Artifacts in measuring aerosol uptake kinetics: the roles of time, concentration and adsorption

In laboratory studies of organic aerosol particles reacting with gas-phase oxidants, high concentrations of radicals are often used to study on the timescale of seconds reactions which may be occurring over days or weeks in the troposphere. Implicit in this approach is the assumption that radical concentration and time are interchangeable parameters, though this has not been established. Here, the kinetics of OH- and Cl-initiated oxidation reactions of model single-component liquid (squalane) and supercooled (brassidic acid and 2-octyldodecanoic acid) organic aerosols are studied by varying separately the radical concentration and the reaction time. Two separate flow tubes with residence times of 2 and 66 s are used, and [OH] and [Cl] are varied by adjusting either the laser photolysis fluence or the radical precursor concentration ([O<sub>3</sub>] or [Cl<sub>2</sub>], respectively) used to generate the radicals. It is found that the rates measured by varying the radical concentration and the reaction time are equal only if the precursor concentrations are the same in the two approaches. Further, the rates depend on the concentrations of the precursor species with a Langmuir-type functional form suggesting that O<sub>3</sub> and Cl<sub>2</sub> saturate the surface of the liquid particles. It is believed that the presence of O<sub>3</sub> inhibits the rate of OH reaction, perhaps by reacting with OH radicals or by O<sub>3</sub> or intermediate species blocking surface sites, while Cl<sub>2</sub> enhances the rate of Cl reaction by participating in a radical chain mechanism. These results have important implications for laboratory experiments in which high concentrations of gas-phase oxidants are used to study atmospheric reactions over short timescales and may explain the variability in recent measurements of the reactive uptake of OH on squalane particles in reactor systems used in this and other laboratories

Technical Note: New methodology for measuring viscosities in small volumes characteristic of environmental chamber particle samples

Herein, a method for the determination of viscosities of small sample volumes is introduced, with important implications for the viscosity determination of particle samples from environmental chambers (used to simulate atmospheric conditions). The amount of sample needed is < 1 μl, and the technique is capable of determining viscosities (η) ranging between 10<sup>−3</sup> and 10<sup>3</sup> Pascal seconds (Pa s) in samples that cover a range of chemical properties and with real-time relative humidity and temperature control; hence, the technique should be well-suited for determining the viscosities, under atmospherically relevant conditions, of particles collected from environmental chambers. In this technique, supermicron particles are first deposited on an inert hydrophobic substrate. Then, insoluble beads (~1 μm in diameter) are embedded in the particles. Next, a flow of gas is introduced over the particles, which generates a shear stress on the particle surfaces. The sample responds to this shear stress by generating internal circulations, which are quantified with an optical microscope by monitoring the movement of the beads. The rate of internal circulation is shown to be a function of particle viscosity but independent of the particle material for a wide range of organic and organic-water samples. A calibration curve is constructed from the experimental data that relates the rate of internal circulation to particle viscosity, and this calibration curve is successfully used to predict viscosities in multicomponent organic mixtures

Adsorptive uptake of water by semisolid secondary organic aerosols

Aerosol climate effects are intimately tied to interactions with water. Here we combine hygroscopicity measurements with direct observations about the phase of secondary organic aerosol (SOA) particles to show that water uptake by slightly oxygenated SOA is an adsorption-dominated process under subsaturated conditions, where low solubility inhibits water uptake until the humidity is high enough for dissolution to occur. This reconciles reported discrepancies in previous hygroscopicity closure studies. We demonstrate that the difference in SOA hygroscopic behavior in subsaturated and supersaturated conditions can lead to an effect up to about 30% in the direct aerosol forcinghighlighting the need to implement correct descriptions of these processes in atmospheric models. Obtaining closure across the water saturation point is therefore a critical issue for accurate climate modeling.Peer reviewe

Clinical approach for the classification of congenital uterine malformations

A more objective, accurate and non-invasive estimation of uterine morphology is nowadays feasible based on the use of modern imaging techniques. The validity of the current classification systems in effective categorization of the female genital malformations has been already challenged. A new clinical approach for the classification of uterine anomalies is proposed. Deviation from normal uterine anatomy is the basic characteristic used in analogy to the American Fertility Society classification. The embryological origin of the anomalies is used as a secondary parameter. Uterine anomalies are classified into the following classes: 0, normal uterus; I, dysmorphic uterus; II, septate uterus (absorption defect); III, dysfused uterus (fusion defect); IV, unilateral formed uterus (formation defect); V, aplastic or dysplastic uterus (formation defect); VI, for still unclassified cases. A subdivision of these main classes to further anatomical varieties with clinical significance is also presented. The new proposal has been designed taking into account the experience gained from the use of the currently available classification systems and intending to be as simple as possible, clear enough and accurate as well as open for further development. This proposal could be used as a starting point for a working group of experts in the field