Photochemical Reactivities of N-Butane and Other Paraffinic Hydrocarbons

Photooxidation of lower-reactivity paraffinic hydrocarbons with nitrogen oxide was investigated. Maximum oxidant yield occurred at much lower ratios of hydrocarbon to nitrogen oxide than in more reactive systems such as propylene-nitrogen oxide mixtures. Appreciable oxidant yields were obtained even from irradiation of propane-nitrogen oxide mixtures at low ratios of nitrogen oxide to propane. These results, and nitrogen dioxide and oxidant dosages computed from these measurements, substantiate the importance of reactivity characteristics in formulation of decisions on control of hydrocarbons and nitrogen oxides.     

Photochemical Reactivities of Exhausts from 1966 Model Automobiles Equipped to Reduce Hydrocarbon Emissions

During the summer of 1966, a selected group of automobiles from the Cincinnati phase of the GSA study were used in an irradiation chamber study. The study was conducted to evaluate the photochemical air pollution potential of representative models of the equipped and unequipped automobiles. Only one set of automobiles, the unequipped Chevelles, produced exhaust capable upon irradiation of forming significant levels of oxidant and PAN. Neither the equipped Chevelles nor any of the Fords or Plymouths, whether equipped or unequipped, produced exhaust having the characteristics necessary to form oxidant or PAN upon irradiation. The eye irritation level reported by the panel upon irradiation of exhaust from unequipped Chevelles was much higher than that produced by the irradiated exhausts from any of the other types of automobiles. Overall, there does appear to be some small improvement with respect to eye irritation in comparing equipped with unequipped automobiles. To a large extent, the improvement in the air pollution potential of exhaust from equipped Chevelles compared to the unequipped Chevelles can be attributed to the reduction in the hydrocarbon to nitrogen oxide ratio. The irradiated exhaust from equipped Chevelles, except for aldehyde levels, is about the same in photochemical air pollution potential as are the exhausts from both equipped and unequipped Fords and Plymouths which are maintained under lean operating conditions. Such irradiation chamber measurements are related to exhaust not hydrocarbon reactivities. Hydrocarbon reactivities can be obtained by direct measurement of reactive and nonreactive hydrocarbons in the automotive emissions.     

The Fate of Aromatic Hydrocarbons in Photochemical Smog Systems: Toluene

The economic impact of various ozone concentrations on California agriculture is examined using an economic model of crop production that accounts for interdependence among crops. Such interdependence recognizes that net economic effects are determined not only by yield sensitivity to ozone but also by market conditions that affect relative crop prices and profitability. Changes in crop yields due to alternations in ambient ozone concentrations are used to drive the economic model. The predicted yield changes are derived from NCLAN data under a range of assumptions concerning functional form and yield effects. The results indicate that the economic effects of ozone are substantial for 13 included crops. The economic estimates display varying sensitivity to the functional form of the response relationship. The need for additional experimental data to more precisely define the relationship depends on the range of policy actions being considered.     

Analysis of Ozone and Nitric Oxide by a Chemiluminescent Method in Laboratory and Atmospheric Studies of Photochemical Smog

A prototype instrument monitoring ozone or nitric oxide has been used for photochemical smog studies in the laboratory and the atmosphere. The principle of the detector is based on the chemiluminescent reaction     

Atmospheric Chemistry of Toxic Contaminants. 2. Saturated Aliphatics: Acetaldehyde,Dioxane, Ethylene Glycol Ethers,Propylene Oxide

Detailed mechanisms are outlined for the chemical reactions that contribute to In-situ formation and atmospheric removal of the saturated aliphatic contaminants acetaldehyde, dioxane, ethylene glycol ethers (methyl, ethyl, n-butyl) and propylene oxide. In-situ formation Is of major Importance for acetaldehyde. In-situ removal Involves reaction with OH (all compounds) and, for acetaldehyde, photolysis and reaction with NO3. Acetaldehyde, dioxane, and the ethers are rapidly removed (half-lives of less than one day), leading to PAN (acetaldehyde) and to 2-oxodioxane and formaldehyde (dioxane). Reaction products of the glycol ethers include a large number of hydroxyesters, hydroxyacids, and hydroxycarbonyls. Propylene oxide reacts only slowly with OH, with an atmospheric half-life of 3-10 days, to yield formaldehyde, acetaldehyde, and PAN. Uncertainties in the reaction mechanisms for dioxane, the glycol ethers, and propylene oxide are discussed and include C-C vs C-0 bond scission in alkoxy radicals as well as alkoxy radical unimolecular decomposition vs reaction with oxygen.     

Photochemical production of organic matter triplet states in water samples from mountain lakes, located below or above the tree line

The production of triplet states (T(*)) of chromophoric dissolved organic matter (CDOM), reacting with the probe molecule 2,4,6-trimethylphenol (TMP) was measured upon irradiation of water samples, taken from lakes located in a mountain area (NW Italy) between 1450 and 2750 m above sea level. The lakes are located below or above the tree line and surrounded by different vegetation types (trees, alpine meadows or exposed rocks). The most photoactive samples belonged to lakes below the tree line and their fluorescence spectra and CDOM optical features suggested the presence of a relatively elevated amount of humic (allochthonous) material. The lowest (negligible) photoactivity was found for a lake surrounded by exposed rocks. Its CDOM showed an important autochthonous contribution (due to in-lake productivity) and considerably higher spectral slope compared to the other samples, suggesting low CDOM molecular weight and/or aromaticity. Among the samples, CDOM photoactivity (measured as the rate of TMP-reactive T(*) photoproduction) decreased with changing vegetation type in the order: trees, meadows, rocks. It could be connected with decreasing contribution from catchment runoff and increasing contribution from autochthonous processes and possibly precipitation.