Trace Gas Emissions from Laboratory Biomass Fires Measured by Open-Path Fourier Transform Infrared Spectroscopy: Fires in Grass and Surface Fuels

The trace gas emissions from six biomass fires, including three grass fires, were measured using a Fourier transform infrared (FTIR) spectrometer coupled to an open-path, multipass cell (OP-FTIR). The quantified emissions consisted of carbon dioxide, nitric oxide, water vapor, carbon monoxide, methane, ammonia, ethylene, acetylene, isobutene, methanol, acetic acid, formic acid, formaldehyde, and hydroxyacetaldehyde. By including grass fires in this study we have now measured smoke composition from fires in each major vegetation class. The emission ratios of the oxygenated compounds, formaldehyde, methanol, and acetic acid, were 1–2% of CO in the grass fires, similar to our other laboratory and field measurements but significantly higher than in some other studies. These oxygenated compounds are important, as they affect O3 and HOx chemistry in both biomass fire plumes and the free troposphere. The OP-FTIR data and the simultaneously collected canister data indicated that the dominant C4 emission was isobutene (C4H8) and not 1-butene. The rate constant for the reaction of isobutene with the OH radical is 60% larger than that of 1-butene. We estimate that 67±9% of the fuel nitrogen was volatilized with the major nitrogen emissions, ammonia, and nitric oxide, accounting for 22±8%

Modulation of Multiple Sclerosis and its Animal Model experimental Autoimmune encephalomyelitis by Food and Gut Microbiota

Multiple sclerosis (MS) is an autoimmune neurological disease characterized by chronic inflammation of the central nervous system (CNS), leading to demyelination, axonal damage, and symptoms such as fatigue and disability. Although the cause of MS is not known, the infiltration of peripherally activated immune cells into the CNS has a key pathogenic role. Accumulating evidence supports an important role of diet and gut microbiota in immune-mediated diseases. Preclinical as well as clinical studies suggest a role for gut microbiota and dietary components in MS. Here, we review these recent studies on gut microbiota and dietary interventions in MS and its animal model experimental autoimmune encephalomyelitis. We also propose directions for future research

Stereospecific decarboylative allylation of sulfones

This document is the Accepted Manuscript version of a Published Work that appeared in final form in the Journal of the American Chemical Society, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://doi.org/10.1021/ja104196x.Allyl sulfonyl acetic esters undergo highly stereospecific, palladium-catalyzed decarboxylative allylation. The reaction allows the stereospecific formation of tertiary homoallylic sulfones in high yield. In contrast to related reactions that proceed at -100 °C and require highly basic preformed organometallics, the decarboxylative coupling described herein occurs under mild non-basic conditions and requires no stoichiometric additives. Allylation of the intermediate α-sulfonyl anion is more rapid than racemization, leading to a highly enantiospecific process. DFT calculations indicate that the barrier for racemization is 9.9 kcal/mol and thus the barrier of allylation must be <9.9 kcal/mol

Prescription Opioid Use among Pregnant Women Enrolled in Rhode Island Medicaid

Objective: Our objective was to identify the patterns of opioid use among pregnant women enrolled in RI Medicaid. Methods: This study used linked RI Medicaid and RI Birth Certificate data from 01/01/2006 to 12/31/2016. We examined temporal trends of prescription opioid dispensings and identified risk factors associated with opioids use during pregnancy. Results: Among 25,500 RI Medicaid enrolled pregnant women who delivered a live baby from 2008 to 2016, 1,914 (7.5%) received at least one prescription for an opioid medication during pregnancy, 810 (3.2%) were during the first trimester, 633 (2.5%) during the second trimester, and 866 (3.4%) during the third trimester. Of these, 213 (0.8%) women received 3 or more opioids during pregnancy. The prevalence of prescription opioids dispensed in pregnant women increased from 4.9% in 2008 to 9.6% in 2015 (β SD: 0.66 0.28, P=0.05). Conclusions: Prescription opioid use during pregnancy has increased among women enrolled in RI Medicaid

Measurements of Excess O3, CO2, CO, CH4, C2H4, C2H2, HCN, NO, NH3, HCOOH, CH3COOH, HCHO, and CH3OH in 1997 Alaskan Biomass Burning Plumes by Airborne Fourier Transform Infrared Spectroscopy (AFTIR)

We used an airborne Fourier transform infrared spectrometer (AFTIR), coupled to a flow-through, air-sampling cell, on a King Air B-90 to make in situ trace gas measurements in isolated smoke plumes from four, large, boreal zone wildfires in interior Alaska during June 1997. AFTIR spectra acquired near the source of the smoke plumes yielded excess mixing ratios for 13 of the most common trace gases: water, carbon dioxide, carbon monoxide, methane, nitric oxide, formaldehyde, acetic acid, formic acid, methanol, ethylene, acetylene, ammonia and hydrogen cyanide. Emission ratios to carbon monoxide for formaldehyde, acetic acid, and methanol were 2.2±0.4%, 1.3±0.4%, and 1.4±0.1%, respectively. For each oxygenated organic compound, a single linear equation fits our emission factors from Alaska, North Carolina, and laboratory fires as a function of modified combustion efficiency (MCE). A linear equation for predicting the NH3/NOx emission ratio as a function of MCE fits our Alaskan AFTIR results and those from many other studies. AFTIR spectra collected in downwind smoke that had aged 2.2±1 hours in the upper, early plume yielded ΔO3/ΔCO ratios of 7.9±2.4% resulting from O3 production rates of ∼50 ppbv h−1. The ΔNH3/ΔCO ratio in another plume decreased to 1/e of its initial value in ∼2.5 hours. A set of average emission ratios and emission factors for fires in Alaskan boreal forests is derived. We estimate that the 1997 Alaskan fires emitted 46±11 Tg of CO2

Trace Gas and Particle Emissions from Fires in Large Diameter and Belowground Biomass Fuels

[1] We adopt a working definition of residual smoldering combustion (RSC) as biomass combustion that produces emissions that are not lofted by strong fire-induced convection. RSC emissions can be produced for up to several weeks after the passage of a flame front and they are mostly unaffected by flames. Fuels prone to RSC include downed logs, duff, and organic soils. Limited observations in the tropics and the boreal forest suggest that RSC is a globally significant source of emissions to the troposphere. This source was previously uncharacterized. We measured the first emission factors (EF) for RSC in a series of laboratory fires and in a wooded savanna in Zambia, Africa. We report EFRSC for both particles with diameter \u3c2.5 μm (PM2.5) and the major trace gases as measured by open-path Fourier transform infrared (OP-FTIR) spectroscopy. The major trace gases include carbon dioxide, carbon monoxide, methane, ethane, ethene, acetylene, propene, formaldehyde, methanol, acetic acid, formic acid, glycolaldehyde, phenol, furan, ammonia, and hydrogen cyanide. We show that a model used to predict trace gas EF for fires in a wide variety of aboveground fine fuels fails to predict EF for RSC. For many compounds, our EF for RSC-prone fuels from the boreal forest and wooded savanna are very different from the EF for the same compounds measured in fire convection columns above these ecosystems. We couple our newly measured EFRSC with estimates of fuel consumption by RSC to refine emission estimates for fires in the boreal forest and wooded savanna. We find some large changes in estimates of biomass fire emissions with the inclusion of RSC. For instance, the wooded savanna methane EF increases by a factor of 2.5 even when RSC accounts for only 10% of fuel consumption. This shows that many more measurements of fuel consumption and EF for RSC are needed to improve estimates of biomass burning emissions

NGC 7582: The Prototype Narrow-Line X-ray Galaxy

NGC 7582 is a candidate prototype of the Narrow Line X-ray Galaxies (NLXGs) found in deep X-ray surveys. An ASCA observation shows the hard (> 3 keV) X-ray continuum of NGC 7582 drops 40% in ~6 ks, implying an AGN, while the soft band (< 3 keV) does not drop in concert with the hard continuum, requiring a separate component. The X-ray spectrum of NGC 7582 also shows a clear 0.5-2 keV soft (kT = 0.8 (+0.9,-0.3) keV or Gamma = 2.4 +/- 0.6; L(X) = 6 x 10**40 ergs s**-1) low--energy component, in addition to a heavily absorbed [N(H) = (6 +/- 2)\times 10**22 cm**-2 ] and variable 2-10 keV power law [Gamma = 0.7 (+0.3,-0.4); L(X) = (1.7-2.3) x 10**42 ergs s**-1]. This is one of the flattest 2-10 keV slopes in any AGN observed with ASCA. (The ROSAT HRI image of NGC 7582 further suggests extent to the SE.) These observations make it clear that the hard X-ray emission of NGC 7582, the most "narrow-line" of the NLXGs, is associated with an AGN. The strong suggestion is that all NLXGs are obscured AGNs, as hypothesized to explain the X-ray background spectral paradox. The separate soft X-ray component makes NGC 7582 (and by extension other NLXGs) detectable as a ROSAT source.Comment: text: Latex2e 10 pages, including 1 table, and 2 postscript figures via psfi

Increasing Resiliency to Natural Hazards—A Strategic Plan for the Multi-Hazards Demonstration Project in Southern California

The U.S. Geological Survey (USGS) is initiating a new project designed to improve resiliency to natural hazards in southern California through the application of science to community decision making and emergency response. The Multi-Hazards Demonstration Project will assist the region’s communities to reduce their risk from natural hazards by directing new and existing research towards the community’s needs, improving monitoring technology, producing innovative products, and improving dissemination of the results. The natural hazards to be investigated in this project include coastal erosion, earthquakes, floods, landslides, tsunamis, and wildfires. Americans are more at risk from natural hazards now than at any other time in our Nation’s history. Southern California, in particular, has one of the Nation’s highest potentials for extreme catastrophic losses due to natural hazards, with estimates of expected losses exceeding $3 billion per year. These losses can only be reduced through the decisions of the southern California community itself. To be effective, these decisions must be guided by the best information about hazards, risk, and the cost-effectiveness of mitigation technologies. The USGS will work with collaborators to set the direction of the research and to create multi-hazard risk frameworks where communities can apply the results of scientific research to their decision-making processes. Partners include state, county, city, and public-lands government agencies, public and private utilities, companies with a significant impact and presence in southern California, academic researchers, the Federal Emergency Management Agency (FEMA), National Oceanic and Atmospheric Administration (NOAA), and local emergency response agencies. Prior to the writing of this strategic plan document, three strategic planning workshops were held in February and March 2006 at the USGS office in Pasadena to explore potential relationships. The goal of these planning sessions was to determine the external organizations’ needs for mitigation efforts before potential natural hazard events, and response efforts during and after the event. On the basis of input from workshop participants, four priority areas were identified for future research to address. They are (1) helping decision makers design planning scenarios, (2) improving upon the mapping of multiple hazards in urban areas, (3) providing real-time information from monitoring networks, and (4) integrating information in a risk and decision-making analysis. Towards this end, short-term and out-year goals have been outlined with the priorities in mind. First-year goals are (1) to engage the user community to establish the structures and processes for communications and interactions, (2) to develop a program to create scenarios of anticipated disasters, beginning in the first year with a scenario of a southern San Andreas earthquake that triggers secondary hazards, (3) to compile existing datasets of geospatial data, and (4) to target research efforts to support more complete and robust products in future years. Both the first-year and out-year goals have been formulated around a working-group structure that builds on existing research strengths within the USGS. The project is intended to demonstrate how developments in methodology and products can lead to improvement in our management of natural hazards in an urban environment for application across the Nation

The co-ordination chemistry of tris(3,5-dimethylpyrazolyl) methane manganese carbonyl complexes: Synthetic, electrochemical and DFT studies

The tricarbonyl [Mn(CO)3{HC(pz′)3}][PF6] 1+[PF6]− (pz′ = 3,5-dimethylpyrazolyl) reacts with a range of P-, N- and C-donor ligands, L, in the presence of trimethylamine oxide to give [Mn(CO)2L{HC(pz′)3}]+ {L = PEt33+, P(OEt)34+, P(OCH2)3CEt 5+, py 6+, MeCN 7+, CNBut8+ and CNXyl 9+}. The complex [Mn(CO)2(PMe3){HC(pz′)3}]+2+ is formed by reaction of 7+ with PMe3. Complexes 2+ and 6+ were structurally characterised by X-ray diffraction methods. Reaction of 7+ with half a molar equivalent of 4,4′-bipyridine gives a purple compound assumed to be the bridged dimer [{HC(pz′)3}Mn(CO)2(μ-4,4′-bipy)Mn(CO)2{HC(pz′)3}]2+102+. The relative electron donating ability of HC(pz′)3 has been established by comparison with the cyclopentadienyl and tris(pyrazolyl)borate analogues. Cyclic voltammetry shows that each of the complexes undergoes an irreversible oxidation. The correlation between the average carbonyl stretching frequency and the oxidation potential for complexes of P- and C-donor ligands is coincident with the correlation observed for [Mn(CO)3−mLm(η-C5H5−nMen)]. The data for complexes of N-donor ligands, however, are not coincident due to the presence of a node (and phase change) between the metal and the N-donor in the HOMO of the complex as suggested by preliminary DFT calculations