Measurements of I/SVOCs in biomass-burning smoke using solid-phase extraction disks and two-dimensional gas chromatography

Biomass-burning organic-aerosol (OA) emissions are known to exhibit semi-volatile behavior that impacts OA loading during plume transport. Because such semi-volatile behavior depends in part on OA composition, improved speciation of intermediate and semi-volatile organic compounds (I/SVOCs) emitted during fires is needed to assess the competing effects of primary OA volatilization and secondary OA production. In this study, 18 laboratory fires were sampled in which a range of fuel types were burned. Emitted I/SVOCs were collected onto Teflon filters and solid-phase extraction (SPE) disks to qualitatively characterize particulate and gaseous I/SVOCs, respectively. Derivatized filter extracts were analyzed using comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry (GC×GC-TOFMS). Quality control tests were performed using biomass-burning relevant standards and demonstrate the utility of SPE disks for untargeted analysis of air samples. The observed chromatographic profiles of I/SVOCs in coniferous fuel-derived smoke samples were well correlated with each other, but poorly correlated with other fuel types (e.g., herbaceous and chaparral fuels). Emissions of benzenediol isomers were also shown to be fuel dependent. The combined Teflon and SPE filter data captured differences in gas-particle partitioning of the benzenediol isomers, with hydroquinone having a significantly higher particle-phase fraction than catechol due to its lower volatility. Additionally, the speciated volatility distribution of I/SVOCs in smoke from a rotten-log fire was estimated to evaluate the composition of potentially volatilized primary OA, which was entirely attributed to oxygenated (or other heteroatomic) compounds. The isomer-dependent partitioning and the speciated volatility distributions both suggest the need for better understanding of gas-phase and heterogenous reaction pathways of biomass-burning-derived I/SVOCs in order to represent the atmospheric chemistry of smoke in models

Application of an enhanced discrete element method to oil and gas drilling processes

The authors present results on the use of the discrete element method (DEM) for the simulation of drilling processes typical in the oil and gas exploration industry. The numerical method uses advanced DEM techniques using a local definition of the DEM parameters and combined FEM-DEM procedures. This paper presents a step by step procedure to build a DEM model for analysis of the soil region coupled to a FEM model for discretizing the drilling tool that reproduces the drilling mechanics of a particular drill bit. A parameter study has been performed to determine the model parameters in order to maintain accurate solutions with reduced computational cost

Similar local but different systemic metabolomic responses of closely related pine subspecies to folivory by caterpillars of the processionary moth

Plants respond locally and systemically to herbivore attack. Most of the research conducted on plant-herbivore relationships at elemental and molecular levels have focused on the elemental composition or/and certain molecular compounds or specific families of defensive metabolites showing that herbivores tend to select plant individuals or species with higher nutrient concentrations and to avoid those with higher levels of defensive compounds. We performed stoichiometric and metabolomics, local and systemic, analyses in two subspecies of Pinus sylvestris under the attack by the caterpillars of the pine processionary moth, an important pest in the Mediterranean Basin. Both pine subspecies responded locally to folivory mainly by increasing the relative concentrations of terpenes and some phenolics. Systemic responses differed between subspecies and most of the metabolites presented intermediate concentrations between those of the affected parts and unattacked trees. Our results support the hypothesis that foliar nutrient concentrations are not a key factor of an alleged plant selection by adult female processionary moths for oviposition since folivory was not associated with any of the elements analyzed. Phenolic compounds did not generally increase in the attacked trees questioning thus their commonly proposed induction by folivory attack and their anti-feeding properties. Herbivory attack produced a general systemic shift in pines, including both primary and secondary metabolisms, that was less intense and chemically different from the local responses. Local pine responses were similar between subspecies while systemic responses were more distant between them

Are the metabolomic responses to folivory of closely related plant species linked to macroevolutionary and plant-folivore coevolutionary processes?

Altres ajuts: MAGRAMA/OAPN-022/2008The debate whether the coevolution of plants and insects or macroevolutionary processes (phylogeny) is the main driver determining the arsenal of molecular defensive compounds of plants remains unresolved. Attacks by herbivorous insects affect not only the composition of defensive compounds in plants but also the entire metabolome. Metabolomes are the final products of genotypes and are constrained by macroevolutionary processes, so closely related species should have similar metabolomic compositions and may respond in similar ways to attacks by folivores. We analyzed the elemental compositions and metabolomes of needles from three closely related Pinus species with distant coevolutionary histories with the caterpillar of the processionary moth respond similarly to its attack. All pines had different metabolomes and metabolic responses to herbivorous attack. The metabolomic variation among the species and the responses to folivory reflected their macroevolutionary relationships, with P. pinaster having the most divergent metabolome. The concentrations of terpenes were in the attacked trees supporting the hypothesis that herbivores avoid plant individuals with higher concentrations. Our results suggest that macroevolutionary history plays important roles in the metabolomic responses of these pine species to folivory, but plant-insect coevolution probably constrains those responses. Combinations of different evolutionary factors and trade-offs are likely responsible for the different responses of each species to folivory, which is not necessarily exclusively linked to plant-insect coevolution

Search for Very High-energy Emission from the Millisecond Pulsar PSR J0218+4232

Acciari, V. A., et al. (MAGIC Collaboration)PSR J0218+4232 is one of the most energetic millisecond pulsars known and has long been considered as one of the best candidates for very high-energy (VHE; >100 GeV) ?-ray emission. Using 11.5 yr of Fermi Large Area Telescope (LAT) data between 100 MeV and 870 GeV, and ~90 hr of Major Atmospheric Gamma Imaging Cherenkov (MAGIC) observations in the 20 GeV to 20 TeV range, we searched for the highest energy ?-ray emission from PSR J0218+4232. Based on the analysis of the LAT data, we find evidence for pulsed emission above 25 GeV, but see no evidence for emission above 100 GeV (VHE) with MAGIC. We present the results of searches for ?-ray emission, along with theoretical modeling, to interpret the lack of VHE emission. We conclude that, based on the experimental observations and theoretical modeling, it will remain extremely challenging to detect VHE emission from PSR J0218+4232 with the current generation of Imaging Atmospheric Cherenkov Telescopes, and maybe even with future ones, such as the Cherenkov Telescope Array.The financial support of the German BMBF, MPG and HGF; the Italian INFN and INAF; the Swiss National Fund SNF; the ERDF under the Spanish Ministerio de Ciencia e Innovación (MICINN) (FPA2017-87859-P, FPA2017-85668-P, FPA2017-82729-C6-5-R, FPA2017-90566- REDC, PID2019-104114RB-C31, PID2019-104114RB-C32, PID2019-105510GB-C31,PID2019-107847RB-C41, PID2019- 107847RB-C42, PID2019-107988GB-C22); the Indian Department of Atomic Energy; the Japanese ICRR, the University of Tokyo, JSPS, and MEXT; the Bulgarian Ministry of Education and Science, National RI Roadmap Project DO1-268/16.12.2019 and the Academy of Finland grant No. 320045 is gratefully acknowledged. This work was also supported by the Spanish Centro de Excelencia “Severo Ochoa” SEV-2016-0588 and CEX2019-000920-S, and “María de Maeztu” CEX2019-000918- M, the Unidad de Excelencia “María de Maeztu” MDM-2015- 0509-18-2 and the “la Caixa” Foundation (fellowship LCF/BQ/ PI18/11630012) and by the CERCA program of the Generalitat de Catalunya; by the Croatian Science Foundation (HrZZ) Project IP2016-06-9782 and the University of Rijeka Project 13.12.1.3.02; by the DFG Collaborative Research Centers SFB823/C4 and SFB876/C3; the Polish National Research Centre grant UMO2016/22/M/ST9/00382; and by the Brazilian MCTIC, CNPq and FAPERJ

Similar local, but different systemic, metabolomic responses of closely related pine subspecies to folivory by caterpillars of the processionary moth

ABSTRACT Plants respond locally and systemically to herbivore attack. Most of the research conducted on plant-herbivore relationships at element and molecular levels have focused on the elemental composition or/and certain molecular compounds or specific families of defence metabolites showing that herbivores tend to select plant individuals or species with higher nutrient concentrations and avoid those with higher levels of defence compounds. We performed stoichiometric and metabolomics, both local and systemic, analyses in two subspecies of Pinus sylvestris under attack from caterpillars of the pine processionary moth, an important pest in the Mediterranean Basin. Both pine subspecies responded locally to folivory mainly by increasing relative concentrations of terpenes and some phenolics. Systemic responses differed between pine subspecies, and most of the metabolites presented intermediate concentrations between those of the affected parts and unattacked trees. Our results support the hypothesis that foliar nutrient concentrations are not a key factor for plant selection by adult female processionary moths for oviposition, since folivory was not associated with any of the elements analysed. Phenolic compounds generally did not increase in the attacked trees, questioning the suggestion of induction of phenolics following folivory attack and the anti-feeding properties of phenolics. Herbivory attack produced a general systemic shift in pines, in both primary and secondary metabolism, which was less intense and chemically different from the local responses. Local pine responses were similar between pine subspecies, while systemic responses were more distant

Similar local, but different systemic, metabolomic responses of closely related pine subspecies to folivory by caterpillars of the processionary moth

ABSTRACT Plants respond locally and systemically to herbivore attack. Most of the research conducted on plant-herbivore relationships at element and molecular levels have focused on the elemental composition or/and certain molecular compounds or specific families of defence metabolites showing that herbivores tend to select plant individuals or species with higher nutrient concentrations and avoid those with higher levels of defence compounds. We performed stoichiometric and metabolomics, both local and systemic, analyses in two subspecies of Pinus sylvestris under attack from caterpillars of the pine processionary moth, an important pest in the Mediterranean Basin. Both pine subspecies responded locally to folivory mainly by increasing relative concentrations of terpenes and some phenolics. Systemic responses differed between pine subspecies, and most of the metabolites presented intermediate concentrations between those of the affected parts and unattacked trees. Our results support the hypothesis that foliar nutrient concentrations are not a key factor for plant selection by adult female processionary moths for oviposition, since folivory was not associated with any of the elements analysed. Phenolic compounds generally did not increase in the attacked trees, questioning the suggestion of induction of phenolics following folivory attack and the anti-feeding properties of phenolics. Herbivory attack produced a general systemic shift in pines, in both primary and secondary metabolism, which was less intense and chemically different from the local responses. Local pine responses were similar between pine subspecies, while systemic responses were more distant

First Results from High Angular Resolution ALMA Observations Toward the HL Tau Region

We present Atacama Large Millimeter/submillimeter Array (ALMA) observations from the 2014 Long Baseline Campaign in dust continuum and spectral line emission from the HL Tau region. The continuum images at wavelengths of 2.9, 1.3, and 0.87 mm have unprecedented angular resolutions of 0.075 arcseconds (10 AU) to 0.025 arcseconds (3.5 AU), revealing an astonishing level of detail in the circumstellar disk surrounding the young solar analogue HL Tau, with a pattern of bright and dark rings observed at all wavelengths. By fitting ellipses to the most distinct rings, we measure precise values for the disk inclination (46.72pm0.05 degrees) and position angle (+138.02pm0.07 degrees). We obtain a high-fidelity image of the 1.0 mm spectral index ($\alpha$), which ranges from $\alpha\sim2.0$ in the optically-thick central peak and two brightest rings, increasing to 2.3-3.0 in the dark rings. The dark rings are not devoid of emission, we estimate a grain emissivity index of 0.8 for the innermost dark ring and lower for subsequent dark rings, consistent with some degree of grain growth and evolution. Additional clues that the rings arise from planet formation include an increase in their central offsets with radius and the presence of numerous orbital resonances. At a resolution of 35 AU, we resolve the molecular component of the disk in HCO+ (1-0) which exhibits a pattern over LSR velocities from 2-12 km/s consistent with Keplerian motion around a ~1.3 solar mass star, although complicated by absorption at low blue-shifted velocities. We also serendipitously detect and resolve the nearby protostars XZ Tau (A/B) and LkHa358 at 2.9 mm.Comment: 11 pages, 5 figures, 2 tables, accepted for publication in the Astrophysical Journal Letter

Measurements of I/SVOCs in biomass-burning smoke using solid-phase extraction disks and two-dimensional gas chromatography

Biomass-burning organic-aerosol (OA) emissions are known to exhibit semi-volatile behavior that impacts OA loading during plume transport. Because such semi-volatile behavior depends in part on OA composition, improved speciation of intermediate and semi-volatile organic compounds (I/SVOCs) emitted during fires is needed to assess the competing effects of primary OA volatilization and secondary OA production. In this study, 18 laboratory fires were sampled in which a range of fuel types were burned. Emitted I/SVOCs were collected onto Teflon filters and solid-phase extraction (SPE) disks to qualitatively characterize particulate and gaseous I/SVOCs, respectively. Derivatized filter extracts were analyzed using comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry (GC&thinsp;×&thinsp;GC-TOFMS). Quality control tests were performed using biomass-burning relevant standards and demonstrate the utility of SPE disks for untargeted analysis of air samples. The observed chromatographic profiles of I/SVOCs in coniferous fuel-derived smoke samples were well correlated with each other, but poorly correlated with other fuel types (e.g., herbaceous and chaparral fuels). Emissions of benzenediol isomers were also shown to be fuel dependent. The combined Teflon and SPE filter data captured differences in gas-particle partitioning of the benzenediol isomers, with hydroquinone having a significantly higher particle-phase fraction than catechol due to its lower volatility. Additionally, the speciated volatility distribution of I/SVOCs in smoke from a rotten-log fire was estimated to evaluate the composition of potentially volatilized primary OA, which was entirely attributed to oxygenated (or other heteroatomic) compounds. The isomer-dependent partitioning and the speciated volatility distributions both suggest the need for better understanding of gas-phase and heterogenous reaction pathways of biomass-burning-derived I/SVOCs in order to represent the atmospheric chemistry of smoke in models.</p