Comment on: “The measurement of tropospheric OH radicals by laser-induced fluorescence spectroscopy during the POPCORN Field Campaign” by Hofzumahaus et al. and “Intercomparison of tropospheric OH radical measurements by multiple folded long-path laser absorption and laser induced fluorescence” by Brauers et al.

Calibration of laser induced fluorescence (LIF) instruments that measure OH is challenging because it is difficult to reliably introduce a known amount of this reactive radical into a measurement apparatus. In a recent paper, Hofzumahaus et al., [1996] describe a novel and seemingly simple technique to accomplish this goal: they dissociate trace quantities of water vapor in air with a low pressure mercury (Hg) lamp to produce low concentrations (10^5 - 10^9 cm^(-3)) of OH (R1)

Four Years of Airborne Measurements of Wildfire Emissions in California, with a Focus on the Evolution of Emissions During the Soberanes Megafire

Biomass burning is an important source of trace gases and particles which can influence air quality on local, regional, and global scales. With wildfire events increasing due to changes in land use, increasing population, and climate change, characterizing wildfire emissions and their evolution is vital. In this work we report in situ airborne measurements of carbon dioxide (CO2), methane (CH4), water vapor (H2O), ozone (O3), and formaldehyde (HCHO) from nine wildfire events in California between 2013 and 2016, which were sampled as part of the Alpha Jet Atmospheric eXperiment (AJAX) based at NASA Ames Research Center. One of those fires, the Soberanes Megafire, began on 22 July 2016 and burned for three months. During that time, five flights were executed to sample emissions near and downwind of the Soberanes wildfire. In situ data are used to determine enhancement ratios (ERs), or excess mixing ratio relative to CO2, as well as assess O3 production from the fire. Changes in the emissions as a function of fire evolution are explored. Air quality impacts downwind of the fire are addressed using ground-based monitoring site data, satellite smoke products, and the Community Multiscale Air Quality (CMAQ) photochemical grid model

Validation of the Harvard Lyman-α in situ water vapor instrument: Implications for the mechanisms that control stratospheric water vapor

Building on previously published details of the laboratory calibrations of the Harvard Lyman-α photofragment fluorescence hygrometer (HWV) on the NASA ER-2 and WB-57 aircraft, we describe here the validation process for HWV, which includes laboratory calibrations and intercomparisons with other Harvard water vapor instruments at water vapor mixing ratios from 0 to 10 ppmv, followed by in-flight intercomparisons with the same Harvard hygrometers. The observed agreement exhibited in the laboratory and during intercomparisons helps corroborate the accuracy of HWV. In light of the validated accuracy of HWV, we present and evaluate a series of intercomparisons with satellite and balloon borne water vapor instruments made from the upper troposphere to the lower stratosphere in the tropics and midlatitudes. Whether on the NASA ER-2 or WB-57 aircraft, HWV has consistently measured about 1–1.5 ppmv higher than the balloon-borne NOAA/ESRL/GMD frost point hygrometer (CMDL), the NOAA Cryogenic Frost point Hygrometer (CFH), and the Microwave Limb Sounder (MLS) on the Aura satellite in regions of the atmosphere where water vapor is <10 ppmv. Comparisons in the tropics with the Halogen Occultation Experiment (HALOE) on the Upper Atmosphere Research Satellite show large variable differences near the tropopause that converge to ~10% above 460 K, with HWV higher. Results we show from the Aqua Validation and Intercomparison Experiment (AquaVIT) at the AIDA chamber in Karlsruhe do not reflect the observed in-flight differences. We illustrate that the interpretation of the results of comparisons between modeled and measured representations of the seasonal cycle of water entering the lower tropical stratosphere is dictated by which data set is used

The Development and Deployment of a Ground-Based, Laser-Induced Fluorescence Instrument for the In Situ Detection of Iodine Monoxide Radicals

High abundances of iodine monoxide (IO) are known to exist and to participate in local photochemistry of the marine boundary layer. Of particular interest are the roles IO plays in the formation of new particles in coastal marine environments and in depletion episodes of ozone and mercury in the Arctic polar spring. This paper describes a ground-based instrument that measures IO at mixing ratios less than one part in 1012. The IO radical is measured by detecting laser-induced fluorescence at wavelengths longer that 500 nm. Tunable visible light is used to pump the A23/2 (v = 2) X23/2 (v = 0) transition of IO near 445 nm. The laser light is produced by a solid-state, Nd:YAG-pumped Ti:Sapphire laser at 5 kHz repetition rate. The laser-induced fluorescence instrument performs reliably with very high signal-to-noise ratios (>10) achieved in short integration times (<1 min). The observations from a validation deployment to the Shoals Marine Lab on Appledore Island, ME are presented and are broadly consistent with in situ observations from European Coastal Sites. Mixing ratios ranged from the instrumental detection limit (<1 pptv) to 10 pptv. These data represent the first in situ point measurements of IO in North America

Formation of large (?100 ?m) ice crystals near the tropical tropopause

International audienceRecent high-altitude aircraft measurements with in situ imaging instruments indicated the presence of relatively large (?100 ?m length), thin (aspect ratios of ?6:1 or larger) hexagonal plate ice crystals near the tropical tropopause in very low concentrations (?1). These crystals were not produced by deep convection or aggregation. We use simple growth-sedimentation calculations as well as detailed cloud simulations to evaluate the conditions required to grow the large crystals. Uncertainties in crystal aspect ratio leave a range of possibilities, which could be constrained by knowledge of the water vapor concentration in the air where the crystal growth occurred. Unfortunately, water vapor measurements made in the cloud formation region near the tropopause with different instruments ranged from 3 ppmv). On the other hand, if the crystal aspect ratios are quite a bit larger (?10:1), then H2O concentrations toward the low end of the measurement range (?2?2.5 ppmv) would suffice to grow the large crystals. Gravity-wave driven temperature and vertical wind perturbations only slightly modify the H2O concentrations needed to grow the crystals. We find that it would not be possible to grow the large crystals with water concentrations less than 2 ppmv, even with assumptions of a very high aspect ratio of 15 and steady upward motion of 2 cm s?1 to loft the crystals in the tropopause region. These calculations would seem to imply that the measurements indicating water vapor concentrations less than 2 ppmv are implausible, but we cannot rule out the possibility that higher humidity prevailed upstream of the aircraft measurements and the air was dehydrated by the cloud formation. Simulations of the cloud formation with a detailed model indicate that homogeneous freezing should generate ice concentrations larger than the observed concencentrations (20 L?1), and even concentrations as low as 20 L?1 should have depleted the vapor in excess of saturation and prevented growth of large crystals. It seems likely that the large crystals resulted from ice nucleation on effective heterogeneous nuclei at low ice supersaturations. Improvements in our understanding of detailed cloud microphysical processes require resolution of the water vapor measurement discrepancies in these very cold, dry regions of the atmosphere

Organic Nitrate Chemistry and Its Implications for Nitrogen Budgets in an Isoprene- and Monoterpene-Rich Atmosphere: Constraints From Aircraft (SEAC4RS) and Ground-Based (SOAS) Observations in the Southeast US

Formation of organic nitrates (RONO2) during oxidation of biogenic volatile organic compounds (BVOCs: isoprene, monoterpenes) is a significant loss pathway for atmospheric nitrogen oxide radicals (NOx), but the chemistry of RONO2 formation and degradation remains uncertain. Here we implement a new BVOC oxidation mechanism (including updated isoprene chemistry, new monoterpene chemistry, and particle uptake of RONO2) in the GEOS-Chem global chemical transport model with approximately 25 times 25 km(exp 2) resolution over North America. We evaluate the model using aircraft (SEAC4RS) and ground-based (SOAS) observations of NOx, BVOCs, and RONO2 from the Southeast US in summer 2013. The updated simulation successfully reproduces the concentrations of individual gas- and particle-phase RONO2 species measured during the campaigns. Gas-phase isoprene nitrates account for 2550 of observed RONO2 in surface air, and we find that another 10 is contributed by gas-phase monoterpene nitrates. Observations in the free troposphere show an important contribution from long-lived nitrates derived from anthropogenic VOCs. During both campaigns, at least 10 of observed boundary layer RONO2 were in the particle phase. We find that aerosol uptake followed by hydrolysis to HNO3 accounts for 60 of simulated gas-phase RONO2 loss in the boundary layer. Other losses are 20 by photolysis to recycle NOx and 15 by dry deposition. RONO2 production accounts for 20 of the net regional NOx sink in the Southeast US in summer, limited by the spatial segregation between BVOC and NOx emissions. This segregation implies that RONO2 production will remain a minor sink for NOx in the Southeast US in the future even as NOx emissions continue to decline. XXXX We have used airborne and ground-based observations from two summer 2013 campaigns in the Southeast US (SEAC4RS, SOAS) to better understand the chemistry and impacts of alkyl and multi-functional organic nitrates (RONO2). We used the observations, along with findings from recent laboratory, field, and modeling studies, to update and evaluate biogenic volatile organic compound (BVOC) oxidation schemes in the GEOS-Chem chemical transport model (CTM). From there, we used the updated CTM with 0:25 0:3125 ( 2525 km2) horizontal resolution to examine RONO2 speciation, chemical production/loss processes, and importance as a sink for NOx. Our improved mechanism provides a state-of-the-science description of isoprene oxidation in the presence of NOx, wit

Quantitative constraints on the atmospheric chemistry of nitrogen oxides: An analysis along chemical coordinates

In situ observations Of NO_2, NO, NO_y, ClONO_2, OH, O_3, aerosol surface area, spectrally resolved solar radiation, pressure and temperature obtained from the ER-2 aircraft during the Photochemistry of Ozone Loss in the Arctic Region in Summer (POLARIS) experiments are used to examine the factors controlling the fast photochemistry connecting NO and NO_2 and the slower chemistry connecting NO_x and HNO_3. Our analysis uses “chemical coordinates” to examine gradients of the difference between a model and precisely calibrated measurements to provide a quantitative assessment of the accuracy of current photochemical models. The NO/NO_2 analysis suggests that reducing the activation energy for the NO+O_3 reaction by 1.7 kJ/mol will improve model representation of the temperature dependence of the NO/NO_2 ratio in the range 215–235 K. The NO_x/HNO_3 analysis shows that systematic errors in the relative rate coefficients used to describe NO_x loss by the reaction OH + NO_2 → HNO_3 and by the reaction set NO_2 + O_3 → NO_3; NO_2 + NO_3 → N_(2)O_5; N_(2)O_5 + H_(2)O → 2HNO_3 are in error by +8.4% (+30/−45%) (OH+NO_2 too fast) in models using the Jet Propulsion Laboratory 1997 recommendations [DeMore et al., 1997]. Models that use recommendations for OH+NO2 and OH+HNO_3 based on reanalysis of recent and past laboratory measurements are in error by 1.2% (+30/−45%) (OH+NO_2 too slow). The +30%/−45% error limit reflects systematic uncertainties, while the statistical uncertainty is 0.65%. This analysis also shows that the POLARIS observations only modestly constrain the relative rates of the major NO_x production reactions HNO3 + OH → H_(2)O + NO_3 and HNO_3 + hν → OH + NO_2. Even under the assumption that all other aspects of the model are perfect, the POLARIS observations only constrain the rate coefficient for OH+HNO_3 to a range of 65% around the currently recommended value