Molecular corridors and kinetic regimes in the multiphase chemical evolution of secondary organic aerosol

The dominant component of atmospheric, organic aerosol is that derived from the oxidation of volatile organic compounds (VOCs), so-called secondary organic aerosol (SOA). SOA consists of a multitude of organic compounds, only a small fraction of which has historically been identified. Formation and evolution of SOA is a complex process involving coupled chemical reaction and mass transport in the gas and particle phases. Current SOA models do not embody the full spectrum of reaction and transport processes, nor do they identify the dominant rate-limiting steps in SOA formation. Based on molecular identification of SOA oxidation products, we show here that the chemical evolution of SOA from a variety of VOC precursors adheres to characteristic "molecular corridors" with a tight inverse correlation between volatility and molar mass. The slope of these corridors corresponds to the increase in molar mass required to decrease volatility by one order of magnitude (-dM / dlogC_0). It varies in the range of 10–30 g mol^(−1), depending on the molecular size of the SOA precursor and the O : C ratio of the reaction products. Sequential and parallel reaction pathways of oxidation and dimerization or oligomerization progressing along these corridors pass through characteristic regimes of reaction-, diffusion-, or accommodation-limited multiphase chemical kinetics that can be classified according to reaction location, degree of saturation, and extent of heterogeneity of gas and particle phases. The molecular corridors and kinetic regimes help to constrain and describe the properties of the products, pathways, and rates of SOA evolution, thereby facilitating the further development of aerosol models for air quality and climate

Relativistic Hartree-Bogoliubov description of ground-state properties of Ni and Sn isotopes

The Relativistic Hartree Bogoliubov (RHB) theory is applied in the description of ground-state properties of Ni and Sn isotopes. The NL3 parameter set is used for the effective mean-field Lagrangian, and pairing correlations are described by the pairing part of the finite range Gogny interaction D1S. Fully self-consistent RHB solutions are calculated for the Ni ($28\leq N\leq 50$) and Sn ($50\leq N\leq 82$) isotopes. Binding energies, neutron separation energies, and proton and neutron $rms$ radii are compared with experimental data. The model predicts a reduction of the spin-orbit potential with the increase of the number of neutrons. The resulting energy splittings between spin-orbit partners are discussed, as well as pairing properties calculated with the finite range effective interaction in the $pp$ channel.Comment: 11 pages, RevTex, 12 p.s figures, submitted to Phys. Rev.

Seasonal cycle and temperature dependence of pinene oxidation products, dicarboxylic acids and nitrophenols in fine and coarse air particulate matter

Filter samples of fine and coarse air particulate matter (PM) collected over a period of one year in central Europe (Mainz, Germany) were analyzed for water-soluble organic compounds (WSOCs), including the α- and β-pinene oxidation products pinic acid, pinonic acid and 3-methyl-1,2,3-butanetricarboxylic acid (3-MBTCA), as well as a variety of dicarboxylic acids and nitrophenols. Seasonal variations and other characteristic features in fine, coarse, and total PM (TSP) are discussed with regard to aerosol sources and sinks in comparison to data from other studies and regions. The ratios of adipic acid and phthalic acid to azelaic acid indicate that the investigated aerosol samples were mainly influenced by biogenic sources. A strong Arrhenius-type correlation was found between the 3-MBTCA concentration and inverse temperature (<i>R</i><sup>2</sup> = 0.79, <i>n</i> = 52, <i>E</i><sub>a</sub> = 126 ± 10 kJ mol<sup>−1</sup>, temperature range 275–300 K). Model calculations suggest that the temperature dependence observed for 3-MBTCA can be explained by enhanced photochemical production due to an increase of hydroxyl radical (OH) concentration with increasing temperature, whereas the influence of gas-particle partitioning appears to play a minor role. The results indicate that the OH-initiated oxidation of pinonic acid is the rate-limiting step in the formation of 3-MBTCA, and that 3-MBTCA may be a suitable tracer for the chemical aging of biogenic secondary organic aerosol (SOA) by OH radicals. An Arrhenius-type temperature dependence was also observed for the concentration of pinic acid (<i>R</i><sup>2</sup> = 0.60, <i>n</i> = 56, <i>E</i><sub>a</sub> = 84 ± 9 kJ mol<sup>−1</sup>); it can be tentatively explained by the temperature dependence of biogenic pinene emission as the rate-limiting step of pinic acid formation

Lattice Gauge Description of Colliding Nuclei

We propose a novel formalism for simultaneously describing both, the hard and soft parton dynamics in ultrarelativistic collisions of nuclei. The emission of gluons from the initially coherent parton configurations of the colliding nuclei and low-$p_t$ color coherence effects are treated in the framework of a Yang-Mills transport equation on a coupled lattice-particle system. A collision term is added to the transport equation to account for the remaining intermediate and high-$p_t$ interactions in an infrared finite manner.Comment: 8 page

Temperature and humidity dependence of secondary organic aerosol yield from the ozonolysis of ?-pinene

International audienceThe temperature dependence of secondary organic aerosol (SOA) formation from ozonolysis of ?-pinene was studied in a flow reactor at 263 K?303 K and 1007 hPa under dry and humid conditions (0% and 26%?68% relative humidity, respectively). The observed SOA yields were of similar magnitude as predicted by a two-product model based on detailed gas phase chemistry (Jenkin, 2004), reaching maximum values of 0.18?0.39 at high particle mass concentrations (Mo). Under dry conditions, however, the measurement data exhibited significant oscillatory deviations from the predicted linear increase with inverse temperature (up to 50% at high Mo). Under humid conditions the SOA yield exhibited a linear decrease with inverse temperature, which is opposite to modelled temperature dependence and implies that the model substantially overestimates the yield at low temperatures and underestimates it at high temperatures (deviations up to 80% at high Mo). For the atmospherically relevant concentration level of Mo=10 ?g m?3 and temperature range 263 K?293 K, the results from humid experiments in this study indicate that the SOA yield of ?-pinene ozonolysis may be well represented by an average value of 0.15 with an uncertainty estimate of ±0.05. When fitting the measurement data with a two-product model, both the partitioning coefficients (Kom,i) and the stoichiometric yields (?i) of the low-volatile and semi-volatile model species were found to vary with temperature. The results indicate that not only the reaction product vapour pressures but also the relative contributions of different gas-phase or multiphase reaction channels are strongly dependent on temperature and the presence of water vapour. In fact, the oscillatory positive temperature dependence observed under dry conditions and the negative temperature dependence observed under humid conditions indicate that the SOA yield is governed much more by the temperature and humidity dependence of the involved chemical reactions than by vapour pressure temperature dependencies. We suggest that the elucidation and modelling of SOA formation need to take into account the effects of temperature and humidity on the pathways and kinetics of the involved chemical reactions as well as on the gas-particle partitioning of the reaction products

Temperature dependence of secondary organic aerosol yield from the ozonolysis of ?-pinene

International audienceThe temperature dependence of secondary organic aerosol (SOA) formation from ozonolysis of ?-pinene was studied in a flow reactor at 263?303 K and 1007 hPa. The observed SOA yields were of similar magnitude as predicted by a two-product model based on detailed gas phase chemistry (Jenkin, 2004), reaching maximum values of 0.22?0.39 at high particle mass concentrations. However, the measurement data exhibited significant deviations (up to 50%) from the predicted linear dependence on inverse temperature. When fitting the measurement data with a two-product model, we found that both the partitioning coefficients (Kom,i) and the stoichiometric yields (?i) of the low-volatile and semi-volatile species vary with temperature. The results indicate that not only the reaction product vapour pressures but also the relative contributions of different gas-phase or multiphase reaction channels are dependent on temperature. We suggest that the modelling of secondary organic aerosol formation in the atmosphere needs to take into account the effects of temperature on the pathways and kinetics of the involved chemical reactions as well as on the gas-particle partitioning of the reaction products

Coordinate-space solution of the Skyrme-Hartree-Fock-Bogolyubov equations within spherical symmetry. The program HFBRAD (v1.0)

We describe the first version (v1.00) of the code HFBRAD which solves the Skyrme-Hartree-Fock or Skyrme-Hartree-Fock-Bogolyubov equations in the coordinate representation within the spherical symmetry. A realistic representation of the quasiparticle wave functions on the space lattice allows for performing calculations up to the particle drip lines. Zero-range density-dependent interactions are used in the pairing channel. The pairing energy is calculated by either using a cut-off energy in the quasiparticle spectrum or the regularization scheme proposed by A. Bulgac and Y. Yu.Comment: 39 pages, 9 figure

Oligomerization and Nitration of the Grass Pollen Allergen Phl p 5 by Ozone, Nitrogen Dioxide, and Peroxynitrite: Reaction Products, Kinetics, and Health Effects

The allergenic and inflammatory potential of proteins can be enhanced by chemical modification upon exposure to atmospheric or physiological oxidants. The molecular mechanisms and kinetics of such modifications, however, have not yet been fully resolved. We investigated the oligomerization and nitration of the grass pollen allergen Phl p 5 by ozone (O(3)), nitrogen dioxide (NO(2)), and peroxynitrite (ONOO(–)). Within several hours of exposure to atmospherically relevant concentration levels of O(3) and NO(2), up to 50% of Phl p 5 were converted into protein oligomers, likely by formation of dityrosine cross-links. Assuming that tyrosine residues are the preferential site of nitration, up to 10% of the 12 tyrosine residues per protein monomer were nitrated. For the reaction with peroxynitrite, the largest oligomer mass fractions (up to 50%) were found for equimolar concentrations of peroxynitrite over tyrosine residues. With excess peroxynitrite, the nitration degrees increased up to 40% whereas the oligomer mass fractions decreased to 20%. Our results suggest that protein oligomerization and nitration are competing processes, which is consistent with a two-step mechanism involving a reactive oxygen intermediate (ROI), as observed for other proteins. The modified proteins can promote pro-inflammatory cellular signaling that may contribute to chronic inflammation and allergies in response to air pollution

Proton drip-line nuclei in Relativistic Hartree-Bogoliubov theory

Ground-state properties of spherical even-even nuclei $14\leq Z \leq 28$ and $N=18,20,22$ are described in the framework of Relativistic Hartree Bogoliubov (RHB) theory. The model uses the NL3 effective interaction in the mean-field Lagrangian, and describes pairing correlations by the pairing part of the finite range Gogny interaction D1S. Binding energies, two-proton separation energies, and proton $rms$ radii that result from fully self-consistent RHB solutions are compared with experimental data. The model predicts the location of the proton drip-line. The isospin dependence of the effective spin-orbit potential is discussed, as well as pairing properties that result from the finite range interaction in the $pp$ channel.Comment: 12 pages, RevTex, 10 p.s figures, submitted to Phys. Rev.