundance of the "raw" population of PAHs and PAH-related materials in the ISM. From there, we will move on to explore our laboratory simulations of the photochemical evolution of realistic mixed molecular ices under conditions which simulate those encountered in the ISM and in evolving planetary systems. Particular attention will be paid to the surprisingly complex array of organic species that are produced in these ices from such a deceptively simple inventory of starting materials. In addition, we will explore the chemistry of PAHs under these conditions and consider its potential for transforming that rich repository of pre-biotic organic "ore" into materials of greater importance to Astrobiology.

Hudgins, Douglas M.↗

The Origin of Carbon-Bearing Volatiles in a Continental Hydrothermal System in the Great Basin: Water Chemistry and Isotope Characterizations

Hydrothermal systems on Earth are active centers in the crust where organic molecules can be synthesized biotically or abiotically under a wide range of physical and chemical conditions [1-3]. Not only are volatile species (CO, CO2, H2, and hydrocarbons) a reflection of deep-seated hydrothermal alteration processes, but they also form an important component of biological systems. Studying carbon-bearing fluids from hydrothermal systems is of specific importance to understanding (bio-)geochemical processes within these systems. With recent detection of methane in the martian atmosphere [4-7] and the possibility of its hydrothermal origin [8, 9], understanding the formation mechanisms of methane may provide constraints on the history of the martian aqueous environments and climate.

Fu, Qi↗

Fluorescent labels for in situ wet chemistry experiments

We evaluate a wide selection of dyes and suggest a panel that would be the most likely to succeed in a simple flight instrument with a single excitation laser. We also investigate fluorescent semiconductor quantum dots as additions to or replacements for these organic dyes.

in situ wet chemistry experiments quantum dots Mar↗

The Diversity of Refractory Organic Material in Comets

Organic matter exists in comets (most notably in 81P/Wild 2 [Stardust], 67P/Churyomov- Gerasimenko (67P/C-G) [Rosetta], chondritic porous IDPS, and UCAMMs) and in primitive carbonaceous chondrites that likely retain some chemistry that reflects an origin in the prenatal cold molecular cloud (Alexander+2017). Heavy isotopic enrichments, 15N/14N and possibly D/H, signify preserved molecular cloud organics. In the cold outer disk, if grains are lofted above the disk mid-plane then organics likely experience significant UV processing (Ciesla+2012). In remote sensing of comet comae, organics in the dust are considered refractory or semirefractory. Semi-refractory organics have limited comae lifetimes and produce distributed sources of molecules (H2CO and CO). Rosetta's close passes of 67P/C-G's nucleus (10-15 km) reveals a distributed source of glycine, methyl amine and ethylamine (Altwegg+2016). Cometary samples and primitive meteorites have two types of organic matter: (1) acid-insoluble organic matter (IOM), which is a macromolecular polymer with a mixture of aromatic and aliphatic moieties, and (2) labile, soluble organics, which includes the amino acids, such as glycine (Stardust, Elsila+2009). Meteoritic IOM is robust, withstanding experimental temperatures of 1200 K (Dobrica+2011, Cody+2008). Nanoglobules are a type of IOM; they have a distinct physical structure, but often share the same chemistry as the other IOM from the same meteorite. Moderate-sized PAHs (20 C-atoms) are detected in Stardust samples (Clemett+2010). Refractory organic IOM is ubiquitous yet has a great diversity of abundances between cometary samples. IOM is in primitive chondrites, 67P/C-G (Rosetta), 81P/Wild 2 (Stardust), 1P/Halley, 26P/Grigg-Skjellerup, UCAMMs, anhydrous IDPs, and in chondritic porous IDPs (CP IDPs) and larger cluster IDPs (e.g., Fray+2016, Fomenkova+94, Busemann+ 09, Dobrica+2011, Dobrica+2012). 81P's refractory organic matter is of two types (De Gregorio+2011): nanoglobules of highly aromatic refractory organic matter and polyaromatic carbonyl-containing organic matter, which is similar to IOM in primitive meteorites and IDPs. Fray+2017 estimate that 50% of carbon in 67P/C-G is in IOM. 67P/C-G's organics appear to lack the soluble organic matter, aliphatic carbon, amino acids, and PAHs (Fray+2016). Other notable aspects of the diversity in IOM in cometary samples are the ranges of atomic ratios of N/C, O/C, and H/C, and the range of isotopic enrichments of 15N/14N and D/H. Aqueous and thermal processing on asteroids changes the balance of soluble to insoluble organics, and may be important for diversifying the range of OM delivered to Earth.

Wooden, Diane↗

Future Climate Impacts of Direct Radiative Forcing Anthropogenic Aerosols, Tropospheric Ozone, and Long-lived Greenhouse Gases

Long-lived greenhouse gases (GHGs) are the most important driver of climate change over the next century. Aerosols and tropospheric ozone (O3) are expected to induce significant perturbations to the GHG-forced climate. To distinguish the equilibrium climate responses to changes in direct radiative forcing of anthropogenic aerosols, tropospheric ozone, and GHG between present day and year 2100, four 80-year equilibrium climates are simulated using a unified tropospheric chemistry-aerosol model within the Goddard Institute for Space Studies (GISS) general circulation model (GCM) 110. Concentrations of sulfate, nitrate, primary organic (POA) carbon, secondary organic (SOA) carbon, black carbon (BC) aerosols, and tropospheric ozone for present day and year 2100 are obtained a priori by coupled chemistry-aerosol GCM simulations, with emissions of aerosols, ozone, and precursors based on the Intergovernmental Panel on Climate Change (IPCC) Special Report on Emissions Scenario (SRES) A2. Changing anthropogenic aerosols, tropospheric ozone, and GHG from present day to year 2100 is predicted to perturb the global annual mean radiative forcing by +0.18 (considering aerosol direct effects only), +0.65, and +6.54 W m(sup -2) at the tropopause, and to induce an equilibrium global annual mean surface temperature change of +0.14, +0.32, and +5.31 K, respectively, with the largest temperature response occurring at northern high latitudes. Anthropogenic aerosols, through their direct effect, are predicted to alter the Hadley circulation owing to an increasing interhemispheric temperature gradient, leading to changes in tropical precipitation. When changes in both aerosols and tropospheric ozone are considered, the predicted patterns of change in global circulation and the hydrological cycle are similar to those induced by aerosols alone. GHG-induced climate changes, such as amplified warming over high latitudes, weakened Hadley circulation, and increasing precipitation over the Tropics and high latitudes, are consistent with predictions of a number of previous GCM studies. Finally, direct radiative forcing of anthropogenic aerosols is predicted to induce strong regional cooling over East and South Asia. Wintertime rainfall over southeastern China and the Indian subcontinent is predicted to decrease because of the increased atmospheric stability and decreased surface evaporation, while the geographic distribution of precipitation is also predicted to be altered as a result of aerosol-induced changes in wind flow.

Chen, Wei-Ting↗

Strategies for Distinguishing Abiotic Chemistry from Martian Biochemistry in Samples Returned from Mars

A key goal in the search for evidence of extinct or extant life on Mars will be the identification of chemical biosignatures including complex organic molecules common to all life on Earth. These include amino acids, the monomer building blocks of proteins and enzymes, and nucleobases, which serve as the structural basis of information storage in DNA and RNA. However, many of these organic compounds can also be formed abiotically as demonstrated by their prevalence in carbonaceous meteorites [1]. Therefore, an important challenge in the search for evidence of life on Mars will be distinguishing between abiotic chemistry of either meteoritic or martian origin from any chemical biosignatures from an extinct or extant martian biota. Although current robotic missions to Mars, including the 2011 Mars Science Laboratory (MSL) and the planned 2018 ExoMars rovers, will have the analytical capability needed to identify these key classes of organic molecules if present [2,3], return of a diverse suite of martian samples to Earth would allow for much more intensive laboratory studies using a broad array of extraction protocols and state-of-theart analytical techniques for bulk and spatially resolved characterization, molecular detection, and isotopic and enantiomeric compositions that may be required for unambiguous confirmation of martian life. Here we will describe current state-of-the-art laboratory analytical techniques that have been used to characterize the abundance and distribution of amino acids and nucleobases in meteorites, Apollo samples, and comet- exposed materials returned by the Stardust mission with an emphasis on their molecular characteristics that can be used to distinguish abiotic chemistry from biochemistry as we know it. The study of organic compounds in carbonaceous meteorites is highly relevant to Mars sample return analysis, since exogenous organic matter should have accumulated in the martian regolith over the last several billion years and the analytical techniques previously developed for the study of extraterrestrial materials can be applied to martian samples.

Glavin, D. P.↗

Conditions of the Martian atmosphere and surface in the remote past and their relevance to the question of life on Mars

Although the Viking Landers failed to find any evidence of life on the surface of Mars, much remains unknown. Study of returned samples can answer some of these questions. The search for organic compounds, the building blocks of life forms based on carbon chemistry, should continue. The question of life on Mars is still an open one, and deserves to be addressed by the study of returned samples. Whether life developed and evolved on Mars or not depends critically on the history of the Martian atmosphere and hydrosphere. The exobiology of Mars is thus inextrically intertwined with the nature of its paleoatmosphere and the ancient state of the planet's regolith, which may still be preserved in the polar caps and underground. Core samples from such sites could answer some of the questions.

Pang, Kevin D.↗

Friction and Wear Management Using Solvent Partitioning of Hydrophilic-Surface-Interactive Chemicals Contained in Boundary Layer-Targeted Emulsions

Lubrication additives of the current invention require formation of emulsions in base lubricants, created with an aqueous salt solution plus a single-phase compound such that partitioning within the resulting emulsion provides thermodynamically targeted compounds for boundary layer organization thus establishing anti-friction and/or anti-wear. The single-phase compound is termed "boundary layer organizer", abbreviated BLO. These emulsion-contained compounds energetically favor association with tribologic surfaces in accord with the Second Law of Thermodynamics, and will organize boundary layers on those surfaces in ways specific to the chemistry of the salt and BLO additives. In this way friction modifications may be provided by BLOs targeted to boundary layers via emulsions within lubricating fluids, wherein those lubricating fluids may be water-based or oil-based.

Richmond, Robert Chaffee↗

Classification of Ascension Island and Natal Ozonesondes Using Self-Organizing Maps

Ozone profiles from balloon-borne ozonesondes are used for development of satellite algorithms and in chemistry-climate model initialization, assimilation and evaluation. An important issue in the application of these profiles is how best to treat variations where varying photochemical and dynamical influences can cause the ozone mixing ratio in the tropospheric segments of the profile to change by of a factor of 2-3 within a day. Clustering techniques are an ideal way to approach the statistical classification of profile data and we apply self-organizing maps to tropical tropospheric SHADOZ data, hypothesizing that the data will sort according to various influences on ozone, namely anthropogenic sources like biomass burning, meteorological conditions, and stratospheric or extra-tropical intrusions. Self-organizing maps, that use a learning algorithm to reveal the most prominent features of a data set according to a specified number of clusters, have been determined for the 1998-2009 SHADOZ profiles over Ascension Island (512 profiles, 7.98 deg. S, 14.42 deg. W) and Natal, Brazil (425 profiles, 5.42degS, 35.38degW). The 2 × 2 self-organizing map, which creates 4 clusters, reveals that deviations from the average ozone in the free troposphere include both increased ozone resulting from seasonal biomass burning in Africa and locally reduced ozone brought about by convective lifting of unpolluted boundary-layer air. Expanding to a 4 × 4 self-organizing map shows how biomass burning influences the yearly cycle of tropospheric ozone at Ascension Island and captures the seasonality of ozone at both Ascension Island and Natal. Comparing Ascension Island and Natal using a 4 × 4 self-organizing map at each site reveals similarities in mid-tropospheric ozone, but shows differences in lower-tropospheric ozone due to Ascension Island being closer to African biomass burning and more affected by descent from the mean Walker circulation, with less convective activity, than Natal.

algorithms↗

Survey of application of radiation to preparative chemistry

The use of radiation for preparative chemistry in liquid solutions is investigated. General principles are presented and preparations involving reduction, oxidation, polymerization, and decomposition are given. The use of various solvents, water, other inorganic liquids and organic liquids for this purpose is discussed. Finally, a commentary is made on some specific applications where radiation chemistry as a preparative technique may be useful.

Philipp, W. H.↗

Ah, Sweet Mystery of Life, OSIRIS-REx May Find You

The nature of the origin of life is a topic that has engaged people since ancient times. Where did we come from? What was the first life? How are we related? Are we alone? The study of biologic remains and environments preserved in rocks (fossils) and biochemical pathways and structures found across organisms (molecular fossils) can address these questions. Molecular evidence shows that all life on Earth is related fundamentally, biology shares a genetic language, related molecular machinery, and common chemistry By looking at the details of genetic and protein sequences more detailed relationships can be determined for modern organisms.

origin of life↗

Potential Precursor Compounds for Chlorohydrocarbons Detected in Gale Crater, Mars, by the SAM Instrument Suite on the Curiosity Rover

The detection of chlorinated organic compounds in near-surface sedimentary rocks by the Sample Analysis at Mars (SAM) instrument suite aboard the Mars Science Laboratory Curiosity rover represents an important step toward characterizing habitable environments on Mars. However, this discovery also raises questions about the identity and source of their precursor compounds and the processes by which they become chlorinated. Here we present the results of analog experiments, conducted under conditions similar to SAM gas chromatography-mass spectrometry analyses, in which we pyrolyzed potential precursor compounds in the presence of various Cl salts and Fe oxides that have been identified in Martian sediments. While chloromethanes could not be unambiguously identified, 1,2-dichloropropane (1,2-DCP), which is one of the chlorinated compounds identified in SAM data, is formed from the chlorination of aliphatic precursors. Additionally, propanol produced more 1,2-DCP than nonfunctionalized aliphatics such as propane or hexanes. Chlorinated benzenes ranging from chlorobenzene to hexachlorobenzene were identified in experiments with benzene carboxylic acids but not with benzene or toluene. Lastly, the distribution of chlorinated benzenes depended on both the substrate species and the nature and concentration of the Cl salt. Ca and Mg perchlorate, both of which release O2 in addition to Cl2 and HCl upon pyrolysis, formed less chlorobenzene relative to the sum of all chlorinated benzenes than in experiments with ferric chloride. FeCl3, a Lewis acid, catalyzes chlorination but does not aid combustion. Accordingly, both the precursor chemistry and sample mineralogy exert important controls on the distribution of chlorinated organics.

Miller, Kristen E.↗

First Optical Constants of Laboratory-Generated Organic Refractory Materials (Tholins) Produced in the NASA Ames COSmIC Facility from the Visible to the Near Infrared (0.4–1.6 μm): Application to Titan’s Aerosols

We have measured the complex refractive indices, from 0.4 to 1.6μm, of five laboratory-generated organic refractory materials (tholins) produced at low temperature(150 K)using plasma chemistry in the stream of a supersonic expansion in NASA Ames’ COsmic SImulation Chamber(COSmIC)facility. Three samples were produced from N2:CH4gas precursors(with different voltages inducing different degrees of ionization in the plasma), one sample was produced from N2:CH4:C2H2, and one sample was produced from Ar:CH4in order to produce a purely carbonaceous sample. The optical constants, n and k, of the samples were determined using spectral reflectance measurements. We observe that both n and k appear to be correlated with the nitrogen content in the solid sample, with samples containing more nitrogen having higher n and k. Comparisons to previous laboratory studies and Titan aerosol optical constants derived from observations show that the COSmIC tholins with a higher nitrogen content (higher n and k)are closer analogs of Titan aerosols. We also present a new analysis of Cassini Visible Infrared Mapping Spectrometer observations of Titan’s atmosphere in the visible to near infrared using the COSmIC tholin optical constants in a radiative transfer model. The COSmIC tholin sample produced from N2:CH4with the lowest energy level has a spectral behavior that appears well suited to reproduce the observed Titan aerosol properties. This study has therefore demonstrated that this COSmIC tholin sample has valuable and promising optical properties for the analysis of Cassini’s Titan atmospheric observations.

Optical Constants↗

Unified Mars detection system

A life-detection system is described which is designed to detect and characterize possible Martian biota and to gather information about the chemical environment of Mars, especially the water and amino acid contents of the soil. The system is organized around a central mass spectrometer that can sensitively analyze trace gases from a variety of different experiments. Some biological assays and soil-chemistry tests that have been performed in the laboratory as typical experiment candidates for the system are discussed, including tests for soil-organism metabolism, measurements of soil carbon contents, and determinations of primary aliphatic amines (amino acids and protein) in soils. Two possible test strategies are outlined, and the operational concept of the detection system is illustrated. Detailed descriptions are given for the mass spectrometer, gas inlet, incubation box, test cell modules, seal drive mechanism, soil distribution assembly, and electronic control system.

Martin, J. P.↗

Hydrothermal Decomposition of Amino Acids and Origins of Prebiotic Meteoritic Organic Compounds

The organic compounds found in carbonaceous chondrite meteorites provide insight into primordial solar system chemistry. Evaluating the formation and decomposition mechanisms of meteoritic amino acids may aid our understanding of the origins of life and homochirality on Earth. The amino acid glycine is widespread in meteorites and other extraterrestrial environments; other amino acids, such as isovaline, are found with enantiomeric excesses in some meteorites. The relationship between meteoritic amino acids and other compounds with similar molecular structures, such as aliphatic monoamines and monocarboxylic acids is unclear; experimental results evaluating the decomposition of amino acids have produced inconclusive results about the preferred pathways, reaction intermediates, and if the conditions applied may be compatible with those occurring inside meteoritic parent bodies. In this work, we performed extensive tandem metadynamics, umbrella sampling, and committor analysis to simulate the neutral mild hydrothermal decomposition mechanisms of glycine and isovaline and put them into context for the origins of meteoritic organic compounds. Our ab initio simulations aimed to determine free energy profiles and decomposition pathways for glycine and isovaline. We found that under our modeled conditions, methylammonium, glycolic acid, and sec-butylamine are the most likely decomposition products. These results suggest that meteoritic aliphatic monocarboxylic acids are not produced from decomposition of meteoritic amino acids. Our results also indicate that the decomposition of L-isovaline prefers an enantioselective pathway resulting in the production of (S)-sec-butylamine.

Enhanced sampling↗

Proposing an International Collaboration on Lightweight Autonomous Vehicles to Conduct Scientific Traverses and Surveys over Antarctica and the Surrounding Sea Ice

We have continued to develop a concept for use of autonomous rovers, originally developed for use in planetary exploration, in polar science on Earth; the concept was the subject of a workshop, and this report summarizes and extends that workshop. The workshop on Antarctic Autonomous Scientific Vehicles and Traverses met at the National Geographic Society on February 14 and 15, 2001 to discuss scientific objectives and benefits of the use of autonomous rovers. The participants enthusiastically viewed rovers as being uniquely valuable for such tasks as data taking on tedious or repetitive routes, traverses in polar night, difficult or hazardous routes, extremely remote regions, routes requiring only simple instrumentation, traverses that must be conducted at low speed, augments of manned traverses, and scientific procedures not compatible with human presence or combustion engines. The workshop has concluded that instrumented autonomous vehicles, of the type being developed for planetary exploration, have the potential to contribute significantly to the way science in conducted in Antarctica while also aiding planetary technology development, and engaging the public's interest. Specific objectives can be supported in understanding ice sheet mass balance, sea ice heat and momentum exchange, and surface air chemistry processes. In the interval since the workshop, we have concluded that organized program to employ such rovers to perform scientific tasks in the Fourth International Polar Year would serve the objectives of that program well.

polar science↗

Constraining Remote Oxidation Capacity with ATom Observations

The global oxidation capacity, defined as the tropospheric mean concentration of the hydroxyl radical (OH), controls the lifetime of reactive trace gases in the atmosphere such as methane and carbon monoxide (CO). Models tend to underestimate the methane lifetime and CO concentrations throughout the troposphere, which is consistent with excessive OH. Approximately half the oxidation of methane and non-methane volatile organic compounds (VOCs) is thought to occur over the oceans where oxidant chemistry has received little validation due to a lack of observational constraints. We use observations from the first two deployments of the NASA ATom aircraft campaign during July–August 2016 and January–February 2017 to evaluate the oxidation capacity over the remote oceans and its representation in the GEOS-Chem chemical transport model. The model successfully simulates the magnitude and vertical profile of remote OH within the measurement uncertainties. Comparisons against the drivers of OH production (water vapor, ozone, and NOy concentrations, ozone photolysis frequencies) also show minimal bias with the exception of wintertime NOy, for which a model overestimate may indicate insufficient wet scavenging and/or missing loss on seasalt aerosol but large uncertainties remain that require further studies of NOy partitioning and removal in the troposphere. During the ATom-1 deployment, OH reactivity (OHR) below 3 km is significantly enhanced, and this is not captured by the sum of its measured components (cOHRobs) or by the model (cOHRmod). This enhancement could suggest missing reactive VOCs but cannot be explained by new estimates of ocean VOC sources and additional modeled reactivity in this region would be difficult to reconcile with the full suite of ATom measurement constraints. The model generally reproduces the magnitude and seasonality of cOHRobs but underestimates the contribution of oxygenated VOC, mainly acetaldehyde, which is severely underestimated throughout the troposphere despite its calculated lifetime of less than a day. Missing model acetaldehyde in previous studies was attributed to measurement uncertainties that have been largely resolved. Observations of peroxyacetic acid (PAA) provide new support for remote levels of acetaldehyde. The underestimate in modeled acetaldehyde and PAA is present throughout the year in both hemispheres and peaks during Northern Hemisphere summer. The addition of ocean VOC sources in the model increases annual surface cOHRmod by 10 % and improves model-measurement agreement for acetaldehyde particularly in winter but cannot resolve the model summertime bias. Doing so would require a 100 Tg yr−1 source of a long-lived unknown precursor throughout the year with significant additional emissions in the Northern Hemisphere summer. Improving the model bias for remote acetaldehyde and PAA is unlikely to fully resolve previously reported model global biases in OH and methane lifetime, suggesting that future work should examine the sources and sinks of OH over land.

Travis, Katherine R.↗