Thermodynamics of the formation of sulfuric acid dimers in the binary (H_2SO_4–H_2O) and ternary (H_2SO_4–H_2O–NH_3) system

Sulfuric acid is an important gas influencing atmospheric new particle formation (NPF). Both the binary (H_2SO_4–H_2O) system and the ternary system involving ammonia (H_2SO_4–H_2O–NH_3) may be important in the free troposphere. An essential step in the nucleation of aerosol particles from gas-phase precursors is the formation of a dimer, so an understanding of the thermodynamics of dimer formation over a wide range of atmospheric conditions is essential to describe NPF. We have used the CLOUD chamber to conduct nucleation experiments for these systems at temperatures from 208 to 248 K. Neutral monomer and dimer concentrations of sulfuric acid were measured using a chemical ionization mass spectrometer (CIMS). From these measurements, dimer evaporation rates in the binary system were derived for temperatures of 208 and 223 K. We compare these results to literature data from a previous study that was conducted at higher temperatures but is in good agreement with the present study. For the ternary system the formation of H_2SO_4·NH_3 is very likely an essential step in the formation of sulfuric acid dimers, which were measured at 210, 223, and 248 K. We estimate the thermodynamic properties (dH and dS) of the H_2SO_4·NH_3 cluster using a simple heuristic model and the measured data. Furthermore, we report the first measurements of large neutral sulfuric acid clusters containing as many as 10 sulfuric acid molecules for the binary system using chemical ionization–atmospheric pressure interface time-of-flight (CI-APi-TOF) mass spectrometry

Scale-free networks are not robust under neutral evolution

Recently it has been shown that a large variety of different networks have power-law (scale-free) distributions of connectivities. We investigate the robustness of such a distribution in discrete threshold networks under neutral evolution. The guiding principle for this is robustness in the resulting phenotype. The numerical results show that a power-law distribution is not stable under such an evolution, and the network approaches a homogeneous form where the overall distribution of connectivities is given by a Poisson distribution.Comment: Submitted for publicatio

Self-organized critical neural networks

A mechanism for self-organization of the degree of connectivity in model neural networks is studied. Network connectivity is regulated locally on the basis of an order parameter of the global dynamics which is estimated from an observable at the single synapse level. This principle is studied in a two-dimensional neural network with randomly wired asymmetric weights. In this class of networks, network connectivity is closely related to a phase transition between ordered and disordered dynamics. A slow topology change is imposed on the network through a local rewiring rule motivated by activity-dependent synaptic development: Neighbor neurons whose activity is correlated, on average develop a new connection while uncorrelated neighbors tend to disconnect. As a result, robust self-organization of the network towards the order disorder transition occurs. Convergence is independent of initial conditions, robust against thermal noise, and does not require fine tuning of parameters.Comment: 5 pages RevTeX, 7 figures PostScrip

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

Topological Evolution of Dynamical Networks: Global Criticality from Local Dynamics

We evolve network topology of an asymmetrically connected threshold network by a simple local rewiring rule: quiet nodes grow links, active nodes lose links. This leads to convergence of the average connectivity of the network towards the critical value $K_c =2$ in the limit of large system size $N$. How this principle could generate self-organization in natural complex systems is discussed for two examples: neural networks and regulatory networks in the genome.Comment: 4 pages RevTeX, 4 figures PostScript, revised versio

Comparison of chemical characteristics of 495 biomass burning plumes intercepted by the NASA DC-8 aircraft during the ARCTAS/CARB-2008 field campaign

This paper compares measurements of gaseous and particulate emissions from a wide range of biomass-burning plumes intercepted by the NASA DC-8 research aircraft during the three phases of the ARCTAS-2008 experiment: ARCTAS-A, based out of Fairbanks, Alaska, USA (3 April to 19 April 2008); ARCTAS-B based out of Cold Lake, Alberta, Canada (29 June to 13 July 2008); and ARCTAS-CARB, based out of Palmdale, California, USA (18 June to 24 June 2008). Approximately 500 smoke plumes from biomass burning emissions that varied in age from minutes to days were segregated by fire source region and urban emission influences. The normalized excess mixing ratios (NEMR) of gaseous (carbon dioxide, acetonitrile, hydrogen cyanide, toluene, benzene, methane, oxides of nitrogen and ozone) and fine aerosol particulate components (nitrate, sulfate, ammonium, chloride, organic aerosols and water soluble organic carbon) of these plumes were compared. A detailed statistical analysis of the different plume categories for different gaseous and aerosol species is presented in this paper. The comparison of NEMR values showed that CH4 concentrations were higher in air-masses that were influenced by urban emissions. Fresh biomass burning plumes mixed with urban emissions showed a higher degree of oxidative processing in comparison with fresh biomass burning only plumes. This was evident in higher concentrations of inorganic aerosol components such as sulfate, nitrate and ammonium, but not reflected in the organic components. Lower NOx NEMRs combined with high sulfate, nitrate and ammonium NEMRs in aerosols of plumes subject to long-range transport, when comparing all plume categories, provided evidence of advanced processing of these plumes

Surface spin-flop transition in a uniaxial antiferromagnetic Fe/Cr superlattice induced by a magnetic field of arbitrary direction

We studied the transition between the antiferromagnetic and the surface spin-flop phases of a uniaxial antiferromagnetic [Fe(14 \AA)/Cr(11 \AA]$_{\rm x20}$ superlattice. For external fields applied parallel to the in-plane easy axis, the layer-by-layer configuration, calculated in the framework of a mean-field one-dimensional model, was benchmarked against published polarized neutron reflectivity data. For an in-plane field $H$ applied at an angle $\psi \ne 0$ with the easy axis, magnetometry shows that the magnetization $M$ vanishes at H=0, then increases slowly with increasing $H$. At a critical value of $H$, a finite jump in $M(H)$ is observed for $\psi<5^{\rm o}$, while a smooth increase of $M$ $vs$ $H$ is found for $\psi>5^{\rm o}$. A dramatic increase in the full width at half maximum of the magnetic susceptibility is observed for $\psi \ge 5^{\rm o}$. The phase diagram obtained from micromagnetic calculations displays a first-order transition to a surface spin-flop phase for low $\psi$ values, while the transition becomes continuous for $\psi$ greater than a critical angle, $\psi_{\rm max} \approx 4.75^{\rm o}$. This is in fair agreement with the experimentally observed results.Comment: 24 pages, 7 figure

Coral Communities, in Contrast to Fish Communities, Maintain a High Assembly Similarity along the Large Latitudinal Gradient along the Saudi Red Sea Coast

The Saudi Arabian Red Sea coast is characterized by a strong environmental gradient from north (28.5°N) to south (16.5°N) with challenging conditions for coral growth particularly in the south (high temperature and nutrient input). We investigated whether assemblies of reef-building corals and the distribution of functional groups follow a latitudinal pattern in the Red Sea, and whether these changes affect the assembly structure of coral associated organisms (e.g. fishes). Functional groups were defined based on life-history traits and functional role. 13 reefs along the north-south gradient, including 5 potentially polluted reefs were investigated. Results showed a substantially weaker latitudinal shift in the assembly structure of coral communities than of fishes communities and of other benthic reef taxa. Competitive fast growing branching and tabular species (mainly Acropora), as well as rather stresstolerant slow growing bulky species (e.g. Porites, Goniastrea, Favites, Favia) were fairly evenly distributed along the north-south axis despite strong changes of environmental conditions. This seems on the one hand attributable to the high species richness within a given functional group (functional redundancy) and on the other hand to a high acclimatization / adaptation potential of some Red Sea coral species. The prime ecosystem service of the coral community, the provision of a habitat complex, is thereby maintained throughout the gradient. In contrast to the coral community, the assembly of the fish community shifts along the environmental gradient with higher abundances of small wrasses and butterfly fishes in the north, and overall higher abundance of fishes including large fishes in the south. This shift seems linked to higher food availability in the south. Altered assembly structures of coral communities were found in reefs close to a source of pollution with either an increased relative abundance of stresstolerant species or a general decrease of coral abundance, latter case accompanied by a substantial reduction in fish abundance

Synthesis of magnetite nanoparticles by the method of co-precipitation and study of the influence of the reaction medium on their magnetic properties

Magnetite nanoparticles were obtained using the co-precipitation method under various synthesis conditions. The phase composition was investigated using X-ray diffraction analysis. The saturation magnetization of the obtained magnetic nanoparticles was investigated using vibrating-sample magnetometer. As a result, the samples obtained in a nitrogen atmosphere reveal a higher saturation magnetization value than the ones obtained in air