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Montzka, D. D.

Publications and source records attributed to Montzka, D. D..

The Effect of Entrainment Through Atmospheric Boundary Layer Growth on Observed and Modeled Surface Ozone in the Colorado Front Range

Ozone concentrations at the Earth's surface are controlled by meteorological and chemical processes and are a function of advection, entrainment, deposition, and net chemical production/loss. The relative contributions of these processes vary in time and space. Understanding the relative importance of these processes controlling surface ozone concentrations is an essential component for designing effective regulatory strategies. Here we focus on the diurnal cycle of entrainment through atmospheric boundary layer (ABL) growth in the Colorado Front Range. Aircraft soundings and surface observations collected in July/August 2014 during the DISCOVER-AQ/FRAPPÉ (Deriving Information on Surface conditions from Column and Vertically Resolved Observations Relevant to Air Quality/Front Range Air Pollution and Photochemistry Éxperiment) campaigns and equivalent data simulated by a regional chemical transport model are analyzed. Entrainment through ABL growth is most important in the early morning, fumigating the surface at a rate of ~5 ppbv/h. The fumigation effect weakens near noon and changes sign to become a small dilution effect in the afternoon on the order of -1 ppbv/h. The chemical transport model WRF-Chem (Weather Research and Forecasting Model with chemistry) underestimates ozone at all altitudes during this study on the order of 10-15 ppbv. The entrainment through ABL growth is overestimated by the model in the order of 0.6-0.8 ppbv/h. This results from differences in boundary layer growth in the morning and ozone concentration jump across the ABL top in the afternoon. This implicates stronger modeled fumigation in the morning and weaker modeled dilution after 11:00 LT.

Entrainment through ABL Growth↗

Reactive Nitrogen, Ozone and Ozone Production in the Arctic Troposphere and the Impact of Stratosphere-Troposphere Exchange

We analyze the aircraft observations obtained during the Arctic Research of the Composition of the Troposphere from Aircraft and Satellite (ARCTAS) mission together with the GEOS-5 CO simulation to examine O3 and NOy in the Arctic and sub-Arctic region and their source attribution. Using a number of marker tracers and their probability density distributions, we distinguish various air masses from the background troposphere and examine their contribution to NOx, O3, and O3 production in the Arctic troposphere. The background Arctic troposphere has mean O3 of approximately 60 ppbv and NOx of approximately 25 pptv throughout spring and summer with CO decreases from approximately 145 ppbv in spring to approximately 100 ppbv in summer. These observed CO, NOx and O3 mixing ratios are not notably different from the values measured during the 1988 ABLE-3A and the 2002 TOPSE field campaigns despite the significant changes in the past two decades in processes that could have changed the Arctic tropospheric composition. Air masses associated with stratosphere-troposphere exchange are present throughout the mid and upper troposphere during spring and summer. These air masses with mean O3 concentration of 140-160 ppbv are the most important direct sources of O3 in the Arctic troposphere. In addition, air of stratospheric origin is the only notable driver of net O3 formation in the Arctic due to its sustainable high NOx (75 pptv in spring and 110 pptv in summer) and NOy (approximately 800 pptv in spring and approximately 1100 pptv in summer) levels. The ARCTAS measurements present observational evidence suggesting significant conversion of nitrogen from HNO3 to NOx and then to PAN (a net formation of approximately 120 pptv PAN) in summer when air of stratospheric origin is mixed with tropospheric background during stratosphere-to-troposphere transport. These findings imply that an adequate representation of stratospheric O3 and NOy input are essential in accurately simulating O3 and NOx photochemistry as well as the atmospheric budget of PAN in tropospheric chemistry transport models of the Arctic. Anthropogenic and biomass burning pollution plumes observed during ARCTAS show highly elevated hydrocarbons and NOy (mostly in the form of NOx and PAN), but do not contribute significantly to O3 in the Arctic troposphere except in some of the aged biomass burning plumes sampled during spring. Convection and/or lightning influences are negligible sources of O3 in the Arctic troposphere but can have significant impacts in the upper troposphere in the continental sub-Arctic during summer.

Liang, Q.↗

Emissions from Biomass Burning in the Yucatan

In March 2006 two instrumented aircraft made the first detailed field measurements of biomass burning (BB) emissions in the Northern Hemisphere tropics as part of the MILAGRO project. The aircraft were the National Center for Atmospheric Research C-130 and a University of Montana/US Forest Service Twin Otter. The initial emissions of up to 49 trace gas or particle species were measured from 20 deforestation and crop residue fires on the Yucatan peninsula. This included two trace gases useful as indicaters of BB (HCN and acetonitrile) and several rarely, or never before, measured species: OH, peroxyacetic acid, propanoic acid, hydrogen peroxide, methane sulfonic acid, and sulfuric acid. Crop residue fires emitted more organic acids and ammonia than deforestation fires, but the emissions from the main fire types were otherwise fairly similar. The Yucatan fires emitted unusually amounts of SO2 and particle chloride, likely due to a strong marine influence on the peninsula.

Yokelson, R.↗

Inferring Ozone Production in an Urban Atmosphere using Measurements of Peroxynitric Acid

Observations of peroxynitric acid (HO2NO2) obtained simultaneously with those of NO and NO2 provide a sensitive measure of the ozone photochemical production rate. We illustrate this technique for constraining the ozone production rate with observations obtained from the NCAR C-130 aircraft platform during the Megacity Initiative: Local and Global Research Observations (MILAGRO) intensive in Mexico during the spring of 2006. Sensitive and selective measurements of HO2NO2 were made in situ using chemical ionization mass spectrometry (CIMS). Observations were compared to modeled HO2NO2 concentrations obtained from the NASA Langley highly-constrained photochemical time-dependent box model. The median observed-to-calculated ratio of HO2NO2 is 1.18. At NOx levels greater than 15 ppbv, the photochemical box model underpredicts observations with an observed-to-calculated ratio of HO2NO2 of 1.57. As a result, we find that at high NOx, the ozone production rate calculated using measured HO2NO2 is faster than predicted using accepted photochemistry. Inclusion of an additional HOx source from the reaction of excited state NO2 with H2O or reduction in the rate constant of the reaction of OH with NO2 improves the agreement.

Spencer, K. M.↗

Nitric Acid Uptake on Subtropical Cirrus Cloud Particles

The redistribution of HNO3 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 HNO3 with the NOAA chemical ionization mass spectrometer. The instrument measures HNO3 with two independent channels of detection connected to separate forward and downward facing inlets that allow a determination of the amount of HNO3 condensed on ice particles. Subtropical cirrus clouds, as indicated by the presence of ice particles, were observed coincident with condensed-phase HNO3 at temperatures of 197-224 K and pressures of 122-224 hPa. Maximum levels of condensed-phase HNO3 approached the gas-phase equivalent of 0.8 ppbv. Ice particle surface coverages as high as 1.4 # 10(exp 14) molecules/ square cm were observed. A dissociative Langmuir adsorption model, when using an empirically derived HNO3 adsorption enthalpy of -11.0 kcal/mol, effectively describes the observed molecular coverages to within a factor of 5. The percentage of total HNO3 in the condensed phase ranged from near zero to 100% in the observed cirrus clouds. With volume-weighted mean particle diameters up to 700 ?m and particle fall velocities up to 10 m/s, some observed clouds have significant potential to redistribute HNO3 in the upper troposphere.

Popp, P. J.↗

Redistribution of reactive odd nitrogen in the lower arctic stratosphere

In-situ measurements of total reactive odd nitrogen NO(y), were made from the NASA DC-8 aircraft in the lower arctic stratosphere during the 1989 Airborne Arctic Stratospheric Expedition. Throughout January and February, NO(y) mixing ratios were typically between 0.5 and 3 parts per billion by volume (ppbv) at altitudes between 10 and 12.5 km. During several flights late in the mission, events of unusually light NO(y) occurred with mixing ratios up to 12 ppbv at these altitudes. Simultaneous measurements of N2O, O3, and H2O during these events suggest that large changes in NO(y) are not expected. The elevated NO(y) values are interpreted as a vertical redistribution of NO(y) in the lower stratosphere resulting from gravitational sedimentation of aerosol particles containing HNO3. No evidence of the redistribution of H2O is noted, consistent with observations of denitrification without dehydration higher in the stratosphere.

Huebler, G.↗