D. J. Knapp

Nitric Acid Uptake on Subtropical Cirrus Cloud Particles

The redistribution of HNO 3 via uptake and sedimentation by cirrus cloud particles is considered an important term in the upper tropospheric budget of reactive nitrogen. Numerous cirrus cloud encounters by the NASA WB-57F high-altitude research aircraft during the Cirrus Regional Study of Tropical Anvils and Cirrus Layers-Florida Area Cirrus Experiment (CRYSTAL-FACE) were accompanied by the observation of condensed-phase HNO 3 with the NOAA chemical ionization mass spectrometer. The instrument measures HNO 3 with two independent channels of detection connected to separate forward and downward facing inlets that allow a determination of the amount of HNO 3 condensed on ice particles. Subtropical cirrus clouds, as indicated by the presence of ice particles, were observed coincident with condensed-phase HNO 3 at temperatures of 197-224 K and pressures of 122-224 hPa. Maximum levels of condensed-phase HNO 3 approached the gas-phase equivalent of 0.8 ppbv. Ice particle surface coverages as high as 1.4 x 10 14 molecules cm -2 were observed. A dissociative Langmuir adsorption model, when using an empirically derived HNO 3 adsorption enthalpy of -11.0 kcal mol -1 , electively describes the observed molecular coverages to within a factor of 5. The percentage of total HNO 3 in the condensed phase ranged from near zero to 100% in the observed cirrus clouds. With volume-weighted mean particle diameters up to 700 μm and particle fall velocities up to 10 m s -1 , some observed clouds have significant potential to redistribute HNO 3 in the upper troposphere.

Evidence of the effect of summertime midlatitude convection on the subtropical lower stratosphere from CRYSTAL‐FACE tracer measurements

[1] Trace gas and particle measurements taken during the CRYSTAL-FACE mission are used to examine mixing in the summer subtropical lower stratosphere. Vigorous convection in the central and eastern United States injected a significant amount of tropospheric air into the lower stratosphere, which was subsequently advected over the region sampled during the CRYSTAL-FACE mission. Aerosols produced by biomass burning were observed over Florida during a time period with a large number of forest fires in the western United States and eastern Canada, providing evidence of convective injection of tropospheric air into the lower stratosphere. The circumstances of the large-scale flow pattern in the upper troposphere and lower stratosphere, vigorous summertime convection, abundant forest fires, and the downstream sampling allow a unique view of mixing in the lower stratosphere. We calculate the fractions of midlatitude tropospheric air in the sampled lower stratosphere and mixing rates on the basis of consistency between a number of tracer-tracer correlations. The tropospheric endpoints to the mixing estimates give an indication of midlatitude continental convective input into the lower stratosphere. We also discuss the possible impact of summertime midlatitude convection on the composition of the stratosphere as a whole.

Oxidation of mercury by bromine in the subtropical Pacific free troposphere

Mercury is a global toxin that can be introduced to ecosystems through atmospheric deposition. Mercury oxidation is thought to occur in the free troposphere by bromine radicals, but direct observational evidence for this process is currently unavailable. During the 2013 Nitrogen, Oxidants, Mercury and Aerosol Distributions, Sources and Sinks campaign, we measured enhanced oxidized mercury and bromine monoxide in a free tropospheric air mass over Texas. We use trace gas measurements, air mass back trajectories, and a chemical box model to confirm the origin and chemical history of the sampled air mass. We find the presence of elevated oxidized mercury to be consistent with oxidation of elemental mercury by bromine atoms in this subsiding upper tropospheric air mass within the subtropical Pacific High, where dry atmospheric conditions are conducive to oxidized mercury accumulation. Our results support the role of bromine as the dominant oxidant of mercury in the upper troposphere.

Impact of Bay-Breeze Circulations on Surface Air Quality and Boundary Layer Export

Meteorological and air-quality model simulations are analyzed alongside observations to investigate the role of the Chesapeake Bay breeze on surface air quality, pollutant transport, and boundary layer venting. A case study was conducted to understand why a particular day was the only one during an 11-day ship-based field campaign on which surface ozone was not elevatedin concentrationover the ChesapeakeBay relative to theclosestupwindsiteandwhyhigh ozoneconcentrations wereobservedaloftbyinsitu aircraftobservations. Results show that southerly winds during the overnight and early-morning hours prevented the advection of air pollutants from the Washington, D.C., and Baltimore, Maryland, metropolitan areas over the surface waters of the bay. A strong and prolonged bay breeze developed during the late morning and early afternoon along the western coastline of the bay. The strength and duration of the bay breeze allowed pollutants to converge, resulting in high concentrations locally near the bay-breeze front within the Baltimore metropolitan area, where they were then lofted to the top of the planetary boundary layer (PBL). Near the top of the PBL, these pollutants were horizontally advected to a region with lower PBL heights, resulting in pollution transportoutoftheboundarylayerandintothefreetroposphere. Thiselevatedlayerofairpollutionaloftwas transported downwind into New England by early the following morning where it likely mixed down to the surface, affecting air quality as the boundary layer grew.

Large vertical gradient of reactive nitrogen oxides in the boundary layer: Modeling analysis of DISCOVER-AQ 2011 observations

An often used assumption in air pollution studies is a well-mixed boundary layer (BL), where pollutants are evenly distributed. Because of the difficulty in obtaining vertically resolved measurements, the validity of the assumption has not been thoroughly evaluated. In this study, we usemore than 200 vertical profiles observed in the Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality (DISCOVER-AQ) aircraft campaign in July 2011 to examine the vertical distributions of pollutants over the Washington-Baltimore area. While many long-lived species are well mixed in daytime, the observed average vertical profile of NOx shows a large negative gradient with increasing altitude in the BL. Our analysis suggests that the magnitude of the NOx gradient is highly sensitive to atmospheric stability. We investigate how parameterizations of the BL and land-surface processes impact vertical profiles in a 1-D chemical transport model, using three BL schemes (Asymmetric Convective Model version 2 (ACM2), Yonsei University (YSU), and Mellor-Yamada-Janjic (MYJ)) and two land-surface schemes (Noah and Rapid Update Cycle (RUC)). The model reasonably reproduces the median vertical profiles of NOx under different BL stability conditions within 30% of observations, classified based on potential temperature gradient and BL height. Comparisons with NOx observations for individual vertical profiles reveal that while YSU performs better in the turbulent and deep BL case, in general, ACM2 (RMSE=2.0ppbv) outperforms YSU (RMSE=2.5ppbv) and MYJ (RMSE=2.2ppbv). Results also indicate that the land-surface schemes in the Weather Research and Forecasting (WRF) model have a small impact on the NOx gradient. Usingmodel simulations, we analyze the impact of BL NOx gradient on the calculation of the ozone production rate and satellite NO2 retrieval. We show that using surface measurements and the well-mixed BL assumption causes a~45%highbias in the estimated BL ozoneproduction rate and that the variability of NO2 vertical profiles is responsible for 5–10% variability in the retrieved NO2 tropospheric vertical columns.

Airborne quantification of upper tropospheric NOx production from lightning in deep convective storms over the United States Great Plains

The reported range for global production of nitrogen oxides (NOx = NO + NO2) by lightning remains large (e.g., 32 to 664 mol NOx flash−1), despite incorporating results from over 30 individual laboratory, theoretical, and field studies since the 1970s. Airborne and ground-based observations from the Deep Convective Clouds and Chemistry experiment in May and June 2012 provide a new data set for calculating moles of NOx produced per lightning flash, P(NOx), in thunderstorms over the United States Great Plains. This analysis utilizes a combination of in situ observations of storm inflow and outflow from three instrumented aircraft, three-dimensional spatial information from ground-based radars and satellite observations, and spatial and temporal information for intracloud and cloud-to-ground lightning flashes from ground-based lightning mapping arrays. Evaluation of two analysis methods (e.g., a volume-based approach and a flux-based approach) for converting enhancements in lightning-produced NOx from volume-based mixing ratios to moles NOx flash−1 suggests that both methods equally approximate P(NOx) for storms with elongated anvils, while the volume-based approach better approximates P(NOx) for storms with circular-shaped anvils. Results from the more robust volume-based approach for three storms sampled over Oklahoma and Colorado during DC3 suggest a range of 142 to 291 (average of 194) moles NOx flash−1 (or 117–332 mol NOx flash−1 including uncertainties). Although not vastly different from the previously reported range for storms occurring in the Great Plains (e.g., 21–465 mol NOx flash−1), results from this analysis of DC3 storms offer more constrained upper and lower limits for P(NOx) in this geographical region.

Mercury Emission Ratios from Coal-Fired Power Plants in the Southeastern United States during NOMADSS

We use measurements made onboard the National Science Foundations C-130 research aircraft during the 2013 Nitrogen, Oxidants, Mercury, and Aerosol Distributions, Sources, and Sinks (NOMADSS) experiment to examine total Hg (THg) emission ratios (EmRs) for six coal-fired power plants (CFPPs) in the southeastern U.S. We compare observed enhancement ratios (ERs) with EmRs calculated using Hg emissions data from two inventories: the National Emissions Inventory (NEI) and the Toxics Release Inventory (TRI). For four CFPPs, our measured ERs are strongly correlated with EmRs based on the 2011 NEI (r(2) = 0.97), although the inventory data exhibit a -39% low bias. Our measurements agree best (to within ±32%) with the NEI Hg data when the latter were derived from on-site emissions measurements. Conversely, the NEI underestimates by approximately 1 order of magnitude the ERs we measured for one previously untested CFPP. Measured ERs are uncorrelated with values based on the 2013 TRI, which also tends to be biased low. Our results suggest that the Hg inventories can be improved by targeting CFPPs for which the NEI- and TRI-based EmRs have significant disagreements. We recommend that future versions of the Hg inventories should provide greater traceability and uncertainty estimates.

Arctic springtime observations of volatile organic compounds during the OASIS‐2009 campaign

Gas-phase volatile organic compounds (VOCs) were measured at three vertical levels between 0.6 m and 5.4 m in the Arctic boundary layer in Barrow, Alaska, for the Ocean-Atmosphere-Sea Ice-Snowpack (OASIS)-2009 field campaign during March–April 2009. C4-C8 nonmethane hydrocarbons (NMHCs) and oxygenated VOCs (OVOCs), including alcohols, aldehydes, and ketones, were quantified multiple times per hour, day and night, during the campaign using in situ fast gas chromatography-mass spectrometry. Three canister samples were also collected daily and subsequently analyzed for C2-C5 NMHCs. The NMHCs and aldehydes demonstrated an overall decrease in mixing ratios during the experiment, whereas acetone and 2-butanone showed increases. Calculations of time-integrated concentrations of Br atoms, ∫[Br]dt, yielded values as high as (1.34 ± 0.27) × 1014 cm−3 s during the longest observed ozone depletion event (ODE) of the campaign and were correlated with the steady state Br calculated at the site during this time. Both chlorine and bromine chemistry contributed to the large perturbations on the production and losses of VOCs. Notably, acetaldehyde, propanal, and butanal mixing ratios dropped below the detection limit of the instrument (3 parts per trillion by volume (pptv) for acetaldehyde and propanal, 2 pptv for butanal) during several ODEs due to Br chemistry. Chemical flux calculations of OVOC production and loss are consistent with localized high Cl-atom concentrations either regionally or within a very shallow surface layer, while the deeper Arctic boundary layer provides a continuous source of precursor alkanes to maintain the OVOC mixing ratios.

Correction to “Nitric acid uptake on subtropical cirrus cloud particles”

Aeronomy Laboratory, National Oceanic and Atmospheric Administration, Boulder, Colorado, USA. Also at Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, Colorado, USA. Institut fur Physik der Atmosphare, Deutsches Zentrum fur Luftand Raumfahrt Oberpfaffenhofen, Wessling, Germany. Atmospheric Chemistry Division, National Center for Atmospheric Research, Boulder, Colorado, USA. Universidad Nacional Autonoma de Mexico, Centro de Ciencias de la Atmosfera, Ciudad Universitaria, Mexico City, Mexico. Department of Meteorology, University of Utah, Salt Lake City, Utah, USA. Atmospheric Research Project, Harvard University, Cambridge, Massachusetts, USA. Division of Geology and Planetary Sciences, California Institute of Technology, Pasadena, California, USA. Now at Department of Mechanical and Aeronautical Engineering, Clarkson University, Potsdam, New York, USA. NASA Ames Research Center, Moffett Field, California, USA. Jet Propulsion Laboratory, California Institute of Technology, Pasadena, California, USA. JOURNAL OF GEOPHYSICAL RESEARCH, VOL. 109, D08306, doi:10.1029/2004JD004781, 2004