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  • 1
    Publication Date: 2019-09-11
    Description: Hydroxymethyl hydroperoxide (HMHP), formed in the reaction of the C1 Criegee intermediate with water, is among the most abundant organic peroxides in the atmosphere. Although reaction with OH is thought to represent one of the most important atmospheric removal processes for HMHP, this reaction has been largely unstudied in the laboratory. Here, we present measurements of the kinetics and products formed in the reaction of HMHP with OH. HMHP was oxidized by OH in an environmental chamber; the decay of the hydroperoxide and the formation of formic acid and formaldehyde were monitored over time using CF3O- chemical ionization mass spectrometry (CIMS) and laser induced fluorescence (LIF). The loss of HMHP by reaction with OH is measured relative to the loss of 1,2-butanediol [k1;2-butanediol+OH = (27:0 5:6) 10- exp12 cm3 molecule-1s-1]. We find that HMHP reacts with OH at 295 K with a rate coefficient of (7.1 1.5) 10-12 cm3 molecule-1s-1, with the formic acid to formaldehyde yield in a ratio of 0:880:21 and independent of NO concentration (31010 1.51013 molecule cm-3). We suggest that, exclusively, abstraction of the methyl hydrogen of HMHP results in formic acid while abstraction of the hydroperoxy hydrogen results in formaldehyde. We further evaluate the relative importance of HMHP sinks and use global simulations from GEOS-Chem to estimate that HMHP oxidation by OH contributes 1.7 Tg yr-1 (1-3%) of global annual formic acid production.
    Keywords: Inorganic, Organic and Physical Chemistry; Geosciences (General)
    Type: GSFC-E-DAA-TN68989 , Journal of Physical Chemistry A (ISSN 1089-5639) (e-ISSN 1520-5215); 122; 30; 6292-6302
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  • 2
    Publication Date: 2019-10-05
    Description: Recent studies suggest overestimates in current U.S. emission inventories of nitrogen oxides (NOx=NO+NO2). Here, we expand a previously developed Fuel-based Inventory of motor-Vehicle Emissions (FIVE) to the continental U.S. for the year 2013, and evaluate our estimates of mobile source emissions with the U.S. Environmental Protection Agency's National Emissions Inventory (NEI) interpolated to 2013. We find that mobile source emissions of NOx and carbon monoxide (CO) in the NEI are higher than FIVE by 28% and 90%, respectively. Using a chemical transport model, we model mobile source emissions from FIVE, and find consistent levels of urban NOx and CO as measured during the Southeast Nexus (SENEX) Study in 2013. Lastly, we assess the sensitivity of ozone (O3) over the Eastern U.S. to uncertainties in mobile source NOx emissions and biogenic volatile organic compound (VOC) emissions. The ground-level O3 is sensitive to reductions in mobile source NOx emissions, most notably in the Southeastern U.S. and during O3 exceedance events, under the revised standard proposed in 2015 (〉70 ppb, 8-hr maximum). This suggests that decreasing mobile source NOx emissions could help in meeting more stringent O3 standards in the future.
    Keywords: Environment Pollution
    Type: GSFC-E-DAA-TN61544 , Environmental Science and Technology (ISSN 0013-936X) (e-ISSN 1520-5851); 52; 13; 7360–7370
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  • 3
    Publication Date: 2018-05-03
    Description: Minerals, Vol. 8, Pages 192: Oyonite, Ag3Mn2Pb4Sb7As4S24, a New Member of the Lillianite Homologous Series from the Uchucchacua Base-Metal Deposit, Oyon District, Peru Minerals doi: 10.3390/min8050192 Authors: Luca Bindi Cristian Biagioni Frank N. Keutsch The new mineral species oyonite, ideally Ag3Mn2Pb4Sb7As4S24, has been discovered in the Uchucchacua base-metal deposit, Oyon district, Catajambo, Lima Department, Peru, as very rare black metallic subhedral to anhedral crystals, up to 100 μm in length, associated with orpiment, tennantite/tetrahedrite, menchettiite, and other unnamed minerals of the system Pb-Ag-Sb-Mn-As-S, in calcite matrix. Its Vickers hardness (VHN100) is 137 kg/mm2 (range 132–147). In reflected light, oyonite is weakly to moderately bireflectant and weakly pleochroic from dark grey to a dark green. Internal reflections are absent. Reflectance values for the four COM wavelengths [Rmin, Rmax (%) (λ in nm)] are: 33.9, 40.2 (471.1); 32.5, 38.9 (548.3), 31.6, 38.0 (586.6); and 29.8, 36.5 (652.3). Electron microprobe analysis gave (in wt %, average of 5 spot analyses): Cu 0.76 (2), Ag 8.39 (10), Mn 3.02 (7), Pb 24.70 (25), As 9.54 (12), Sb 28.87 (21), S 24.30 (18), total 99.58 (23). Based on 20 cations per formula unit, the chemical formula of oyonite is Cu0.38Ag2.48Mn1.75Pb3.79Sb7.55As4.05S24.12. The main diffraction lines are (d in Å, hkl and relative intensity): 3.34 (−312; 40), 3.29 (−520; 100), 2.920 (−132; 40), 2.821 (−232; 70), 2.045 (004; 50). The crystal structure study revealed oyonite to be monoclinic, space group P21/n, with unit-cell parameters a = 19.1806 (18), b = 12.7755 (14), c = 8.1789 (10) Å, β = 90.471 (11)°, V = 2004.1 (4) Å3, Z = 2. The crystal structure was refined to a final R1 = 0.032 for 6272 independent reflections. Oyonite belongs to the Sb-rich members of the andorite homeotypic sub-series within the lillianite homologous series. The name oyonite is after the Oyon district, Lima Department, Peru, the district where the type locality (Uchucchacua mine) is located.
    Electronic ISSN: 2075-163X
    Topics: Geosciences
    Published by MDPI Publishing
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  • 4
    Publication Date: 2018-04-20
    Description: Gliomas with histone H3 lysine27-to-methionine mutations (H3K27M-glioma) arise primarily in the midline of the central nervous system of young children, suggesting a cooperation between genetics and cellular context in tumorigenesis. Although the genetics of H3K27M-glioma are well characterized, their cellular architecture remains uncharted. We performed single-cell RNA sequencing in 3321 cells from six primary H3K27M-glioma and matched models. We found that H3K27M-glioma primarily contain cells that resemble oligodendrocyte precursor cells (OPC-like), whereas more differentiated malignant cells are a minority. OPC-like cells exhibit greater proliferation and tumor-propagating potential than their more differentiated counterparts and are at least in part sustained by PDGFRA signaling. Our study characterizes oncogenic and developmental programs in H3K27M-glioma at single-cell resolution and across genetic subclones, suggesting potential therapeutic targets in this disease.
    Keywords: Genetics, Medicine, Diseases
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 5
    Publication Date: 2018-01-27
    Description: Analytical Chemistry DOI: 10.1021/acs.analchem.7b04438
    Print ISSN: 0003-2700
    Electronic ISSN: 1520-6882
    Topics: Chemistry and Pharmacology
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  • 6
    Publication Date: 2018
    Description: 〈div data-abstract-type="normal"〉 〈p〉Agmantinite, ideally Ag〈span〉2〈/span〉MnSnS〈span〉4〈/span〉, is a new mineral from the Uchucchacua polymetallic deposit, Oyon district, Catajambo, Lima Department, Peru. It occurs as orange–red crystals up to 100 μm across. Agmantinite is translucent with adamantine lustre and possesses a red streak. It is brittle. Neither fracture nor cleavage were observed. Based on the empirical formula the calculated density is 4.574 g/cm〈span〉3〈/span〉. On the basis of chemically similar compounds the Mohs hardness is estimated at between 2 to 2½. In plane-polarised light agmantinite is white with red internal reflections. It is weakly bireflectant with no observable pleochroism with red internal reflections. Between crossed polars, agmantinite is weakly anisotropic with reddish brown to greenish grey rotation tints. The reflectances (〈span〉R〈/span〉〈span〉min〈/span〉 and 〈span〉R〈/span〉〈span〉max〈/span〉) for the four standard wavelengths are: 19.7 and 22.0 (470 nm); 20.5 and 23.2 (546 nm); 21.7 and 2.49 (589 nm); and 20.6 and 23.6 (650 nm), respectively.〈/p〉 〈p〉Agmantinite is orthorhombic, space group 〈span〉P〈/span〉2〈span〉1〈/span〉〈span〉nm〈/span〉, with unit-cell parameters: 〈span〉a〈/span〉 = 6.632(2), 〈span〉b〈/span〉 = 6.922(2), 〈span〉c〈/span〉 = 8.156(2) Å, 〈span〉V〈/span〉 = 374.41(17) Å〈span〉3〈/span〉, 〈span〉a〈/span〉:〈span〉b〈/span〉:〈span〉c〈/span〉 0.958:1:1.178 and 〈span〉Z〈/span〉 = 2. The crystal structure was refined to 〈span〉R〈/span〉 = 0.0575 for 519 reflections with 〈span〉I 〉〈/span〉 2σ(〈span〉I〈/span〉). Agmantinite is the first known mineral of 〈span〉〈span〉〈img data-mimesubtype="gif" data-type="simple" src="http://static.cambridge.org/resource/id/urn:cambridge.org:id:binary:20190522072108342-0385:S0026461X18001391:S0026461X18001391_inline1.gif"〉 〈span data-mathjax-type="texmath"〉 〈/span〉 〈/span〉〈/span〉〈span〉M〈/span〉〈span〉II〈/span〉〈span〉M〈/span〉〈span〉IV〈/span〉S〈span〉4〈/span〉 type that is derived from wurtzite rather than sphalerite by ordered substitution of Zn, analogous to the substitution pattern for deriving stannite from sphalerite. The six strongest X-ray powder-diffraction lines derived from single-crystal X-ray diffraction data [〈span〉d〈/span〉 in Å (intensity)] are: 3.51 (s), 3.32 (w), 3.11 (vs), 2.42 (w), 2.04 (m) and 1.88 (m). The empirical formula (based on 8 apfu) is (Ag〈span〉1.94〈/span〉Cu〈span〉0.03〈/span〉)〈span〉Σ1.97〈/span〉(Mn〈span〉0.98〈/span〉Zn〈span〉0.05〈/span〉)〈span〉Σ1.03〈/span〉Sn〈span〉0.97〈/span〉S〈span〉4.03〈/span〉.The crystal structure-derived formula is Ag〈span〉2〈/span〉(Mn〈span〉0.69〈/span〉Zn〈span〉0.31〈/span〉)〈span〉Σ1.00〈/span〉SnS〈span〉4〈/span〉 and the simplified formula is Ag〈span〉2〈/span〉MnSnS〈span〉4〈/span〉.〈/p〉 〈p〉The name is for the composition and the new mineral and mineral name have been approved by the International Mineralogical Association Commission on New Minerals, Nomenclature and Classification (IMA2014-083).〈/p〉 〈/div〉
    Print ISSN: 0026-461X
    Electronic ISSN: 1471-8022
    Topics: Geosciences
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  • 7
    Publication Date: 2018
    Description: 〈div data-abstract-type="normal"〉〈p〉Structural data for weishanite, an alloy of Au, Ag and Hg, were collected for the first time from a crystal from the Keystone Mine, Colorado, USA. The structure was solved in the space group 〈span〉P〈/span〉6〈span〉3〈/span〉/〈span〉mmc〈/span〉 with the unit cell 〈span〉a〈/span〉 = 2.9348(8) and 〈span〉c〈/span〉 = 4.8215(18) Å] and refined to 〈span〉R〈/span〉 = 0.0299 for 40 observed reflections [4σ(〈span〉F〈/span〉) level] and four parameters and to 〈span〉R〈/span〉 = 0.0356 for all 47 independent reflections. The weishanite structure can be considered a derivative of the zinc structure, with Au, Ag and Hg disordered in the same structural position. On this basis, we suggest that the formula is normalized to 1 atom with 〈span〉Z〈/span〉 = 2, leading, for the sample investigated, to Au〈span〉0.41〈/span〉Ag〈span〉0.31〈/span〉Hg〈span〉0.28〈/span〉 (electron microprobe data). Accordingly, weishanite can be considered the Au-rich isotype of schachnerite. A comparison with other Au/Ag-Hg alloys is presented together with a critical discussion about the nomenclature rules to be applied to alloys and simple metals.〈/p〉〈/div〉
    Print ISSN: 0026-461X
    Electronic ISSN: 1471-8022
    Topics: Geosciences
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  • 8
    Publication Date: 2018-10-26
    Description: Organic nitrate chemistry is the primary control over the lifetime of nitrogen oxides (NOx) in rural and remote continental locations. As NOx emissions decrease, organic nitrate chemistry becomes increasingly important to urban air quality. However, the lifetime of individual organic nitrates and the reactions that lead to their production and removal remain relatively poorly constrained, causing organic nitrates to be poorly represented by models. Guided by recent laboratory and field studies, we developed a detailed gas-phase chemical mechanism representing most of the important individual organic nitrates. We use this mechanism within the Weather Research and Forecasting (WRF) model coupled with Chemistry (WRF-Chem) to describe the role of organic nitrates in nitrogen oxide chemistry and in comparisons to observations. We find the daytime lifetime of total organic nitrates with respect to all loss mechanisms to be 2.6h in the model. This is consistent with analyses of observations at a rural site in central Alabama during the Southern Oxidant and Aerosol Study (SOAS) in summer 2013. The lifetime of the first-generation organic nitrates is ∼2h versus the 3.2h lifetime of secondary nitrates produced by oxidation of the first-generation nitrates. The different generations are subject to different losses, with dry deposition to the surface being the dominant loss process for the second-generation organic nitrates and chemical loss being dominant for the first-generation organic nitrates. Removal by hydrolysis is found to be responsible for the loss of ∼30% of the total organic nitrate pool.
    Print ISSN: 1680-7316
    Electronic ISSN: 1680-7324
    Topics: Geosciences
    Published by Copernicus on behalf of European Geosciences Union (EGU).
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  • 9
    Publication Date: 2018-06-07
    Description: The photooxidation of methyl vinyl ketone (MVK) was investigated in the atmospheric simulation chamber SAPHIR for conditions at which organic peroxy radicals (RO2) mainly reacted with NO (“high NO” case) and for conditions at which other reaction channels could compete (“low NO” case). Measurements of trace gas concentrations were compared to calculated concentration time series applying the Master Chemical Mechanism (MCM version 3.3.1). Product yields of methylglyoxal and glycolaldehyde were determined from measurements. For the high NO case, the methylglyoxal yield was (19 ± 3) % and the glycolaldehyde yield was (65 ± 14) %, consistent with recent literature studies. For the low NO case, the methylglyoxal yield reduced to (5 ± 2) % because other RO2 reaction channels that do not form methylglyoxal became important. Consistent with literature data, the glycolaldehyde yield of (37 ± 9) % determined in the experiment was not reduced as much as implemented in the MCM, suggesting additional reaction channels producing glycolaldehyde. At the same time, direct quantification of OH radicals in the experiments shows the need for an enhanced OH radical production at low NO conditions similar to previous studies investigating the oxidation of the parent VOC isoprene and methacrolein, the second major oxidation product of isoprene. For MVK the model–measurement discrepancy was up to a factor of 2. Product yields and OH observations were consistent with assumptions of additional RO2 plus HO2 reaction channels as proposed in literature for the major RO2 species formed from the reaction of MVK with OH. However, this study shows that also HO2 radical concentrations are underestimated by the model, suggesting that additional OH is not directly produced from RO2 radical reactions, but indirectly via increased HO2. Quantum chemical calculations show that HO2 could be produced from a fast 1,4-H shift of the second most important MVK derived RO2 species (reaction rate constant 0.003 s−1). However, additional HO2 from this reaction was not sufficiently large to bring modelled HO2 radical concentrations into agreement with measurements due to the small yield of this RO2 species. An additional reaction channel of the major RO2 species with a reaction rate constant of (0.006 ± 0.004) s−1 would be required that produces concurrently HO2 radicals and glycolaldehyde to achieve model–measurement agreement. A unimolecular reaction similar to the 1,5-H shift reaction that was proposed in literature for RO2 radicals from MVK would not explain product yields for conditions of experiments in this study. A set of H-migration reactions for the main RO2 radicals were investigated by quantum chemical and theoretical kinetic methodologies, but did not reveal a contributing route to HO2 radicals or glycolaldehyde.
    Print ISSN: 1680-7316
    Electronic ISSN: 1680-7324
    Topics: Geosciences
    Published by Copernicus on behalf of European Geosciences Union (EGU).
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  • 10
    Publication Date: 2018-06-13
    Description: Organic nitrate chemistry is the primary control over the lifetime of nitrogen oxides (NOx) in rural and remote continental locations. As NOx emissions decrease, organic nitrate chemistry becomes increasingly important to urban air quality. However, the lifetime of individual organic nitrates and the reactions that lead to their production and removal remain relatively poorly constrained, causing organic nitrates to be poorly represented by models. Guided by recent laboratory and field studies, we developed a detailed gas phase chemical mechanism representing most of the important individual organic nitrates. We use this mechanism within the WRF-Chem model to describe the role of organic nitrates in nitrogen oxide chemistry and in comparisons to observations. We find the daytime lifetime of total organic nitrates with respect to all loss mechanisms to be 2.6h in the model. This is consistent with analyses of observations at a rural site in central Alabama during the Southern Oxidant and Aerosol Study (SOAS) in summer 2013. The lifetime of the first-generation organic nitrates is ~2h versus the 3.2h lifetime of secondary nitrates produced by oxidation of the first-generation nitrates. The different generations are subject to different losses, with dry deposition to the surface dominant loss process for the second-generation organic nitrates, and chemical loss dominant for the first-generation organic nitrates. Removal by hydrolysis is found to be responsible for the loss of ~30% of the total organic nitrate pool.
    Electronic ISSN: 1680-7375
    Topics: Geosciences
    Published by Copernicus on behalf of European Geosciences Union (EGU).
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