Diagnostic studies of the HxOy-NzOy-O3 photochemical system using data from NASA GTE field expeditions

Spring 1084 GTE CITE-1 flight data from the field exercise was obtained from a GTE Data Archive Tape. Chemical and supporting meteorological data taken over the Pacific Ocean was statistically and diagnostically analyzed to identify the key processes affecting the concentrations of ozone and its chemical precursors in the region. The analysis was completed. The analysis of the GTE CITE-2 data is being performed in collaboration with Dr. D.D. Davis and other GTE scientists. Initial results of the analysis were presented and work begun on the paper describing the results

Possible atmospheric lifetimes and chemical reaction mechanisms for selected HCFCs, HFCs, CH3CCl3, and their degradation products against dissolution and/or degradation in seawater and cloudwater

For a wide variety of atmospheric species including CO2, HNO3, and SO2, dissolution in seawater or cloudwater followed by hydrolysis or chemical reaction represents a primary pathway for removal from the atmosphere. In order to determine if this mechanism can also remove significant amounts of atmospheric chlorofluorocarbons (HCFC's), fluorocarbons (HFC's), and their degradation products, an investigation was undertaken as part of the Alternative Fluorocarbons Environmental Acceptability Study (AFEAS). In this investigation, the rates at which CHCl2CF3 (HCFC-123), CCl2FCH3 (HCFC-141b), CClF2CH3 (HCFC-142b), CHClF2 (HCFC-22), CHClFCF3 (HCFC-124) CH2FCF3 (HFC-134a) CHF2CH3 (HFC-152a), CHF2CF3 (HFC-125), and CH3CCl3 can be dissolved in the oceans and in cloudwater were estimated from the species' thermodynamic and chemical properties using simple mathematical formulations to simulate the transfer of gases from the atmosphere to the ocean or cloudwater. The ability of cloudwater and rainwater to remove gas phase degradation products of these compounds was also considered as was the aqueous phase chemistry of the degradation products. The results of this investigation are described

Diagnostic studies of the HxOy-NxOy-O3 photochemical system using data from NASA GTE field expeditions

The research effort supported in part by the subject grant focused on three related topics. Our major effort was concentrated on the analysis of data gathered during GTE field expeditions. Ancillary efforts were directed at: the development and application of a Global Chemical Transport Model for the study of the atmospheric reactive nitrogen budget; the development and application of a one-dimensional, time dependent cloud model for the study of the impact of in-cloud aqueous phase chemistry on the atmospheric sulfur budget; and mechanistic studies of the chemical processes involved in dry deposition of ozone to vegetative surfaces. In the sections below, we briefly summarize the central conclusions of each of these efforts. These discussions are followed by a listing of the papers completed during the granting period and the graduate students supported by funds from the grant. Reprints and preprints of all papers completed with support from the grant are attached as appendices

Source characteristics of volatile organic compounds during high ozone episodes in Hong Kong, Southern China

International audienceMeasurements of Volatile Organic Compounds (VOC) are analyzed to characterize the sources impacting the Hong Kong area. The ratios of different VOC species, m,p-xylenes-to-ethylbenzene, C6H14-to-toluene and p-xylene-to-total xylenes are used for diagnostic analyses. Photochemical age analysis shows that the sources of reactive aromatics, the most important contributor to the photochemical reactivity, do not appear to be preferentially located in downtown Hong Kong. In addition, they do not appear to be dominated by mobile emissions based on the analyses of speciated VOC data from an earlier study, but related to industrial, waterfront, and fuel-storage activities. The ratios, p-xylene-to-total xylenes and dSO2/dNOy, suggest that the anomalously high pollutant concentrations in western Hong Kong in the early morning hours of two episode days appear to have come from transport of urban-type emissions. Comparison of observed ambient ratios of selected VOC and their ratios in the speciated VOC emission inventories for Hong Kong and adjacent Pearl River Delta (PRD) Region give mixed results. The observed ratio C6H14-to-toluene is consistent with the speciated version of the VOC emission inventory. The ratios of selected alkanes are not. This may be caused by the inaccuracies in the inventory and/or the speciation method

The vertical distribution of soluble gases in the troposphere

The thermodynamic properties of several water‐soluble gases are reviewed to determine the likely effect of the atmospheric water cycle on their vertical profiles. We find that gaseous HCl, HNO3, and HBr are sufficiently soluble in water to suggest that their vertical profiles in the troposphere have a similar shape to that of water vapor. Thus we predict that HCl, HNO3, and HBr exhibit a steep negative gradient with altitude roughly equal to the altitude gradient of water vapor. Therefore, ground‐based sources of inorganic chlorine, odd nitrogen, and inorganic bromine compounds are not likely to directly affect the stratosphere in the mean. Calculations also show that while SO2 and NH3 are significantly affected by the atmospheric water cycle, their abundances may not decrease with altitude as rapidly as does water vapor. Copyright 1974 by the American Geophysical Union

Reactive intermediates revealed in secondary organic aerosol formation from isoprene

Isoprene is a significant source of atmospheric organic aerosol; however, the oxidation pathways that lead to secondary organic aerosol (SOA) have remained elusive. Here, we identify the role of two key reactive intermediates, epoxydiols of isoprene (IEPOX = β-IEPOX + δ-IEPOX) and methacryloylperoxynitrate (MPAN), which are formed during isoprene oxidation under low- and high-NO_x conditions, respectively. Isoprene low-NO_x SOA is enhanced in the presence of acidified sulfate seed aerosol (mass yield 28.6%) over that in the presence of neutral aerosol (mass yield 1.3%). Increased uptake of IEPOX by acid-catalyzed particle-phase reactions is shown to explain this enhancement. Under high-NO_x conditions, isoprene SOA formation occurs through oxidation of its second-generation product, MPAN. The similarity of the composition of SOA formed from the photooxidation of MPAN to that formed from isoprene and methacrolein demonstrates the role of MPAN in the formation of isoprene high-NO_x SOA. Reactions of IEPOX and MPAN in the presence of anthropogenic pollutants (i.e., acidic aerosol produced from the oxidation of SO_2 and NO_2, respectively) could be a substantial source of “missing urban SOA” not included in current atmospheric models

Regional simulation of anthropogenic sulfur over East Asia and its sensitivity to model parameters

We discuss a series of simulations of anthropogenic sulfur over East Asia with a SO 2 /SO 4 2− chemistry-transport model driven in on-line mode by a regional climate model. Sensitivity to OH and H 2 O 2 concentration, cloud parameters, SO 2 dry deposition and emission strength is analyzed and the different components of the sulfur budget are examined. The SO 2 and SO 2− 4 column burdens show pronounced variability at temporal scales from seasonal to synoptic and sub-daily, with SO 2 and SO 2− 4 behaving differently due to the interplay of chemical conversion, removal and transport processes. Both SO 2 and SO 2− 4 show marked spatial variability, with emission being the dominant term in regulating the SO 2 spatial distribution. The atmospheric SO 2 and SO 2− 4 amounts show close to a linear response to surface emission. Aqueous phase SO 2 →SO 2− 4 conversion and wet removal are the primary factors that regulate the SO 2− 4 amounts, with dry deposition and gas phase SO 2 →SO 2− 4 conversion being of secondary importance. Aqueous phase conversion and dry deposition are the dominant loss mechanisms for SO 2 . The model shows low sensitivity to variations in OH, H 2 O 2 , and cloud parameters, while the sensitivity to prescribed dry deposition velocity is more pronounced. Overall, our results are in line with previous modeling studies and with very limited available observations. DOI: 10.1034/j.1600-0889.2001.d01-14.

Aerosol radiative, physical, and chemical properties in Beijing during June 1999

Beijing experiences air pollution such that the sky overhead is gray much of the time even on cloudless days. In order to understand the cause of this problem, the aerosol light scattering coefficient σ_(sp) and absorption coefficient σ_(ap) were measured under dry conditions (instrumental relative humidity 1.0 μm), the submicron aerosol was responsible for ∼80% of the light scattering at 530 nm. The largest contribution to the PM2.5 aerosol mass was due to organic compounds, which accounted for ∼30% of the mass. The contributions of sulfate, ammonium, and nitrate to the PM2.5 mass concentration were ∼15%, 5%, and 8%, respectively. Mineral aerosol contributed ∼16% to the PM2.5 aerosol mass. These data show that combustion-related particles rather than wind-blown dust dominated the light extinction budget during June 1999