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At least 73 records · Page 4

Trends in source gases

Source gases are defined as those gases that, by their breakdown, introduce into the stratosphere halogen, hydrogen, and nitrogen compounds that are important in stratospheric ozone destruction. Given here is an update of the existing concentration time series for chlorocarbons, nitrous oxide, and methane. Also reviewed is information on halogen containing species and the use of these data for establishing trends. Also reviewed is evidence on trends in trace gases that influence tropospheric chemistry and thus the tropospheric lifetimes of source gases, such as carbon dioxide, carbon monoxide, or nitrogen oxides. Much of the information is given in tabular form.

Ehhalt, D. H.↗

Overview of the polar ozone issue

The causes of the Antarctic ozone depletion are discussed together with the role of the polar stratospheric clouds (PSCs, which are ice clouds that form towards spring over Antarctica in the altitude range of 10-20 km) in the process of ozone depletion. Evidence is presented suggesting that heterogeneous chemical reactions occurring on the surfaces of the PSCs could dramatically deplete the abundances of reactive nitrogen compounds and enhance those of reactive chlorine species which are responsible for ozone depletion. It was also shown that the surface reactions are not limited to ice clouds but can also take place on the liquid sulfuric acid aerosols present at lower latitudes, indicating that heterogeneous chemistry may take place to some extent on a global scale. Finaly, observations of low-abundance NO2 in north polar regions suggests that heterogeneous removal of reactive nitrogen may well be occurring in the Arctic, with possible attendant applications for Arctic ozone.

Solomon, Susan↗

A model study of the effects of intermittent loss on odd nitrogen concentrations in the lower troposphere

A time-dependent box model of the lower troposphere which includes a description of photochemical and physical processes has been developed. This model has been applied to the calculation of nitric acid and NO(x)(NO + NO2) concentrations over a diurnal cycle which includes precipitation. Nitric acid concentrations and the HNO3/NO(x) ratio are found to be highly variable under the assumptions regarding the frequency, duration, and intensity of precipitation employed in this model. The chemistry of odd nitrogen compounds during the night is potentially important in establishing the level of nitric acid in the lower troposphere. These calculations also indicate that relatively large errors may occur when the continuity equation describing nitric acid variations is averaged over a diurnal cycle which includes precipitation. Interpretation of simultaneous measurements of HNO3 and NO(x) will require some knowledge of the history of the observed air mass and may require an improved understanding of nighttime odd nitrogen chemistry.

Stewart, R. W.↗

Synthesis of Ultra‐Incompressible and Recoverable Carbon Nitrides Featuring CN 4 Tetrahedra

Abstract Carbon nitrides featuring three‐dimensional frameworks of CN 4 tetrahedra are one of the great aspirations of materials science, expected to have a hardness greater than or comparable to diamond. After more than three decades of efforts to synthesize them, no unambiguous evidence of their existence has been delivered. Here, the high‐pressure high‐temperature synthesis of three carbon–nitrogen compounds,tI14‐C 3 N 4 ,hP126‐C 3 N 4 , andtI24‐CN 2 , in laser‐heated diamond anvil cells, is reported. Their structures are solved and refined using synchrotron single‐crystal X‐ray diffraction. Physical properties investigations show that these strongly covalently bonded materials, ultra‐incompressible and superhard, also possess high energy density, piezoelectric, and photoluminescence properties. The novel carbon nitrides are unique among high‐pressure materials, as being produced above 100 GPa they are recoverable in air at ambient conditions.

Chemistry↗

Taxogenomic Analysis of a Novel Yeast Species, Lachancea rosae Sp. Nov. F.A., Isolated From the Wild Rose Rosa californica

A novel Saccharomycotina yeast strain, yHQL494, was isolated from the rose hip of the wild rose Rosa californica from Castle Crags State Park, California, USA. Phylogenetic analyses of both whole genome data and the sequences from the D1/D2 region of the large ribosomal subunit (LSU) rRNA gene placed strain yHQL494 within the genus Lachancea and grouped it into a clade with Lachancea lanzarotensis and Lachancea meyersii. Taxogenomic analyses were conducted on publicly available genome sequences to gain a deeper insight into the carbon and nitrogen gene-trait associations across the Lachancea clade. The results of these analyses were found to be consistent across Lachancea species. Growth assays and microscopic analyses were conducted to determine the physiological characteristics of strain yHQL494, including the presence of hyphae or pseudohyphae, ascospore formation, fermentation abilities, and assimilation of carbon and nitrogen compounds. Based on the phenotypic and genomic characteristics of the strain yHQL494 T (=NRRL Y-64858 T , =CBS 18,574 T ), we propose a new species, Lachancea rosae sp. nov. f.a.

Bajgain, Yakendra [Villanova Univ., PA (United Sta↗

Facile All-Optical Method for In Situ Detection of Low Amounts of Ammonia

As a key precursor for nitrogenous compounds and fertilizer, ammonia affects our lives in numerous ways. Rapid and sensitive detection of ammonia is essential, both in environmental monitoring and in process control for industrial production. Here we report a novel and nonperturbative method that allows rapid detection of ammonia at low concentrations, based on the all-optical detection of surface-enhanced Raman signals. We show that this simple and affordable approach enables ammonia probing at selected regions of interest with high spatial resolution, making in situ and operando observations possible.

09 BIOMASS FUELS↗

Two decades of bacterial ecology and evolution in a freshwater lake

Ecology and evolution are considered distinct processes that interact on contemporary time scales in microbiomes. Here, to observe these processes in a natural system, we collected a two-decade, 471-metagenome time series from Lake Mendota (Wisconsin, USA). We assembled 2,855 species-representative genomes and found that genomic change was common and frequent. By tracking strain composition via single nucleotide variants, we identified cyclical seasonal patterns in 80% and decadal shifts in 20% of species. In the dominant freshwater family Nanopelagicaceae, environmental extremes coincided with shifts in strain composition and positive selection of amino acid and nucleic acid metabolism genes. Further, these genes identify organic nitrogen compounds as potential drivers of freshwater responses to global change. Seasonal and long-term strain dynamics could be regarded as ecological processes or, equivalently, as evolutionary change. Rather than as distinct interacting processes, we propose a conceptualization of ecology and evolution as a continuum to better describe change in microbial communities.

59 BASIC BIOLOGICAL SCIENCES↗

Theoretical analysis of the OH-initiated atmospheric oxidation reactions of imidazole

Imidazoles are present in Earth's atmosphere in both the gas-phase and in aerosol particles, and have been implicated in the formation of brown carbon aerosols. The gas-phase oxidation of imidazole (C 3 N 2 H 4 ) by hydroxyl radicals has been shown to be preferentially initiated via OH-addition to position C5, producing the 5-hydroxyimidazolyl radical adduct. However, the fate of this adduct upon reaction with O 2 in the atmospheric gas-phase is currently unknown. We employed an automated approach to investigate the reaction mechanism and kinetics of imidazole's OH-initiated gas-phase oxidation, in the presence of O 2 and NO x . The explored mechanism included reactions available to first-generation RO 2 radicals, as well as alkoxyl radicals produced from RO 2 + NO reactions. Product distributions were obtained by assembling and solving a master equation, under conditions relevant to the Earth's atmosphere. Our calculations show a complex, branched reaction mechanism, which nevertheless converges to yield two major closed-shell products: 4H-imidazol-4-ol (4H-4ol) and N,N′-diformylformamidine (FMF). At 298 K and 1 atm, we estimate the yields of 4H-4ol and FMF from imidazole oxidation initiated via OH-addition to position C5 to be 34 : 66, 12 : 85 and 2 : 95 under 10 ppt, 100 ppt and 1 ppb of NO respectively. This work also revealed O 2 -migration pathways between the α-N-imino peroxyl radical isomers. This reaction channel is fast for the first-generation RO 2 radicals, and may be important during the atmospheric oxidation of other unsaturated organic nitrogen compounds as well.

Almeida, Thomas Golin↗

Multi-omics of a model bacterial consortium deciphers details of chitin decomposition in soil

Soil microorganisms interact to carry out decomposition of complex organic carbon and nitrogen compounds, such as chitin, but the high diversity and complexity of the soil microbiome and habitat have posed a challenge to elucidating such interactions. Here, we sought to address this challenge by analysis of a model soil consortium (MSC-2) consisting of eight soil bacterial species. Our aim was to elucidate the specific roles of the member species during chitin metabolism. Samples were collected from MSC-2 incubated in chitin-enriched soil over 3 months. Multi-omics was used to understand how the community composition, transcripts, proteins, and chitin decomposition shifted over time. The data clearly and consistently revealed a temporal shift during chitin decomposition with defined contributions by individual species. A Streptomyces genus member (sp001905665) was a key player in early steps of chitin decomposition, with other MSC-2 members being central in carrying out later steps. These results illustrate how multi-omics applied to a defined consortium untangles the interactions between soil microorganisms.

chitin↗

Simultaneous expression of an endogenous spermidine synthase and a butanol dehydrogenase from Thermoanaerobacter pseudethanolicus in Clostridium thermocellum results in increased resistance to acetic acid and furans, increased ethanol production and an increase in thermotolerance

Abstract Background Sensitivity to inhibitors derived from the pretreatment of plant biomass is a barrier to the consolidated bioprocessing of these complex substrates to fuels and chemicals by microbes. Spermidine is a low molecular weight aliphatic nitrogen compound ubiquitous in microorganisms, plants, and animals and is often associated with tolerance to stress. We recently showed that overexpression of the endogenous spermidine synthase enhanced tolerance of the Gram-positive bacterium, Clostridium thermocellum to the furan derivatives furfural and HMF. Results Here we show that co-expression with an NADPH-dependent heat-stable butanol dehydrogenase from Thermoanaerobacter pseudethanolicus further enhanced tolerance to furans and acetic acid and most strikingly resulted in an increase in thermotolerance at 65 °C. Conclusions Tolerance to fermentation inhibitors will facilitate the use of plant biomass substrates by thermophiles in general and this organism in particular. The ability to grow C. thermocellum at 65 °C has profound implications for metabolic engineering.

09 BIOMASS FUELS↗

Meanders as a scaling motif for understanding of floodplain soil microbiome and biogeochemical potential at the watershed scale

Abstract Background Biogeochemical exports from watersheds are modulated by the activity of microorganisms that function over micron scales. Here, we tested the hypothesis that meander-bound regions share a core microbiome and exhibit patterns of metabolic potential that broadly predict biogeochemical processes in floodplain soils along a river corridor. Results We intensively sampled the microbiomes of floodplain soils located in the upper, middle, and lower reaches of the East River, Colorado. Despite the very high microbial diversity and complexity of the soils, we reconstructed 248 quality draft genomes representative of subspecies. Approximately one third of these bacterial subspecies was detected across all three locations at similar abundance levels, and ~ 15% of species were detected in two consecutive years. Within the meander-bound floodplains, we did not detect systematic patterns of gene abundance based on sampling position relative to the river. However, across meanders, we identified a core floodplain microbiome that is enriched in capacities for aerobic respiration, aerobic CO oxidation, and thiosulfate oxidation with the formation of elemental sulfur. Given this, we conducted a transcriptomic analysis of the middle floodplain. In contrast to predictions made based on the prominence of gene inventories, the most highly transcribed genes were relatively rare amoCAB and nxrAB (for nitrification) genes, followed by genes involved in methanol and formate oxidation, and nitrogen and CO 2 fixation. Within all three meanders, low soil organic carbon correlated with high activity of genes involved in methanol, formate, sulfide, hydrogen, and ammonia oxidation, nitrite oxidoreduction, and nitrate and nitrite reduction. Overall, the results emphasize the importance of sulfur, one-carbon and nitrogen compound metabolism in soils of the riparian corridor. Conclusions The disparity between the scale of a microbial cell and the scale of a watershed currently limits the development of genomically informed predictive models describing watershed biogeochemical function. Meander-bound floodplains appear to serve as scaling motifs that predict aggregate capacities for biogeochemical transformations, providing a foundation for incorporating riparian soil microbiomes in watershed models. Widely represented genetic capacities did not predict in situ activity at one time point, but rather they define a reservoir of biogeochemical potential available as conditions change.

54 ENVIRONMENTAL SCIENCES↗

Characterizing New Particle Formation and Growth (Field Campaign Report)

New particle formation (NPF) and subsequent growth to sizes at which the aerosol particles can act as cloud condensation nuclei (CCN) is critical for understanding and modeling aerosol-climate interactions (Gordon et al. 2017, Dunne et al. 2016). While sulfuric acid is generally understood to play a central role in NPF and growth, measured sulfuric acid concentrations are insufficient to explain measured formation and growth rates in many locations even when stabilization by ammonia is considered (Kulmala et al. 2014, Riipinen et al. 2012). Extensive laboratory investigations have revealed that amines (Almeida et al. 2013), other reduced nitrogen compounds (Glasoe et al. 2015), and/or oxidized organic compounds (Kirkby et al. 2016) can enhance new particle formation rates and thus may explain, at least in part, the gap between our understanding of new particle formation and the measurements. Our knowledge, however, of the relative importance of these various pathways remains incomplete due to the limited number of ambient measurements, particularly in diverse ecosystems. Agricultural land use areas are particularly understudied despite accounting for ~41% of global land cover (Ellis et al. 2010). Improving our understanding of NPF requires measurements of NPF and the precursors to NPF and growth in a variety of ecosystems and ideally across seasons.

54 ENVIRONMENTAL SCIENCES↗

EVT 16s Data and Large Supplementary Files

Soil microorganisms often interact to carry out decomposition of complex organic carbon and nitrogen compounds, such as chitin, but the high diversity and complexity of the soil microbiome and habitat has posed a challenge to elucidating such interactions between soil microorganisms. Here, we seek to address this challenge through analysis of a model soil consortium (MSC-2) of eight soil bacterial species. Our aim was to elucidate specific roles of the member species during chitin metabolism. Samples were collected from MSC-2 incubated in chitin-enriched soil over three months. Multi-omics was used to understand how the community composition, transcripts, proteins and chitin decomposition shifted over time. The data clearly and consistently revealed a temporal shift during chitin decomposition with defined contributions by individual species. A Streptomyces genus member (sp001905665) was a key player in early steps of chitin decomposition, with other MSC-2 members being central in carrying out later steps. These results illustrate how multi-omics applied to a defined consortium untangles interactions between soil microorganisms.

McClure, Ryan [Pacific Northwest National Laborato↗

Reduced Late Bombardment on Rocky Exoplanets around M Dwarfs

Ocean-vaporizing impacts of chemically reduced planetesimals onto the early Earth have been suggested to catalyze atmospheric production of reduced nitrogen compounds and trigger prebiotic synthesis despite an oxidized lithosphere. While geochemical evidence supports a dry, highly reduced late veneer on Earth, the composition of late-impacting debris around lower-mass stars is subject to variable volatile loss as a result of their hosts' extended pre-main-sequence phase. We perform simulations of late-stage planet formation across the M-dwarf mass spectrum to derive upper limits on reducing bombardment epochs in Hadean-analog environments. We contrast the solar system scenario with varying initial volatile distributions due to extended primordial runaway greenhouse phases on protoplanets and the desiccation of smaller planetesimals by internal radiogenic heating. We find a decreasing rate of late-accreting reducing impacts with decreasing stellar mass. Young planets around stars ≤0.4 M ⊙ experience no impacts of sufficient mass to generate prebiotically relevant concentrations of reduced atmospheric compounds once their stars have reached the main sequence. For M-dwarf planets to not exceed Earth-like concentrations of volatiles, both planetesimals, and larger protoplanets must undergo extensive devolatilization processes and can typically emerge from long-lived magma ocean phases with sufficient atmophile content to outgas secondary atmospheres. Our results suggest that transiently reducing surface conditions on young rocky exoplanets are favored around FGK stellar types relative to M dwarfs.

79 ASTRONOMY AND ASTROPHYSICS↗

Dynamic infrared gas analysis from longleaf pine fuel beds burned in a wind tunnel: observation of phenol in pyrolysis and combustion phases

Pyrolysis is the first step in a series of chemical and physical processes that produce flammable organic gases from wildland fuels that can result in a wildland fire. We report results using a new time-resolved Fourier transform infrared (FTIR) method that correlates the measured FTIR spectrum with an infrared thermal image sequence, enabling the identification and quantification of gases within different phases of the fire process. The flame from burning fuel beds composed of pine needles (Pinus palustris) and mixtures of sparkleberry, fetterbush, and inkberry plants was the natural heat source for pyrolysis. Extractive gas samples were analyzed and identified in both static and dynamic modes synchronized to thermal infrared imaging: a total of 29 gases were identified including small alkanes, alkenes, aldehydes, nitrogen compounds, and aromatics, most previously measured by FTIR in wildland fires. This study presents one of the first identifications of phenol associated with both pre-combustion and combustion phases using ca. 1 Hz temporal resolution. Preliminary results indicate ~2.5× greater phenol emissions from sparkleberry and inkberry compared to fetterbush, with differing temporal profiles.

09 BIOMASS FUELS↗

Organic contamination analysis: High resolution mass spectrometric analysis of surface organics on selected areas of Surveyor 3

The mirror and middle shroud were extracted for organics by washing the surfaces with solvents. The techniques are discussed. Ion microprobe analyses of the primarily atomic species are presented. The sources of the organic contaminants are: (1) hydrocarbons from lubricating oils and general terrestrial contamination, (2) dioctyl phthalate, probably from polyethylene bagging material (the plasticizer), (3) carboxylic acids from decomposition of grease and general terrestrial contamination, (4) silicones from sources such as lubricating oil, (5) outgassing of electronics and plasticizer, (6) vinyl alcohol and styrene copolymer, probably from electronic insulation, and (7) nitrogenous compounds from the lunar module and possibly Surveyor 3 engine exhaust.

Simoneit, B. R.↗

Origin of organic matter in early solar system. VI - Catalytic synthesis of nitriles, nitrogen bases and porphyrin-like pigments.

A variety of nitrogen compounds have been synthesized by a static Fischer-Tropsch type reaction from CO, D2 and ND3, with Ni-Fe and Al2O3 catalysts. In this reaction, the gas is heated to 500-700 C for about 0.5 hr, and then cycled through lower temperatures (100-400 C) for 1-14 days. Products were analyzed by mass spectrometry in conjunction with gas chromatography and other chromatographic techniques. Compounds produced include alkyl cyanides, pyrroles, porphyrin-like compounds, guanidines, hydantoin, uracil and its derivatives, thymine, adenine, guanine, xanthine, melamine, as well as alkanes, alkenes and aromatic hydrocarbons. Such reactions may have been involved in the production of interstellar molecules, organic compounds in meteorites, and prebiotic organic matter on planets.

Hayatsu, R.↗