Rynda C. Hudman

Surface and Lightning Sources of Nitrogen Oxides over the United States: Magnitudes, Chemical Evolution, and Outflow

[1] We use observations from two aircraft during the ICARTT campaign over the eastern United States and North Atlantic during summer 2004, interpreted with a global 3-D model of tropospheric chemistry (GEOS-Chem) to test current understanding of regional sources, chemical evolution, and export of NOx. The boundary layer NOx data provide top-down verification of a 50% decrease in power plant and industry NOx emissions over the eastern United States between 1999 and 2004. Observed NOx concentrations at 8–12 km altitude were 0.55 ± 0.36 ppbv, much larger than in previous U.S. aircraft campaigns (ELCHEM, SUCCESS, SONEX) though consistent with data from the NOXAR program aboard commercial aircraft. We show that regional lightning is the dominant source of this upper tropospheric NOx and increases upper tropospheric ozone by 10 ppbv. Simulating ICARTT upper tropospheric NOx observations with GEOS-Chem requires a factor of 4 increase in modeled NOx yield per flash (to 500 mol/ flash). Observed OH concentrations were a factor of 2 lower than can be explained from current photochemical models, for reasons that are unclear. A NOy-CO correlation analysis of the fraction f of North American NOx emissions vented to the free troposphere as NOy (sum of NOx and its oxidation products) shows observed f = 16 ± 10% and modeled f = 14 ± 9%, consistent with previous studies. Export to the lower free troposphere is mostly HNO3 but at higher altitudes is mostly PAN. The model successfully simulates NOy export efficiency and speciation, supporting previous model estimates of a large U.S. anthropogenic contribution to global tropospheric ozone through PAN export.

Impacts of climate change from 2000 to 2050 on wildfire activity and carbonaceous aerosol concentrations in the western United States

[1] We investigate the impact of climate change on wildfire activity and carbonaceous aerosol concentrations in the western United States. We regress observed area burned onto observed meteorological fields and fire indices from the Canadian Fire Weather Index system and find that May–October mean temperature and fuel moisture explain 24–57% of the variance in annual area burned in this region. Applying meteorological fields calculated by a general circulation model (GCM) to our regression model, we show that increases in temperature cause annual mean area burned in the western United States to increase by 54% by the 2050s relative to the present day. Changes in area burned are ecosystem dependent, with the forests of the Pacific Northwest and Rocky Mountains experiencing the greatest increases of 78 and 175%, respectively. Increased area burned results in near doubling of wildfire carbonaceous aerosol emissions by midcentury. Using a chemical transport model driven by meteorology from the same GCM, we calculate that climate change will increase summertime organic carbon (OC) aerosol concentrations over the western United States by 40% and elemental carbon (EC) concentrations by 20% from 2000 to 2050. Most of this increase (75% for OC and 95% for EC) is caused by larger wildfire emissions with the rest caused by changes in meteorology and for OC by increased monoterpene emissions in a warmer climate. Such an increase in carbonaceous aerosol would have important consequences for western U.S. air quality and visibility.

Ozone production in transpacific Asian pollution plumes and implications for ozone air quality in California

[1] We examine the ozone production efficiency in transpacific Asian pollution plumes, and the implications for ozone air quality in California, by using aircraft and surface observations in April–May 2002 from the Intercontinental Transport and Chemical Transformation 2002 (ITCT 2K2) campaign off the California coast and the Pacific Exploration of Asian Continental Emission–B (PEACE-B) campaign over the northwest Pacific. The observations are interpreted with a global three-dimensional chemical transport model (GEOS-CHEM). The model reproduces the mean features observed for CO, reactive nitrogen oxides (NOy), and ozone but underestimates the strong (20 ppbv) stratospheric contribution to ozone in the middle troposphere. The ITCT 2K2 aircraft sampled two major transpacific Asian pollution plumes, one on 5 May at 5–8 km altitude with CO up to 275 ppbv but no elevated ozone and one on 17 May at 2.5–4 km altitude with CO up to 225 ppbv and ozone up to 90 ppbv. We show that the elevated ozone in the latter plume is consistent with production from peroxyacetylnitrate (PAN) decomposition during subsidence of the plume over the northeast Pacific. This production is particularly efficient because of the strong radiation and low humidity of the subsiding environment. We argue that such PAN decomposition represents a major and possibly dominant component of the ozone enhancement in transpacific Asian pollution plumes. Strong dilution of Asian pollution plumes takes place during entrainment in the U.S. boundary layer, greatly reducing their impact at U.S. surface sites. California mountain sites are more sensitive to Asian pollution because of their exposure to the free troposphere. Model results indicate a mean Asian pollution enhancement of 7 ppbv ozone at Sequoia National Park in May 2002 on those days when the 8-hour average ozone concentration exceeded 80 ppbv. INDEX TERMS: 0368 Atmospheric Composition and Structure: Troposphere—constituent transport and chemistry; 0365 Atmospheric Composition and Structure: Troposphere—composition and chemistry; 0345 Atmospheric Composition and Structure: Pollution—urban and regional (0305); KEYWORDS: ozone, Asian pollution, ITCT 2K2, PEACE-B, transpacific transport

Inventory of boreal fire emissions for North America in 2004: Importance of peat burning and pyroconvective injection

The summer of 2004 was one of the largest fire seasons on record for Alaska and western Canada. We construct a daily bottom-up fire emission inventory for that season, including consideration of peat burning and high-altitude (buoyant) injection, and evaluate it in a global chemical transport model (the GEOS-Chem CTM) simulation of CO through comparison with MOPITT satellite and ICARTT aircraft observations. The inventory is constructed by combining daily area burned reports and MODIS fire hot spots with estimates of fuel consumption and emission factors based on ecosystem type. We estimate the contribution from peat burning using drainage and peat distribution maps for Alaska and Canada; 17% of the reported 5.1 × 106 ha burned were located in peatlands in 2004. Our total estimate of North American fire emissions during the summer of 2004 is 30 Tg CO, including 11 Tg from peat. Including peat burning in the GEOS-Chem simulation improves agreement with MOPITT observations. The long-range transport of fire plumes observed by MOPITT suggests that the largest fires injected a significant fraction of their emissions in the upper troposphere.

Biogenic versus anthropogenic sources of CO in the United States

Aircraft observations of carbon monoxide (CO) from the ICARTT campaign over the eastern United States in summer 2004 (July 1–August 15), interpreted with a global 3-D model of tropospheric chemistry (GEOS-Chem), show that the national anthropogenic emission inventory from the U.S. Environmental Protection Agency (93 Tg CO y−1) is too high by 60% in summer. Our best estimate of the CO anthropogenic source for the ICARTT period is 6.4 Tg CO, including 4.6 Tg from direct emission and 1.8 Tg CO from oxidation of anthropogenic volatile organic compounds (VOCs). The biogenic CO source for the same period from the oxidation of isoprene and other biogenic VOCs is 8.3 Tg CO, and is independently constrained by ICARTT observations of formaldehyde (HCHO). Anthropogenic emissions of CO in the U.S. have decreased to the point that they are now lower than the biogenic source in summer.

Summertime influence of Asian pollution in the free troposphere over North America

We analyze aircraft observations obtained during INTEX-A (1 July to 14 August 2004) to examine the summertime influence of Asian pollution in the free troposphere over North America. By applying correlation analysis and principal component analysis (PCA) to the observations between 6 and 12 km, we find dominant influences from recent convection and lightning (13% of observations), Asia (7%), the lower stratosphere (7%), and boreal forest fires (2%), with the remaining 71% assigned to background. Asian air masses are marked by high levels of CO, O_3, HCN, PAN, C_2H_2, C_6H_6, methanol, and SO_4^(2–). The partitioning of NO_y species in the Asian plumes is dominated by PAN (∼600 pptv), with varying NO_x/HNO_3 ratios in individual plumes, consistent with individual transit times of 3–9 days. Export of Asian pollution occurred in warm conveyor belts of midlatitude cyclones, deep convection, and in typhoons. Compared to Asian outflow measurements during spring, INTEX-A observations display lower levels of anthropogenic pollutants (CO, C_3H_8, C_2H_6, C_6H_6) due to shorter summer lifetimes; higher levels of biogenic tracers (methanol and acetone) because of a more active biosphere; and higher levels of PAN, NO_x, HNO_3, and O_3 reflecting active photochemistry, possibly enhanced by efficient NO_y export and lightning. The high ΔO_3/ΔCO ratio (0.76 mol/mol) in Asian plumes during INTEX-A is due to strong photochemical production and, in some cases, mixing with stratospheric air along isentropic surfaces. The GEOS-Chem global model captures the timing and location of the Asian plumes. However, it significantly underestimates the magnitude of observed enhancements in CO, O_3, PAN and NO_x.

Ozone-CO correlations determined by the TES satellite instrument in continental outflow regions

0.4– 1.0 mol mol � 1 and consistent with ICARTT data. The GEOS-Chem model reproduces the O3-CO enhancement ratios observed in continental outflow, but model correlations are stronger and more extensive. We show that the discrepancy can be explained by spectral measurement errors in the TES data. These errors will decrease in future data releases, which should enable TES to provide better information on O3-CO correlations. Citation: Zhang, L., et al. (2006), Ozone-CO correlations determined by the TES satellite instrument in continental outflow regions, Geophys. Res. Lett., 33, L18804, doi:10.1029/2006GL026399.

Summary of the cloud chemistry modeling intercomparison: Photochemical box model simulation

Received 19 June 2002; revised 13 September 2002; accepted 11 November 2002; published 8 April 2003. [1] We report results of a cloud chemistry numerical modeling intercomparison, which shows good agreement among gas-aqueous photochemistry box models that are being used in the community. For the case studied, cloud chemistry depleted concentrations of CH2O, CH3OOH, HNO3, and O3, while H2O2 (in the absence of sulfur chemistry), NO, and NO2 increased. Because parcels of air usually flow in and out of cloud in a matter of minutes rather than remain in cloud for an hour, an optional simulation was performed in which frequent brief cloud encounters were represented. Representing a cloud intermittently rather than continuously does not alter the total concentration of many of the species. However CH2O and HCOOH concentrations are decreased and increased, respectively, because of the timing of the CH2O production during clear-sky intervals and its destruction during cloudy intervals. Further differences between a continuous cloud simulation and an intermittent cloud simulation are expected if pH is allowed to vary during the cloud periods. Simulating an intermittent cloud brought out the importance of using a chemistry time step that is a multiple of the cloud time step because deviations of results from a simulation in which the chemistry time step did not coincide with the appearance and disappearance of cloud were quite large. To better quantify the effect of cloud on HOx photochemistry, future investigations should include nonmethane hydrocarbon and sulfur chemistry. Future cloud chemistry modeling intercomparisons should bring in cloud physical and chemical measurements so that the models can be evaluated with observations. INDEX TERMS: 0320 Atmospheric Composition and Structure: Cloud physics and chemistry; 0365 Atmospheric Composition and Structure: Troposphere—composition and chemistry; 0399 Atmospheric Composition and Structure: General or miscellaneous; KEYWORDS: cloud chemistry, photochemical models, tropospheric chemistry