Near-UV photolysis cross sections of CH_3OOH and HOCH_2OOH determined via action spectroscopy

Knowledge of molecular photolysis cross sections is important for determining atmospheric lifetimes and fates of many species. A method and laser apparatus for measurement of these cross sections in the near-ultraviolet (UV) region is described. The technique is based on action spectroscopy, where the yield of a photodissociation product (in this case OH) is measured as a function of excitation energy. For compounds yielding OH, this method can be used to measure near-UV photodissociation cross section as low as 10−23 cm2 molecule−1. The method is applied to determine the photodissociation cross sections for methyl hydroperoxide (CH3OOH; MHP) and hydroxymethyl hydroperoxide (HOCH2OOH; HMHP) in the 305–365 nm wavelength range. The measured cross sections are in good agreement with previous measurements of absorption cross sections

Near-IR photodissociation of peroxy acetyl nitrate

Measurements of the C-H overtone transition strengths combined with estimates of the photodissociation cross sections for these transitions suggest that near-IR photodissociation of peroxy acetyl nitrate (PAN) is less significant (Jnear−IR ~3×10^−8 s^−1 at noon) in the lower atmosphere than competing sinks resulting from unimolecular decomposition and ultraviolet photolysis. This is in contrast to the photochemical behavior of a related peroxy nitrate, pernitric acid (PNA), that undergoes rapid near-IR photolysis in the atmosphere with Jnear−IR ~10^−5 s^−1 at noon (Roehl et al., 2002). This difference is attributed to the larger binding energy and larger number of vibrational degrees of 10 freedom in PAN, which make 4[Greek nu]CH the lowest overtone excitation with a high photodissociation yield (as opposed to 2[Greek nu]OH in PNA)

α-pinene photooxidation under controlled chemical conditions – Part 2: SOA yield and composition in low- and high-NO_x environments

The gas-phase oxidation of α-pinene produces a large amount of secondary organic aerosol (SOA) in the atmosphere. A number of carboxylic acids, organosulfates and nitrooxy organosulfates associated with α-pinene have been found in field samples and some are used as tracers of α-pinene oxidation. α-pinene reacts readily with OH and O_3 in the atmosphere followed by reactions with both HO_2 and NO. Due to the large number of potential reaction pathways, it can be difficult to determine what conditions lead to SOA. To better understand the SOA yield and chemical composition from low- and high-NO_x OH oxidation of α-pinene, studies were conducted in the Caltech atmospheric chamber under controlled chemical conditions. Experiments used low O_3 concentrations to ensure that OH was the main oxidant and low α-pinene concentrations such that the peroxy radical (RO_2) reacted primarily with either HO_2 under low-NO_x conditions or NO under high-NO_x conditions. SOA yield was suppressed under conditions of high-NO_x. SOA yield under high-NO_x conditions was greater when ammonium sulfate/sulfuric acid seed particles (highly acidic) were present prior to the onset of growth than when ammonium sulfate seed particles (mildly acidic) were present; this dependence was not observed under low-NO_x conditions. When aerosol seed particles were introduced after OH oxidation, allowing for later generation species to be exposed to fresh inorganic seed particles, a number of low-NO_x products partitioned to the highly acidic aerosol. This indicates that the effect of seed acidity and SOA yield might be under-estimated in traditional experiments where aerosol seed particles are introduced prior to oxidation. We also identify the presence of a number of carboxylic acids that are used as tracer compounds of α-pinene oxidation in the field as well as the formation of organosulfates and nitrooxy organosulfates. A number of the carboxylic acids were observed under all conditions, however, pinic and pinonic acid were only observed under low-NO_x conditions. Evidence is provided for particle-phase sulfate esterification of multi-functional alcohols

Formation and Propagation of Discontinuity for Boltzmann Equation in Non-Convex Domains

The formation and propagation of singularities for Boltzmann equation in bounded domains has been an important question in numerical studies as well as in theoretical studies. Consider the nonlinear Boltzmann solution near Maxwellians under in-flow, diffuse, or bounce-back boundary conditions. We demonstrate that discontinuity is created at the non-convex part of the grazing boundary, then propagates only along the forward characteristics inside the domain before it hits on the boundary again.Comment: 39 pages, 5 Figure

Measured HDO/H_2O ratios across the tropical tropopause

We present the first simultaneous measurements of HDO and H_2O in the tropical upper troposphere (UT) and lower stratosphere (LS) as derived from infrared solar absorption spectra acquired by the Atmospheric Trace Molecule Spectroscopy (ATMOS) experiment. We find, surprisingly, that the observed HDO/H_2O ratio does not decrease with altitude in this region despite a factor of 4–5 decrease in the water vapor mixing ratio. This observation is inconsistent with the view that dehydration in the tropical UT/LS is by gradual processes, and suggests a major role by convective processes

On the speed of approach to equilibrium for a collisionless gas

We investigate the speed of approach to Maxwellian equilibrium for a collisionless gas enclosed in a vessel whose wall are kept at a uniform, constant temperature, assuming diffuse reflection of gas molecules on the vessel wall. We establish lower bounds for potential decay rates assuming uniform $L^p$ bounds on the initial distribution function. We also obtain a decay estimate in the spherically symmetric case. We discuss with particular care the influence of low-speed particles on thermalization by the wall.Comment: 22 pages, 1 figure; submitted to Kinetic and Related Model

α-pinene photooxidation under controlled chemical conditions – Part 1: Gas-phase composition in low- and high-NO_x environments

The OH oxidation of α-pinene under both low- and high-NO_x environments was studied in the Caltech atmospheric chambers. Ozone was kept low to ensure OH was the oxidant. The initial α-pinene concentration was 20–50 ppb to ensure that the dominant peroxy radical pathway under low-NO_x conditions is reaction with HO_2, produced from reaction of OH with H_2O_2, and under high-NO_x conditions, reactions with NO. Here we present the gas-phase results observed. Under low-NO_x conditions the main first generation oxidation products are a number of α-pinene hydroxy hydroperoxides and pinonaldehyde, accounting for over 40% of the yield. In all, 65–75% of the carbon can be accounted for in the gas phase; this excludes first-generation products that enter the particle phase. We suggest that pinonaldehyde forms from RO_2 + HO_2 through an alkoxy radical channel that regenerates OH, a mechanism typically associated with acyl peroxy radicals, not alkyl peroxy radicals. The OH oxidation and photolysis of α-pinene hydroxy hydroperoxides leads to further production of pinonaldehyde, resulting in total pinonaldehyde yield from low-NO_x OH oxidation of ~33%. The low-NO_x OH oxidation of pinonaldehyde produces a number of carboxylic acids and peroxyacids known to be important secondary organic aerosol components. Under high-NO_x conditions, pinonaldehyde was also found to be the major first-generation OH oxidation product. The high-NO_x OH oxidation of pinonaldehyde did not produce carboxylic acids and peroxyacids. A number of organonitrates and peroxyacyl nitrates are observed and identified from α-pinene and pinonaldehyde

On Strong Convergence to Equilibrium for the Boltzmann Equation with Soft Potentials

The paper concerns $L^1$- convergence to equilibrium for weak solutions of the spatially homogeneous Boltzmann Equation for soft potentials (-4\le \gm<0), with and without angular cutoff. We prove the time-averaged $L^1$-convergence to equilibrium for all weak solutions whose initial data have finite entropy and finite moments up to order greater than 2+|\gm|. For the usual $L^1$-convergence we prove that the convergence rate can be controlled from below by the initial energy tails, and hence, for initial data with long energy tails, the convergence can be arbitrarily slow. We also show that under the integrable angular cutoff on the collision kernel with -1\le \gm<0, there are algebraic upper and lower bounds on the rate of $L^1$-convergence to equilibrium. Our methods of proof are based on entropy inequalities and moment estimates.Comment: This version contains a strengthened theorem 3, on rate of convergence, considerably relaxing the hypotheses on the initial data, and introducing a new method for avoiding use of poitwise lower bounds in applications of entropy production to convergence problem

Role of aldehyde chemistry and NO_x concentrations in secondary organic aerosol formation

Aldehydes are an important class of products from atmospheric oxidation of hydrocarbons. Isoprene (2-methyl-1,3-butadiene), the most abundantly emitted atmospheric non-methane hydrocarbon, produces a significant amount of secondary organic aerosol (SOA) via methacrolein (a C_4-unsaturated aldehyde) under urban high-NO_x conditions. Previously, we have identified peroxy methacryloyl nitrate (MPAN) as the important intermediate to isoprene and methacrolein SOA in this NO_x regime. Here we show that as a result of this chemistry, NO_2 enhances SOA formation from methacrolein and two other α, β-unsaturated aldehydes, specifically acrolein and crotonaldehyde, a NO_x effect on SOA formation previously unrecognized. Oligoesters of dihydroxycarboxylic acids and hydroxynitrooxycarboxylic acids are observed to increase with increasing NO_2/NO ratio, and previous characterizations are confirmed by both online and offline high-resolution mass spectrometry techniques. Molecular structure also determines the amount of SOA formation, as the SOA mass yields are the highest for aldehydes that are α, β-unsaturated and contain an additional methyl group on the α-carbon. Aerosol formation from 2-methyl-3-buten-2-ol (MBO232) is insignificant, even under high-NO_2 conditions, as PAN (peroxy acyl nitrate, RC(O)OONO_2) formation is structurally unfavorable. At atmospherically relevant NO_2/NO ratios (3–8), the SOA yields from isoprene high-NO_x photooxidation are 3 times greater than previously measured at lower NO_2/NO ratios. At sufficiently high NO_2 concentrations, in systems of α, β-unsaturated aldehydes, SOA formation from subsequent oxidation of products from acyl peroxyl radicals+NO_2 can exceed that from RO_2+HO_2 reactions under the same inorganic seed conditions, making RO_2+NO_2 an important channel for SOA formation

Biomass burning and urban air pollution over the Central Mexican Plateau

Observations during the 2006 dry season of highly elevated concentrations of cyanides in the atmosphere above Mexico City (MC) and the surrounding plains demonstrate that biomass burning (BB) significantly impacted air quality in the region. We find that during the period of our measurements, fires contribute more than half of the organic aerosol mass and submicron aerosol scattering, and one third of the enhancement in benzene, reactive nitrogen, and carbon monoxide in the outflow from the plateau. The combination of biomass burning and anthropogenic emissions will affect ozone chemistry in the MC outflow