The composition of air-exposed surfaces can have a strong impact on air quality and chemical exposure in the indoor environment. Third hand smoke (THS), which includes surface-deposited cigarette smoke residue along with the collection of gases evolved from such residues, is becoming increasingly recognized as an important source of long-term tobacco smoke exposure. While studies have described gas/surface partitioning behaviour and some multiphase reaction systems involving THS, the possibility of time-dependent changes in chemical composition due to chemical reactivity that is endogenous to the deposited film has yet to be investigated. In this study, sidestream cigarette smoke was allowed to deposit on glass surfaces that were either clean or pre-coated with chemicals that may be oxidized by reactive oxygen species found in the smoke. Surface films included a low volatility antioxidant, tris(2-carboxyethyl)phosphine (TCEP), and two compounds relevant to surface films found within buildings, oleic acid (OA) and squalene (SQ). Upon deposition, oxidation products of nicotine, TCEP, OA, and SQ were formed over time periods of hours to weeks. The inherent oxidative potential of cigarette smoke deposited as a THS film can therefore initiate and sustain oxidation chemistry, transforming the chemical composition of surface films over long periods of time after initial smoke deposition. An interpretation of the THS oxidation results is provided in the context of other types of deposited particulate air pollutants with known oxidative potential that may be introduced to indoor environments. Continued study of THS and deposited surface films found indoors should consider the concept that chemical reservoirs found on surfaces may be reactive, that the chemical composition of indoor surface films may be time-dependent, and that the deposition of aerosol particles can act as a mechanism to initiate oxidation in surface films.
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Emerging investigator series: deposited particles and human lung lining fluid are dynamic, chemically-complex reservoirs leading to thirdhand smoke emissions and exposure
Thirdhand smoke (THS) persists in locations where smoking previously occurred and can be transported into non-smoking environments, leading to non-smoker exposure. Laboratory experiments using high-resolution mass spectrometry demonstrate that deposited particulate matter (PM) and smoke-exposed surrogate lung lining fluid (LLF) are substantial, chemically-complex reservoirs of gas-phase THS emissions, including hazardous air pollutants, polycyclic aromatic compounds, and nitrogen/oxygen-containing species. Both PM and LLF are persistent real-world THS reservoirs that chemically evolve over time, and can act as vehicles for the transport and emission of reactive pollutants and their reaction byproducts (e.g., acrolein). Deposited PM on clothes, furnishings, bodies, and/or airways will emit volatile to semi-volatile gases over long lifetimes, which can re-partition to other indoor materials and increase their overall persistence. On the other hand, LLF off-gassing consists predominantly of volatile organic compounds in amounts influenced by their aqueous solubilities, and their persistence in breath will be prolonged by re-distribution across internal aqueous reservoirs, as corroborated by multicompartment modeling in this study.
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- NSF-PAR ID:
- 10348417
- Date Published:
- Journal Name:
- Environmental Science: Atmospheres
- ISSN:
- 2634-3606
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract Many of the population centres in southeast Australia were swathed in bushfire smoke during the 2019–2020 austral summer. Bushfires burning during what is now known as the Black Summer was historically large and severe, and the fire season historically long. The chemical composition in the gas and aerosol phase of aged plumes measured near Wollongong, NSW in early 2020 is reported in this work. Enhancement ratios to carbon monoxide are presented for thirteen species (acetaldehyde, acetone, acetonitrile, black carbon aerosol, benzene, methane, methacrolein + methyl vinyl ketone, methyl ethyl ketone, methanol, ammonium ion PM1fraction, nitrate ion PM1fraction, organic PM1fraction and PM2.5). Observed plume composition is comparable to that measured in fresh smoke from Australian fires reported in the literature. Enhancements of biogenic volatile organic compounds such as isoprene (smoke-effected period mean 1 ppb, maximum 6 ppb) were observed along with elevated concentrations of particulate variables. Enhancement ratios reported here can be used in plume modelling of landscape-scale fires and assist in concentration estimates of infrequently measured atmospheric pollutants. The relative toxicological contribution of species present in the plumes was determined for plume exposure at the measurement site and for concentrated plumes at a population centre case study. Similar results were apparent at both locations. Contributions to the toxicological loading were dominated by respirable particles (~ 52–63% total contribution), formaldehyde (~ 30–39% total contribution) and acrolein. This is a reminder to consider the toxicological contributions in the gas phase when considering health impacts of population exposure to bushfire smoke.
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Sahar Zahiri (Ed.)more » « less
Sub-micron particles are ubiquitous in the indoor environment, especially during wildfire smoke episodes, and have a higher impact on human health than larger particles. Conventional fibrous air filters installed in heating, ventilation, and air conditioning (HVAC) systems play an important role in controlling indoor air quality by removing various air pollutants, including particulate matter (PM). However, it is evident that the removal efficiency of wildfire smoke PM and its effect on filter performance is significantly under-studied. This study delves into the size-specific removal efficiency of pine needle smoke, a representative of wildfire smoke and emissions. We test an array of filter media with minimum efficiency reporting values (MERV) spanning 11–15. Both size-resolved particle number concentrations and mass concentrations were measured using an Optical Particle Sizer (OPS, TSI, Inc.) and a Scanning Mobility Particle Sizer (SMPS, TSI, Inc.). Furthermore, we characterize the filter media morphology and smoke particles deposited on filter fibers using Scanning Electron Microscopy (SEM) to gain insights into the interaction dynamics of these particles. Our findings add to the comprehension of the relationship between MERV designations and smoke removal efficiency. Such insight can inform standards and guidelines and equip decision-makers with the knowledge needed to initiate measures for mitigating the impact of air pollution, specifically on the indoor environment.
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In 2019/2020, Australia experienced its largest wildfire season on record. Smoke covered hundreds of square kilometers across the southeastern coast and reached the site of the 2020 COALA (Characterizing Organics and Aerosol Loading over Australia) field campaign in New South Wales. Using a subset of nighttime observations made by a proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS), we calculate emission ratios (ERs) and factors (EFs) for 21 volatile organic compounds (VOCs). We restrict our analysis to VOCs with sufficiently high lifetimes to be minimally impacted by oxidation over the ~8 h between when the smoke was emitted and when it arrived at the field site. We use oxidized VOC to VOC ratios to assess the total amount of radical oxidation: maleic anhydride/furan to assess OH oxidation, and (cis-2-butenediol + furanone)/furan to assess NO3 oxidation. We compare ERs calculated from the freshest portion of the plume to ERs calculated using the entire nighttime period. Finding good agreement between the two, we are able to extend our analysis to VOCs measured in more chemically aged portions of the plume. Our analysis provides ERs and EFs for 9 compounds not previously reported for temperate forests in Australia: acrolein, pentanones/methylbutanal, methyl propanoate, methyl methacrylate, propene, maleic anhydride, benzaldehyde, methyl guaiacol, and methylbenzoic acid. We compare our results with two studies in similar Australian biomes, and two studies focused on US temperate forests. We find mixed agreement for EFs presented from previous studies of Australian wildfires, and generally good agreement with studies focused on fires in the Western US. This suggests that comprehensive field measurements of biomass burning VOC emissions in other regions may be applicable to Australian temperate forests.more » « less
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D1EA00107H
