Mechanisms of Photochemical Air Pollution

Selected aspects of the chemistry of photochemical air pollution is discussed and some important, unresolved problems dilineated. The reactive species considered include NO₂, O₃, O(³P), O(¹D), O₂(¹Δ_g), OH and HO₂. Both the kinetics and mechanicsms of the reactions constituting the major tropospheric sources and sinks of these species are treated where available. The application of this information in both computer and smog chamber simulations of photochemical smog is discussed.     

Recent results from the TCV tokamak

During the first two years of operation, the TCV tokamak has produced a large variety of plasma shapes and magnetic configurations, with 1.0B _tor1.46T,I _p800kA,k2.05, –0.71. A new shape control algorithm, based on a finite element reconstruction of the plasma current in real time, has been implemented. Vertical growth rates up to 1000s^–1 have been stabilized using the external coil system. Ohmic H-modes with Troyon factors ( _tor aB/I _p) up to two and densities up to 2.25×10²⁰m^–3, corresponding to the Greenwald limit, have been obtained in diverted discharges. Limiter H-modes with line averaged electron densities up to 1.7×10²⁰m^–3 have been obtained in elongated D-shaped plasmas with 360 kAI _P600 kA.Presented at 17^th Symposium Plasma Physics and Technology, Prague, June 13–16, 1995.This work was partly supported by the Fonds National Suisse de la Recherche Scientifique.     

Evaluation of a simple plasma catecholamine extraction procedure prior to high-performance liquid chromatography and electrochemical detection

The modified extraction method for catecholamines described in this study is reproducible, simple, rapid, economical and relatively hazard-free. This method is based on the principle that plasma catecholamines are selectively adsorbed on acid-washed alumina at pH 8.6 and then eluted at a pH between 1.0 and 2.0. No statistically significant differences were obtained by using either 0.5 or 1.0 ml of plasma with 0.5 or 1.0 ml of Tris buffer. A 15-min mixing time during the adsorption and desorption steps was found to be practical, but any standardized time up to 1 h can be used. If the washing step was omitted, the catecholamines could not be eluted from the acid-washed alumina. To prevent dilution, the alumina had to be centrifuged and not aspirated to dryness after the washing step. An amount of 50 mg of WA-4 alumina was found to be the most practical in this study. Extracted or unextracted plasma as well as catecholamine standards were stable for four months at -20 degrees C.     

Wavelength dependence of the I(52P12,32) branching ratio from ICN Ã state photolysis

Quantum yields for the production of I(5²P$\text{1}\text{2}$) atoms from the photolysis of ICN in the à state continuum are presented as a function of wavelength. Evidence is presented for the existence of at least three electronic states giving rise to the absorption spectra. Primary photophysical processes involved in the dissociation of ICN are discussed.     

Gauge-invariant localization of infinitely many gravitational energies from all possible auxiliary structures

The problem of finding a covariant expression for the distribution and conservation of gravitational energy–momentum dates to the 1910s. A suitably covariant infinite-component localization is displayed, reflecting Bergmann’s realization that there are infinitely many conserved gravitational energy–momenta. Initially use is made of a flat background metric (or rather, all of them) or connection, because the desired gauge invariance properties are obvious. Partial gauge-fixing then yields an appropriate covariant quantity without any background metric or connection; one version is the collection of pseudotensors of a given type, such as the Einstein pseudotensor, in every coordinate system. This solution to the gauge covariance problem is easily adapted to any pseudotensorial expression (Landau–Lifshitz, Goldberg, Papapetrou or the like) or to any tensorial expression built with a background metric or connection. Thus the specific functional form can be chosen on technical grounds such as relating to Noether’s theorem and yielding expected values of conserved quantities in certain contexts and then rendered covariant using the procedure described here. The application to angular momentum localization is straightforward. Traditional objections to pseudotensors are based largely on the false assumption that there is only one gravitational energy rather than infinitely many.     

Non-parametric Estimation for the M/G/∞ Queue

Given an M/G/ queue with input rate and service-time distribution G, we consider the problem of estimating and G from data on the queue-length process Q = (Q_t). Our motivation is to study departures of G from exponentiality, following recent work of Bingham and Dunham (1997, Ann. Inst. Statist. Math., 49, 667–679).     

A smog chamber and modeling study of the gas phase NOx–air photooxidation of toluene and the cresols

An experimental and modeling study of irradiated toluene–NO_x–air, toluene–benzaldehyde–NO_x–air, and cresol–NO_x–air mixtures at part-per-million concentrations has been carried out. These mixtures were irradiated at 303 ± 1 K in a 5800-liter Teflon-lined, evacuable environmental chamber, with temperature, humidity, light intensity, spectral distribution, and the concentrations of O₃, NO, NO₂, toluene, PAN, formaldehyde, benzaldehyde, o-cresol, m-nitrotoluene, and methyl nitrate beingmonitored as a function of time. For the toluene and toluene–benzaldehyde–NO_x–air runs a variety of initial reactant concentrations were investigated. Cresol–NO_x–air runs were observed to be much less reactive in terms of O₃ formation and NO to NO₂ conversion rates than toluene–NO_x–air runs, with the relative reactivity of the cresol isomers being in the order meta » ortho > para. The addition of benzaldehyde to toluene–NO_x–air mixtures decreased the reactivity, in agreement with previous studies. Alternative mechanistic pathways for the NO_x photooxidations of aromaticsystems in general are discussed, and the effects of varying these mechanistic alternatives on the model predictions for the toluene and o-cresol–NO_x–air systems are examined. Fits of the calculations to most of the experimental concentration–time profiles could be obtained to within the experimental uncertainty for two of the mechanistic options considered. In both cases it is assumed that (1) O₂ adds to the OH–toluene adduct ～75% of the time forming, after a further addition of O₂, a C₇ bicyclic peroxy radical, and (2) this C₇ bicyclic peroxy radical reacts with NO ～75% of the time to ultimately form α-dicarbonyls and conjugated γ-dicarbonyls (e.g., methylglyoxal + 2-butene-1,4-dial) and ～25% of the time to form organic nitrates. The major uncertainties in the mechanisms concern (1) the structure of the bicyclicperoxy intermediate, and (2) the γ-dicarbonyl photooxidation mechanism. Good fits to the o-cresol concentration–time profiles in the toluene–NO_x runs are obtained if it is assumed that o7-cresol reacts rapidly with NO₃ radicals. However, it is observed that the model underpredicts nitrotoluene yields by a factor of ～10, but this is in any case a minor product. It is concluded that further experimental work will be required toadequately validate the assumptions incorporated in the aromatic photooxidation mechanisms presented here.     

List of subject

We report the high resolution emission (S₁ → S₀, T₁ → S₀) and laser single site singlet excitation (S₁ ← S₀) spectra for the various insertion sites of coronene in n-heptane cooled to 1.5 K. The observation of site splitting of doubly degenerate vibrations and weak electric dipole forbidden 0, 0 bands in the S₁ → S₀ and T₁ → S₀ spectra indicates that the ground state, the first excited singlet and lowest triplet states are all distorted. In these spectra, the intensity distribution of the various sites in the 0, 0 bands suggests that the distortion is different from site to site but similar in S₀, S₁ and T₁. Identical ordering of the sites in S₁ S₀ and S₁ S₀ spectra as well as the observation of weak shifts in the vibrational frequencies in the two states implies the absence of strong pseudo Jahn-Teller forces in the first excited singlet state. We propose, further, that this is also true for the triplet state. This conclusion is supported by the similarity in zero-field splitting parameters of coronene and deuterated coronene. Taken together, these results indicate strongly that the distortion of coronene in n-heptane is primarily crystal field induced and is not greatly changed upon excitation of the molecule to its lowest excited states.     

Identification of mononitropyrenes and mononitrofluoranthenes in air particulate matter via fused silica gas,chromatography combined with negative ion atmospheric pressure ionization mass spectrometry

This paper describes the use of high resolution capillary gas chromatography combined with negative ion atmospheric pressure ionization mass spectrometry (NIAPIMS) for the analysis of an air particulate extract for mononitropyrenes and mononitrofluoranthenes, some of which are powerful bacterial mutagens. The results are compared to those obtained by the electron impact mass spectrometric analysis of the same sample In addition, the NIAPIMS method confirmed the identification of 4-nitropyrene in the ambient air sample.