Yields of oxidized volatile organic compounds during the OH radical initiated oxidation of isoprene, methyl vinyl ketone, and methacrolein under high-NO_x conditions

We present first-generation and total production yields of glyoxal, methylglyoxal, glycolaldehyde, and hydroxyacetone from the oxidation of isoprene, methyl vinyl ketone (MVK), and methacrolein (MACR) with OH under high NO_x conditions. Several of these first-generation yields are not included in commonly used chemical mechanisms, such as the Leeds Master Chemical Mechanism (MCM) v. 3.2. The first-generation yield of glyoxal from isoprene was determined to be 2.1 (±0.6)%. Inclusion of first-generation production of glyoxal, glycolaldehyde and hydroxyacetone from isoprene greatly improves performance of an MCM based model during the initial part of the experiments. In order to further improve performance of the MCM based model, higher generation glyoxal production was reduced by lowering the first-generation yield of glyoxal from C5 hydroxycarbonyls. The results suggest that glyoxal production from reaction of OH with isoprene under high NO_x conditions can be approximated by inclusion of a first-generation production term together with secondary production only via glycolaldehyde. Analogously, methylglyoxal production can be approximated by a first-generation production term from isoprene, and secondary production via MVK, MACR and hydroxyacetone. The first-generation yields reported here correspond to less than 5% of the total oxidized yield from isoprene and thus only have a small effect on the fate of isoprene. However, due to the abundance of isoprene, the combination of first-generation yields and reduced higher generation production of glyoxal from C5 hydroxycarbonyls is important for models that include the production of the small organic molecules from isoprene

Analysis of photochemical and dark glyoxal uptake: Implications for SOA formation

The dependence of glyoxal uptake onto deliquesced ammonium sulfate seed aerosol was studied under photochemical (light + hydroxyl radical (OH)) and dark conditions. In this study, the chemical composition of aerosol formed from glyoxal is identical in the presence or absence of OH. In addition, there was no observed OH dependence on either glyoxal uptake or glyoxal-driven aerosol growth for this study. These findings demonstrate that, for the system used here, glyoxal uptake is not affected by the presence of OH. In combination with previous studies, this shows that the exact nature of the type of seed aerosol, in particular the presence of a coating, has a large influence on fast photochemical uptake of glyoxal. Due to the challenge of relating this seed aerosol dependence to ambient conditions, this work highlights the resulting difficulty in quantitatively including SOA formation from glyoxal in models

α-pinene photooxidation under controlled chemical conditions – Part 2: SOA yield and composition in low- and high-NO_x environments

The gas-phase oxidation of α-pinene produces a large amount of secondary organic aerosol (SOA) in the atmosphere. A number of carboxylic acids, organosulfates and nitrooxy organosulfates associated with α-pinene have been found in field samples and some are used as tracers of α-pinene oxidation. α-pinene reacts readily with OH and O_3 in the atmosphere followed by reactions with both HO_2 and NO. Due to the large number of potential reaction pathways, it can be difficult to determine what conditions lead to SOA. To better understand the SOA yield and chemical composition from low- and high-NO_x OH oxidation of α-pinene, studies were conducted in the Caltech atmospheric chamber under controlled chemical conditions. Experiments used low O_3 concentrations to ensure that OH was the main oxidant and low α-pinene concentrations such that the peroxy radical (RO_2) reacted primarily with either HO_2 under low-NO_x conditions or NO under high-NO_x conditions. SOA yield was suppressed under conditions of high-NO_x. SOA yield under high-NO_x conditions was greater when ammonium sulfate/sulfuric acid seed particles (highly acidic) were present prior to the onset of growth than when ammonium sulfate seed particles (mildly acidic) were present; this dependence was not observed under low-NO_x conditions. When aerosol seed particles were introduced after OH oxidation, allowing for later generation species to be exposed to fresh inorganic seed particles, a number of low-NO_x products partitioned to the highly acidic aerosol. This indicates that the effect of seed acidity and SOA yield might be under-estimated in traditional experiments where aerosol seed particles are introduced prior to oxidation. We also identify the presence of a number of carboxylic acids that are used as tracer compounds of α-pinene oxidation in the field as well as the formation of organosulfates and nitrooxy organosulfates. A number of the carboxylic acids were observed under all conditions, however, pinic and pinonic acid were only observed under low-NO_x conditions. Evidence is provided for particle-phase sulfate esterification of multi-functional alcohols

Role of aldehyde chemistry and NO_x concentrations in secondary organic aerosol formation

Aldehydes are an important class of products from atmospheric oxidation of hydrocarbons. Isoprene (2-methyl-1,3-butadiene), the most abundantly emitted atmospheric non-methane hydrocarbon, produces a significant amount of secondary organic aerosol (SOA) via methacrolein (a C_4-unsaturated aldehyde) under urban high-NO_x conditions. Previously, we have identified peroxy methacryloyl nitrate (MPAN) as the important intermediate to isoprene and methacrolein SOA in this NO_x regime. Here we show that as a result of this chemistry, NO_2 enhances SOA formation from methacrolein and two other α, β-unsaturated aldehydes, specifically acrolein and crotonaldehyde, a NO_x effect on SOA formation previously unrecognized. Oligoesters of dihydroxycarboxylic acids and hydroxynitrooxycarboxylic acids are observed to increase with increasing NO_2/NO ratio, and previous characterizations are confirmed by both online and offline high-resolution mass spectrometry techniques. Molecular structure also determines the amount of SOA formation, as the SOA mass yields are the highest for aldehydes that are α, β-unsaturated and contain an additional methyl group on the α-carbon. Aerosol formation from 2-methyl-3-buten-2-ol (MBO232) is insignificant, even under high-NO_2 conditions, as PAN (peroxy acyl nitrate, RC(O)OONO_2) formation is structurally unfavorable. At atmospherically relevant NO_2/NO ratios (3–8), the SOA yields from isoprene high-NO_x photooxidation are 3 times greater than previously measured at lower NO_2/NO ratios. At sufficiently high NO_2 concentrations, in systems of α, β-unsaturated aldehydes, SOA formation from subsequent oxidation of products from acyl peroxyl radicals+NO_2 can exceed that from RO_2+HO_2 reactions under the same inorganic seed conditions, making RO_2+NO_2 an important channel for SOA formation

Variabilité spatiale de la teneur en eau de surface des sols nus par mesures in situ et imagerie radar

National audienceOn présente l'analyse géostatistique de la teneur en eau de surface (0-6 cm de profondeur) collectée les 12 et 13 Mars 2009, sur une quinzaine de parcelles de sol nu d'un petit bassin péri-urbain proche de Lyon. Les mesures in situ, ont été collectées à deux échelles : une échelle locale sur des croix de longueur 20m et un pas d'espace de 1m et une échelle parcellaire sur 3 transects avec un pas de 20m environ. Les résultats montrent une corrélation de quelques m à échelle fine et de 20 à 50m à l'échelle de la parcelle. Après correction du bruit, calibration radiométrique et correction des effets géométriques et de pente, la comparaison des moyennes par parcelles issues de l'image radar TerraSAR-X et des mesures in situ est satisfaisante (R2=0.43) mais l'analyse intra-parcellaire reste à affiner. / This paper presents the geostatistical analysis of surface soil water content (0-6 cm depth), collected on March 12-13 2009, in about 15 bare soil fields located in a small suburban catchment close to Lyon. In situ data were sampled at two scales : a local scale on 20m-long crosses with a space step of about 1m; a field scale, with 3 transects and a space scale of about 20m. The results show a correlation of a few meters at the local scale and of about 20-50m at the field scale. After correction of the noise, radiometric calibration, geometric and slope effect correction, the comparison of the field averages derived from the TerraSAR-X image and of in situ data is satisfactory (R2=0.43), but the intra-field variability should be studied in more details

Assessing the Potential of Diverse Forage Mixtures to Reduce Enteric CH\u3csub\u3e4\u3c/sub\u3e Emissions

Enteric methane (CH4) is a main source of agriculture-related greenhouse gasses. Conversely, pasture is increasingly demanded by customers due to both perceived and real benefits regarding animal welfare, environmental aspects and product quality. However, if implemented poorly, CH4 emissions can increase, thus contributing to climate change. One promising option to reduce enteric CH4 emissions are plant specialized metabolites (PSM), and particularly tannins. Consequently, we conducted two complementary experiments to determine to what extent enteric CH4 emissions can be reduced, and how this affects milk yields: a) an in vivo experiment with grazing Jersey cows, where CH4 emissions were quantified using the SF6 tracer technique, and b) an in vitro experiment using the Hohenheim gas test. In the in vivo experiment, a binary mixture consisting of perennial ryegrass (Lolium perenne) and white clover (Trifolium repens) was compared against a diverse mixture consisting of eight species, including birdsfoot trefoil (Lotus corniculatus), and salad burnet (Sanguisorba minor). In the in vitro experiment, the eight species from the in vivo experiment were combined in binary mixtures with perennial ryegrass in increasing proportions, to determine the mitigation potential of each species. Results show an increase in milk yield for the diverse mixture, although this is also accompanied by higher CH4 emissions. Nevertheless, these emissions are lower across both mixtures, when compared with similar trials. This is probably due to a very high digestibility of the ingested forage. With the in vitro experiment, we were able to confirm a substantial potential for CH4 reduction when including species rich in PSM. However, those forbs with the higher anti-methanogenic potential were only present in minor proportions in the pasture. Hence, further research will be required on how to increase the share of the bioactive species with lower competitiveness and confirm their potential in vivo

Análisis de linajes maternos y paternos de bovinos criollo del Centro de Ecología Aaplicada Simón I. Patiño - Bolivia

Se determinaron los linajes maternos y paternos de 33 bovinos Criollo (27 hembras y 6 machos) del Centro de Ecología Aplicada Simón I. Patiño (Ceasip) mediante marcadores genéticos del ADN genómico, mitocondrial y del cromosoma Y. El ADN genómico se extrajo utilizando el kit Wizard ® Genomic Purification. Los linajes maternos se determinaron mediante secuenciación del ADN mitocondrial (región control D-loop) y los linajes paternos se determinaron analizando siete marcadores genéticos del cromosoma Y, dos SNP (Polimorfismo de Nucleótido Simple) y cinco microsatélites (Secuencias Repetidas en Tándem). La diversidad genética se estimó tipificando 18 microsatélites. Se analizaron los datos con MStools, GenePop y Arlequin. La secuenciación de D-loop mitocondrial permitió detectar seis linajes maternos, que incluían cuatro haplotipos mitocondriales de origen europeo y dos africanos. A través del análisis de los marcadores del cromosoma Y se determinaron tres linajes paternos, dos taurinos y uno cebuino. En el hato del Ceasip, la diversidad alélica (na) fue de 6.11, mientras que la heterocigosidad esperada (He) fue de 0.70 y la observada (Ho) fue de 0.68. Los valores de diversidad genética observada en los bovinos del Ceasip son similares a los estimados para la mayoría de los biotipos del Criollo boliviano (na Yacumeño= 6.82; na Saavedreño= 5.95), siendo los valores promedios para el ganado Criollo boliviano analizados anteriormente de na= 6.39, He= 0.72 y Ho= 0.65. Los análisis de Componentes Principales y de distancia genética mostraron que sería factible intercambiar material genético entre las poblaciones Criollo bolivianas sin pérdida significativa de su diversidad genética.Fil: Pereira, J. A. C.. Universidad Autónoma Gabriel René Moreno; BoliviaFil: Giovambattista, Guillermo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico CONICET- La Plata. Instituto de Genética Veterinaria "Ing. Fernando Noel Dulout". Universidad Nacional de La Plata. Facultad de Ciencias Veterinarias. Instituto de Genética Veterinaria; Argentina. Universidad Nacional de La Plata. Facultad de Ciencias Veterinarias; ArgentinaFil: Peña, S.. Centro de Ecología Aplicada Simón I. Patiño; BoliviaFil: Liron, Juan Pedro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico La Plata. Instituto de Genética Veterinaria ; Argentina. Universidad Nacional de La Plata. Facultad de Ciencias Veterinarias; ArgentinaFil: Loza, A. J.. Universidad Autónoma Gabriel René Moreno; BoliviaFil: Posik, Diego Manuel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico La Plata. Instituto de Genética Veterinaria ; Argentina. Universidad Nacional de La Plata. Facultad de Ciencias Veterinarias; ArgentinaFil: Baudoin, M.. Centro de Ecología Aplicada Simón I. Patiño; BoliviaFil: Bomblat, C.. Centro de Ecología Aplicada Simón I. Patiño; Bolivi

Reactive intermediates revealed in secondary organic aerosol formation from isoprene

Isoprene is a significant source of atmospheric organic aerosol; however, the oxidation pathways that lead to secondary organic aerosol (SOA) have remained elusive. Here, we identify the role of two key reactive intermediates, epoxydiols of isoprene (IEPOX = β-IEPOX + δ-IEPOX) and methacryloylperoxynitrate (MPAN), which are formed during isoprene oxidation under low- and high-NO_x conditions, respectively. Isoprene low-NO_x SOA is enhanced in the presence of acidified sulfate seed aerosol (mass yield 28.6%) over that in the presence of neutral aerosol (mass yield 1.3%). Increased uptake of IEPOX by acid-catalyzed particle-phase reactions is shown to explain this enhancement. Under high-NO_x conditions, isoprene SOA formation occurs through oxidation of its second-generation product, MPAN. The similarity of the composition of SOA formed from the photooxidation of MPAN to that formed from isoprene and methacrolein demonstrates the role of MPAN in the formation of isoprene high-NO_x SOA. Reactions of IEPOX and MPAN in the presence of anthropogenic pollutants (i.e., acidic aerosol produced from the oxidation of SO_2 and NO_2, respectively) could be a substantial source of “missing urban SOA” not included in current atmospheric models

Synthesis and Biological Evaluation of Dantrolene-Like Hydrazide and Hydrazone Analogues as Multitarget Agents for Neurodegenerative Diseases

Dantrolene, a drug used for the management of malignant hyperthermia, had been recently evaluated for prospective repurposing as multitarget agent for neurodegenerative syndromes, including Alzheimer's disease (AD). Herein, twenty-one dantrolene-like hydrazide and hydrazone analogues were synthesized with the aim of exploring structure-activity relationships (SARs) for the inhibition of human monoamine oxidases (MAOs) and acetylcholinesterase (AChE), two well-established target enzymes for anti-AD drugs. With few exceptions, the newly synthesized compounds exhibited selectivity toward MAO B over either MAO A or AChE, with the secondary aldimine 9 and phenylhydrazone 20 attaining IC50 values of 0.68 and 0.81 μM, respectively. While no general SAR trend was observed with lipophilicity descriptors, a molecular simplification strategy allowed the main pharmacophore features to be identified, which are responsible for the inhibitory activity toward MAO B. Finally, further in vitro investigations revealed cell protection from oxidative insult and activation of carnitine/acylcarnitine carrier as concomitant biological activities responsible for neuroprotection by hits 9 and 20 and other promising compounds in the examined series

Secondary Organic Aerosol Coating Formation and Evaporation: Chamber Studies Using Black Carbon Seed Aerosol and the Single-Particle Soot Photometer

We report a protocol for using black carbon (BC) aerosol as the seed for secondary organic aerosol (SOA) formation in an environmental chamber. We employ a single-particle soot photometer (SP2) to probe single-particle SOA coating growth dynamics and find that SOA growth on nonspherical BC aerosol is diffusion-limited. Aerosol composition measurements with an Aerodyne high resolution time-of-flight aerosol mass spectrometer (AMS) confirm that the presence of BC seed does not alter the composition of SOA as compared to self-nucleated SOA or condensed SOA on ammonium sulfate seed. We employ a 3-wavelength photoacoustic soot spectrometer (PASS-3) to measure optical properties of the systems studied, including fullerene soot as the surrogate BC seed, nucleated naphthalene SOA from high-NO_x photooxidation, and nucleated α-pinene SOA from low-NO_x photooxidation. A core-and-shell Mie scattering model of the light absorption enhancement is in good agreement with measured enhancements for both the low- and high-NO_x α-pinene photooxidation systems, reinforcing the assumption of a core-shell morphology for coated BC particles. A discrepancy between measured and modeled absorption enhancement factors in the naphthalene photooxidation system is attributed to the wavelength-dependence of refractive index of the naphthalene SOA. The coating of high-NO_x α-pinene SOA decreases after reaching a peak thickness during irradiation, reflecting a volatility change in the aerosol, as confirmed by the relative magnitudes of f_(43) and f_(44) in the AMS spectra. The protocol described here provides a framework by which future studies of SOA optical properties and single-particle growth dynamics may be explored in environmental chambers