Secondary aerosol formation from atmospheric reactions of aliphatic amines

Although aliphatic amines have been detected in both urban and rural atmospheric aerosols, little is known about the chemistry leading to particle formation or the potential aerosol yields from reactions of gas-phase amines. We present here the first systematic study of aerosol formation from the atmospheric reactions of amines. Based on laboratory chamber experiments and theoretical calculations, we evaluate aerosol formation from reaction of OH, ozone, and nitric acid with trimethylamine, methylamine, triethylamine, diethylamine, ethylamine, and ethanolamine. Entropies of formation for alkylammonium nitrate salts are estimated by molecular dynamics calculations enabling us to estimate equilibrium constants for the reactions of amines with nitric acid. Though subject to significant uncertainty, the calculated dissociation equilibrium constant for diethylammonium nitrate is found to be sufficiently small to allow for its atmospheric formation, even in the presence of ammonia which competes for available nitric acid. Experimental chamber studies indicate that the dissociation equilibrium constant for triethylammonium nitrate is of the same order of magnitude as that for ammonium nitrate. All amines studied form aerosol when photooxidized in the presence of NOx with the majority of the aerosol mass present at the peak of aerosol growth consisting of aminium (R3NH+) nitrate salts, which repartition back to the gas phase as the parent amine is consumed. Only the two tertiary amines studied, trimethylamine and triethylamine, are found to form significant non-salt organic aerosol when oxidized by OH or ozone; calculated organic mass yields for the experiments conducted are similar for ozonolysis (15% and 5% respectively) and photooxidation (23% and 8% respectively). The non-salt organic aerosol formed appears to be more stable than the nitrate salts and does not quickly repartition back to the gas phase

Multifractal Scaling, Geometrical Diversity, and Hierarchical Structure in the Cool Interstellar Medium

Multifractal scaling (MFS) refers to structures that can be described as a collection of interwoven fractal subsets which exhibit power-law spatial scaling behavior with a range of scaling exponents (concentration, or singularity, strengths) and dimensions. The existence of MFS implies an underlying multiplicative (or hierarchical, or cascade) process. Panoramic column density images of several nearby star- forming cloud complexes, constructed from IRAS data and justified in an appendix, are shown to exhibit such multifractal scaling, which we interpret as indirect but quantitative evidence for nested hierarchical structure. The relation between the dimensions of the subsets and their concentration strengths (the "multifractal spectrum'') appears to satisfactorily order the observed regions in terms of the mixture of geometries present: strong point-like concentrations, line- like filaments or fronts, and space-filling diffuse structures. This multifractal spectrum is a global property of the regions studied, and does not rely on any operational definition of "clouds.'' The range of forms of the multifractal spectrum among the regions studied implies that the column density structures do not form a universality class, in contrast to indications for velocity and passive scalar fields in incompressible turbulence, providing another indication that the physics of highly compressible interstellar gas dynamics differs fundamentally from incompressible turbulence. (Abstract truncated)Comment: 27 pages, (LaTeX), 13 figures, 1 table, submitted to Astrophysical Journa

Chemical Composition of Gas- and Aerosol-Phase Products from the Photooxidation of Naphthalene

The current work focuses on the detailed evolution of the chemical composition of both the gas- and aerosol-phase constituents produced from the OH-initiated photooxidation of naphthalene under low- and high-NO_x conditions. Under high-NO_x conditions ring-opening products are the primary gas-phase products, suggesting that the mechanism involves dissociation of alkoxy radicals (RO) formed through an RO_2 + NO pathway, or a bicyclic peroxy mechanism. In contrast to the high-NO_x chemistry, ring-retaining compounds appear to dominate the low-NO_x gas-phase products owing to the RO_2 + HO_2 pathway. We are able to chemically characterize 53−68% of the secondary organic aerosol (SOA) mass. Atomic oxygen-to-carbon (O/C), hydrogen-to-carbon (H/C), and nitrogen-to-carbon (N/C) ratios measured in bulk samples by high-resolution electrospray ionization time-of-flight mass spectrometry (HR-ESI-TOFMS) are the same as the ratios observed with online high-resolution time-of-flight aerosol mass spectrometry (HR-ToF-AMS), suggesting that the chemical compositions and oxidation levels found in the chemically-characterized fraction of the particle phase are representative of the bulk aerosol. Oligomers, organosulfates (R-OSO_3), and other high-molecular-weight (MW) products are not observed in either the low- or high-NO_x SOA; however, in the presence of neutral ammonium sulfate seed aerosol, an organic sulfonic acid (R-SO_3), characterized as hydroxybenzene sulfonic acid, is observed in naphthalene SOA produced under both high- and low-NO_x conditions. Acidic compounds and organic peroxides are found to account for a large fraction of the chemically characterized high- and low-NO_x SOA. We propose that the major gas- and aerosol-phase products observed are generated through the formation and further reaction of 2-formylcinnamaldehyde or a bicyclic peroxy intermediate. The chemical similarity between the laboratory SOA and ambient aerosol collected from Birmingham, Alabama (AL) and Pasadena, California (CA) confirm the importance of PAH oxidation in the formation of aerosol within the urban atmosphere

Secondary organic aerosol formation from photooxidation of naphthalene and alkylnaphthalenes: implications for oxidation of intermediate volatility organic compounds (IVOCs)

Current atmospheric models do not include secondary organic aerosol (SOA) production from gas-phase reactions of polycyclic aromatic hydrocarbons (PAHs). Recent studies have shown that primary emissions undergo oxidation in the gas phase, leading to SOA formation. This opens the possibility that low-volatility gas-phase precursors are a potentially large source of SOA. In this work, SOA formation from gas-phase photooxidation of naphthalene, 1-methylnaphthalene (1-MN), 2-methylnaphthalene (2- MN), and 1,2-dimethylnaphthalene (1,2-DMN) is studied in the Caltech dual 28-m^3 chambers. Under high-NO_x conditions and aerosol mass loadings between 10 and 40μgm^(−3), the SOA yields (mass of SOA per mass of hydrocarbon reacted) ranged from 0.19 to 0.30 for naphthalene, 0.19 to 0.39 for 1-MN, 0.26 to 0.45 for 2-MN, and constant at 0.31 for 1,2-DMN. Under low-NO_x conditions, the SOA yields were measured to be 0.73, 0.68, and 0.58, for naphthalene, 1- MN, and 2-MN, respectively. The SOA was observed to be semivolatile under high-NO_x conditions and essentially nonvolatile under low-NO_x conditions, owing to the higher fraction of ring-retaining products formed under low-NO_x conditions. When applying these measured yields to estimate SOA formation from primary emissions of diesel engines and wood burning, PAHs are estimated to yield 3–5 times more SOA than light aromatic compounds over photooxidation timescales of less than 12 h. PAHs can also account for up to 54% of the total SOA from oxidation of diesel emissions, representing a potentially large source of urban SOA

Breakdown of Simple Scaling in Abelian Sandpile Models in One Dimension

We study the abelian sandpile model on decorated one dimensional chains. We determine the structure and the asymptotic form of distribution of avalanche-sizes in these models, and show that these differ qualitatively from the behavior on a simple linear chain. We find that the probability distribution of the total number of topplings $s$ on a finite system of size $L$ is not described by a simple finite size scaling form, but by a linear combination of two simple scaling forms $Prob_L(s) = 1/L f_1(s/L) + 1/L^2 f_2(s/L^2)$, for large $L$, where $f_1$ and $f_2$ are some scaling functions of one argument.Comment: 10 pages, revtex, figures include

Self-Organized States in Cellular Automata: Exact Solution

The spatial structure, fluctuations as well as all state probabilities of self-organized (steady) states of cellular automata can be found (almost) exactly and {\em explicitly} from their Markovian dynamics. The method is shown on an example of a natural sand pile model with a gradient threshold.Comment: 4 pages (REVTeX), incl. 2 figures (PostScript

Fuzzy Intervals for Designing Structural Signature: An Application to Graphic Symbol Recognition

Revised selected papers from Eighth IAPR International Workshop on Graphics RECognition (GREC) 2009.The motivation behind our work is to present a new methodology for symbol recognition. The proposed method employs a structural approach for representing visual associations in symbols and a statistical classifier for recognition. We vectorize a graphic symbol, encode its topological and geometrical information by an attributed relational graph and compute a signature from this structural graph. We have addressed the sensitivity of structural representations to noise, by using data adapted fuzzy intervals. The joint probability distribution of signatures is encoded by a Bayesian network, which serves as a mechanism for pruning irrelevant features and choosing a subset of interesting features from structural signatures of underlying symbol set. The Bayesian network is deployed in a supervised learning scenario for recognizing query symbols. The method has been evaluated for robustness against degradations & deformations on pre-segmented 2D linear architectural & electronic symbols from GREC databases, and for its recognition abilities on symbols with context noise i.e. cropped symbols

Short-Range Ising Spin Glass: Multifractal Properties

The multifractal properties of the Edwards-Anderson order parameter of the short-range Ising spin glass model on d=3 diamond hierarchical lattices is studied via an exact recursion procedure. The profiles of the local order parameter are calculated and analysed within a range of temperatures close to the critical point with four symmetric distributions of the coupling constants (Gaussian, Bimodal, Uniform and Exponential). Unlike the pure case, the multifractal analysis of these profiles reveals that a large spectrum of the $\alpha$-H\"older exponent is required to describe the singularities of the measure defined by the normalized local order parameter, at and below the critical point. Minor changes in these spectra are observed for distinct initial distributions of coupling constants, suggesting an universal spectra behavior. For temperatures slightly above T_{c}, a dramatic change in the $F(\alpha)$ function is found, signalizing the transition.Comment: 8 pages, LaTex, PostScript-figures included but also available upon request. To be published in Physical Review E (01/March 97