Real-time organic aerosol chemical speciation in the indoor environment using extractive electrospray ionization mass spectrometry

Understanding the sources and composition of organic aerosol (OA) in indoor environments requires rapid measurements, since many emissions and processes have short timescales. However, real-time molecular-level OA measurements have not been reported indoors. Here, we present quantitative measurements, at a time resolution of five seconds, of molecular ions corresponding to diverse aerosol-phase species, by applying extractive electrospray ionization mass spectrometry (EESI-MS) to indoor air analysis for the first time, as part of the highly instrumented HOMEChem field study. We demonstrate how the complex spectra of EESI-MS are screened in order to extract chemical information and investigate the possibility of interference from gas-phase semivolatile species. During experiments that simulated the Thanksgiving US holiday meal preparation, EESI-MS quantified multiple species, including fatty acids, carbohydrates, siloxanes, and phthalates. Intercomparisons with Aerosol Mass Spectrometer (AMS) and Scanning Mobility Particle Sizer suggest that EESI-MS quantified a large fraction of OA. Comparisons with FIGAERO-CIMS shows similar signal levels and good correlation, with a range of 100 for the relative sensitivities. Comparisons with SV-TAG for phthalates and with SV-TAG and AMS for total siloxanes also show strong correlation. EESI-MS observations can be used with gas-phase measurements to identify co-emitted gas- and aerosol-phase species, and this is demonstrated using complementary gas-phase PTR-MS observations.     

Measurements and modeling of absorptive partitioning of volatile organic compounds to painted surfaces

Partitioning to surfaces is an important sink for volatile organic compounds (VOCs) indoors, but the mechanisms are not well understood or quantified. Here, a mass spectrometer was coupled to a portable surface reactor and a flow tube to measure partitioning of VOCs into paint films coated onto glass or wallboard, and their subsequent diffusion. A model was developed to extract values of the effective absorbing organic mass concentration of the film, C_w, which is a measure of absorption capacity, and VOC diffusion coefficients, D_f, from VOC time profiles measured during film passivation and depassivation. Values of C_w agreed well with the value estimated from the paint film mass and flow tube air volume, and D_f values (also measured using attenuated total reflectance-Fourier transform infrared spectroscopy) correlated well with VOC vapor saturation concentrations, C*, estimated using a group contribution method. The value of these relationships for estimating key parameters that control VOC partitioning into paint and the fate of VOCs indoors was demonstrated using a house model, which indicated that >50% of VOCs with C* ≤10⁸ μg/m³ (C* of octane, hexanone, and propanol) that contacted a paint film of typical thickness fully permeated the film regardless of emission duration.     

Fast Measurements of the Gas‐Liquid Diffusion Coefficient in the Gaussian Wake of a Spherical Bubble

A fast method is proposed for determining the oxygen gas‐liquid diffusion coefficient from measurements of the fluorescence quenching behind a bubble. The approach consists of capturing pictures of the concentration field at micro‐scale in the laminar bubble wake. The Gaussian concentration profiles measured in the wake are demonstrated to be systematically equivalent to an instantaneous plane diffusion case. The approach permits to accurately evaluate the gas‐liquid diffusivity in a very short time of around one second.     

Impacts of Aerosol Aging on Laser Desorption/Ionization in Single-Particle Mass Spectrometers

Single-particle mass spectrometry (SPMS) has been widely used for characterizing the chemical mixing state of ambient aerosol particles. However, processes occurring during particle ablation and ionization can influence the mass spectra produced by these instruments. These effects remain poorly characterized for complex atmospheric particles. During the 2005 Study of Organic Aerosols in Riverside (SOAR), a thermodenuder was used to evaporate the more volatile aerosol species in sequential temperature steps up to 230°C; the residual aerosol particles were sampled by an aerosol mass spectrometer (AMS) and a single-particle aerosol time-of-flight mass spectrometer (ATOFMS). Removal of the secondary species (e.g., ammonium nitrate/sulfate) through heating permitted assessment of the change in ionization patterns as the composition changed for a given particle type. It was observed that a coating of secondary species can reduce the ionization efficiency by changing the degree of laser absorption or particle ablation, which significantly impacted the measured ion peak areas. Nonvolatile aerosol components were used as pseudo-internal standards (or “reference components”) to correct for this LDI effect. Such corrected ATOFMS ion peak areas correlated well with the AMS measurements of the same species up to 142°C. This work demonstrates the potential to accurately relate SPMS peak areas to the mass of specific aerosol components.

Copyright 2014 American Association for Aerosol Research     

Advanced Monte Carlo simulations of the adsorption of chiral alcohols in a homochiral metal‐organic framework

Grand canonical Monte Carlo (GCMC) simulations with configurational biasing were used to study the enantioselective adsorption of four alkanols in a homochiral metal‐organic framework, known as hybrid organic‐inorganic zeolite analogue HOIZA‐1. Conventional GCMC simulations are not able to converge satisfactorily for this system due to the tight fit of the chiral alcohols in the narrow pores. However, parallel tempering and parallel mole‐fraction GCMC simulations overcome this problem. The simulations show that the enantioselective adsorption of the different (R,S)‐alkanols is due to the specific geometry of the chiral molecules relative to the pore size and shape. © 2014 American Institute of Chemical Engineers AIChE J, 60: 2324–2334, 2014     

Process development for the laser powder bed fusion of WC-Ni Cermets using sintered-agglomerated powder

Although ceramic particle-metal matrix materials (i.e., cermets) can offer superior performance, manufacturing these materials via conventional means is difficult compared to the manufacturing of metal alloys. This study leverages the laser powder bed fusion (LPBF) process to additively manufacture dense tungsten carbide (WC)-17 wt.% nickel (Ni) composite specimens using novel spherical, sintered-agglomerated composite powder. A range of processing parameters yielding high-density specimens was discovered using a sequential series of experiments comprised of single bead, multi-layer, and cylindrical builds. Cylinders with a relative density >99% were fabricated and characterized in terms of microstructure, chemical composition, and hardness. Scanning electron microscopy images show favorable wetting between the Ni binder and carbide particles without any phase segregation and laser processing increased the average carbide particle size. Energy dispersive X-ray and X-ray diffraction analyses detected traces of secondary products after laser processing. For samples processed at high energy densities, complex carbides and carbon agglomerate phases were detected. The maximum hardness of 60.38 Rockwell C is achieved in the printed samples. The successful builds in this study open the way for LPBF of dense WC-Ni parts with a large workable laser power-laser velocity processing window.     

Quantification and source characterization of volatile organic compounds from exercising and application of chlorine-based cleaning products in a university athletic center

Humans spend approximately 90% of their time indoors, impacting their own air quality through occupancy and activities. Human VOC emissions indoors from exercise are still relatively uncertain, and questions remain about emissions from chlorine-based cleaners. To investigate these and other issues, the ATHLETic center study of Indoor Chemistry (ATHLETIC) campaign was conducted in the weight room of the Dal Ward Athletic Center at the University of Colorado Boulder. Using a Vocus Proton-Transfer-Reaction Time-of-Flight Mass Spectrometer (Vocus PTR-TOF), an Aerodyne Gas Chromatograph (GC), an Iodide-Chemical Ionization Time-of-Flight Mass Spectrometer (I-CIMS), and Picarro cavity ringdown spectrometers, we alternated measurements between the weight room and supply air, allowing for determination of VOC, NH₃, H₂O, and CO₂ emission rates per person (emission factors). Human-derived emission factors were higher than previous studies of measuring indoor air quality in rooms with individuals at rest and correlated with increased CO₂ emission factors. Emission factors from personal care products (PCPs) were consistent with previous studies and typically decreased throughout the day. In addition, N-chloraldimines were observed in the gas phase after the exercise equipment was cleaned with a dichlor solution. The chloraldimines likely originated from reactions of free amino acids with HOCl on gym surfaces.     

iCanCloud: A Flexible and Scalable Cloud Infrastructure Simulator

Simulation techniques have become a powerful tool for deciding the best starting conditions on pay-as-you-go scenarios. This is the case of public cloud infrastructures, where a given number and type of virtual machines (in short VMs) are instantiated during a specified time, being this reflected in the final budget. With this in mind, this paper introduces and validates iCanCloud, a novel simulator of cloud infrastructures with remarkable features such as flexibility, scalability, performance and usability. Furthermore, the iCanCloud simulator has been built on the following design principles: (1) it’s targeted to conduct large experiments, as opposed to others simulators from literature; (2) it provides a flexible and fully customizable global hypervisor for integrating any cloud brokering policy; (3) it reproduces the instance types provided by a given cloud infrastructure; and finally, (4) it contains a user-friendly GUI for configuring and launching simulations, that goes from a single VM to large cloud computing systems composed of thousands of machines.     

Complementing retrofit with engagement: exploring energy consumption with social housing tenants

Councils and social housing organisations are looking to retrofit as a way to make their housing more energy efficient. Previous studies on energy use in social housing have generally focussed on the technological aspects (such as the potential savings possible by retrofitting this class of housing across the UK) or have involved one‐off interventions or measures. During a 2‐year period, we worked with previously homeless people to reduce their energy consumption. The 32 participants lived in small blocks of flats (owned by a social housing organisation) that underwent retrofitting with air source heat pumps. We ran a three‐phase tenant engagement programme to compare a range of approaches aimed at energy reduction. It was found that education, social norms and self‐awareness are all key components when it comes to initiating environmentally responsible behaviours. The three approaches complemented each other, and these ought to be considered alongside technology provision if the aim is to reduce energy consumption. A number of reflections on the implementation of medium‐term tenant engagement programmes are also presented. Copyright © 2016 John Wiley & Sons, Ltd.