Search

The House Observations of Microbial and Environmental Chemistry (HOMEChem) study is a collaborative field investigation designed to probe how everyday activities influence the emissions, chemical transformations and removal of trace gases and particles in indoor air. Sequential and layered experiments in a research house included cooking, cleaning, variable occupancy, and window-opening. This paper describes the overall design of HOMEChem and presents preliminary case studies investigating the concentrations of reactive trace gases, aerosol particles, and surface films. Cooking was a large source of VOCs, CO2, NOx, and particles. By number, cooking particles were predominantly in the ultrafine mode. Organic aerosol dominated the submicron mass, and, while variable between meals and throughout the cooking process, was dominated by components of hydrocarbon character and low oxygen content, similar to cooking oil. Air exchange in the house ensured that cooking particles were present for only short periods. During unoccupied background intervals, particle concentrations were lower indoors than outdoors. The cooling coils of the house ventilation system induced cyclic changes in water soluble gases. Even during unoccupied periods, concentrations of many organic trace gases were higher indoors than outdoors, consistent with housing materials being potential sources of these compounds to the outdoor environment. Organic material accumulated on indoor surfaces, and exhibited chemical signatures similar to indoor organic aerosol.

Gas-particle partitioning and hydrolysis of organic nitrates (ON) influences their role as sinks and sources of NOx and their effects on the formation of tropospheric ozone and organic aerosol (OA). Organic nitrates were formed from the photo-oxidation of α-pinene in environmental chamber experiments under varying conditions. A hydrolysis rate of 2 day-1 was found for particle-phase ONs at a relative humidity of 22% or higher; no significant ON hydrolysis was observed at lower relative humidity. The ON gas-particle partitioning is dependent on total OA concentration and temperature, consistent with absorptive partitioning theory. In a volatility basis set the ON partitioning is consistent with mass fractions of [0 0.19 0.29 0.52] at saturations mass concentrations (C*)of [1 10 100 1000] µgm-3. [ABSTRACT FROM AUTHOR]

Secondary organic aerosol (SOA) is transformed after its initial formation, but this chemical aging of SOA is poorly understood. Experiments were conducted in the Carnegie Mellon environmental chamber to form and transform SOA from the photo-oxidation of toluene and other small aromatic volatile organic compounds (VOCs) in the presence of NOx. The effects of chemical aging on organic aerosol (OA) composition, mass yield, volatility and hygroscopicity were explored. Higher exposure to the hydroxyl radical resulted in different OA composition, average carbon oxidation state (...) and mass yield. The OA oxidation state generally increased during photo-oxidation, and the final OA ... ranged from -0.29 to 0.45 in the performed experiments. The volatility of OA formed in these different experiments varied by as much as a factor of 30, demonstrating that the OA formed under different oxidizing conditions can have significantly different saturation concentration. There was no clear correlation between hygroscopicity and oxidation state for this relatively hygroscopic SOA. [ABSTRACT FROM AUTHOR]

Elemental compositions of organic aerosol (OA) particles provide useful constraints on OA sources, chemical evolution, and effects. The Aerodyne high-resolution time-of- flight aerosol mass spectrometer (HR-ToF-AMS) is widely used to measure OA elemental composition. This study evaluates AMS measurements of atomic oxygen-to- carbon (O : C), hydrogen-to-carbon (H : C), organic mass-to-organic carbon (OM : OC), and carbon oxidation state (...C) for a vastly expanded laboratory dataset of multifunctional oxidized OA standards. For the expanded standard dataset, the "Aiken-Explicit" method (Aiken et al., 2008), which uses experimentally measured ion intensities at all ions to determine elemental ratios, reproduces known molecular O:C and H:C ratio values within 20% (average absolute value of relative errors) and 12% respectively. The more commonly used "Aiken-Ambient" method, which uses empirically estimated H2O+ and CO+ ion intensities to avoid gas phase air interferences at these ions, reproduces O:C and H:C of multifunctional oxidized species within 28% and 14% of known values. These values are systematically biased low, however, with larger biases observed for alcohols and simple diacids. A detailed examination of the H2O+, CO+, and CO2+ fragments in the high-resolution mass spectra of the standard compounds indicates that the Aiken-Ambient method underestimates the CO+ and H2O+ produced from many oxidized species. Combined AMS-vacuum ultraviolet (VUV) ionization measurements indicate that these ions are produced by dehydration and decarboxylation on the AMS vaporizer (usually operated at 600 °C). Thermal decomposition is observed to be efficient at vaporizer temperatures down to 200 °C. These results are used together to develop an "Improved-Ambient" elemental analysis method for AMS spectra measured in air. The Improved-Ambient method reduces the systematic biases and reproduces O:C (H : C) ratios of individual oxidized standards within 28% (13 %) of the known molecular values. The error in Improved-Ambient O:C and H:C values is smaller (12% and 4% respectively) for synthetic mixtures of the oxidized organic standards, which are more representative of the complex mix of species present in ambient OA. For ambient OA, the Improved-Ambient method produces O:C (H : C) values that are 27% (11 %) larger than previously published Aiken-Ambient values; a corresponding increase of 9% is observed for OM:OC values. These results imply that ambient OA has a higher relative oxygen content than previously estimated. The ...C values calculated for ambient OA by the two methods agree well, however (average relative difference of 0.06 ...C units). This indicates that ...C is a more robust metric of oxidation than O:C, likely since ...C is not affected by hydration or dehydration, either in the atmosphere or during analysis. [ABSTRACT FROM AUTHOR]

Organic aerosols (OA) represent one of the major constituents of submicron particulate matter (PM1) and comprise a huge variety of compounds emitted by different sources. Three intensive measurement field campaigns to investigate the aerosol chemical composition all over Europe were carried out within the framework of EUCAARI and the intensive campaigns of EMEP during 2008 (May-June and September-October) and 2009 (February-March). In this paper we focus on the identification of the main organic aerosol sources and we propose a standardized methodology to perform source apportionment using positive matrix factorization (PMF) with the multilinear engine (ME-2) on Aerodyne aerosol mass spectrometer (AMS) data. Our source apportionment procedure is tested and applied on 25 datasets accounting for urban, rural, remote and high altitude sites and therefore it is likely suitable for the treatment of AMS-related ambient datasets. For most of the sites, four organic components are retrieved, improving significantly previous source apportionment results where only a separation in primary and secondary OA sources was possible. Our solutions include two primary OA sources, i.e. hydrocarbon-like OA (HOA) and biomass burning OA (BBOA) and two secondary OA components, i.e. semi-volatile oxygenated OA (SV-OOA) and low-volatility oxygenated OA (LV-OOA). For specific sites cooking-related (COA) and marine-related sources (MSA) are also separated. Finally, our work provides a large overview of organic aerosol sources in Europe and an interesting set of highly time resolved data for modeling evaluation purposes. [ABSTRACT FROM AUTHOR]

Simulation of secondary organic aerosol (SOA) in models has been an uncertain component in determining the impacts of atmospheric aerosols on air quality and climate. Recent studies have shown that reactive chlorine can rapidly oxidize volatile organic compounds (VOCs), trigger SOA formation, and alter other oxidants, thus having a potentially significant effect on SOA, which has not been thoroughly investigated at the global scale. Here, we developed a chlorine-SOA simulation within a global chemical transport model along with updated anthropogenic continental chlorine emissions. Our simulations demonstrate that chlorine chemistry increases the annual mean boundary layer SOA by 5-12% over most continents while decreasing SOA by 5-11% over northern Atlantic and Pacific oceans, which are in the right direction to narrow existing discrepancies between models and observations. Notably, sensitivity simulations in China with observed high chlorine levels capture the temporal variations of both observed fine Cl - and organic aerosol, showing an increase in SOA by more than 100%. Our study also reveals that polluted regions, which have ample emissions of both chlorine species and VOCs, exhibit potential chlorinated SOA, which are commonly toxic, contributing up to 15% to total SOA.

A rise in the disinfection of spaces occurred as a result of the COVID-19 pandemic as well as an increase in people wearing facial coverings. Hydrogen peroxide was among the recommended disinfectants for use against the virus. Previous studies have investigated the emissions of hydrogen peroxide associated with the disinfection of spaces and masks; however, those studies did not focus on the emitted byproducts from these processes. Here, we simulate the disinfection of an indoor space with H 2 O 2 while a person wearing a face mask is present in the space by using an environmental chamber with a thermal manikin wearing a face mask over its breathing zone. We injected hydrogen peroxide to disinfect the space and utilized a chemical ionization mass spectrometer (CIMS) to measure the primary disinfectant (H 2 O 2 ) and a Vocus proton transfer reaction time-of-flight mass spectrometer (Vocus PTR-ToF-MS) to measure the byproducts from disinfection, comparing concentrations inside the chamber and behind the mask. Concentrations of the primary disinfectant and the byproducts inside the chamber and behind the mask remained elevated above background levels for 2-4 h after disinfection, indicating the possibility of extended exposure, especially when continuing to wear the mask. Overall, our results point toward the time-dependent impact of masks on concentrations of disinfectants and their byproducts and a need for regular mask change following exposure to high concentrations of chemical compounds., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Growth in unconventional oil and gas development (UOGD) in the United States has increased airborne emissions, raising environmental and human health concerns. To assess the potential impacts on air quality, we deployed instrumentation in Karnes City, Texas, a rural area in the middle of the Eagle Ford Shale. We measured several episodes of elevated Cl 2 levels, reaching maximum hourly averages of 800 ppt, the highest inland Cl 2 concentration reported to date. Concentrations peak during the day, suggesting a strong local source (given the short photolysis lifetime of Cl 2 ) and/or a photoinitiated production mechanism. Well preproduction activity near the measurement site is a plausible source of these high Cl 2 levels via direct emission and photoactive chemistry. ClNO 2 is also observed, but it peaks overnight, consistent with well-known nocturnal formation processes. Observations of organochlorines in the gas and particle phases reflect the contribution of chlorine chemistry to the formation of secondary pollutants in the area. Box modeling results suggest that the formation of ozone at this location is influenced by chlorine chemistry. These results suggest that UOGD can be an important source of reactive chlorine in the atmosphere, impacting radical budgets and the formation of secondary pollutants in these regions.

The development of chemopreventive strategies with the ability to prevent the progression of lung lesions to malignant cancers would reduce the mortality and morbidity resulting from this deadly disease. Delivery of microRNA (miRNA) by inhalation is a novel method for lung cancer prevention. In this study, we investigated the combined efficacy of aerosolized miR-138-5p and miR-200c miRNA mimics in lung cancer prevention. Combination of the two miRNAs inhibited Benzo(a)pyrene (B((a))P)-induced lung adenomas and N-nitroso-tris-chloroethylurea (NTCU)-induced lung squamous cell carcinomas with no detectable side effects. Using single-cell RNA sequencing (scRNA-seq) and imaging mass cytometry (IMC), we found that both miRNAs inhibited programmed cell death ligand 1 (PD-L1) expression. Our flow cytometry results showed that aerosolized delivery of combined miRNAs increased CD4+ and CD8+ T cells and reduced the expression of programmed cell death protein 1 (PD-1) and T-regulatory cells. Our results demonstrated that the delivery of aerosolized microRNAs targeting PD-L1 can be highly effective in preventing lung cancer development and progression in mice., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2023 Zhang, Pan, Xiong, Zheng, McPherson, Lee, Huang, Xu, Chen, Wang, Hildebrandt Ruiz and You.)

Atmospheric simulation chambers continue to be indispensable tools for research in the atmospheric sciences. Insights from chamber studies are integrated into atmospheric chemical transport models, which are used for science-informed policy decisions. However, a centralized data management and access infrastructure for their scientific products had not been available in the United States and many parts of the world. ICARUS (Integrated Chamber Atmospheric data Repository for Unified Science) is an open access, searchable, web-based infrastructure for storing, sharing, discovering, and utilizing atmospheric chamber data [https://icarus.ucdavis.edu]. ICARUS has two parts: a data intake portal and a search and discovery portal. Data in ICARUS are curated, uniform, interactive, indexed on popular search engines, mirrored by other repositories, version-tracked, vocabulary-controlled, and citable. ICARUS hosts both legacy data and new data in compliance with open access data mandates. Targeted data discovery is available based on key experimental parameters, including organic reactants and mixtures that are managed using the PubChem chemical database, oxidant information, nitrogen oxide (NOx) content, alkylperoxy radical (RO 2 ) fate, seed particle information, environmental conditions, and reaction categories. A discipline-specific repository such as ICARUS with high amounts of metadata works to support the evaluation and revision of atmospheric model mechanisms, intercomparison of data and models, and the development of new model frameworks that can have more predictive power in the current and future atmosphere. The open accessibility and interactive nature of ICARUS data may also be useful for teaching, data mining, and training machine learning models., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Mask wearing and bleach disinfectants became commonplace during the COVID-19 pandemic. Bleach generates toxic species including hypochlorous acid (HOCl), chlorine (Cl 2 ), and chloramines. Their reaction with organic species can generate additional toxic compounds. To understand interactions between masks and bleach disinfection, bleach was injected into a ventilated chamber containing a manikin with a breathing system and wearing a surgical or KN95 mask. Concentrations inside the chamber and behind the mask were measured by a chemical ionization mass spectrometer (CIMS) and a Vocus proton transfer reaction mass spectrometer (Vocus PTRMS). HOCl, Cl 2 , and chloramines were observed during disinfection and concentrations inside the chamber are 2-20 times greater than those behind the mask, driven by losses to the mask surface. After bleach injection, many species decay more slowly behind the mask by a factor of 0.5-0.7 as they desorb or form on the mask. Mass transfer modeling confirms the transition of the mask from a sink during disinfection to a source persisting >4 h after disinfection. Humidifying the mask increases reactive formation of chloramines, likely related to uptake of ammonia and HOCl. These experiments indicate that masks are a source of chemical exposure after cleaning events occur.

The hydroxyl radical (OH) is the dominant oxidant in the outdoor environment, controlling the lifetimes of volatile organic compounds (VOCs) and contributing to the growth of secondary organic aerosols. Despite its importance outdoors, there have been relatively few measurements of the OH radical in indoor environments. During the House Observations of Microbial and Environmental Chemistry (HOMEChem) campaign, elevated concentrations of OH were observed near a window during cooking events, in addition to elevated mixing ratios of nitrous acid (HONO), VOCs, and nitrogen oxides (NO X ). Particularly high concentrations were measured during the preparation of a traditional American Thanksgiving dinner, which required the use of a gas stove and oven almost continually for 6 h. A zero-dimensional chemical model underpredicted the measured OH concentrations even during periods when direct sunlight illuminated the area near the window, which increases the rate of OH production by photolysis of HONO. Interferences with measurements of nitrogen dioxide (NO 2 ) and ozone (O 3 ) suggest that unmeasured photolytic VOCs were emitted during cooking events. The addition of a VOC that photolyzes to produce peroxy radicals (RO 2 ), similar to pyruvic acid, into the model results in better agreement with the OH measurements. These results highlight our incomplete understanding of the nature of oxidation in indoor environments.

Fine particulate matter (PM 2.5 ) is a key indicator of urban air quality. Secondary organic aerosol (SOA) contributes substantially to the PM 2.5 concentration. Discrepancies between modeling and field measurements of SOA indicate missing sources and formation mechanisms. Recent studies report elevated concentrations of reactive chlorine species in inland and urban regions, which increase the oxidative capacity of the atmosphere and serve as sources for SOA and particulate chlorides. Chlorine-initiated oxidation of isoprene, the most abundant nonmethane hydrocarbon, is known to produce SOA under pristine conditions, but the effects of anthropogenic influences in the form of nitrogen oxides (NO x ) remain unexplored. Here, we investigate chlorine-isoprene reactions under low- and high-NO x conditions inside an environmental chamber. Organic chlorides including C 5 H 11 ClO 3 , C 5 H 9 ClO 3 , and C 5 H 9 ClO 4 are observed as major gas- and particle-phase products. Modeling and experimental results show that the secondary OH-isoprene chemistry is significantly enhanced under high-NO x conditions, accounting for up to 40% of all isoprene oxidized and leading to the suppression of organic chloride formation. Chlorine-initiated oxidation of isoprene could serve as a source for multifunctional (chlorinated) organic oxidation products and SOA in both pristine and anthropogenically influenced environments.

The interaction between water vapor and atmospheric aerosol leads to enhancement in aerosol water content, which facilitates haze development, but its concentrations, sources, and impacts remain largely unknown in polluted urban environments. Here, we show that the Indian capital, Delhi, which tops the list of polluted capital cities, also experiences the highest aerosol water yet reported worldwide. This high aerosol water promotes secondary formation of aerosols and worsens air pollution. We report that severe pollution events are commonly associated with high aerosol water which enhances light scattering and reduces visibility by 70%. Strong light scattering also suppresses the boundary layer height on winter mornings in Delhi, inhibiting dispersal of pollutants and further exacerbating morning pollution peaks. We provide evidence that ammonium chloride is the largest contributor to aerosol water in Delhi, making up 40% on average, and we highlight that regulation of chlorine-containing precursors should be considered in mitigation strategies.

During the summer months, urban areas are literal hot spots of mosquito-borne disease transmission and air pollution. Public health authorities release aerosolized pesticides directly into the atmosphere to help control adult mosquito populations and thereby reduce the threat of diseases, such as Zika Virus. The primary adulticides (i.e. pesticides used to control adult mosquito populations) in Houston, TX are permethrin and malathion. These adulticides are typically sprayed at night using ultra-low volume sprayers. Particulate matter (PM) samples including total suspended and fine PM (PM < 2.5 μm in aerodynamic diameter) were collected at four ground-based sites across Houston in 2013 and include daytime, nighttime, and 24 h samples. Malathion is initially sprayed as coarse aerosol (5-25 μm), but is measured in fine aerosol (<2.5 μm) and coarse aerosol in the urban atmosphere. Particle size is relevant both for deposition velocities and for human exposure. Atmospheric permethrin concentrations measured in nighttime samples peak at 60 ng m -3 , while malathion nighttime concentrations peak near 40 ng m -3 . Malaoxon, an oxidation product of malathion, was also frequently detected at concentrations >10 ng m -3 , indicating significant nighttime oxidation. Based on the loss of malathion and the increase in malaoxon, the atmospheric half-life of malathion in Houston was estimated at <12 h, which was significantly shorter than previous half-life estimates (∼days). Importantly, malaoxon is estimated to be 22-33 times more toxic to humans than malathion. Both the aerosol size and the half-life are critical for mosquito control, human exposure, and risk assessment of these routine pesticides., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

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., (© 2020 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.)

Formaldehyde is an environmental and occupational chemical carcinogen implicated in the damage of proteins and nucleic acids. However, whether formaldehyde provokes modifications of RNAs such as 8-oxo-7,8-dihydroguanine (8-oxoG) and the role that these modifications play on conferring long-term adverse health effects remains unexplored. Here, we profile 8-oxoG modifications using RNA-immunoprecipitation and RNA sequencing (8-oxoG RIP-seq) to identify 343 RNA transcripts heavily enriched in oxidations in human bronchial epithelial BEAS-2B cell cultures exposed to 1 ppm formaldehyde for 2 h. RNA oxidation altered expression of many transcripts involved in chromatin modification and p53-mediated DNA-damage responses, two pathways that play key roles in sustaining genome integrity and typically deregulated in tumorigenesis. Given that these observations were identified in normal cells exhibiting minimal cell stress and death phenotypes (for example, lack of nuclear shrinkage, F-actin alterations or increased LDH activity); we hypothesize that oxidative modification of specific RNA transcripts following formaldehyde exposure denotes an early process occurring in carcinogenesis analogous to the oxidative events surfacing at early stages of neurodegenerative diseases. As such, we provide initial investigations of RNA oxidation as a potentially novel mechanism underlying formaldehyde-induced tumorigenesis.

The impact of environmentally-induced chemical changes in RNA has been fairly unexplored. Air pollution induces oxidative modifications such as 8-oxo-7,8-dihydroguanine (8-oxoG) in RNAs of lung cells, which could be associated with premature lung dysfunction. We develop a method for 8-oxoG profiling using immunocapturing and RNA sequencing. We find 42 oxidized transcripts in bronchial epithelial BEAS-2B cells exposed to two air pollution mixtures that recreate urban atmospheres. We show that the FDFT1 transcript in the cholesterol biosynthesis pathway is susceptible to air pollution-induced oxidation. This process leads to decreased transcript and protein expression of FDFT1, and reduced cholesterol synthesis in cells exposed to air pollution. Knockdown of FDFT1 replicates alterations seen in air pollution exposure such as transformed cell size and suppressed cytoskeleton organization. Our results argue of a possible novel biomarker and of an unseen mechanism by which air pollution selectively modifies key metabolic-related transcripts facilitating cell phenotypes in bronchial dysfunction.

We evaluate the one-dimensional volatility basis set (1D-VBS) and two-dimensional volatility basis set (2D-VBS) in simulating the aging of SOA derived from toluene and α-pinene against smog-chamber experiments. If we simulate the first-generation products with empirical chamber fits and the subsequent aging chemistry with a 1D-VBS or a 2D-VBS, the models mostly overestimate the SOA concentrations in the toluene oxidation experiments. This is because the empirical chamber fits include both first-generation oxidation and aging; simulating aging in addition to this results in double counting of the initial aging effects. If the first-generation oxidation is treated explicitly, the base-case 2D-VBS underestimates the SOA concentrations and O:C increase of the toluene oxidation experiments; it generally underestimates the SOA concentrations and overestimates the O:C increase of the α-pinene experiments. With the first-generation oxidation treated explicitly, we could modify the 2D-VBS configuration individually for toluene and α-pinene to achieve good model-measurement agreement. However, we are unable to simulate the oxidation of both toluene and α-pinene with the same 2D-VBS configuration. We suggest that future models should implement parallel layers for anthropogenic (aromatic) and biogenic precursors, and that more modeling studies and laboratory research be done to optimize the "best-guess" parameters for each layer.