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

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

Rates of fixation by lightning of carbon and nitrogen in possible primitive atmospheres

A thermochemical-hydrodynamic model of the production of trace species by electrical discharges has been used to estimate the rates of fixation of C and N by lightning in the primitive atmosphere. Calculations for various possible mixtures of CH 4 , CO 2 , N 2 , H 2 , and H 2 O reveal that the prime species produced were probably HCN and NO and that the key parameter determining the rates of fixation was the ratio of C atoms to O atoms in the atmosphere. Atmospheres with C more abundant than O have large HCN fixation rates, in excess of 10 17 molecules J −1 , but small NO yields. However, when O is more abundant than C, the NO fixation rate approaches 10 17 molecules J −1 while the HCN yield is small. The implications for the evolution of life are discussed.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/43346/1/11084_2004_Article_BF00931483.pd

Origin of Ozone NO(x) in the Tropical Troposphere: A Photochemical Analysis of Aircraft Observations Over the South Atlantic Basin

The photochemistry of the troposphere over the South Atlantic basin is examined by modeling of aircraft observations up to 12-km altitude taken during the TRACE A expedition in September-October 1992. A close balance is found in the 0 to 12-km column between photochemical production and loss Of O3, with net production at high altitudes compensating for weak net loss at low altitudes. This balance implies that O3 concentrations in the 0-12 km column can be explained solely by in situ photochemistry; influx from the stratosphere is negligible. Simulation of H2O2, CH3OOH, and CH2O concentrations measured aboard the aircraft lends confidence in the computations of O3 production and loss rates, although there appears to be a major gap in current understanding of CH2O chemistry in the marine boundary layer. The primary sources of NO(x) over the South Atlantic Basin appear to be continental (biomass burning, lightning, soils). There is evidence that NO(x) throughout the 0 to 12-km column is recycled from its oxidation products rather than directly transported from its primary sources. There is also evidence for rapid conversion of HNO3 to NO(x) in the upper troposphere by a mechanism not included in current models. A general representation of the O3 budget in the tropical troposphere is proposed that couples the large scale Walker circulation and in situ photochemistry. Deep convection in the rising branches of the Walker circulation injects NO(x) from combustion, soils, and lightning to the upper troposphere, leading to O3 production; eventually, the air subsides and net O3 loss takes place in the lower troposphere, closing the O3 cycle. This scheme implies a great sensitivity of the oxidizing power of the atmosphere to NO(x) emissions in the tropics