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

Cytosine-to-Uracil Deamination by SssI DNA Methyltransferase

The prokaryotic DNA(cytosine-5)methyltransferase M.SssI shares the specificity of eukaryotic DNA methyltransferases (CG) and is an important model and experimental tool in the study of eukaryotic DNA methylation. Previously, M.SssI was shown to be able to catalyze deamination of the target cytosine to uracil if the methyl donor S-adenosyl-methionine (SAM) was missing from the reaction. To test whether this side-activity of the enzyme can be used to distinguish between unmethylated and C5-methylated cytosines in CG dinucleotides, we re-investigated, using a sensitive genetic reversion assay, the cytosine deaminase activity of M.SssI. Confirming previous results we showed that M.SssI can deaminate cytosine to uracil in a slow reaction in the absence of SAM and that the rate of this reaction can be increased by the SAM analogue 5’-amino-5’-deoxyadenosine. We could not detect M.SssI-catalyzed deamination of C5-methylcytosine (m5C). We found conditions where the rate of M.SssI mediated C-to-U deamination was at least 100-fold higher than the rate of m5C-to-T conversion. Although this difference in reactivities suggests that the enzyme could be used to identify C5-methylated cytosines in the epigenetically important CG dinucleotides, the rate of M.SssI mediated cytosine deamination is too low to become an enzymatic alternative to the bisulfite reaction. Amino acid replacements in the presumed SAM binding pocket of M.SssI (F17S and G19D) resulted in greatly reduced methyltransferase activity. The G19D variant showed cytosine deaminase activity in E. coli, at physiological SAM concentrations. Interestingly, the C-to-U deaminase activity was also detectable in an E. coli ung+ host proficient in uracil excision repair

MEMS 411; Ground Work Station

This project aims to design a support mechanism for ecological field researchers who interact with plants and other samples from the forest floor for long periods. The design aims to recreate the functionality of bending over for long periods of time, while protecting the backs, hips and knees

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

Sucrose diffusion in aqueous solution.

The diffusion of sugar in aqueous solution is important both in nature and in technological applications, yet measurements of diffusion coefficients at low water content are scarce. We report directly measured sucrose diffusion coefficients in aqueous solution. Our technique utilises a Raman isotope tracer method to monitor the diffusion of non-deuterated and deuterated sucrose across a boundary between the two aqueous solutions. At a water activity of 0.4 (equivalent to 90 wt% sucrose) at room temperature, the diffusion coefficient of sucrose was determined to be approximately four orders of magnitude smaller than that of water in the same material. Using literature viscosity data, we show that, although inappropriate for the prediction of water diffusion, the Stokes-Einstein equation works well for predicting sucrose diffusion under the conditions studied. As well as providing information of importance to the fundamental understanding of diffusion in binary solutions, these data have technological, pharmaceutical and medical implications, for example in cryopreservation. Moreover, in the atmosphere, slow organic diffusion may have important implications for aerosol growth, chemistry and evaporation, where processes may be limited by the inability of a molecule to diffuse between the bulk and the surface of a particle