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      Sources of isocyanic acid (HNCO) indoors: a focus on cigarette smoke

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          Abstract

          The sources and sinks of isocyanic acid (HNCO), a toxic gas, in indoor environments are largely uncharacterized.

          Abstract

          The sources and sinks of isocyanic acid (HNCO), a toxic gas, in indoor environments are largely uncharacterized. In particular, cigarette smoke has been identified as a significant source. In this study, controlled smoking of tobacco cigarettes was investigated in both an environmental chamber and a residence in Toronto, Canada using an acetate-CIMS. The HNCO emission ratio from side-stream cigarette smoke was determined to be 2.7 (±1.1) × 10 −3 ppb HNCO/ppb CO. Side-stream smoke from a single cigarette introduced a large pulse of HNCO to the indoor environment, increasing the HNCO mixing ratio by up to a factor of ten from background conditions of 0.15 ppb. Although there was no evidence for photochemical production of HNCO from cigarette smoke in the residence, it was observed in the environmental chamber via oxidation by the hydroxyl radical (1.1 × 10 7 molecules per cm 3), approximately doubling the HNCO mixing ratio after 30 minutes of oxidation. Oxidation of cigarette smoke by O 3 (15 ppb = 4.0 × 10 17 molecules per cm 3) and photo-reaction with indoor fluorescent lights did not produce HNCO. By studying the temporal profiles of both HNCO and CO after smoking, it is inferred that gas-to-surface partitioning of HNCO acts as an indoor loss pathway. Even in the absence of smoking, the indoor HNCO mixing ratios in the Toronto residence were elevated compared to concurrent outdoor measurements by approximately a factor of two.

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          Non-methane organic gas emissions from biomass burning: identification, quantification, and emission factors from PTR-ToF during the FIREX 2016 laboratory experiment

          Abstract. Volatile and intermediate-volatility non-methane organic gases (NMOGs) released from biomass burning were measured during laboratory-simulated wildfires by proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF). We identified NMOG contributors to more than 150 PTR ion masses using gas chromatography (GC) pre-separation with electron ionization, H 3 O + chemical ionization, and NO + chemical ionization, an extensive literature review, and time series correlation, providing higher certainty for ion identifications than has been previously available. Our interpretation of the PTR-ToF mass spectrum accounts for nearly 90 % of NMOG mass detected by PTR-ToF across all fuel types. The relative contributions of different NMOGs to individual exact ion masses are mostly similar across many fires and fuel types. The PTR-ToF measurements are compared to corresponding measurements from open-path Fourier transform infrared spectroscopy (OP-FTIR), broadband cavity-enhanced spectroscopy (ACES), and iodide ion chemical ionization mass spectrometry ( I − CIMS) where possible. The majority of comparisons have slopes near 1 and values of the linear correlation coefficient, R 2 , of > 0.8, including compounds that are not frequently reported by PTR-MS such as ammonia, hydrogen cyanide (HCN), nitrous acid (HONO), and propene. The exceptions include methylglyoxal and compounds that are known to be difficult to measure with one or more of the deployed instruments. The fire-integrated emission ratios to CO and emission factors of NMOGs from 18 fuel types are provided. Finally, we provide an overview of the chemical characteristics of detected species. Non-aromatic oxygenated compounds are the most abundant. Furans and aromatics, while less abundant, comprise a large portion of the OH reactivity. The OH reactivity, its major contributors, and the volatility distribution of emissions can change considerably over the course of a fire.
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            Chemical composition of tobacco and tobacco smoke

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              Biomass burning emissions and potential air quality impacts of volatile organic compounds and other trace gases from fuels common in the US

              Abstract. A comprehensive suite of instruments was used to quantify the emissions of over 200 organic gases, including methane and volatile organic compounds (VOCs), and 9 inorganic gases from 56 laboratory burns of 18 different biomass fuel types common in the southeastern, southwestern, or northern US. A gas chromatograph-mass spectrometry (GC-MS) instrument provided extensive chemical detail of discrete air samples collected during a laboratory burn and was complemented by real-time measurements of organic and inorganic species via an open-path Fourier transform infrared spectroscopy (OP-FTIR) instrument and three different chemical ionization-mass spectrometers. These measurements were conducted in February 2009 at the US Department of Agriculture's Fire Sciences Laboratory in Missoula, Montana and were used as the basis for a number of emission factors reported by Yokelson et al. (2013). The relative magnitude and composition of the gases emitted varied by individual fuel type and, more broadly, by the three geographic fuel regions being simulated. Discrete emission ratios relative to carbon monoxide (CO) were used to characterize the composition of gases emitted by mass; reactivity with the hydroxyl radical, OH; and potential secondary organic aerosol (SOA) precursors for the 3 different US fuel regions presented here. VOCs contributed less than 0.78 % ± 0.12 % of emissions by mole and less than 0.95 % × 0.07 % of emissions by mass (on average) due to the predominance of CO 2 , CO, CH 4 , and NO x emissions; however, VOCs contributed 70–90 (±16) % to OH reactivity and were the only measured gas-phase source of SOA precursors from combustion of biomass. Over 82 % of the VOC emissions by mole were unsaturated compounds including highly reactive alkenes and aromatics and photolabile oxygenated VOCs (OVOCs) such as formaldehyde. OVOCs contributed 57–68 % of the VOC mass emitted, 41–54 % of VOC-OH reactivity, and aromatic-OVOCs such as benzenediols, phenols, and benzaldehyde were the dominant potential SOA precursors. In addition, ambient air measurements of emissions from the Fourmile Canyon Fire that affected Boulder, Colorado in September 2010 allowed us to investigate biomass burning (BB) emissions in the presence of other VOC sources (i.e., urban and biogenic emissions) and identify several promising BB markers including benzofuran, 2-furaldehyde, 2-methylfuran, furan, and benzonitrile.
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                Author and article information

                Journal
                ESPICZ
                Environmental Science: Processes & Impacts
                Environ. Sci.: Processes Impacts
                Royal Society of Chemistry (RSC)
                2050-7887
                2050-7895
                August 14 2019
                2019
                : 21
                : 8
                : 1334-1341
                Affiliations
                [1 ]Department of Chemistry
                [2 ]University of Toronto
                [3 ]Toronto
                [4 ]Canada
                [5 ]Bucknell University
                [6 ]Lewisburg
                [7 ]USA
                [8 ]Department of Civil and Mineral Engineering
                Article
                10.1039/C9EM00107G
                2a3f85f5-c203-48de-bd86-5c02e94af932
                © 2019

                http://rsc.li/journals-terms-of-use

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