STRUCTURAL CHANGE IN AN ERA OF INCREASED OPENNESS: A BACKGROUND PAPER ON THE STRUCTURE OF U.S. AGRICULTURE

Agribusiness,

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

Simultaneous Measurements of Atmospheric HONO and NO2 via Absorption Spectroscopy using Tunable Mid-Infrared Continuous-wave Quantum Cascade Lasers

Nitrous acid (HONO) is important as a significant source of hydroxyl radical (OH) in the troposphere and as a potent indoor air pollutant. It is thought to be generated in both environments via heterogeneous reactions involving nitrogen dioxide $(NO_2)$. In order to enable fast-response HONO detection suitable for eddy-covariance flux measurements and to provide a direct method that avoids interferences associated with derivatization, we have developed a 2-channel tunable infrared laser differential absorption spectrometer (TILDAS) capable of simultaneous high-frequency measurements of HONO and NO2. Beams from two mid-infrared continuous-wave mode quantum cascade lasers (cw-QCLs) traverse separate 210 m paths through a multi-pass astigmatic sampling cell at reduced pressure for the direct detection of HONO $(1660 cm^{−1})$ and $(NO_2)$ $(1604 cm^{−1})$. The resulting one-second detection limits (S/N=3) are 300 and 30 ppt (pmol/mol) for HONO and $(NO_2)$, respectively. Our HONO quantification is based on revised line-strengths and peak positions for cis-HONO in the 6-micron spectral region that were derived from laboratory measurements. An essential component of ambient HONO measurements is the inlet system and we demonstrate that heated surfaces and reduced pressure minimize sampling artifacts.Earth and Planetary SciencesEngineering and Applied Science

Measurement of Trace Water Vapor in a Carbon Dioxide Removal Assembly Product Stream

The International Space Station Carbon Dioxide Removal Assembly (CDRA) uses regenerable adsorption technology to remove carbon dioxide (COP) from cabin air. Product water vapor measurements from a CDRA test bed at the NASA Marshall Space Flight Center were made using a tunable infrared diode laser differential absorption spectrometer (TILDAS) provided by NASA Glenn Research Center. The TILDAS instrument exceeded all the test specifications, including sensitivity, dynamic range, time response, and unattended operation. During the COP desorption phase, water vapor concentrations as low as 5 ppmv were observed near the peak of CO2 evolution, rising to levels of approx. 40 ppmv at the end of a cycle. Periods of high water concentration (>100 ppmv) were detected and shown to be caused by an experimental artifact. Measured values of total water vapor evolved during a single desorption cycle were as low as 1 mg

Evaluation of nitrogen dioxide chemiluminescence monitors in a polluted urban environment

International audienceData from a recent field campaign in Mexico City are used to evaluate the performance of the EPA Federal Reference Method for monitoring the ambient concentrations of NO2. Measurements of NO2 from standard chemiluminescence monitors equipped with molybdenum oxide converters are compared with those from Tunable Infrared Laser Differential Absorption Spectroscopy (TILDAS) and Differential Optical Absorption Spectroscopy (DOAS) instruments. A significant interference in the chemiluminescence measurement is shown to account for up to 50% of ambient NO2 concentration during afternoon hours. As expected, this interference correlates well with non-NOx reactive nitrogen species (NOz) as well as with ambient O3 concentrations, indicating a photochemical source for the interfering species. A combination of ambient gas phase nitric acid and alkyl and multifunctional alkyl nitrates is deduced to be the primary cause of the interference. Observations at four locations at varying proximities to emission sources indicate that the percentage contribution of HNO3 to the interference decreases with time as the air parcel ages. Alkyl and multifunctional alkyl nitrate concentrations are calculated to reach concentrations as high as several ppb inside the city, on par with the highest values previously observed in other urban locations. Averaged over the MCMA-2003 field campaign, the chemiluminescence monitor interference resulted in an average measured NO2 concentration up to 22% greater than that from co-located spectroscopic measurements. Thus, this interference has the potential to initiate regulatory action in areas that are close to non-attainment and may mislead atmospheric photochemical models used to assess control strategies for photochemical oxidants

Laboratory kinetic studies of OH and CO2 relevant to upper atmospheric radiation balance

During the first year of this program, we have made considerable progress toward the measurement of the dipole moments of vibrationally excited OH radicals. Our primary accomplishments have been 1) the modification of the original slit jet spectrometer for the study of radical species and 2) the observation of infrared chemiluminescence from the vibrationally excited OH radicals formed in the H + ozone reaction in the supersonic jet. We are optimistic that we will soon observe OH* laser induced fluorescence in the jet. Modulation of this fluorescence with microwave radiation in an applied electric field will be the final step required for the precise determination of the vibrational dependence of the OH dipole moment

Implementation of a Markov Chain Monte Carlo method to inorganic aerosol modeling of observations from the MCMA-2003 campaign ? Part II: Model application to the CENICA, Pedregal and Santa Ana sites

International audienceA Markov Chain Monte Carlo model for integrating the observations of inorganic species with a thermodynamic equilibrium model was presented in Part I of this series. Using observations taken at three ground sites, i.e. a residential, industrial and rural site, during the MCMA-2003 campaign in Mexico City, the model is used to analyze the inorganic particle and ammonia data and to predict gas phase concentrations of nitric and hydrochloric acid. In general, the model is able to accurately predict the observed inorganic particle concentrations at all three sites. The agreement between the predicted and observed gas phase ammonia concentration is excellent. The NOz concentration calculated from the NOy, NO and NO2 observations is of limited use in constraining the gas phase nitric acid concentration given the large uncertainties in this measure of nitric acid and additional reactive nitrogen species. Focusing on the acidic period of 9?11 April identified by Salcedo et al. (2006), the model accurately predicts the particle phase observations during this period with the exception of the nitrate predictions after 10:00 a.m. (Central Daylight Time, CDT) on 9 April, where the model underpredicts the observations by, on average, 20%. This period had a low planetary boundary layer, very high particle concentrations, and higher than expected nitrogen dioxide concentrations. For periods when the particle chloride observations are consistently above the detection limit, the model is able to both accurately predict the particle chloride mass concentrations and provide well-constrained HCl (g) concentrations. The availability of gas-phase ammonia observations helps constrain the predicted HCl (g) concentrations. When the particles are aqueous, the most likely concentrations of HCl (g) are in the sub-ppbv range. The most likely predicted concentration of HCl (g) was found to reach concentrations of order 10 ppbv if the particles are dry. Finally, the atmospheric relevance of HCl (g) is discussed in terms of its indicator properties for the possible influence of chlorine-mediated photochemistry in Mexico City

Laboratory Kinetic Studies of OH and CO2 Relevant to Upper Atmospheric Radiation Balance

The purpose of this project was to quantify the rates of two processes which are crucial to our understanding of radiative energy balance in the upper atmosphere. The first process is radiative emission from vibrationally hot OH radicals following the H + O3 reaction in the upper mesosphere. The importance of this process depends strongly on the OH radiative emission coefficients. Our goal was to measure the OH permanent dipole moment in excited vibrational states and to use these measurements to construct an improved OH dipole moment function and improved radiative emission coefficients. Significant progress was made on these experiments including the construction of a supersonic jet source for vibrationally excited OH radicals. Unfortunately, our efforts to transport the OH radicals into a second lower pressure vacuum chamber were not successful, and we were unable to make improved dipole moment measurements for OH. The second key kinetic process which we attempted to quantify during this project is the rate of relaxation of bend-excited CO2 by oxygen atoms. Since excitation of the bending vibrational mode of CO2 is the major cooling mechanism in the upper mesosphere/lower thermosphere, the cooling rate of this region depends crucially on the rate of energy transfer out of this state. It is believed that the most efficient transfer mechanism is via atomic oxygen but the rate for this process has not been directly measured in the laboratory at appropriate temperatures and even the room temperature rate remains controversial. We attempted to directly measure the relaxation rate Of CO2 (010) by oxygen atoms using the discharge flow technique. This experiment was set up at Aerodyne Research. Again, significant progress was achieved in this experiment. A hot CO2 source was set up, bend excited CO2 was detected and the rate of relaxation of bend excited CO2 by He atoms was measured. Unfortunately, the project ran out of time before the oxygen atom kinetic studies could be implemented