Siloxane Emissions and Exposures during the Use of Hair Care Products in Buildings.

Cyclic volatile methyl siloxanes (cVMS) are ubiquitous in hair care products (HCPs). cVMS emissions from HCPs are of concern, given the potential adverse impact of siloxanes on the environment and human health. To characterize cVMS emissions and exposures during the use of HCPs, realistic hair care experiments were conducted in a residential building. Siloxane-based HCPs were tested using common hair styling techniques, including straightening, curling, waving, and oiling. VOC concentrations were measured via proton-transfer-reaction time-of-flight mass spectrometry. HCP use drove rapid changes in the chemical composition of the indoor atmosphere. cVMS dominated VOC emissions from HCP use, and decamethylcyclopentasiloxane (D5) contributed the most to cVMS emissions. cVMS emission factors (EFs) during hair care routines ranged from 110-1500 mg/person and were influenced by HCP type, styling tools, operation temperatures, and hair length. The high temperature of styling tools and the high surface area of hair enhanced VOC emissions. Increasing the hair straightener temperature from room temperature to 210 °C increased cVMS EFs by 50-310%. Elevated indoor cVMS concentrations can result in substantial indoor-to-outdoor transport of cVMS via ventilation (0.4-6 tons D5/year in the U.S.); thus, hair care routines may augment the abundance of cVMS in the outdoor atmosphere.

Influence of Mechanical Ventilation Systems and Human Occupancy on Time-Resolved Source Rates of Volatile Skin Oil Ozonolysis Products in a LEED-Certified Office Building.

Building mechanical ventilation systems are a major driver of indoor air chemistry as their design and operation influences indoor ozone (O3) concentrations, the dilution and transport of indoor-generated volatile organic compounds (VOCs), and indoor environmental conditions. Real-time VOC and O3 measurements were integrated with a building sensing platform to evaluate the influence of mechanical ventilation modes and human occupancy on the dynamics of skin oil ozonolysis products (SOOPs) in an office in a LEED-certified building during the winter. The ventilation system operated under variable recirculation ratios (RRs) from RR = 0 (100% outdoor air) to RR = 1 (100% recirculation air). Time-resolved source rates for 6-methyl-5-hepten-2-one (6-MHO), 4-oxopentanal (4-OPA), and decanal were highly dynamic and changed throughout the day with RR and occupancy. Total SOOP source rates during high-occupancy periods (10:00-18:00) varied from 2500-3000 µg h-1 when RR = 0.1 to 6300-6700 µg h-1 when RR = 1. Source rates for gas-phase reactions, outdoor air, and occupant-associated emissions generally decreased with increasing RR. The recirculation air source rate increased with RR and typically became the dominant source for RR > 0.5. SOOP emissions from surface reservoirs were also a prominent source, contributing 10-50% to total source rates. Elevated per person SOOP emission factors were observed, potentially due to multiple layers of soiled clothing worn during winter.

Real-Time Measurements of Gas-Phase Trichloramine (NCl3) in an Indoor Aquatic Center.

NCl3 is formed as a disinfection byproduct in chlorinated swimming pools and can partition between the liquid and gas phases. Exposure to gas-phase NCl3 has been linked to asthma and can irritate the eyes and respiratory airways, thereby affecting the health and athletic performance of swimmers. This study involved an investigation of the spatiotemporal dynamics of gas-phase NCl3 in an aquatic center during a collegiate swim meet. Real-time (up to 1 Hz) measurements of gas-phase NCl3 were made via a novel on-line derivatization cavity ring-down spectrometer and a proton transfer reaction time-of-flight mass spectrometer. Significant temporal variations in gas-phase NCl3 and CO2 concentrations were observed across varying time scales, from seconds to hours. Gas-phase NCl3 concentrations increased with the number of active swimmers due to swimming-enhanced liquid-to-gas transfer of NCl3, with peak concentrations between 116 and 226 ppb. Strong correlations between concentrations of gas-phase NCl3 with concentrations of CO2 and water (relative humidity) were found and attributed to similar features in their physical transport processes in pool air. A vertical gradient in gas-phase NCl3 concentrations was periodically observed above the water surface, demonstrating that swimmers can be exposed to elevated levels of NCl3 beyond those measured in the bulk air.

Urban Oxidation Flow Reactor Measurements Reveal Significant Secondary Organic Aerosol Contributions from Volatile Emissions of Emerging Importance.

Mobile sampling studies have revealed enhanced levels of secondary organic aerosol (SOA) in source-rich urban environments. While these enhancements can be from rapidly reacting vehicular emissions, it was recently hypothesized that nontraditional emissions (volatile chemical products and upstream emissions) are emerging as important sources of urban SOA. We tested this hypothesis by using gas and aerosol mass spectrometry coupled with an oxidation flow reactor (OFR) to characterize pollution levels and SOA potentials in environments influenced by traditional emissions (vehicular, biogenic), and nontraditional emissions (e.g., paint fumes). We used two SOA models to assess contributions of vehicular and biogenic emissions to our observed SOA. The largest gap between observed and modeled SOA potential occurs in the morning-time urban street canyon environment, for which our model can only explain half of our observation. Contributions from VCP emissions (e.g., personal care products) are highest in this environment, suggesting that VCPs are an important missing source of precursors that would close the gap between modeled and observed SOA potential. Targeted OFR oxidation of nontraditional emissions shows that these emissions have SOA potentials that are similar, if not larger, compared to vehicular emissions. Laboratory experiments reveal large differences in SOA potentials of VCPs, implying the need for further characterization of these nontraditional emissions.

Evaluation of Workplace Exposures to Volatile Chemicals During COVID-19 Building Disinfection Activities with Proton Transfer Reaction Mass Spectrometry.

We conducted an experimental case study to demonstrate the application of proton transfer reaction time-of-flight mass spectrometry (PTR-TOF-MS) for mobile breathing zone (BZ) monitoring of volatile chemical exposures in workplace environments during COVID-19 disinfection activities. The experiments were conducted in an architectural engineering laboratory-the Purdue zero Energy Design Guidance for Engineers (zEDGE) Tiny House, which served as a simulated workplace environment. Controlled disinfection activities were carried out on impermeable high-touch indoor surfaces, including the entry door, kitchen countertop, toilet bowl, bathroom sink, and shower. Worker inhalation exposure to volatile organic compounds (VOCs) was evaluated by attaching the PTR-TOF-MS sampling line to the researcher's BZ while the disinfection activity was carried out throughout the entire building. The results demonstrate that significant spatiotemporal variations in VOC concentrations can occur in the worker's BZ during multi-surface disinfection events. Application of high-resolution monitoring techniques, such as PTR-TOF-MS, are needed to advance characterization of worker exposures towards the development of appropriate mitigation strategies for volatile disinfectant chemicals.

Chemistry and human exposure implications of secondary organic aerosol production from indoor terpene ozonolysis.

Surface cleaning using commercial disinfectants, which has recently increased during the coronavirus disease 2019 pandemic, can generate secondary indoor pollutants both in gas and aerosol phases. It can also affect indoor air quality and health, especially for workers repeatedly exposed to disinfectants. Here, we cleaned the floor of a mechanically ventilated office room using a commercial cleaner while concurrently measuring gas-phase precursors, oxidants, radicals, secondary oxidation products, and aerosols in real-time; these were detected within minutes after cleaner application. During cleaning, indoor monoterpene concentrations exceeded outdoor concentrations by two orders of magnitude, increasing the rate of ozonolysis under low (<10 ppb) ozone levels. High number concentrations of freshly nucleated sub-10-nm particles (≥105 cm-3) resulted in respiratory tract deposited dose rates comparable to or exceeding that of inhalation of vehicle-associated aerosols.

Ethanol-based disinfectant sprays drive rapid changes in the chemical composition of indoor air in residential buildings.

The COVID-19 pandemic has resulted in increased usage of ethanol-based disinfectants for surface inactivation of SARS-CoV-2 in buildings. Emissions of volatile organic compounds (VOCs) and particles from ethanol-based disinfectant sprays were characterized in real-time (1 Hz) via a proton transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS) and a high-resolution electrical low-pressure impactor (HR-ELPI+), respectively. Ethanol-based disinfectants drove sudden changes in the chemical composition of indoor air. VOC and particle concentrations increased immediately after application of the disinfectants, remained elevated during surface contact time, and gradually decreased after wiping. The disinfectants produced a broad spectrum of VOCs with mixing ratios spanning the sub-ppb to ppm range. Ethanol was the dominant VOC emitted by mass, with concentrations exceeding 103 µg m-3 and emission factors ranging from 101 to 102 mg g-1. Listed and unlisted diols, monoterpenes, and monoterpenoids were also abundant. The pressurized sprays released significant quantities (104-105 cm-3) of nano-sized particles smaller than 100 nm, resulting in large deposited doses in the tracheobronchial and pulmonary regions of the respiratory system. Inhalation exposure to VOCs varied with time during the building disinfection events. Much of the VOC inhalation intake (>60 %) occurred after the disinfectant was sprayed and wiped off the surface. Routine building disinfection with ethanol-based sprays during the COVID-19 pandemic may present a human health risk given the elevated production of volatile chemicals and nano-sized particles.

A method for the identification of COVID-19 biomarkers in human breath using Proton Transfer Reaction Time-of-Flight Mass Spectrometry.

BACKGROUND: COVID-19 has caused a worldwide pandemic, making the early detection of the virus crucial. We present an approach for the determination of COVID-19 infection based on breath analysis. METHODS: A high sensitivity mass spectrometer was combined with artificial intelligence and used to develop a method for the identification of COVID-19 in human breath within seconds. A set of 1137 positive and negative subjects from different age groups, collected in two periods from two hospitals in the USA, from 26 August, 2020 until 15 September, 2020 and from 11 September, 2020 until 11 November, 2020, was used for the method development. The subjects exhaled in a Tedlar bag, and the exhaled breath samples were subsequently analyzed using a Proton Transfer Reaction Time-of-Flight Mass Spectrometer (PTR-ToF-MS). The produced mass spectra were introduced to a series of machine learning models. 70% of the data was used for these sub-models' training and 30% was used for testing. FINDINGS: A set of 340 samples, 95 positives and 245 negatives, was used for the testing. The combined models successfully predicted 77 out of the 95 samples as positives and 199 out of the 245 samples as negatives. The overall accuracy of the model was 81.2%. Since over 50% of the total positive samples belonged to the age group of over 55 years old, the performance of the model in this category was also separately evaluated on 339 subjects (170 negative and 169 positive). The model correctly identified 166 out of the 170 negatives and 164 out of the 169 positives. The model accuracy in this case was 97.3%. INTERPRETATION: The results showed that this method for the identification of COVID-19 infection is a promising tool, which can give fast and accurate results.

Electronic Cigarettes and Vaping-Associated Lung Injury (EVALI): A Rural Appalachian Experience.

Background: Electronic cigarette use has increased dramatically since their introduction in 2007. Respiratory complications, particularly lipoid pneumonia, have been reported as early as 2012. An outbreak of pulmonary injury in 2019 has been reported in patients using vaping products.Research Question: To describe a rural Appalachian tertiary center's experience of EVALI and to identify novel mechanisms of pulmonary injury patterns.Study Design and Methods: We present a consecutive case series of 17 patients admitted to our rural, academic, tertiary care institution with EVALI from August 2019 to March 2020. Demographics, baseline characteristics, co-morbidities, vaping behavior, and hospital course were recorded. Broncho-alveolar lavage specimens were assessed for lipid-laden macrophages and hemosiderin-laden macrophages with stains for Oil-Red-O (n = 15) and Prussian Blue (n = 14) respectively.The patient volunteered e-liquid materials (n = 6), and vapors were analyzed using a proton transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS) to describe the chemical profile. Post-discharge interviews were conducted.Results: The most common CT finding was bilateral ground-glass opacities with a predilection for lower lung zones. The most frequent pulmonary injury pattern was lipoid pneumonia. The majority of EVALI patients were critically ill requiring ventilation or ECMO. The most severely ill patients were noted to be positive for iron stains in macrophages and showed higher volatile organic compound (VOC) levels in chemical analysis.Interpretation: Based on our experience, EVALI in rural Appalachia presented with relatively severe respiratory failure. Worse outcomes appear to be correlated to high levels of VOCs, iron deposition in lungs, and concomitant infection.