Showing papers by "James Walega published in 2010"

Chemistry of hydrogen oxide radicals (HO x ) in the Arctic troposphere in spring

Abstract: . We use observations from the April 2008 NASA ARCTAS aircraft campaign to the North American Arctic, interpreted with a global 3-D chemical transport model (GEOS-Chem), to better understand the sources and cycling of hydrogen oxide radicals (HOx≡H+OH+peroxy radicals) and their reservoirs (HOy≡HOx+peroxides) in the springtime Arctic atmosphere. We find that a standard gas-phase chemical mechanism overestimates the observed HO2 and H2O2 concentrations. Computation of HOx and HOy gas-phase chemical budgets on the basis of the aircraft observations also indicates a large missing sink for both. We hypothesize that this could reflect HO2 uptake by aerosols, favored by low temperatures and relatively high aerosol loadings, through a mechanism that does not produce H2O2. We implemented such an uptake of HO2 by aerosol in the model using a standard reactive uptake coefficient parameterization with γ(HO2) values ranging from 0.02 at 275 K to 0.5 at 220 K. This successfully reproduces the concentrations and vertical distributions of the different HOx species and HOy reservoirs. HO2 uptake by aerosol is then a major HOx and HOy sink, decreasing mean OH and HO2 concentrations in the Arctic troposphere by 32% and 31% respectively. Better rate and product data for HO2 uptake by aerosol are needed to understand this role of aerosols in limiting the oxidizing power of the Arctic atmosphere.

Chemical evolution of volatile organic compounds in the outflow of the Mexico City metropolitan area

Abstract: . The volatile organic compound (VOC) distribution in the Mexico City Metropolitan Area (MCMA) and its evolution as it is uplifted and transported out of the MCMA basin was studied during the 2006 MILAGRO/MIRAGE-Mex field campaign. The results show that in the morning hours in the city center, the VOC distribution is dominated by non-methane hydrocarbons (NMHCs) but with a substantial contribution from oxygenated volatile organic compounds (OVOCs), predominantly from primary emissions. Alkanes account for a large part of the NMHC distribution in terms of mixing ratios. In terms of reactivity, NMHCs also dominate overall, especially in the morning hours. However, in the afternoon, as the boundary layer lifts and air is mixed and aged within the basin, the distribution changes as secondary products are formed. The WRF-Chem (Weather Research and Forecasting with Chemistry) model and MOZART (Model for Ozone and Related chemical Tracers) were able to approximate the observed MCMA daytime patterns and absolute values of the VOC OH reactivity. The MOZART model is also in agreement with observations showing that NMHCs dominate the reactivity distribution except in the afternoon hours. The WRF-Chem and MOZART models showed higher reactivity than the experimental data during the nighttime cycle, perhaps indicating problems with the modeled nighttime boundary layer height. A northeast transport event was studied in which air originating in the MCMA was intercepted aloft with the Department of Energy (DOE) G1 on 18 March and downwind with the National Center for Atmospheric Research (NCAR) C130 one day later on 19 March. A number of identical species measured aboard each aircraft gave insight into the chemical evolution of the plume as it aged and was transported as far as 1000 km downwind; ozone was shown to be photochemically produced in the plume. The WRF-Chem and MOZART models were used to examine the spatial extent and temporal evolution of the plume and to help interpret the observed OH reactivity. The model results generally showed good agreement with experimental results for the total VOC OH reactivity downwind and gave insight into the distributions of VOC chemical classes. A box model with detailed gas phase chemistry (NCAR Master Mechanism), initialized with concentrations observed at one of the ground sites in the MCMA, was used to examine the expected evolution of specific VOCs over a 1–2 day period. The models clearly supported the experimental evidence for NMHC oxidation leading to the formation of OVOCs downwind, which then become the primary fuel for ozone production far away from the MCMA.

Impact of Mexico City emissions on regional air quality from MOZART-4 simulations

Abstract: . An extensive set of measurements was made in and around Mexico City as part of the MILAGRO (Megacity Initiative: Local and Global Research Observations) experiments in March 2006. Simulations with the Model for Ozone and Related Chemical Tracers, version 4 (MOZART-4), a global chemical transport model, have been used to provide a regional context for these observations and assist in their interpretation. These MOZART-4 simulations reproduce the aircraft observations generally well, but some differences in the modeled volatile organic compounds (VOCs) from the observations result from incorrect VOC speciation assumed for the emission inventories. The different types of CO sources represented in the model have been "tagged" to quantify the contributions of regions outside Mexico, as well as the various emissions sectors within Mexico, to the regional air quality of Mexico. This analysis indicates open fires have some, but not a dominant, impact on the atmospheric composition in the region around Mexico City when averaged over the month. However, considerable variation in the fire contribution (2–15% of total CO) is seen during the month. The transport and photochemical aging of Mexico City emissions were studied using tags of CO emissions for each day, showing that typically the air downwind of Mexico City was a combination of many ages. Ozone production in MOZART-4 is shown to agree well with the net production rates from box model calculations constrained by the MILAGRO aircraft measurements. Ozone production efficiency derived from the ratio of Ox to NOz is higher in MOZART-4 than in the observations for moderately polluted air. OH reactivity determined from the MOZART-4 results shows the same increase in relative importance of oxygenated VOCs downwind of Mexico City as the reactivity inferred from the observations. The amount of ozone produced by emissions from Mexico City and surrounding areas has been quantified in the model by tracking NO emissions, showing little influence beyond Mexico's borders, and also relatively minor influence from fire emissions on the monthly average tropospheric ozone column.

Characterization of NOx, SO2, ethene, and propene from industrial emission sources in Houston, Texas

Abstract: [1] The Houston-Galveston-Brazoria urban area contains industrial petrochemical sources that emit volatile organic compounds and nitrogen oxides, resulting in rapid and efficient ozone production downwind. During September to October 2006, the NOAA WP-3D aircraft conducted research flights as part of the second Texas Air Quality Study (TexAQS II). We use measurements of NOx, SO2, and speciated hydrocarbons from industrial sources in Houston to derive source emission ratios and compare these to emission inventories and the first Texas Air Quality Study (TexAQS) in 2000. Between 2000 and 2006, NOx/CO2 emission ratios changed by an average of −29% ± 20%, while a significant trend in SO2/CO2 emission ratios was not observed. We find that high hydrocarbon emissions are routine for the isolated petrochemical facilities. Ethene (C2H4) and propene (C3H6) are the major contributors to ozone formation based on calculations of OH reactivity for organic species including C2–C10 alkanes, C2–C5 alkenes, ethyne, and C2–C5 aldehydes and ketones. Measured ratios of C2H4/NOx and C3H6/NOx exceed emission inventory values by factors of 1.4–20 and 1–24, respectively. We examine trends in C2H4/NOx and C3H6/NOx ratios between 2000 and 2006 for the isolated petrochemical sources and estimate a change of −30% ± 30%, with significant day-to-day and within-plume variability. Median ambient mixing ratios of ethene and propene in Houston show decreases of −52% and −48%, respectively, between 2000 and 2006. The formaldehyde, acetaldehyde, and peroxyacetyl nitrate products produced by alkene oxidation are observed downwind, and their time evolution is consistent with the rapid photochemistry that also produces ozone.

Difference frequency generation spectrometer for simultaneous multispecies detection.

Abstract: A difference-frequency generation based spectrometer system for simultaneous ultra-sensitive measurements of formaldehyde (CH2O) and Methane (CH4) is presented. A new multiplexing approach using collinear quasi-phase-matching in a single grating period of periodically poled lithium niobate (PPLN) is discussed and demonstrated for two pairs of pump and signal lasers to generate mid-infrared frequencies at 2831.64 cm−1 and 2916.32 cm−1, respectively. The corresponding absorption signals are discriminated by modulating the DFB diode lasers at modulation frequencies of 40 kHz and 50 kHz, respectively, and using a computer based modulation and de-modulation scheme. In addition, simultaneous measurements of CH2O, CH4 and H2O are demonstrated utilizing both collinear and non-collinear quasi-phase-matching.

Aldehydes in Artic Snow at Barrow (AK) during the Barrow 2009 Field Campaign

Abstract: We found that HCHO was the most abundant aldehyde (1 to 9 μg/L), but significant concentrations of dicarbonyls glyoxal and methylglyoxal were also measured for the first time in Arctic snow Similar concentrations were measured for the continental and marine snowpacks but some frost flowers exhibited HCHO concentrations as high as 150 μg/L Daily cycles in the surface snow were observed for HCHO and CH3CHO but also for the dicarbonyls and we concluded to a photochemical production of these species from organic precursors

Tunable Difference Frequency Generation Laser Spectrometers: Successes, Challenges, and Opportunities

Abstract: We will review the state of development and applications of difference-frequency generation (DFG) based laser spectrometers to atmospheric research and discuss the unique operating conditions and techniques that enable high precision performance for ground and airborne environments.