Pulsed Laval nozzle study of the kinetics of OH with unsaturated hydrocarbons at very low temperatures

The kinetics of reactions of the OH radical with ethene, ethyne (acetylene), propyne (methyl acetylene) and t-butyl-hydroperoxide were studied at temperatures of 69 and 86 K using laser flash-photolysis combined with laser-induced fluorescence spectroscopy. A new pulsed Laval nozzle apparatus is used to provide the low-temperature thermalised environment at a single density of similar to 4 x 10(16) molecule cm(-3) in N-2. The density and temperature within the flow are determined using measurements of impact pressure and rotational populations from laser-induced fluorescence spectroscopy of NO and OH. For ethene, rate coefficients were determined to be k(2) = (3.22 +/- 0.46) x 10(-11) and (2.12 +/- 0.12) x 10(-11) cm(3) molecule(-1) s(-1) at T = 69 and 86 K, respectively, in good agreement with a master-equation calculation utilising an ab initio surface recently calculated for this reaction by Cleary et al. (P. A. Cleary, M. T. Baeza Romero, M. A. Blitz, D. E. Heard, M. J. Pilling, P. W. Seakins and L. Wang, Phys. Chem. Chem. Phys., 2006, 8, 5633-5642) For ethyne, no previous data exist below 210 K and a single measurement at 69 K was only able to provide an approximate upper limit for the rate coefficient of k(3) < 1 x 10(-12) cm(3) molecule(-1) s (-1), consistent with the presence of a small activation barrier of similar to 5 kJ mol (-1) between the reagents and the OH-C2H2 adduct. For propyne, there are no previous measurements below 253 K, and rate coefficients of k(4) = (5.08 +/- 0.65), (5.02 +/- 1.11) and (3.11 +/- 0.09) x 10(-12) cm(3) molecule(-1) s(-1) were obtained at T = 69, 86 and 299 K, indicating a much weaker temperature dependence than for ethene. The rate coefficient k(1) = (7.8 +/- 2.5) x 10(-11) cm(3) molecule(-1) s (-1) was obtained for the reaction of OH with t-butyl-hydroperoxide at T = 86 K. Studies of the reaction of OH with benzene and toluene yielded complex kinetic profiles of OH which did not allow the extraction of rate coefficients. Uncertainties are quoted at the 95% confidence limit and include systematic errors

Ab Initio and Statistical Rate Theory Exploration of the CH (X2Π) + OCS Gas-Phase Reaction

The first theoretical results regarding the gas-phase reaction mechanism and kinetics of the CH (X2Π) + OCS reaction are presented here. This reaction has a proposed importance in the removal of OCS in regions of the interstellar medium (ISM) and has the potential to form the recently observed HCS/HSC isomers, with both constitutional isomers having recently been observed in the L483 molecular cloud in a 40:1 ratio. Statistical rate theory simulations were performed on stationary points along the reaction potential energy surface (PES) obtained from ab initio calculations at the RO-CCSD(T)/aug-cc-pV(Q+d)Z//M06-2X-D3/aug-cc-pV(Q+d)Z level of theory over the temperature and total density range of 150–3000 K and 1011–1024 cm–3, respectively, using a Master Equation analysis. Exploration of the reaction potential energy surface revealed that all three pathways identified to create CS + HCO products required surmounting barriers of 16.5 kJ mol–1 or larger when CH approached the oxygen side of OCS, rendering this product formation negligible below 1000 K, and certainly under low-temperature ISM conditions. In contrast, when CH approaches the sulfur side of OCS, only submerged barriers are found along the reaction potential energy surface to create HCCO + S or CO + HCS, both of which are formed via a strongly bound OCC(H)S intermediate (−358.9 kJ mol–1). Conversion from HCS to HSC is possible via a barrier of 77.8 kJ mol–1, which is still −34.1 kJ mol–1 below the CH + OCS entrance channel. No direct route from CH + OCS to H + CO + CS was found from our ab initio calculations. Rate theory simulations suggest that the reaction has a strong negative temperature dependence, in accordance with the barrierless addition of CH to the sulfur side of OCS. Product branching fractions were also determined from MESMER simulations over the same temperature and total density range. The product branching fraction of CO + HCS reduces from 79% at 150 K to 0.0% at 800 K, while that of HCS dissociation to H + CS + CO increases from 22% at 150 K to 100% at 800 K. The finding of CO + HCS as the major product at the low temperatures relevant to the ISM, instead of H + CS + CO, is in opposition to the current supposition used in the KIDA database and should be adapted in astrochemical models as another source of the HCS isomer

Experimental and Theoretical Investigation of the Reaction of NH2 with NO at Very Low Temperatures

The first experimental study of the low-temperature kinetics of the gas-phase reaction between NH2 and NO has been performed. A pulsed laser photolysis-laser-induced fluorescence technique was used to create and monitor the temporal decay of NH2 in the presence of NO. Measurements were carried out over the temperature range of 24–106 K, with the low temperatures achieved using a pulsed Laval nozzle expansion. The negative temperature dependence of the reaction rate coefficient observed at higher temperatures in the literature continues at these lower temperatures, with the rate coefficient reaching 3.5 × 10–10 cm3 molecule–1 s–1 at T = 26 K. Ab initio calculations of the potential energy surface were combined with rate theory calculations using the MESMER software package in order to calculate and predict rate coefficients and branching ratios over a wide range of temperatures, which are largely consistent with experimentally determined literature values. These theoretical calculations indicate that at the low temperatures investigated for this reaction, only one product channel producing N2 + H2O is important. The rate coefficients determined in this study were used in a gas-phase astrochemical model. Models were run over a range of physical conditions appropriate for cold to warm molecular clouds (10 to 30 K; 104 to 106 cm–3), resulting in only minor changes (<1%) to the abundances of NH2 and NO at steady state. Hence, despite the observed increase in the rate at low temperatures, this mechanism is not a dominant loss mechanism for either NH2 or NO under dark cloud conditions

The influence of clouds on radical concentrations: Observations and modelling studies of HOx during the Hill Cap Cloud Thuringia (HCCT) campaign in 2010

The potential for chemistry occurring in cloud droplets to impact atmospheric composition has been known for some time. However, the lack of direct observations and uncertainty in the magnitude of these reactions led to this area being overlooked in most chemistry transport models. Here we present observations from Mt Schmücke, Germany, of the HO2 radical made alongside a suite of cloud measurements. HO2 concentrations were depleted in-cloud by up to 90% with the rate of heterogeneous loss of HO2 to clouds necessary to bring model and measurements into agreement, demonstrating a dependence on droplet surface area and pH. This provides the first observationally derived assessment for the uptake coefficient of HO2 to cloud droplets and was found to be in good agreement with theoretically derived parameterisations. Global model simulations, including this cloud uptake, showed impacts on the oxidising capacity of the troposphere that depended critically on whether the HO2 uptake leads to production of H2O2 or H2O

The importance of OH radical–neutral low temperature tunnelling reactions in interstellar clouds using a new model

Recent laboratory experiments using a pulsed Laval nozzle apparatus have shown that reactions between a neutral molecule and the radical OH can occur efficiently at low temperatures despite activation energy barriers if there is a hydrogen-bonded complex in the entrance channel which allows the system to tunnel efficiently under the barrier. Since OH is a major radical in the interstellar medium, this class of reactions may well be important in the chemistry that occurs in the gas phase of interstellar clouds. Using a new gas-grain chemical network with both gas-phase reactions and reactions on the surfaces of dust particles, we studied the role of OH–neutral reactions in dense interstellar clouds at 10, 50, and 100 K. We determined that at least one of these reactions can be significant, especially at the lowest temperatures studied, where the rate constants are large. It was found in particular that the reaction between CH3OH and OH provides an effective and unambiguous gas-phase route to the production of the gaseous methoxy radical (CH3O), which has been recently detected in cold, dense interstsellar clouds. The role of other reactions in this class is explored

Comparison of temperature-dependent calibration methods of an instrument to measure OH and HO₂ radicals using laser-induced fluorescence spectroscopy

Laser-induced fluorescence (LIF) spectroscopy has been widely applied to fieldwork measurements of OH radicals and HO2, following conversion to OH, over a wide variety of conditions, on different platforms and in simulation chambers. Conventional calibration of HOx (OH + HO2) instruments has mainly relied on a single method, generating known concentrations of HOx from H2O vapour photolysis in a flow of zero air impinging just outside the sample inlet (SHOx = CHOx . [HOx ], where SHOx is the observed signal and CHOx is the calibration factor). The fluorescence assay by gaseous expansion (FAGE) apparatus designed for HOx measurements in the Highly Instrumented Reactor for Atmospheric Chemistry (HIRAC) at the University of Leeds has been used to examine the sensitivity of FAGE to external gas temperatures (266–348 K). The conventional calibration methods give the temperature dependence of COH (relative to the value at 293 K) of (0.0059±0.0015) K−1 and CHO2 of (0.014±0.013) K−1. Errors are 2σ . COH was also determined by observing the decay of hydrocarbons (typically cyclohexane) caused by OH reactions giving COH (again, relative to the value at 293 K) of (0.0038 ± 0.0007) K−1. Additionally, CHO2 was determined based on the second-order kinetics of HO2 recombination with the temperature dependence of CHO2 , relative to 293 K being (0.0064 ± 0.0034) K−1. The temperature dependence of CHOx depends on the HOx number density, quenching, the relative population of the probed OH rotational level and HOx transmission from the inlet to the detection axis. The first three terms can be calculated and, in combination with the measured values of CHOx, show that HOx transmission increases with temperature. Comparisons with other instruments and the implications of this work are discussed

CMB Imprints of a Pre-Inflationary Climbing Phase

We discuss the implications for cosmic microwave background (CMB) observables, of a class of pre-inflationary dynamics suggested by string models where SUSY is broken due to the presence of D-branes and orientifolds preserving incompatible portions of it. In these models the would-be inflaton is forced to emerge from the initial singularity climbing up a mild exponential potential, until it bounces against a steep exponential potential of "brane SUSY breaking" scenarios, and as a result the ensuing descent gives rise to an inflationary epoch that begins when the system is still well off its eventual attractor. If a pre-inflationary climbing phase of this type had occurred within 6-7 e-folds of the horizon exit for the largest observable wavelengths, displacement off the attractor and initial-state effects would conspire to suppress power in the primordial scalar spectrum, enhancing it in the tensor spectrum and typically superposing oscillations on both. We investigate these imprints on CMB observables over a range of parameters, examine their statistical significance, and provide a semi-analytic rationale for our results. It is tempting to ascribe at least part of the large-angle anomalies in the CMB to pre-inflationary dynamics of this type.Comment: 38 pages, LaTeX, 11 eps figures, references added, matches version to appear in JCA

Reactive Halogens in the Marine Boundary Layer (RHaMBLe): The tropical North Atlantic experiments

The NERC UK SOLAS-funded Reactive Halogens in the Marine Boundary Layer (RHaMBLe) programme comprised three field experiments. This manuscript presents an overview of the measurements made within the two simultaneous remote experiments conducted in the tropical North Atlantic in May and June 2007. Measurements were made from two mobile and one ground-based platforms. The heavily instrumented cruise D319 on the RRS Discovery from Lisbon, Portugal to São Vicente, Cape Verde and back to Falmouth, UK was used to characterise the spatial distribution of boundary layer components likely to play a role in reactive halogen chemistry. Measurements onboard the ARSF Dornier aircraft were used to allow the observations to be interpreted in the context of their vertical distribution and to confirm the interpretation of atmospheric structure in the vicinity of the Cape Verde islands. Long-term ground-based measurements at the Cape Verde Atmospheric Observatory (CVAO) on São Vicente were supplemented by long-term measurements of reactive halogen species and characterisation of additional trace gas and aerosol species during the intensive experimental period. This paper presents a summary of the measurements made within the RHaMBLe remote experiments and discusses them in their meteorological and chemical context as determined from these three platforms and from additional meteorological analyses. Air always arrived at the CVAO from the North East with a range of air mass origins (European, Atlantic and North American continental). Trace gases were present at stable and fairly low concentrations with the exception of a slight increase in some anthropogenic components in air of North American origin, though NOx mixing ratios during this period remained below 20 pptv (note the non-IUPAC adoption in this manuscript of pptv and ppbv, equivalent to pmol mol−1 and nmol mol−1 to reflect common practice). Consistency with these air mass classifications is observed in the time series of soluble gas and aerosol composition measurements, with additional identification of periods of slightly elevated dust concentrations consistent with the trajectories passing over the African continent. The CVAO is shown to be broadly representative of the wider North Atlantic marine boundary layer; measurements of NO, O3 and black carbon from the ship are consistent with a clean Northern Hemisphere marine background. Aerosol composition measurements do not indicate elevated organic material associated with clean marine air. Closer to the African coast, black carbon and NO levels start to increase, indicating greater anthropogenic influence. Lower ozone in this region is possibly associated with the increased levels of measured halocarbons, associated with the nutrient rich waters of the Mauritanian upwelling. Bromide and chloride deficits in coarse mode aerosol at both the CVAO and on D319 and the continuous abundance of inorganic gaseous halogen species at CVAO indicate significant reactive cycling of halogens. Aircraft measurements of O3 and CO show that surface measurements are representative of the entire boundary layer in the vicinity both in diurnal variability and absolute levels. Above the inversion layer similar diurnal behaviour in O3 and CO is observed at lower mixing ratios in the air that had originated from south of Cape Verde, possibly from within the ITCZ. ECMWF calculations on two days indicate very different boundary layer depths and aircraft flights over the ship replicate this, giving confidence in the calculated boundary layer depth

Whole-genome sequencing association analysis of quantitative red blood cell phenotypes: The NHLBI TOPMed program

Whole-genome sequencing (WGS), a powerful tool for detecting novel coding and non-coding disease-causing variants, has largely been applied to clinical diagnosis of inherited disorders. Here we leveraged WGS data in up to 62,653 ethnically diverse participants from the NHLBI Trans-Omics for Precision Medicine (TOPMed) program and assessed statistical association of variants with seven red blood cell (RBC) quantitative traits. We discovered 14 single variant-RBC trait associations at 12 genomic loci, which have not been reported previously. Several of the RBC trait-variant associations (RPN1, ELL2, MIDN, HBB, HBA1, PIEZO1, and G6PD) were replicated in independent GWAS datasets imputed to the TOPMed reference panel. Most of these discovered variants are rare/low frequency, and several are observed disproportionately among non-European Ancestry (African, Hispanic/Latino, or East Asian) populations. We identified a 3 bp indel p.Lys2169del (g.88717175_88717177TCT[4]) (common only in the Ashkenazi Jewish population) of PIEZO1, a gene responsible for the Mendelian red cell disorder hereditary xerocytosis (MIM: 194380), associated with higher mean corpuscular hemoglobin concentration (MCHC). In stepwise conditional analysis and in gene-based rare variant aggregated association analysis, we identified several of the variants in HBB, HBA1, TMPRSS6, and G6PD that represent the carrier state for known coding, promoter, or splice site loss-of-function variants that cause inherited RBC disorders. Finally, we applied base and nuclease editing to demonstrate that the sentinel variant rs112097551 (nearest gene RPN1) acts through a cis-regulatory element that exerts long-range control of the gene RUVBL1 which is essential for hematopoiesis. Together, these results demonstrate the utility of WGS in ethnically diverse population-based samples and gene editing for expanding knowledge of the genetic architecture of quantitative hematologic traits and suggest a continuum between complex trait and Mendelian red cell disorders