Effect of humidity on the composition of isoprene photooxidation secondary organic aerosol

The effect of relative humidity (RH) on the composition and concentrations of gas-phase products and secondary organic aerosol (SOA) generated from the photooxidation of isoprene under high-NO<sub>x</sub> conditions was investigated. Experiments were performed with hydrogen peroxide as the OH precursor and in the absence of seed aerosol. The relative yields of most gas-phase products were the same regardless of initial water vapor concentration with exception of hydroxyacetone and glycolaldehyde, which were considerably affected by RH. A significant change was observed in the SOA composition, with many unique condensed-phase products formed under humid (90 % RH) vs. dry (<2 % RH) conditions, without any detectable effect on the rate and extent of the SOA mass growth. There is a 40 % reduction in the number and relative abundance of distinct particle-phase nitrogen-containing organic compounds (NOC) detected by high resolution mass spectrometry. The suppression of condensation reactions, which produce water as a product, is the most important chemical effect of the increased RH. For example, the total signal from oligomeric esters of 2-methylglyceric acid was reduced by about 60 % under humid conditions and the maximum oligomer chain lengths were reduced by 7–11 carbons. Oligomers formed by addition mechanisms, without direct involvement of water, also decreased at elevated RH but to a much smaller extent. The observed reduction in the extent of condensation-type oligomerization at high RH may have substantial impact on the phase characteristics and hygroscopicity of the isoprene aerosol. The reduction in the amount of organic nitrates in the particle phase has implications for understanding the budget of NOC compounds

Fractional Quantum Mechanics

A path integral approach to quantum physics has been developed. Fractional path integrals over the paths of the L\'evy flights are defined. It is shown that if the fractality of the Brownian trajectories leads to standard quantum and statistical mechanics, then the fractality of the L\'evy paths leads to fractional quantum mechanics and fractional statistical mechanics. The fractional quantum and statistical mechanics have been developed via our fractional path integral approach. A fractional generalization of the Schr\"odinger equation has been found. A relationship between the energy and the momentum of the nonrelativistic quantum-mechanical particle has been established. The equation for the fractional plane wave function has been obtained. We have derived a free particle quantum-mechanical kernel using Fox's H function. A fractional generalization of the Heisenberg uncertainty relation has been established. Fractional statistical mechanics has been developed via the path integral approach. A fractional generalization of the motion equation for the density matrix has been found. The density matrix of a free particle has been expressed in terms of the Fox's H function. We also discuss the relationships between fractional and the well-known Feynman path integral approaches to quantum and statistical mechanics.Comment: 27 page

Aerosol composition and source apportionment in the Mexico City Metropolitan Area with PIXE/PESA/STIM and multivariate analysis

International audienceAerosols play an important role in the atmosphere but are poorly characterized, particularly in urban areas like the Mexico City Metropolitan Area (MCMA). The chemical composition of urban particles must be known to assess their effects on the environment, and specific particulate emissions sources should be identified to establish effective pollution control standards. For these reasons, samples of particulate matter ?2.5 ?m (PM2.5) were collected during the MCMA-2003 Field Campaign for elemental and multivariate analyses. Proton-Induced X-ray Emission (PIXE), Proton-Elastic Scattering Analysis (PESA) and Scanning Transmission Ion Microscopy (STIM) measurements were done to determine concentrations of 19 elements from Na to Pb, hydrogen, and total mass, respectively. The most abundant elements from PIXE analysis were S, Si, K, Fe, Ca, and Al, while the major emissions sources associated with these elements were industry, wind-blown soil, and biomass burning. Wind trajectories suggest that metals associated with industrial emissions came from northern areas of the city whereas soil aerosols came from the southwest and increased in concentration during dry conditions. Elemental markers for fuel oil combustion, V and Ni, correlated with a large SO2 plume to suggest an anthropogenic, rather than volcanic, emissions source. By subtracting major components of soil and sulfates determined by PIXE analysis from STIM total mass measurements, we estimate that approximately 50% of non-volatile PM2.5 consisted of carbonaceous material

BCL-2 Expression is Prognostic for Improved Survival in Non-small Cell Lung Cancer

ObjectiveWe used a large patient population to identify immunohistochemical biomarkers to enable improved prognostication in patients with non-small cell lung carcinoma (NSCLC).MethodsA tissue microarray was constructed using duplicate 0.6 mm cores of formalin-fixed paraffin-embedded tissue blocks from 609 patients with NSCLC. Immunohistochemical was used to detect 11 biomarkers including epidermal growth factor receptor, Her2, Her3, p53, p63, bcl-1, bcl-2, Thyroid transcription factor, carcinoembryonic antigen, chromogranin, and synaptophysin. A clinical database was generated prospectively at the time of tissue collection. Survival outcomes were obtained from a Provincial Cancer Registry database. Univariate and multivariate analyses were performed to look for a relationship between biomarker expression, smoking history, and survival.ResultsSurvival data for 535 cases were available. As of June 2005, 429 patients (80%) had died; of these 286 (54%) died of lung cancer, 117 (22%) died of other known causes, and for 26 (5%) the cause of death was not available. Univariate analysis revealed that bcl-2 (p = 0.007) was the only biomarker prognostic for improved overall survival (OS). bcl-2 (p = 0.021) and p63 (p = 0.025) were both found to be prognostic for improved disease-specific survival (DSS). Multivariate analysis (using age and biomarker expression) revealed that bcl-2 expression is prognostic for improved OS (p = 0.005) and DSS (p = 0.021).ConclusionsOur results suggest that bcl-2 expression is prognostic for improved OS and DSS in NSCLC. Testing for bcl-2 expression in a prospective study will help to determine its clinical relevance in prognostication

On bulk singularities in the random normal matrix model

We extend the method of rescaled Ward identities of Ameur-Kang-Makarov to study the distribution of eigenvalues close to a bulk singularity, i.e. a point in the interior of the droplet where the density of the classical equilibrium measure vanishes. We prove results to the effect that a certain "dominant part" of the Taylor expansion determines the microscopic properties near a bulk singularity. A description of the distribution is given in terms of a special entire function, which depends on the nature of the singularity (a Mittag-Leffler function in the case of a rotationally symmetric singularity).Comment: This version clarifies on the proof of Theorem

Path Integral Approach to the Non-Relativistic Electron Charge Transfer

A path integral approach has been generalized for the non-relativistic electron charge transfer processes. The charge transfer - the capture of an electron by an ion passing another atom or more generally the problem of rearrangement collisions is formulated in terms of influence functionals. It has been shown that the electron charge transfer process can be treated either as electron transition problem or as elastic scattering of ion and atom in the some effective potential field. The first-order Born approximation for the electron charge transfer cross section has been reproduced to prove the adequacy of the path integral approach for this problem.Comment: 19 pages, 1 figure, to appear in Journal of Physics B: Atomic, Molecular & Optical, vol.34, 200

Processing of soot in an urban environment: case study from the Mexico City Metropolitan Area

Chemical composition, size, and mixing state of atmospheric particles are critical in determining their effects on the environment. There is growing evidence that soot aerosols play a particularly important role in both climate and human health, but still relatively little is known of their physical and chemical nature. In addition, the atmospheric residence times and removal mechanisms for soot are neither well understood nor adequately represented in regional and global climate models. To investigate the effect of locality and residence time on properties of soot and mixing state in a polluted urban environment, particles of diameter 0.2–2.0 μm were collected in the Mexico City Metropolitan Area (MCMA) during the MCMA-2003 Field Campaign from various sites within the city. Individual particle analysis by different electron microscopy methods coupled with energy dispersed x-ray spectroscopy, and secondary ionization mass spectrometry show that freshly-emitted soot particles become rapidly processed in the MCMA. Whereas fresh particulate emissions from mixed-traffic are almost entirely carbonaceous, consisting of soot aggregates with liquid coatings suggestive of unburned lubricating oil and water, ambient soot particles which have been processed for less than a few hours are heavily internally mixed, primarily with ammonium sulfate. Single particle analysis suggests that this mixing occurs through several mechanisms that require further investigation. In light of previously published results, the internally-mixed nature of processed soot particles is expected to affect heterogeneous chemistry on the soot surface, including interaction with water during wet-removal

Influence of crustal dust and sea spray supermicron particle concentrations and acidity on inorganic NO_3^- aerosol during the 2013 Southern Oxidant and Aerosol Study

Inorganic aerosol composition was measured in the southeastern United States, a region that exhibits high aerosol mass loading during the summer, as part of the 2013 Southern Oxidant and Aerosol Study (SOAS) campaign. Measurements using a Monitor for AeRosols and GAses (MARGA) revealed two periods of high aerosol nitrate (NO_^3−) concentrations during the campaign. These periods of high nitrate were correlated with increased concentrations of supermicron crustal and sea spray aerosol species, particularly Na^+ and Ca^(2+), and with a shift towards aerosol with larger (1 to 2.5 μm) diameters. We suggest this nitrate aerosol forms by multiphase reactions of HNO_3 and particles, reactions that are facilitated by transport of crustal dust and sea spray aerosol from a source within the United States. The observed high aerosol acidity prevents the formation of NH_4NO_3, the inorganic nitrogen species often dominant in fine-mode aerosol at higher pH. Calculation of the rate of the heterogeneous uptake of HNO_3 on mineral aerosol supports the conclusion that aerosol NO_3^− is produced primarily by this process, and is likely limited by the availability of mineral cation-containing aerosol surface area. Modeling of NO_3^− and HNO_3 by thermodynamic equilibrium models (ISORROPIA II and E-AIM) reveals the importance of including mineral cations in the southeastern United States to accurately balance ion species and predict gas–aerosol phase partitioning