A measurement of the vibrational band strength for the upsilon sub 3 band of the HO2 radical

The HO2 radicals generated in a discharge-flow system were observed with tunable diode laser absorption in the P-branch of the nu(3) vibrationall band at 1080/cm. The observed line positions agree with those calculated from the molecular constants for the nu(3) bland obtained from a previous study using laser magnetic resonance spectroscopy. The band strength was determined by observing line center absoptions when HO2 is produced in the reaction F + H2O2 yields HO2 + HF (k1) with a measured concentration of atomic fluorine and excess hydrogen peroxide. F-atom concentrations are measured by diode laser absorption of the spin-orbit transition at 404/cm. The analysis accounts for HO2 losses due to the reactions of HO2 + HO2 yields H2O2 + O2 (k3) and F + HO2 yields HF + O2 (k4). The line strength for the 6(15) 7(16) F(1) transition is 2.9 x 10 to the 21st power sq cm/molecule/cm which corresponds to a nu(3) band strength of 34 +/- 9 sq/cm(STP atm). This value is a factor of 6 lower than previous ab initio calculations. These results will be useful in assessing the feasibility of atmospheric measurements of HO2 using infrared absorption techniques

Mass fluxes and isofluxes of methane (CH4) at a New Hampshire fen measured by a continuous wave quantum cascade laser spectrometer

We have developed a mid‐infrared continuous‐wave quantum cascade laser direct‐absorption spectrometer (QCLS) capable of high frequency (≥1 Hz) measurements of 12CH4 and 13CH4 isotopologues of methane (CH4) with in situ 1‐s RMS image precision of 1.5 ‰ and Allan‐minimum precision of 0.2 ‰. We deployed this QCLS in a well‐studied New Hampshire fen to compare measurements of CH4 isoflux by eddy covariance (EC) to Keeling regressions of data from automated flux chamber sampling. Mean CH4 fluxes of 6.5 ± 0.7 mg CH4 m−2 hr−1 over two days of EC sampling in July, 2009 were indistinguishable from mean autochamber CH4 fluxes (6.6 ± 0.8 mgCH4 m−2 hr−1) over the same period. Mean image composition of emitted CH4 calculated using EC isoflux methods was −71 ± 8 ‰ (95% C.I.) while Keeling regressions of 332 chamber closing events over 8 days yielded a corresponding value of −64.5 ± 0.8 ‰. Ebullitive fluxes, representing ∼10% of total CH4 fluxes at this site, were on average 1.2 ‰ enriched in 13C compared to diffusive fluxes. CH4 isoflux time series have the potential to improve process‐based understanding of methanogenesis, fully characterize source isotopic distributions, and serve as additional constraints for both regional and global CH4 modeling analysis

Stratospheric aircraft exhaust plume and wake chemistry studies

This report documents progress to date in an ongoing study to analyze and model emissions leaving a proposed High Speed Civil Transport (HSCT) from when the exhaust gases leave the engine until they are deposited at atmospheric scales in the stratosphere. Estimates are given for the emissions, summarizing relevant earlier work (CIAP) and reviewing current propulsion research efforts. The chemical evolution and the mixing and vortical motion of the exhaust are analyzed to track the exhaust and its speciation as the emissions are mixed to atmospheric scales. The species tracked include those that could be heterogeneously reactive on the surfaces of the condensed solid water (ice) particles and on exhaust soot particle surfaces. Dispersion and reaction of chemical constituents in the far wake are studied with a Lagrangian air parcel model, in conjunction with a radiation code to calculate the net heating/cooling. Laboratory measurements of heterogeneous chemistry of aqueous sulfuric acid and nitric acid hydrates are also described. Results include the solubility of HCl in sulfuric acid which is a key parameter for modeling stratospheric processing. We also report initial results for condensation of nitric acid trihydrate from gas phase H2O and HNO3

Intercomparison of field measurements of nitrous acid (HONO) during the SHARP campaign

Because of the importance of HONO as a radical reservoir, consistent and accurate measurements of its concentration are needed. As part of SHARP (Study of Houston Atmospheric Radical Precursors), time series of HONO were obtained by six different measurement techniques on the roof of the Moody Tower at the University of Houston. Techniques used were long path differential optical absorption spectroscopy (DOAS), stripping coil-visible absorption photometry (SC-AP), long path absorption photometry (LOPAP® ), mist chamber/ion chromatography (MC-IC), quantum cascade-tunable infrared laser differential absorption spectroscopy (QC-TILDAS), and ion drift-chemical ionization mass spectrometry (ID-CIMS). Various combinations of techniques were in operation from 15 April through 31 May 2009. All instruments recorded a similar diurnal pattern of HONO concentrations with higher median and mean values during the night than during the day. Highest values were observed in the final 2 weeks of the campaign. Inlets for the MC-IC, SC-AP, and QC-TILDAS were collocated and agreed most closely with each other based on several measures. Largest differences between pairs of measurements were evident during the day for concentrations ~100 parts per trillion (ppt). Above ~ 200 ppt, concentrations from the SC-AP, MC-IC, and QC-TILDAS converged to within about 20%, with slightly larger discrepancies when DOAS was considered. During the first 2 weeks, HONO measured by ID-CIMS agreed with these techniques, but ID-CIMS reported higher values during the afternoon and evening of the final 4 weeks, possibly from interference from unknown sources. A number of factors, including building related sources, likely affected measured concentrations

Towards a stable and absolute atmospheric carbon dioxide instrument using spectroscopic null method

We present a novel spectral method to measure atmospheric carbon dioxide (CO2) with high precision and stability without resorting to calibration tanks during long-term operation. This spectral null method improves precision by reducing spectral proportional noise associated with laser emission instabilities. We employ sealed quartz cells with known CO2 column densities to serve as the permanent internal references in the null method, which improve the instrument's stability and accuracy. A prototype instrument – ABsolute Carbon dioxide (ABC) is developed using this new approach. The instrument has a one-second precision of 0.02 ppm, which averages down to 0.007 ppm within one minute. Long-term stability of within 0.1 ppm is achieved without any calibrations for over a one-month period. These results have the potential for eliminating the need for calibration cylinders for high accuracy field measurements of carbon dioxide

Characterization of on-road vehicle emissions in the Mexico City Metropolitan Area using a mobile laboratory in chase and fleet average measurement modes during the MCMA-2003 field campaign

A mobile laboratory was used to measure on-road vehicle emission ratios during the MCMA-2003 field campaign held during the spring of 2003 in the Mexico City Metropolitan Area (MCMA). The measured emission ratios represent a sample of emissions of in-use vehicles under real world driving conditions for the MCMA. From the relative amounts of NO_x and selected VOC's sampled, the results indicate that the technique is capable of differentiating among vehicle categories and fuel type in real world driving conditions. Emission ratios for NO_x, NO_y, NH₃, H₂CO, CH₃CHO, and other selected volatile organic compounds (VOCs) are presented for chase sampled vehicles in the form of frequency distributions as well as estimates for the fleet averaged emissions. Our measurements of emission ratios for both CNG and gasoline powered "colectivos" (public transportation buses that are intensively used in the MCMA) indicate that – in a mole per mole basis – have significantly larger NO_x and aldehydes emissions ratios as compared to other sampled vehicles in the MCMA. Similarly, ratios of selected VOCs and NO_y showed a strong dependence on traffic mode. These results are compared with the vehicle emissions inventory for the MCMA, other vehicle emissions measurements in the MCMA, and measurements of on-road emissions in U.S. cities. We estimate NO_x emissions as 100 600±29 200 metric tons per year for light duty gasoline vehicles in the MCMA for 2003. According to these results, annual NO_x emissions estimated in the emissions inventory for this category are within the range of our estimated NO_x annual emissions. Our estimates for motor vehicle emissions of benzene, toluene, formaldehyde, and acetaldehyde in the MCMA indicate these species are present in concentrations higher than previously reported. The high motor vehicle aldehyde emissions may have an impact on the photochemistry of urban areas

Equilibrium configurations of fluids and their stability in higher dimensions

We study equilibrium shapes, stability and possible bifurcation diagrams of fluids in higher dimensions, held together by either surface tension or self-gravity. We consider the equilibrium shape and stability problem of self-gravitating spheroids, establishing the formalism to generalize the MacLaurin sequence to higher dimensions. We show that such simple models, of interest on their own, also provide accurate descriptions of their general relativistic relatives with event horizons. The examples worked out here hint at some model-independent dynamics, and thus at some universality: smooth objects seem always to be well described by both ``replicas'' (either self-gravity or surface tension). As an example, we exhibit an instability afflicting self-gravitating (Newtonian) fluid cylinders. This instability is the exact analogue, within Newtonian gravity, of the Gregory-Laflamme instability in general relativity. Another example considered is a self-gravitating Newtonian torus made of a homogeneous incompressible fluid. We recover the features of the black ring in general relativity.Comment: 42 pages, 11 Figures, RevTeX4. Accepted for publication in Classical and Quantum Gravity. v2: Minor corrections and references adde

Stratospheric aircraft exhaust plume and wake chemistry

Progress to date in an ongoing study to analyze and model emissions leaving a proposed High Speed Civil Transport (HSCT) from when the exhaust gases leave the engine until they are deposited at atmospheric scales in the stratosphere is documented. A kinetic condensation model was implemented to predict heterogeneous condensation in the plume regime behind an HSCT flying in the lower stratosphere. Simulations were performed to illustrate the parametric dependence of contrail droplet growth on the exhaust condensation nuclei number density and size distribution. Model results indicate that the condensation of water vapor is strongly dependent on the number density of activated CN. Incorporation of estimates for dilution factors into a Lagrangian box model of the far-wake regime with scale-dependent diffusion indicates negligible decrease in ozone and enhancement of water concentrations of 6-13 times background, which decrease rapidly over 1-3 days. Radiative calculations indicate a net differential cooling rate of the plume about 3K/day at the beginning of the wake regime, with a total subsidence ranging between 0.4 and 1 km. Results from the Lagrangian plume model were used to estimate the effect of repeated superposition of aircraft plumes on the concentrations of water and NO(y) along a flight corridor. Results of laboratory studies of heterogeneous chemistry are also described. Kinetics of HCl, N2O5 and ClONO2 uptake on liquid sulfuric acid were measured as a function of composition and temperature. Refined measurements of the thermodynamics of nitric acid hydrates indicate that metastable dihydrate may play a role in the nucleation of more stable trihydrates PSC's

Canopy-Atmosphere Exchange of Carbon, Water and Energy at Harvard Forest EMS Tower since 1991

Stomatal conductance influences both photosynthesis and transpiration, thereby coupling the carbon and water cycles and affecting surface–atmosphere energy exchange. The environmental response of stomatal conductance has been measured mainly on the leaf scale, and theoretical canopy models are relied on to upscale stomatal conductance for application in terrestrial ecosystem models and climate prediction. Here we estimate stomatal conductance and associated transpiration in a temperate deciduous forest directly on the canopy scale via two independent approaches: (i) from heat and water vapor exchange and (ii) from carbonyl sulfide (OCS) uptake. We use the eddy covariance method to measure the net ecosystem–atmosphere exchange of OCS, and we use a flux-gradient approach to separate canopy OCS uptake from soil OCS uptake. We find that the seasonal and diurnal patterns of canopy stomatal conductance obtained by the two approaches agree (to within ±6 % diurnally), validating both methods. Canopy stomatal conductance increases linearly with above-canopy light intensity (in contrast to the leaf scale, where stomatal conductance shows declining marginal increases) and otherwise depends only on the diffuse light fraction, the canopy-average leaf-to-air water vapor gradient, and the total leaf area. Based on stomatal conductance, we partition evapotranspiration (ET) and find that evaporation increases from 0 to 40 % of ET as the growing season progresses, driven primarily by rising soil temperature and secondarily by rainfall. Counterintuitively, evaporation peaks at the time of year when the soil is dry and the air is moist. Our method of ET partitioning avoids concerns about mismatched scales or measurement types because both ET and transpiration are derived from eddy covariance data. Neither of the two ecosystem models tested predicts the observed dynamics of evaporation or transpiration, indicating that ET partitioning such as that provided here is needed to further model development and improve our understanding of carbon and water cycling