Liquid-liquid phase separation and morphology of internally mixed dicarboxylic acids/ammonium sulfate/water particles

Knowledge of the physical state and morphology of internally mixed organic/inorganic aerosol particles is still largely uncertain. To obtain more detailed information on liquid-liquid phase separation (LLPS) and morphology of the particles, we investigated complex mixtures of atmospherically relevant dicarboxylic acids containing 5, 6, and 7 carbon atoms (C5, C6 and C7) having oxygen-to-carbon atomic ratios (O:C) of 0.80, 0.67, and 0.57, respectively, mixed with ammonium sulfate (AS). With micrometer-sized particles of C5/AS/H_2O, C6/AS/H_2O and C7/AS/H_2O as model systems deposited on a hydrophobically coated substrate, laboratory experiments were conducted for various organic-to-inorganic dry mass ratios (OIR) using optical microscopy and Raman spectroscopy. When exposed to cycles of relative humidity (RH), each system showed significantly different phase transitions. While the C5/AS/H_2O particles showed no LLPS with OIR = 2:1, 1:1 and 1:4 down to 20% RH, the C6/AS/H_2O and C7/AS/H_2O particles exhibit LLPS upon drying at RH 50 to 85% and ~90%, respectively, via spinodal decomposition, growth of a second phase from the particle surface or nucleation-and-growth mechanisms depending on the OIR. This suggests that LLPS commonly occurs within the range of O:C < 0.7 in tropospheric organic/inorganic aerosols. To support the comparison and interpretation of the experimentally observed phase transitions, thermodynamic equilibrium calculations were performed with the AIOMFAC model. For the C7/AS/H_2O and C6/AS/H_2O systems, the calculated phase diagrams agree well with the observations while for the C5/AS/H_2O system LLPS is predicted by the model at RH below 60% and higher AS concentration, but was not observed in the experiments. Both core-shell structures and partially engulfed structures were observed for the investigated particles, suggesting that such morphologies might also exist in tropospheric aerosols

Nondispersive solutions to the L2-critical half-wave equation

We consider the focusing $L^2$-critical half-wave equation in one space dimension $$i \partial_t u = D u - |u|^2 u,$$ where $D$ denotes the first-order fractional derivative. Standard arguments show that there is a critical threshold $M_* > 0$ such that all $H^{1/2}$ solutions with $\| u \|_{L^2} < M_*$ extend globally in time, while solutions with $\| u \|_{L^2} \geq M_*$ may develop singularities in finite time. In this paper, we first prove the existence of a family of traveling waves with subcritical arbitrarily small mass. We then give a second example of nondispersive dynamics and show the existence of finite-time blowup solutions with minimal mass $\| u_0 \|_{L^2} = M_*$. More precisely, we construct a family of minimal mass blowup solutions that are parametrized by the energy $E_0 >0$ and the linear momentum $P_0 \in \R$. In particular, our main result (and its proof) can be seen as a model scenario of minimal mass blowup for $L^2$-critical nonlinear PDE with nonlocal dispersion.Comment: 51 page

Vapor pressures of substituted polycarboxylic acids are much lower than previously reported

The partitioning of compounds between the aerosol and gas phase is a primary focus in the study of the formation and fate of secondary organic aerosol. We present measurements of the vapor pressure of 2-methylmalonic (isosuccinic) acid, 2-hydroxymalonic (tartronic) acid, 2-methylglutaric acid, 3-hydroxy-3-carboxy-glutaric (citric) acid and DL-2,3-dihydroxysuccinic (DL-tartaric) acid, which were obtained from the evaporation rate of supersaturated liquid particles levitated in an electrodynamic balance. Our measurements indicate that the pure component liquid vapor pressures at 298.15 K for tartronic, citric and tartaric acids are much lower than the same quantity that was derived from solid state measurements in the only other room temperature measurement of these materials (made by Booth et al., 2010). This strongly suggests that empirical correction terms in a recent vapor pressure estimation model to account for the inexplicably high vapor pressures of these and similar compounds should be revisited, and that due caution should be used when the estimated vapor pressures of these and similar compounds are used as inputs for other studies

New and extended parameterization of the thermodynamic model AIOMFAC: calculation of activity coefficients for organic-inorganic mixtures containing carboxyl, hydroxyl, carbonyl, ether, ester, alkenyl, alkyl, and aromatic functional groups

We present a new and considerably extended parameterization of the thermodynamic activity coefficient model AIOMFAC (Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients) at room temperature. AIOMFAC combines a Pitzer-like electrolyte solution model with a UNIFAC-based group-contribution approach and explicitly accounts for interactions between organic functional groups and inorganic ions. Such interactions constitute the salt-effect, may cause liquid-liquid phase separation, and affect the gas-particle partitioning of aerosols. The previous AIOMFAC version was parameterized for alkyl and hydroxyl functional groups of alcohols and polyols. With the goal to describe a wide variety of organic compounds found in atmospheric aerosols, we extend here the parameterization of AIOMFAC to include the functional groups carboxyl, hydroxyl, ketone, aldehyde, ether, ester, alkenyl, alkyl, aromatic carbon-alcohol, and aromatic hydrocarbon. Thermodynamic equilibrium data of organic-inorganic systems from the literature are critically assessed and complemented with new measurements to establish a comprehensive database. The database is used to determine simultaneously the AIOMFAC parameters describing interactions of organic functional groups with the ions H^+, Li^+, Na^+, K^+, NH_(4)^+, Mg^(2+), Ca^(2+), Cl^−, Br^−, NO_(3)^−, HSO_(4)^−, and SO_(4)^(2−). Detailed descriptions of different types of thermodynamic data, such as vapor-liquid, solid-liquid, and liquid-liquid equilibria, and their use for the model parameterization are provided. Issues regarding deficiencies of the database, types and uncertainties of experimental data, and limitations of the model, are discussed. The challenging parameter optimization problem is solved with a novel combination of powerful global minimization algorithms. A number of exemplary calculations for systems containing atmospherically relevant aerosol components are shown. Amongst others, we discuss aqueous mixtures of ammonium sulfate with dicarboxylic acids and with levoglucosan. Overall, the new parameterization of AIOMFAC agrees well with a large number of experimental datasets. However, due to various reasons, for certain mixtures important deviations can occur. The new parameterization makes AIOMFAC a versatile thermodynamic tool. It enables the calculation of activity coefficients of thousands of different organic compounds in organic-inorganic mixtures of numerous components. Models based on AIOMFAC can be used to compute deliquescence relative humidities, liquid-liquid phase separations, and gas-particle partitioning of multicomponent mixtures of relevance for atmospheric chemistry or in other scientific fields

Nitrate affects transcriptional regulation of UPBEAT1 and ROS localisation in roots of Zea mays L.

Nitrogen is an indispensable nutrient for crops but its availability in agricultural soils is subject to considerable fluctuation. Plants have developed plastic responses to external N fluctuations in order to optimise their development. The coordinated action of nitric oxide and auxin seems to allow the cells of the transition zone (TZ) of the root apex of N-deprived maize to rapidly sense nitrate. Preliminary results support the hypothesis that reactive oxygen species (ROS) signalling might also have a role in this pathway, probably through a putative maize orthologue of UPBEAT1 (UPB1). To expand on this hypothesis and better understand the different roles played by different root portions, we investigated the dynamics of ROS production, and the molecular and biochemical regulation of the main components of ROS production and scavenging in tissues of the Meristem, Transition Zone, Elongation Zone and Maturation Zone of maize roots. The results suggest that the inverse regulation of ZmUPB1 and ZmPRX112 transcription observed in cells of the TZ in response to nitrogen depletion or nitrate supply affects the balance between H2O2 and O2 12 in the root apex and consequently triggers differential root growth. This explanation is supported by additional results on the overall metabolic and transcriptional regulation of ROS homeostasis

Do topology and ferromagnetism cooperate at the EuS/Bi2_2Se3_3 interface?

We probe the local magnetic properties of interfaces between the insulating ferromagnet EuS and the topological insulator Bi$_2$Se$_3$ using low energy muon spin rotation (LE-$\mu$SR). We compare these to the interface between EuS and the topologically trivial metal, titanium. Below the magnetic transition of EuS, we detect strong local magnetic fields which extend several nm into the adjacent layer and cause a complete depolarization of the muons. However, in both Bi$_2$Se$_3$ and titanium we measure similar local magnetic fields, implying that their origin is mostly independent of the topological properties of the interface electronic states. In addition, we use resonant soft X-ray angle resolved photoemission spectroscopy (SX-ARPES) to probe the electronic band structure at the interface between EuS and Bi$_2$Se$_3$. By tuning the photon energy to the Eu anti-resonance at the Eu $M_5$ pre-edge we are able to detect the Bi$_2$Se$_3$ conduction band, through a protective Al$_2$O$_3$ capping layer and the EuS layer. Moreover, we observe a signature of an interface-induced modification of the buried Bi$_2$Se$_3$ wave functions and/or the presence of interface states

Entwicklung eines regionalen Ausbildungsmodells „Ökolandbau und Vermarktung“ an der Fachhochschule Eberswalde im Rahmen des Bundesförderprogramms Regionen Aktiv

In September 2004 a new B. Sc. study course for Organic Farming and Marketing started at the University of Applied Sciences Eberswalde. Supported by the Federal Ministry of Consumer Protection, Food and Agriculture program “Regionen Aktiv” an innovative education model was established. Focussing on rural development farmers, processors and trading partners were involved in the development of topics for the study programme

Theory of Coherent Time-dependent Transport in One-dimensional Multiband Semiconductor Superlattices

We present an analytical study of one-dimensional semiconductor superlattices in external electric fields, which may be time-dependent. A number of general results for the (quasi)energies and eigenstates are derived. An equation of motion for the density matrix is obtained for a two-band model, and the properties of the solutions are analyzed. An expression for the current is obtained. Finally, Zener-tunneling in a two-band tight-binding model is considered. The present work gives the background and an extension of the theoretical framework underlying our recent Letter [J. Rotvig {\it et al.}, Phys. Rev. Lett. {\bf 74}, 1831 (1995)], where a set of numerical simulations were presented.Comment: 15 pages, Revtex 3.0, uses epsf, 2 ps figures attache