A solar powered handheld plasma source for microbial decontamination applications

A fully portable atmospheric pressure air plasma system is reported to be suitable for the microbial decontamination of both surfaces and liquids. The device operates in quiescent air, and includes an integrated battery which is charged from a solar cell and weighs less than 750 g, making it highly amenable for a wide variety of applications beyond the laboratory. Using particle imaging velocimetry to visualise air flows around the device, the geometric configuration of the plasma generating electrodes was enhanced to induce a gas flow on the order of 0.5 m s-1 directed towards a sample placed downstream, thus improving the transport of plasma generated reactive species to the sample. The microbial decontamination efficiency of the system was assessed using potable water samples inoculated with common waterborne organisms Escherichia coli and Pseudomonas fluorescens. The reduction in the number of microorganisms was found to be in the range of 2-8 log and was strongly dependent on the plasma generation conditions

Atmospheric fates of Criegee intermediates in the ozonolysis of isoprene

We use a large laboratory, modeling, and field dataset to investigate the isoprene + O_3 reaction, with the goal of better understanding the fates of the C_1 and C_4 Criegee intermediates in the atmosphere. Although ozonolysis can produce several distinct Criegee intermediates, the C_1 stabilized Criegee (CH_2OO, 61 ± 9%) is the only one observed to react bimolecularly. We suggest that the C_4 Criegees have a low stabilization fraction and propose pathways for their decomposition. Both prompt and non-prompt reactions are important in the production of OH (28% ± 5%) and formaldehyde (81% ± 16%). The yields of unimolecular products (OH, formaldehyde, methacrolein (42 ± 6%) and methyl vinyl ketone (18 ± 6%)) are fairly insensitive to water, i.e., changes in yields in response to water vapor (≤4% absolute) are within the error of the analysis. We propose a comprehensive reaction mechanism that can be incorporated into atmospheric models, which reproduces laboratory data over a wide range of relative humidities. The mechanism proposes that CH_2OO + H_2O (k_((H_2O)) ∼ 1 × 10^(−15) cm^3 molec^(−1) s^(−1)) yields 73% hydroxymethyl hydroperoxide (HMHP), 6% formaldehyde + H_2O_2, and 21% formic acid + H_2O; and CH_2OO + (H_2O)_2 (k_((H_2O)_2) ∼ 1 × 10^(−12) cm^3 molec^(−1) s^(−1)) yields 40% HMHP, 6% formaldehyde + H_2O_2, and 54% formic acid + H_2O. Competitive rate determinations (k_(SO_2/k(H_2O)n=1,2) ∼ 2.2 (±0.3) × 10^4) and field observations suggest that water vapor is a sink for greater than 98% of CH2OO in a Southeastern US forest, even during pollution episodes ([SO_2] ∼ 10 ppb). The importance of the CH_2OO + (H_2O)n reaction is demonstrated by high HMHP mixing ratios observed over the forest canopy. We find that CH_2OO does not substantially affect the lifetime of SO_2 or HCOOH in the Southeast US, e.g., CH_2OO + SO_2 reaction is a minor contribution (<6%) to sulfate formation. Extrapolating, these results imply that sulfate production by stabilized Criegees is likely unimportant in regions dominated by the reactivity of ozone with isoprene. In contrast, hydroperoxide, organic acid, and formaldehyde formation from isoprene ozonolysis in those areas may be significant

Synergistic O_3 + OH oxidation pathway to extremely low-volatility dimers revealed in β-pinene secondary organic aerosol

Dimeric compounds contribute significantly to the formation and growth of atmospheric secondary organic aerosol (SOA) derived from monoterpene oxidation. However, the mechanisms of dimer production, in particular the relevance of gas- vs. particle-phase chemistry, remain unclear. Here, through a combination of mass spectrometric, chromatographic, and synthetic techniques, we identify a suite of dimeric compounds (C_(15–19)H_(24–32)O_(5–11)) formed from concerted O3 and OH oxidation of β-pinene (i.e., accretion of O_3- and OH-derived products/intermediates). These dimers account for an appreciable fraction (5.9–25.4%) of the β-pinene SOA mass and are designated as extremely low-volatility organic compounds. Certain dimers, characterized as covalent dimer esters, are conclusively shown to form through heterogeneous chemistry, while evidence of dimer production via gas-phase reactions is also presented. The formation of dimers through synergistic O_3 + OH oxidation represents a potentially significant, heretofore-unidentified source of low-volatility monoterpene SOA. This reactivity also suggests that the current treatment of SOA formation as a sum of products originating from the isolated oxidation of individual precursors fails to accurately reflect the complexity of oxidation pathways at play in the real atmosphere. Accounting for the role of synergistic oxidation in ambient SOA formation could help to resolve the discrepancy between the measured atmospheric burden of SOA and that predicted by regional air quality and global climate models

A Systems level characterization and tradespace evaluation of a simulated airborne fourier transform infrared spectrometer for gas detection

The remote sensing gas detection problem is one with no straightforward solution. While success has been achieved in detecting and identifying gases released from industrial stacks and other large plumes, the fugituve gas detection problem is far more complex. Fugitive gas represents a far smaller target and may be generated by leaking pipes, vents, or small scale chemical production. The nature of fugitive gas emission is such that one has no foreknowledge of the location, quantity, or transient rate of the targeted effluent which requires one to cover a broad area with high sensitivity. In such a scenario, a mobile airborne platform would be a likely candidate. Further, the spectrometer used for gas detection should be capable of rapid scan rates to prevent spatial and spectral smearing, while maintaining high resolution to aid in species identification. Often, insufficient signal to noise (SNR) prevents spectrometers from delivering useful results under such conditions. While common dispersive element spectrometers (DES) suffer from decreasing SNR with increasing spectral dispersion, Fourier Transform Spectrometers (FTS) generally do not and would seemingly be an ideal choice for such an application. FTS are ubiquitous in chemical laboratories and in use as ground based spectrometers, but have not become as pervasive in mobile applications. While FTS spectrometers would otherwise be ideal for high resolution rapid scanning in search of gaseous effluents, when conducted via a mobile platform the process of optical interferogram formation to form spectra is corrupted when the input signal is temporally unstable. This work seeks to explore the tradespace of an airborne Michelson based FTS in terms of modeling and characterizing the performance degradation over a variety of environmental and optical parameters. The major variables modeled and examined include: maximum optical path distance (resolution), scan rate, platform velocity, altitude, atmospheric and background emissivity variability, gas target parameters such as temperature, concentration-pathlength, confuser gas presence, and optical effects including apodization effects, single and double-sided interferograms, internal mirror positional accuracy errors, and primary mirror jitter effects. It is through an understanding of how each of the aforementioned variables impacts the gas detection performance that one can constrain design parameters in developing and engineering an FTS suitable to the airborne environment. The instrument model was compared to output from ground-based FTS instruments as well as airborne data taken from the Airborne Hyperspectral Imager (AHI) and found to be in good agreement. Monte Carlo studies were used to map the impact of the performance variables and unique detection algorithms, based on common detection scores, were used to quantify performance degradation. Scene-based scenarios were employed to evaluate performance of a scanning FTS under variable and complex conditions. It was found that despite critical sampling errors and rapidly varying radiance signals, while losing the ability to reproduce a radiometrically accurate spectrum, an FTS offered the unique ability to reproduce spectral evidence of a gas in scenarios where a dispersive element spectrometer (DES) might not

Profil spectral des raies d'absorption du dioxyde de carbone en vue d'application à l'étude de l'atmosphère de la Terre par télédétection

This work is devoted to the theoretical and experimental studies of the spectral shape of isolated absorption lines of carbon dioxide, a key species of the Earth's atmosphere. The objective of this PhD thesis is to test the different line-shape models that take into account various velocity effects affecting the spectral shape of CO2 absorption lines. The experimental part consists of measurements of spectroscopic parameters of pure CO2 using a tunable External Cavity Diode Laser setup. In the theoretical part, different spectral profiles were used to fit the measured spectra. The results show that the Voigt profile leads to important residuals and it is thus necessary to take into account both Dicke narrowing and the speed dependence of collisional parameters to adequately describe the experimental spectral profile. The HTP profile, developed recently, was also used to model the spectral profile of CO2 lines. This model has been validated by this study. Molecular dynamics simulations for pure CO2 and CO2 perturbed by N2 were also conducted to study more precisely the “non-Voigt” effects observed. The goal here was to determine the influence of several parameters on these effects. We compared the theoretical simulations with our measurements. For pure CO2, we could show that the intermolecular potential chosen to model the existing interactions had no influence on the evolution of these effects as a function of pressure. Furthermore, no rovibrational dependence could be found. The results for CO2 mixed in N2 showed a dependence of the evolution of these effects depending on the CO2/N2 mixing ratio.Ce travail est consacré aux études théoriques et expérimentales du profil spectral des raies d'absorption du dioxyde de carbone, une espèce clé dans l'atmosphère de la Terre. Le but de ce travail est de tester les différents modèles du profil spectral des raies d'absorption de CO2. Dans un premier temps, des mesures des paramètres spectroscopiques du CO2 pur dans l'infrarouge proche en utilisant un système de diode laser à cavité externe ont été effectuées. Différents modèles de profil spectral ont été utilisés pour ajuster les spectres mesurés. Les résultats montrent que le profil de Voigt mène à de larges différences avec les spectres mesurés et qu’il est nécessaire de prendre en compte à la fois des changements de vitesse et des dépendances en vitesse des paramètres collisionnels pour décrire correctement le profil spectral. Le modèle HTP a alors été utilisé pour modéliser le profil spectral de CO2. Ce modèle a donc pu être testé et validé par cette étude. Des simulations de dynamique moléculaire pour CO2 pur et CO2 perturbé par N2 ont ensuite été effectuées afin d’étudier plus précisément les effets non-Voigt observés. Le but a été ici de déterminer l’influence de plusieurs paramètres sur ces effets. Nous avons alors pu comparer les simulations à des mesures. Pour le CO2 pur, nous avons pu montrer que le choix du potentiel intermoléculaire pour modéliser les interactions existantes n’avait pas d’influence sur l’évolution de ces effets avec la pression. Aucune dépendance rovibrationelle n’a pu être mise en évidence. Les résultats pour CO2 dans N2 ont montré une dépendance de l’évolution de ces effets en fonction du rapport de mélange utilisé