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1.
Artículo en Inglés | MEDLINE | ID: mdl-38953218

RESUMEN

The Chemical Assessment of Surfaces and Air (CASA) study aimed to understand how chemicals transform in the indoor environment using perturbations (e.g., cooking, cleaning) or additions of indoor and outdoor pollutants in a well-controlled test house. Chemical additions ranged from individual compounds (e.g., gaseous ammonia or ozone) to more complex mixtures (e.g., a wildfire smoke proxy and a commercial pesticide). Physical perturbations included varying temperature, ventilation rates, and relative humidity. The objectives for CASA included understanding (i) how outdoor air pollution impacts indoor air chemistry, (ii) how wildfire smoke transports and transforms indoors, (iii) how gases and particles interact with building surfaces, and (iv) how indoor environmental conditions impact indoor chemistry. Further, the combined measurements under unperturbed and experimental conditions enable investigation of mitigation strategies following outdoor and indoor air pollution events. A comprehensive suite of instruments measured different chemical components in the gas, particle, and surface phases throughout the study. We provide an overview of the test house, instrumentation, experimental design, and initial observations - including the role of humidity in controlling the air concentrations of many semi-volatile organic compounds, the potential for ozone to generate indoor nitrogen pentoxide (N2O5), the differences in microbial composition between the test house and other occupied buildings, and the complexity of deposited particles and gases on different indoor surfaces.

2.
ACS EST Air ; 1(6): 511-524, 2024 Jun 14.
Artículo en Inglés | MEDLINE | ID: mdl-38884193

RESUMEN

Secondary organic aerosol (SOA) from acid-driven reactive uptake of isoprene epoxydiols (IEPOX) contributes up to 40% of organic aerosol (OA) mass in fine particulate matter. Previous work showed that IEPOX substantially converts particulate inorganic sulfates to surface-active organosulfates (OSs). This decreases aerosol acidity and creates a viscous organic-rich shell that poses as a diffusion barrier, inhibiting additional reactive uptake of IEPOX. To account for this "self-limiting" effect, we developed a phase-separation box model to evaluate parameterizations of IEPOX reactive uptake against time-resolved chamber measurements of IEPOX-SOA tracers, including 2-methyltetrols (2-MT) and methyltetrol sulfates (MTS), at ~ 50% relative humidity. The phase-separation model was most sensitive to the mass accommodation coefficient, IEPOX diffusivity in the organic shell, and ratio of the third-order reaction rate constants forming 2-MT and MTS ( k M T / k M T S ). In particular, k M T / k M T S had to be lower than 0.1 to bring model predictions of 2-MT and MTS in closer agreement with chamber measurements; prior studies reported values larger than 0.71. The model-derived rate constants favor more particulate MTS formation due to 2-MT likely off-gassing at ambient-relevant OA loadings. Incorporating this parametrization into chemical transport models is expected to predict lower IEPOX-SOA mass and volatility due to the predominance of OSs.

3.
Environ Sci Technol ; 58(24): 10675-10684, 2024 Jun 18.
Artículo en Inglés | MEDLINE | ID: mdl-38843196

RESUMEN

Isoprene has the highest atmospheric emissions of any nonmethane hydrocarbon, and isoprene epoxydiols (IEPOX) are well-established oxidation products and the primary contributors forming isoprene-derived secondary organic aerosol (SOA). Highly acidic particles (pH 0-3) widespread across the lower troposphere enable acid-driven multiphase chemistry of IEPOX, such as epoxide ring-opening reactions forming methyltetrol sulfates through nucleophilic attack of sulfate (SO42-). Herein, we systematically demonstrate an unexpected decrease in SOA formation from IEPOX on highly acidic particles (pH < 1). While IEPOX-SOA formation is commonly assumed to increase at low pH when more [H+] is available to protonate epoxides, we observe maximum SOA formation at pH 1 and less SOA formation at pH 0.0 and 0.4. This is attributed to limited availability of SO42- at pH values below the acid dissociation constant (pKa) of SO42- and bisulfate (HSO4-). The nucleophilicity of HSO4- is 100× lower than SO42-, decreasing SOA formation and shifting particulate products from low-volatility organosulfates to higher-volatility polyols. Current model parameterizations predicting SOA yields for IEPOX-SOA do not properly account for the SO42-/HSO4- equilibrium, leading to overpredictions of SOA formation at low pH. Accounting for this underexplored acidity-dependent behavior is critical for accurately predicting SOA concentrations and resolving SOA impacts on air quality.


Asunto(s)
Aerosoles , Compuestos Epoxi/química , Concentración de Iones de Hidrógeno , Equilibrio Ácido-Base
4.
Analyst ; 149(12): 3405-3415, 2024 Jun 10.
Artículo en Inglés | MEDLINE | ID: mdl-38712891

RESUMEN

Per- and polyfluoroalkyl substances (PFAS) are manufactured chemicals that have been detected across the globe. Fluorotelomer alcohols (FTOHs) are one PFAS class commonly found in indoor air due to emissions from consumer products (e.g., textiles and food packaging) and are human metabolic, atmospheric oxidative, and industrial precursors of perfluoroalkyl carboxylic acids (PFCAs). We developed a quantitative method for real-time analysis of gas-phase FTOHs, perfluoroalkyl acids (PFCAs and GenX), one perfluorooctane sulfonamide (EtFOSA), one fluorotelomer diol (FTdiOH), and one fluorinated ether (E2) using high-resolution time-of-flight chemical ionization mass spectrometry equipped with iodide reagent ion chemistry (I-HR-ToF-CIMS). Herein, we present a direct liquid injection method for external calibration, providing detection limits of 0.19-3.1 pptv for 3 s averaging and 0.02-0.44 pptv for 120 s averaging, with the exception of E2, which had detection limits of 1700 and 220 pptv for 3- and 120 s averaging, respectively. These calibrations enabled real-time gas-phase quantification of 6 : 2 FTOH in room air while microwaving popcorn, with an average peak air concentration of 31.6 ± 4.5 pptv measured 2 meters from a closed microwave. Additionally, 8 : 2 and 10 : 2 FTOH concentrations in indoor air were measured in the presence and absence of a rain jacket, with observed peak concentrations of 110 and 25 pptv, respectively. Our work demonstrates the ability of I-HR-ToF-CIMS to provide real-time air measurements of PFAS relevant to indoor human exposure settings and allow for PFAS source identification. We expect that real-time quantification of other gas-phase PFAS classes is possible, enabling advances in understanding PFAS sources, chemistry, and partitioning.

5.
Ann Am Thorac Soc ; 21(3): 365-376, 2024 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-38426826

RESUMEN

Indoor sources of air pollution worsen indoor and outdoor air quality. Thus, identifying and reducing indoor pollutant sources would decrease both indoor and outdoor air pollution, benefit public health, and help address the climate crisis. As outdoor sources come under regulatory control, unregulated indoor sources become a rising percentage of the problem. This American Thoracic Society workshop was convened in 2022 to evaluate this increasing proportion of indoor contributions to outdoor air quality. The workshop was conducted by physicians and scientists, including atmospheric and aerosol scientists, environmental engineers, toxicologists, epidemiologists, regulatory policy experts, and pediatric and adult pulmonologists. Presentations and discussion sessions were centered on 1) the generation and migration of pollutants from indoors to outdoors, 2) the sources and circumstances representing the greatest threat, and 3) effective remedies to reduce the health burden of indoor sources of air pollution. The scope of the workshop was residential and commercial sources of indoor air pollution in the United States. Topics included wood burning, natural gas, cooking, evaporative volatile organic compounds, source apportionment, and regulatory policy. The workshop concluded that indoor sources of air pollution are significant contributors to outdoor air quality and that source control and filtration are the most effective measures to reduce indoor contributions to outdoor air. Interventions should prioritize environmental justice: Households of lower socioeconomic status have higher concentrations of indoor air pollutants from both indoor and outdoor sources. We identify research priorities, potential health benefits, and mitigation actions to consider (e.g., switching from natural gas to electric stoves and transitioning to scent-free consumer products). The workshop committee emphasizes the benefits of combustion-free homes and businesses and recommends economic, legislative, and education strategies aimed at achieving this goal.


Asunto(s)
Contaminantes Atmosféricos , Contaminación del Aire Interior , Contaminación del Aire , Humanos , Niño , Estados Unidos , Contaminación del Aire Interior/efectos adversos , Contaminación del Aire Interior/prevención & control , Contaminación del Aire Interior/análisis , Gas Natural , Monitoreo del Ambiente , Contaminación del Aire/efectos adversos , Contaminación del Aire/prevención & control , Contaminación del Aire/análisis , Contaminantes Atmosféricos/efectos adversos , Contaminantes Atmosféricos/análisis , Material Particulado/análisis
6.
Environ Sci Technol ; 58(9): 4268-4280, 2024 Mar 05.
Artículo en Inglés | MEDLINE | ID: mdl-38393751

RESUMEN

Sub-Saharan Africa is a hotspot for biomass burning (BB)-derived carbonaceous aerosols, including light-absorbing organic (brown) carbon (BrC). However, the chemically complex nature of BrC in BB aerosols from this region is not fully understood. We generated smoke in a chamber through smoldering combustion of common sub-Saharan African biomass fuels (hardwoods, cow dung, savanna grass, and leaves). We quantified aethalometer-based, real-time light-absorption properties of BrC-containing organic-rich BB aerosols, accounting for variations in wavelength, fuel type, relative humidity, and photochemical aging conditions. In filter samples collected from the chamber and Botswana in the winter, we identified 182 BrC species, classified into lignin pyrolysis products, nitroaromatics, coumarins, stilbenes, and flavonoids. Using an extensive set of standards, we determined species-specific mass and emission factors. Our analysis revealed a linear relationship between the combined BrC species contribution to chamber-measured BB aerosol mass (0.4-14%) and the mass-absorption cross-section at 370 nm (0.2-2.2 m2 g-1). Hierarchical clustering resolved key molecular-level components from the BrC matrix, with photochemically aged emissions from leaf and cow-dung burning showing BrC fingerprints similar to those found in Botswana aerosols. These quantitative findings could potentially help refine climate model predictions, aid in source apportionment, and inform effective air quality management policies for human health and the global climate.


Asunto(s)
Contaminantes Atmosféricos , Contaminación del Aire , Humanos , Anciano , Carbono , Biomasa , Monitoreo del Ambiente , Contaminación del Aire/análisis , Aerosoles/análisis , Contaminantes Atmosféricos/análisis , Material Particulado/análisis
7.
Chem Res Toxicol ; 36(11): 1814-1825, 2023 11 20.
Artículo en Inglés | MEDLINE | ID: mdl-37906555

RESUMEN

Hydroxyl radical (·OH)-initiated oxidation of isoprene, the most abundant nonmethane hydrocarbon in the atmosphere, is responsible for substantial amounts of secondary organic aerosol (SOA) within ambient fine particles. Fine particulate 2-methyltetrol sulfate diastereoisomers (2-MTSs) are abundant SOA products formed via acid-catalyzed multiphase chemistry of isoprene-derived epoxydiols with inorganic sulfate aerosols under low-nitric oxide conditions. We recently demonstrated that heterogeneous ·OH oxidation of particulate 2-MTSs leads to the particle-phase formation of multifunctional organosulfates (OSs). However, it remains uncertain if atmospheric chemical aging of particulate 2-MTSs induces toxic effects within human lung cells. We show that inhibitory concentration-50 (IC50) values decreased from exposure to fine particulate 2-MTSs that were heterogeneously aged for 0 to 22 days by ·OH, indicating increased particulate toxicity in BEAS-2B lung cells. Lung cells further exhibited concentration-dependent modulation of oxidative stress- and inflammatory-related gene expression. Principal component analysis was carried out on the chemical mixtures and revealed positive correlations between exposure to aged multifunctional OSs and altered expression of targeted genes. Exposure to particulate 2-MTSs alone was associated with an altered expression of antireactive oxygen species (ROS)-related genes (NQO-1, SOD-2, and CAT) indicative of a response to ROS in the cells. Increased aging of particulate 2-MTSs by ·OH exposure was associated with an increased expression of glutathione pathway-related genes (GCLM and GCLC) and an anti-inflammatory gene (IL-10).


Asunto(s)
Butadienos , Estrés Oxidativo , Humanos , Anciano , Especies Reactivas de Oxígeno , Oxidación-Reducción , Butadienos/toxicidad
8.
Sci Adv ; 9(41): eadh8263, 2023 10 13.
Artículo en Inglés | MEDLINE | ID: mdl-37831770

RESUMEN

Wildfires are increasing in frequency, raising concerns that smoke can permeate indoor environments and expose people to chemical air contaminants. To study smoke transformations in indoor environments and evaluate mitigation strategies, we added smoke to a test house. Many volatile organic compounds (VOCs) persisted days following the smoke injection, providing a longer-term exposure pathway for humans. Two time scales control smoke VOC partitioning: a faster one (1.0 to 5.2 hours) that describes the time to reach equilibrium between adsorption and desorption processes and a slower one (4.8 to 21.2 hours) that describes the time for indoor ventilation to overtake adsorption-desorption equilibria in controlling the air concentration. These rates imply that vapor pressure controls partitioning behavior and that house ventilation plays a minor role in removing smoke VOCs. However, surface cleaning activities (vacuuming, mopping, and dusting) physically removed surface reservoirs and thus reduced indoor smoke VOC concentrations more effectively than portable air cleaners and more persistently than window opening.


Asunto(s)
Contaminación del Aire Interior , Compuestos Orgánicos Volátiles , Humanos , Compuestos Orgánicos Volátiles/análisis , Humo , Monitoreo del Ambiente
9.
Environ Sci Technol ; 57(40): 15173-15183, 2023 Oct 10.
Artículo en Inglés | MEDLINE | ID: mdl-37757488

RESUMEN

Partitioning of per- and polyfluoroalkyl substances (PFAS) to indoor materials, including clothing, may prolong the residence time of PFAS indoors and contribute to exposure. During the Indoor PFAS Assessment (IPA) Campaign, we measured concentrations of nine neutral PFAS in air and cotton cloth in 11 homes in North Carolina, for up to 9 months. Fluorotelomer alcohols (i.e., 6:2 FTOH, 8:2 FTOH, and 10:2 FTOH) are the dominant target species in indoor air, with concentrations ranging from 1.8 to 49 ng m-3, 1.2 to 53 ng m-3, and 0.21 to 5.7 ng m-3, respectively. In cloth, perfluorooctane sulfonamidoethanols (i.e., MeFOSE and EtFOSE) accumulated most significantly over time, reaching concentrations of up to 0.26 ng cm-2 and 0.24 ng cm-2, respectively. From paired measurements of neutral PFAS in air and suspended cloth, we derived cloth-air partition coefficients (Kca) for 6:2, 8:2, and 10:2 FTOH; ethylperfluorooctane sulfonamide (EtFOSA); MeFOSE; and EtFOSE. Mean log(Kca) values range from 4.7 to 6.6 and are positively correlated with the octanol-air partition coefficient. We investigated the effect of the cloth storage method on PFAS accumulation and the influence of home characteristics on air concentrations. Temperature had the overall greatest effect. This study provides valuable insights into PFAS distribution, fate, and exposure indoors.


Asunto(s)
Contaminantes Atmosféricos , Fluorocarburos , Monitoreo del Ambiente , North Carolina , Contaminantes Atmosféricos/análisis , Fluorocarburos/análisis
10.
Environ Sci Process Impacts ; 25(6): 1031-1048, 2023 Jun 21.
Artículo en Inglés | MEDLINE | ID: mdl-37166155

RESUMEN

Humidity plays an important role in the surface removal and concentrations of indoor pollutants such as ozone; however, the indoor surface dynamics and chemistry of organic peroxides is largely unknown. Organic hydroperoxides (ROOHs) are known to participate in the multiphase chemistry of outdoor aerosols and clouds, suggesting that reactive uptake in condensed grime on indoor surfaces is plausible, particularly in humid homes. Here, the effect of relative humidity (RH) on the deposition velocity (vd) and reaction probability (γ) of a model ROOH to naturally soiled indoor glass surfaces was investigated; specifically, by using authentic isoprene hydroxy hydroperoxide (1,2-ISOPOOH) as the model compound. Glass was soiled in 3 local homes for 1+ years and characterized. The removal of ISOPOOH by soiled and clean glass was measured under 5-6%, 56-58%, and 83-84% RH conditions using a novel flow reactor designed for indoor surfaces coupled to an iodide chemical ionization high-resolution time-of-flight mass spectrometer (I-HR-TOF-CIMS). The vd and γ increased with increasing RH, ranging from 0.001-0.059 cm s-1 and 0.4-4.6 (×10-6), respectively, on soiled glass surfaces. The vd and γ ranged from only 0.001-0.016 cm s-1 and 0.1-0.8 (×10-6), respectively, across RH conditions on clean glass, demonstrating a greater RH effect on soiled materials than clean. Loss rates calculated under humid conditions to soiled glass (∼1-6 h-1) were competitive in scale with ventilation rates in typical residences, indicating the importance of surface uptake for indoor ROOH concentrations. This work provides parameters for predictive modeling of indoor ROOHs. To our knowledge, these are the first direct measurements of the vd of an ROOH to naturally soiled indoor surfaces.


Asunto(s)
Contaminantes Atmosféricos , Contaminación del Aire Interior , Ozono , Contaminantes Atmosféricos/análisis , Peróxidos , Humedad , Ozono/química , Contaminación del Aire Interior/análisis
11.
Chemosphere ; 315: 137722, 2023 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-36592832

RESUMEN

While high-resolution MS (HRMS) can be used for identification and quantification of novel per- and polyfluorinated alkyl substances (PFAS), low-resolution MS/MS is the more commonly used and affordable approach for routine PFAS monitoring. Of note, perfluoropentanoic acid (PFPeA) and perfluorobutanoic acid (PFBA), two of the smaller carboxylic acid containing-PFAS, have only one major MS/MS transition, preventing the use of qualitative transitions for verification on low-resolution instrumentation. Recently our lab has observed widespread chemical interference in the quantitative ion channel for PFPeA (263 â†’ 219) and PFBA (213 â†’ 169) in numerous matrices. PFPeA interference was investigated using HRMS and putatively assigned as a diprotic unsaturated fatty acid (263.1288 Da) in shellfish and a separate interferent (13C isotope of 262.1087 Da) in hot cocoa, which had been previously described by the FDA. PFBA interference caused by saturated oxo-fatty acids, previously demonstrated in tissue, was also observed in liquid condensate from a residential air conditioning unit. Therefore, in support of PFAS analysis on low-resolution instrumentation, authors recommend several adjustments to analytical methods including altering liquid chromatography (LC) conditions as well as using matched internal standards to investigate and expressly confirm PFBA and PFPeA detections in both biological and environmental samples.


Asunto(s)
Fluorocarburos , Espectrometría de Masas en Tándem , Cromatografía Liquida , Fluorocarburos/análisis , Ácidos Grasos
12.
Environ Sci Technol ; 56(23): 16611-16620, 2022 12 06.
Artículo en Inglés | MEDLINE | ID: mdl-36378716

RESUMEN

Acid-driven multiphase chemistry of isoprene epoxydiols (IEPOX) with inorganic sulfate aerosols contributes substantially to secondary organic aerosol (SOA) formation, which constitutes a large mass fraction of atmospheric fine particulate matter (PM2.5). However, the atmospheric chemical sinks of freshly generated IEPOX-SOA particles remain unclear. We examined the role of heterogeneous oxidation of freshly generated IEPOX-SOA particles by gas-phase hydroxyl radical (•OH) under dark conditions as one potential atmospheric sink. After 4 h of gas-phase •OH exposure (∼3 × 108 molecules cm-3), chemical changes in smog chamber-generated IEPOX-SOA particles were assessed by hydrophilic interaction liquid chromatography coupled with electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (HILIC/ESI-HR-QTOFMS). A comparison of the molecular-level compositional changes in IEPOX-SOA particles during aging with or without •OH revealed that decomposition of oligomers by heterogeneous •OH oxidation acts as a sink for •OH and maintains a reservoir of low-volatility compounds, including monomeric sulfate esters and oligomer fragments. We propose tentative structures and formation mechanisms for previously uncharacterized SOA constituents in PM2.5. Our results suggest that this •OH-driven renewal of low-volatility products may extend the atmospheric lifetimes of particle-phase IEPOX-SOA by slowing the production of low-molecular weight, high-volatility organic fragments and likely contributes to the large quantities of 2-methyltetrols and methyltetrol sulfates reported in PM2.5.


Asunto(s)
Contaminantes Atmosféricos , Sulfatos , Sulfatos/química , Atmósfera/química , Hemiterpenos , Butadienos , Aerosoles/química , Material Particulado/análisis , Polvo/análisis , Oxidación-Reducción , Estrés Oxidativo , Contaminantes Atmosféricos/análisis
13.
Environ Sci Process Impacts ; 24(12): 2272-2283, 2022 Dec 14.
Artículo en Inglés | MEDLINE | ID: mdl-36349377

RESUMEN

Large fluoropolymer manufacturing facilities are major known sources of per- and polyfluoroalkyl substances (PFAS), many of which accumulate in groundwater, surface water, crops, wildlife, and people. Prior studies have measured high PFAS concentrations in groundwater, drinking water, soil, as well as dry and wet deposition near fluoropolymer facilities; however, much less is known about near-source PFAS air concentrations. We measured airborne PFAS on PM2.5 filters in close proximity to a major fluoropolymer manufacturing facility (Chemours' Fayetteville Works) located near Fayetteville, North Carolina, USA. Weekly PM2.5 filter samples collected over a six-month field campaign using high-volume air samplers at locations 3.7 km apart, north-northeast and south-southwest of the facility were analyzed for thirty-four targeted ionic PFAS species by liquid chromatography coupled to electrospray ionization tandem mass spectrometry. Twelve emerging and ten legacy PFAS compounds were detected. Thirteen PFAS were found at higher concentrations in these nearfield samples than at regional background sites, suggesting a local source for these compounds. Five emerging and five legacy PFAS compounds had maximum concentrations exceeding 1 pg m-3. PFBA, PFHxA, PFHxDA, PFOS, PMPA, NVHOS, PFO5DoA, and Nafion BP1 contributed the most to the total (legacy + emerging) PFAS concentration (86%). Six PFAS, specifically PFBA, PFOS, PFO5DoA, Nafion BP1, Nafion BP2, and Nafion BP4, provide a consistent representative profile of elevated species across the two sites (with detection frequency >50%). To our knowledge, this is the first study to report both legacy and emerging ionic PFAS in air in close proximity to a U.S. fluoropolymer manufacturing facility.


Asunto(s)
Ácidos Alcanesulfónicos , Agua Potable , Fluorocarburos , Contaminantes Químicos del Agua , Humanos , Fluorocarburos/análisis , Polímeros de Fluorocarbono/análisis , Contaminantes Químicos del Agua/análisis , Agua Potable/análisis , Instalaciones Industriales y de Fabricación , Material Particulado/análisis , Ácidos Alcanesulfónicos/análisis
15.
Atmos Environ (1994) ; 2682022 Jan 01.
Artículo en Inglés | MEDLINE | ID: mdl-34899026

RESUMEN

Per- and polyfluoroalkyl substances (PFASs), with their water- and heat-resistant properties, have been widely used in industrial and consumer products, including floor waxes. Adverse health effects are associated with PFAS exposures (e.g., increased risk of cancer and immunotoxicity); however, exposures resulting from the use of PFAS-containing products are poorly understood. This study examines PFAS emissions during professional floor stripping/waxing and their potential for occupational exposures. We measured PFASs in dust and airborne particulate matter (PM2.0, aerodynamic diameter ≤ 2.0 µm) before, during, and after floor stripping/waxing activities in three rooms in a university building. PM2.0 samples were analyzed for 34 targeted PFASs by ultra-high performance liquid chromatography coupled to electrospray ionization triple quadrupole mass spectrometer (UHPLC/ESI-MS/MS). In total, ten PFASs were detected in PM2.0 collected during floor waxing. Five were consistently higher during floor stripping/waxing compared to before (two with 95% confidence interval): perfluoro-2-methoxyacetic acid, perfluorobutanoic acid, perfluorohexanoic acid, perfluoroheptanoic acid, and perfluorooctane sulfonic acid. For these five, estimated exposures during floor stripping were 80.6, 320.5, 83.8, 29.6, and 157.7 pg m-3 per hour of floor stripping, respectively, one order of magnitude greater than typical residential indoor and two orders of magnitude greater than ambient outdoor concentrations. Estimated emission rates were 3.0, 9.6, 3.4, 1.5, and 6.5 ng h-1m-2, respectively (34.6% uncertainty). Inhalation occupational exposures were in the range of 9.42-23.2 pg per kg body weight per hour of floor stripping across the five PFASs.

18.
Environ Sci Technol ; 53(15): 8682-8694, 2019 Aug 06.
Artículo en Inglés | MEDLINE | ID: mdl-31335134

RESUMEN

Acid-driven multiphase chemistry of isoprene epoxydiols (IEPOX), key isoprene oxidation products, with inorganic sulfate aerosol yields substantial amounts of secondary organic aerosol (SOA) through the formation of organosulfur compounds. The extent and implications of inorganic-to-organic sulfate conversion, however, are unknown. In this article, we demonstrate that extensive consumption of inorganic sulfate occurs, which increases with the IEPOX-to-inorganic sulfate concentration ratio (IEPOX/Sulfinorg), as determined by laboratory measurements. Characterization of the total sulfur aerosol observed at Look Rock, Tennessee, from 2007 to 2016 shows that organosulfur mass fractions will likely continue to increase with ongoing declines in anthropogenic Sulfinorg, consistent with our laboratory findings. We further demonstrate that organosulfur compounds greatly modify critical aerosol properties, such as acidity, morphology, viscosity, and phase state. These new mechanistic insights demonstrate that changes in SO2 emissions, especially in isoprene-dominated environments, will significantly alter biogenic SOA physicochemical properties. Consequently, IEPOX/Sulfinorg will play an important role in understanding the historical climate and determining future impacts of biogenic SOA on the global climate and air quality.


Asunto(s)
Atmósfera , Pentanos , Aerosoles , Butadienos , Hemiterpenos , Sulfatos , Tennessee
19.
Environ Sci Process Impacts ; 21(8): 1364-1373, 2019 Aug 14.
Artículo en Inglés | MEDLINE | ID: mdl-31157809

RESUMEN

Characterization of residential indoor air is important to understanding exposures to airborne chemicals. While it is well known that non-polar VOCs are elevated indoors, polar VOCs remain poorly characterized. Recent measurements showed that total polar water-soluble organic gas (WSOG) concentrations are also much higher indoors than directly outdoors (on average 15× greater at 13 homes, on a carbon-mass basis). This work aims to chemically characterize these WSOG mixtures. Acetic, lactic, and formic acids account for 41% on average (30-54% across homes), of the total WSOG-carbon collected inside each home. Remaining WSOGs were characterized via high-resolution positive-mode electrospray ionization mass spectrometry. In total, 98 individual molecular formulas were detected. On average 67% contained the elements CHO, 11% CHN, 11% CHON, and 11% contained sulfur, phosphorus, or chlorine. Some molecular formulas are consistent with compounds having known indoor sources such as diethylene glycol (m/z+ 117.091, C4H10O3), hexamethylenetetramine (m/z+ 141.113, C6H12N4), and methacrylamide (m/z+ 86.060, C4H7NO). Exposure pathways, potential doses, and implications are discussed.


Asunto(s)
Contaminantes Atmosféricos/química , Contaminación del Aire Interior/análisis , Exposición a Riesgos Ambientales/análisis , Gases/química , Vivienda/normas , Contaminantes Atmosféricos/análisis , Ácidos Carboxílicos/química , Gases/análisis , Humanos , Agua/química
20.
Environ Sci Technol ; 53(4): 1812-1821, 2019 02 19.
Artículo en Inglés | MEDLINE | ID: mdl-30633495

RESUMEN

Water-soluble organic gas (WSOG) concentrations are elevated in homes. However, WSOG sources, sinks, and concentration dynamics are poorly understood. We observed substantial variations in 23 residential indoor WSOG concentrations measured in real time in a North Carolina, U.S., home over several days with a high-resolution time-of-flight chemical ionization mass spectrometer equipped with iodide reagent ion chemistry (I-HR-ToF-CIMS). Concentrations of acetic, formic, and lactic acids ranged from 30-130, 15-53, and 2.5-360 µg m-3, respectively. Concentrations of several WSOGs, including acetic and formic acids, decreased considerably (∼30-50%) when the air conditioner (AC) cycled on, suggesting that the AC system is an important sink for indoor WSOGs. In contrast to nonpolar organic gases, indoor WSOG loss rate coefficients were substantial for compounds with high oxygen-to-carbon (O/C) ratios (e.g., 1.6-2.2 h-1 for compounds with O/C > 0.75 when the AC system was off). Loss rate coefficients in the AC system were more uncertain but were estimated to be 1.5 h-1. Elevated concentrations of lactic acid coincided with increased human occupancy and cooking. We report several WSOGs emitted from cooking and cleaning as well as transported in from outdoors. In addition to indoor air chemistry, these results have implications to exposure and human health.


Asunto(s)
Contaminantes Atmosféricos , Contaminación del Aire Interior , Monitoreo del Ambiente , Gases , Humanos , North Carolina , Agua
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