Cloud condensation nucleus (CCN) behavior of organic aerosol particles generated by atomization of water and methanol solutions

Cloud condensation nucleus (CCN) experiments were carried out for malonic acid, succinic acid, oxalacetic acid, DL-malic acid, glutaric acid, DL-glutamic acid monohydrate, and adipic acid, using both water and methanol as atomization solvents, at three operating supersaturations (0.11%, 0.21%, and 0.32%) in the Caltech three-column CCN instrument (CCNC3). Predictions of CCN behavior for five of these compounds were made using the Aerosol Diameter Dependent Equilibrium Model (ADDEM). The experiments presented here expose important considerations associated with the laboratory measurement of the CCN behavior of organic compounds. Choice of atomization solvent results in significant differences in CCN activation for some of the compounds studied, which could result from residual solvent, particle morphology differences, and chemical reactions between the particle and gas phases. Also, significant changes in aerosol size distribution occurred after classification in a differential mobility analyzer (DMA) for malonic acid and glutaric acid. Filter analysis of adipic acid atomized from methanol solution indicates that gas-particle phase reactions may have taken place after atomization and before the methanol was removed from the sample gas stream. Careful consideration of these experimental issues is necessary for successful design and interpretation of laboratory CCN measurements

Re-identification of c. 15 700 cal yr BP tephra bed at Kaipo Bog, eastern North Island: implications for dispersal of Rotorua and Puketarata tephra beds.

A 10 mm thick, c. 15 700 calendar yr BP (c. 13 100 14C yr BP) rhyolitic tephra bed in the well-studied montane Kaipo Bog sequence of eastern North Island was previously correlated with Maroa-derived Puketarata Tephra. We revise this correlation to Okataina-derived Rotorua Tephra based on new compositional data from biotite phenocrysts and glass. The new correlation limits the known dispersal of Puketarata Tephra (sensu stricto, c. 16 800 cal yr BP) and eliminates requirements to either reassess its age or to invoke dual Puketarata eruptive events. Our data show that Rotorua Tephra comprises two glass-shard types: an early-erupted low-K2O type that was dispersed mostly to the northwest, and a high-K2O type dispersed mostly to the south and southeast, contemporary with late-stage lava extrusion. Late-stage Rotorua eruptives contain biotite that is enriched in FeO compared with biotite from Puketarata pyroclastics. The occurrence of Rotorua Tephra in Kaipo Bog (100 km from the source) substantially extends its known distribution to the southeast. Our analyses demonstrate that unrecognised syn-eruption compositional and dispersal changes can cause errors in fingerprinting tephra deposits. However, the compositional complexity, once recognised, provides additional fingerprinting criteria, and also documents magmatic and dispersal processes

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

Interactions of asbestos-activated macrophages with an experimental fibrosarcoma

Supernatants from in vivo asbestos-activated macrophages failed to show any cytostatic activity against a syngeneic fibrosarcoma cell line in vitro. UICC chrysotile-induced peritoneal exudate cells also failed to demonstrate any growth inhibitory effect on the same cells in Winn assays of tumor growth. Mixing UICC crocidolite with inoculated tumor cells resulted in a dose-dependent inhibition of tumor growth; this could, however, be explained by a direct cytostatic effect on the tumor cells of high doses of crocidolite, which was observed in vitro

Existence of Ricci flows of incomplete surfaces

We prove a general existence result for instantaneously complete Ricci flows starting at an arbitrary Riemannian surface which may be incomplete and may have unbounded curvature. We give an explicit formula for the maximal existence time, and describe the asymptotic behaviour in most cases.Comment: 20 pages; updated to reflect galley proof correction

Solid state and sub-cooled liquid vapour pressures of substituted dicarboxylic acids using Knudsen Effusion Mass Spectrometry (KEMS) and Differential Scanning Calorimetry

Solid state vapour pressures of a selection of atmospherically important substituted dicarboxylic acids have been measured using Knudsen Effusion Mass Spectrometry (KEMS) over a range of 20 K (298–318 K). Enthalpies of fusion and melting points obtained using Differential Scanning Calorimetry (DSC) were used to obtain sub-cooled liquid vapour pressures. They have been compared to estimation methods used on the E-AIM website. These methods are shown to poorly represent – OH groups in combination with COOH groups. Partitioning calculations have been performed to illustrate the impact of the different estimation methods on organic aerosol mass compared to the use of experimental data

Controlling magnetic order and quantum disorder in molecule-based magnets.

We investigate the structural and magnetic properties of two molecule-based magnets synthesized from the same starting components. Their different structural motifs promote contrasting exchange pathways and consequently lead to markedly different magnetic ground states. Through examination of their structural and magnetic properties we show that [Cu(pyz)(H 2 O)(gly) 2 ](ClO 4 ) 2 may be considered a quasi-one-dimensional quantum Heisenberg antiferromagnet whereas the related compound [Cu(pyz)(gly)](ClO 4 ) , which is formed from dimers of antiferromagnetically interacting Cu 2+ spins, remains disordered down to at least 0.03 K in zero field but shows a field-temperature phase diagram reminiscent of that seen in materials showing a Bose-Einstein condensation of magnons

Asymptotic stability, concentration, and oscillation in harmonic map heat-flow, Landau-Lifshitz, and Schroedinger maps on R^2

We consider the Landau-Lifshitz equations of ferromagnetism (including the harmonic map heat-flow and Schroedinger flow as special cases) for degree m equivariant maps from R^2 to S^2. If m \geq 3, we prove that near-minimal energy solutions converge to a harmonic map as t goes to infinity (asymptotic stability), extending previous work down to degree m = 3. Due to slow spatial decay of the harmonic map components, a new approach is needed for m=3, involving (among other tools) a "normal form" for the parameter dynamics, and the 2D radial double-endpoint Strichartz estimate for Schroedinger operators with sufficiently repulsive potentials (which may be of some independent interest). When m=2 this asymptotic stability may fail: in the case of heat-flow with a further symmetry restriction, we show that more exotic asymptotics are possible, including infinite-time concentration (blow-up), and even "eternal oscillation".Comment: 34 page

Ricci flow for homogeneous compact models of the universe

Using quaternions, we give a concise derivation of the Ricci tensor for homogeneous spaces with topology of the 3-dimensional sphere. We derive explicit and numerical solutions for the Ricci flow PDE and discuss their properties. In the collapse (or expansion) of these models, the interplay of the various components of the Ricci tensor are studied. We dedicate this paper to honor the work of Josh Goldberg.Comment: 18 pages, 2 figure