Characterizing an extractive electrospray ionization (EESI) source for the online mass spectrometry analysis of organic aerosols.

Organic compounds comprise a major fraction of tropospheric aerosol and understanding their chemical complexity is a key factor for determining their climate and health effects. We present and characterize here a new online technique for measuring the detailed chemical composition of organic aerosols, namely extractive electrospray ionization mass spectrometry (EESI-MS). Aerosol particles composed of soluble organic compounds were extracted into and ionized by a solvent electrospray, producing molecular ions from the aerosol with minimal fragmentation. We demonstrate here that the technique has a time resolution of seconds and is capable of making stable measurements over several hours. The ion signal in the MS was linearly correlated with the mass of aerosol delivered to the EESI source over the range tested (3-600 μg/m(3)) and was independent of particle size and liquid water content, suggesting that the entire particle bulk is extracted for analysis. Tandem MS measurements enabled detection of known analytes in the sub-μg/m(3) range. Proof-of-principle measurements of the ozonolysis of oleic acid aerosol (20 μg/m(3)) revealed the formation of a variety of oxidation products in good agreement with previous offline studies. This demonstrates the technique's potential for studying the product-resolved kinetics of aerosol-phase chemistry at a molecular level with high sensitivity and time resolution.This is the author's accepted manuscript. The final version is published by ACS in Environmental Science and Technology and can be found here: http://pubs.acs.org/doi/abs/10.1021/es305199h?prevSearch=%255BContrib%253A%2Bgallimore%252C%2Bp.%2Bj.%255D&searchHistoryKey=

1064 nm Dispersive Raman Microspectroscopy and Optical Trapping of Pharmaceutical Aerosols.

Raman spectroscopy is a powerful tool for investigating chemical composition. Coupling Raman spectroscopy with optical microscopy (Raman microspectroscopy) and optical trapping (Raman tweezers) allows microscopic length scales and, hence, femtolitre volumes to be probed. Raman microspectroscopy typically uses UV/visible excitation lasers, but many samples, including organic molecules and complex tissue samples, fluoresce strongly at these wavelengths. Here we report the development and application of dispersive Raman microspectroscopy designed around a near-infrared continuous wave 1064 nm excitation light source. We analyze microparticles (1-5 μm diameter) composed of polystyrene latex and from three real-world pressurized metered dose inhalers (pMDIs) used in the treatment of asthma: salmeterol xinafoate (Serevent), salbutamol sulfate (Salamol), and ciclesonide (Alvesco). For the first time, single particles are captured, optically levitated, and analyzed using the same 1064 nm laser, which permits a convenient nondestructive chemical analysis of the true aerosol phase. We show that particles exhibiting overwhelming fluorescence using a visible laser (514.5 nm) can be successfully analyzed with 1064 nm excitation, irrespective of sample composition and irradiation time. Spectra are acquired rapidly (1-5 min) with a wavelength resolution of 2 nm over a wide wavenumber range (500-3100 cm-1). This is despite the microscopic sample size and low Raman scattering efficiency at 1064 nm. Spectra of individual pMDI particles compare well to bulk samples, and the Serevent pMDI delivers the thermodynamically preferred crystal form of salmeterol xinafoate. 1064 nm dispersive Raman microspectroscopy is a promising technique that could see diverse applications for samples where fluorescence-free characterization is required with high spatial resolution

Resonant electron transmission through a finite quantum spin chain

Electron transport in a finite one dimensional quantum spin chain (with ferromagnetic exchange) is studied within an $s-d$ exchange Hamiltonian. Spin transfer coefficients strongly depend on the sign of the $s-d$ exchange constant. For a ferromagnetic coupling, they exhibit a novel resonant pattern, reflecting the salient features of the combined electron-spin system. Spin-flip processes are inelastic and feasible at finite voltage or at finite temperature.Comment: 4 pages including 4 .eps figure

Measuring Aerosol Phase Changes and Hygroscopicity with a Microresonator Mass Sensor.

The interaction between atmospheric aerosol particles and water vapor influences aerosol size, phase, and composition, parameters which critically influence their impacts in the atmosphere. Methods to accurately measure aerosol water uptake for a wide range of particle types are therefore merited. We present here a new method for characterizing aerosol hygroscopicity, an impaction stage containing a microelectromechanical systems (MEMS) microresonator. We find that deliquescence and efflorescence relative humidities (RHs) of sodium chloride and ammonium sulfate are easily diagnosed via changes in resonant frequency and peak sharpness. These agree well with literature values and thermodynamic models. Furthermore, we demonstrate that, unlike other resonator-based techniques, full hygroscopic growth curves can be derived, including for an inorganic-organic mixture (sodium chloride and malonic acid) which remains liquid at all RHs. The response of the microresonator frequency to temperature and particle mechanical properties and the resulting limitations when measuring hygroscopicity are discussed. MEMS resonators show great potential as miniaturized ambient aerosol mass monitors, and future work will consider the applicability of our approach to complex ambient samples. The technique also offers an alternative to established methods for accurate thermodynamic measurements in the laboratory

1064 nm Dispersive Raman Micro-Spectroscopy and Optical Trapping of Pharmaceutical Aerosols

Raman spectroscopy is a powerful tool for investigating chemical composition. Coupling Raman spectroscopy with optical microscopy (Raman microspectroscopy) and optical trapping (Raman tweezers) allows microscopic length scales and, hence, femtolitre volumes to be probed. Raman microspectroscopy typically uses UV/visible excitation lasers, but many samples, including organic molecules and complex tissue samples, fluoresce strongly at these wavelengths. Here we report the development and application of dispersive Raman microspectroscopy designed around a near-infrared continuous wave 1064 nm excitation light source. We analyze microparticles (1-5 pm diameter) composed of polystyrene latex and from three real-world pressurized metered dose inhalers (pMDIs) used in the treatment of asthma: salmeterol xinafoate (Serevent), salbutamol sulfate (Salamol), and ciclesonide (Alvesco). For the first time, single particles are captured, optically levitated, and analyzed using the same 1064 nm laser, which permits a convenient nondestructive chemical analysis of the true aerosol phase. We show that particles exhibiting overwhelming fluorescence using a visible laser (514.5 nm) can be successfully analyzed with 1064 nm excitation, irrespective of sample composition and irradiation time. Spectra are acquired rapidly (1-5 min) with a wavelength resolution of 2 nm over a wide wavenumber range (500-3100 cm(-1)). This is despite the microscopic sample size and low Raman scattering efficiency at 1064 nm. Spectra of individual pMDI particles compare well to bulk samples, and the Serevent pMDI delivers the thermodynamically preferred crystal form of salmeterol xinafoate. 1064 nm dispersive Raman microspectroscopy is a promising technique that could see diverse applications for samples where fluorescence-free characterization is required with high spatial resolution

A light-driven burst of hydroxyl radicals dominates oxidation chemistry in newly activated cloud droplets.

Aerosol particles and their interactions with clouds are one of the most uncertain aspects of the climate system. Aerosol processing by clouds contributes to this uncertainty, altering size distributions, chemical composition, and radiative properties. Many changes are limited by the availability of hydroxyl radicals in the droplets. We suggest an unrecognized potentially substantial source of OH formation in cloud droplets. During the first few minutes following cloud droplet formation, the material in aerosols produces a near-UV light-dependent burst of hydroxyl radicals, resulting in concentrations of 0.1 to 3.5 micromolar aqueous OH ([OH]aq). The source of this burst is previously unrecognized chemistry between iron(II) and peracids. The contribution of the "OH burst" to total OH in droplets varies widely, but it ranges up to a factor of 5 larger than previously known sources. Thus, this new process will substantially enhance the impact of clouds on aerosol properties

Experimental Results for Communications Blackout Amelioration Using Crossed Electric and Magnetic Fields

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/77188/1/AIAA-45490-250.pd

Viral Gastroenteritis Associated with Genogroup II Norovirus among U.S. Military Personnel in Turkey, 2009

The present study demonstrates that multiple NoV genotypes belonging to genogroup II contributed to an acute gastroenteritis outbreak at a US military facility in Turkey that was associated with significant negative operational impact. Norovirus (NoV) is an important pathogen associated with acute gastroenteritis among military populations. We describe the genotypes of NoV outbreak occurred at a United States military facility in Turkey. Stool samples were collected from 37 out of 97 patients presenting to the clinic on base with acute gastroenteritis and evaluated for bacterial and viral pathogens. NoV genogroup II (GII) was identified by RT-PCR in 43% (16/37) stool samples. Phylogenetic analysis of a 260 base pair fragment of the NoV capsid gene from ten stool samples indicated the circulation of multiple and rare genotypes of GII NoV during the outbreak. We detected four GII.8 isolates, three GII.15, two GII.9 and a sole GII.10 NoV. Viral sequences could be grouped into four clusters, three of which have not been previously reported in Turkey. The fact that current NoV outbreak was caused by rare genotypes highlights the importance of norovirus strain typing. While NoV genogroup II is recognized as causative agent of outbreak, circulation of current genotypes has been rarely observed in large number of outbreaks

Megacity and local contributions to regional air pollution : An aircraft case study over London

In July 2017 three research flights circumnavigating the megacity of London were conducted as a part of the STANCO training school for students and early career researchers organised by EUFAR (European Facility for Airborne Research). Measurements were made from the UK's Facility for Airborne Atmospheric Measurements (FAAM) BAe-146-301 atmospheric research aircraft with the aim to sample, characterise and quantify the impact of megacity outflow pollution on air quality in the surrounding region. Conditions were extremely favourable for airborne measurements, and all three flights were able to observe clear pollution events along the flight path. A small change in wind direction provided sufficiently different air mass origins over the 2 d such that a distinct pollution plume from London, attributable marine emissions and a double-peaked dispersed area of pollution resulting from a combination of local and transported emissions were measured. We were able to analyse the effect of London emissions on air quality in the wider region and the extent to which local sources contribute to pollution events. The background air upwind of London was relatively clean during both days; concentrations of CO were 88-95 ppbv, total (measured) volatile organic compounds (VOCs) were 1.6-1.8 ppbv and NOx was 0.7- 0.8 ppbv. Downwind of London, we encountered elevations in all species with CO>100 ppbv, VOCs 2.8-3.8 ppbv, CH4>2080 ppbv and NOx>4 ppbv, and peak concentrations in individual pollution events were higher still. Levels of O3 were inversely correlated with NOx during the first flight, with O3 concentrations of 37 ppbv upwind falling to 26 ppbv in the well-defined London plume. Total pollutant fluxes from London were estimated through a vertical plane downwind of the city. Our calculated CO2 fluxes are within the combined uncertainty of those estimated previously, but there was a greater disparity in our estimates of CH4 and CO. On the second day, winds were lighter and downwind O3 concentrations were elevated to 39-43 ppbv (from 32 to 35 ppbv upwind), reflecting the contribution of more aged pollution to the regional background. Elevations in pollutant concentrations were dispersed over a wider area than the first day, although we also encountered a number of clear transient enhancements from local sources. This series of flights demonstrated that even in a region of megacity outflow, such as the south-east of the UK, local fresh emissions and more distant UK sources of pollution can all contribute substantially to pollution events. In the highly complex atmosphere around a megacity where a high background level of pollution mixes with a variety of local sources at a range of spatial and temporal scales and atmospheric dynamics are further complicated by the urban heat island, the use of pollutant ratios to track and determine the ageing of air masses may not be valid. The individual sources must therefore all be well-characterised and constrained to understand air quality around megacities such as London. Research aircraft offer that capability through targeted sampling of specific sources and longitudinal studies monitoring trends in emission strength and profiles over time

Update on the Nested Hall Thruster Subsystem for the NextSTEP XR-100 Program

Under the NextSTEP program led by Aerojet Rocketdyne in collaboration with NASA Glenn Research Center the University of Michigan, and the Jet Propulsion Laboratory, the XR-100 100 kW Electric Propulsion system is being developed to Technology Readiness Level (TRL) 5. As part of this program, the X3, a Nested Hall Thruster (NHT) designed to operate at powers up to 200kW, is being further developed through parallel modeling and experimental efforts with the ultimate goal of supporting a 100kW-100hr system test in the final year of the NextSTEP program. Recent developments for the X3 subsystem are presented including a summary of testing and modeling results and design updates in anticipation of a risk reduction test scheduled for the summer of 2018