Characterization of PFAS air emissions from thermal application of fluoropolymer dispersions on fabrics.

During thermal processes utilized in affixing fluoropolymer coatings dispersion to fibers and fabrics, coating components are vaporized. It is suspected that per- and polyfluoroalkyl substances (PFAS) from the dispersions may undergo chemical transformations at the temperatures used, leading to additional emitted PFAS thermal byproducts. It is important to characterize these emissions to support evaluation of the resulting environmental and health impacts. In this study, a bench-scale system was built to simulate this industrial process via thermal application of dispersions to fiberglass utilizing relevant temperatures and residence times in sequential drying, baking, and sintering steps. Experiments were performed with two commercially available dispersions and a simple model mixture containing a single PFAS (6:2 fluorotelomer alcohol [6:2 FTOH]). Vapor-phase emissions were sampled and characterized by several off-line and real-time mass spectrometry techniques for targeted and nontargeted PFAS. Results indicate that multiple PFAS thermal transformation products and multiple nonhalogenated organic species were emitted from the exit of the high temperature third (sintering) furnace when 6:2 FTOH was the only PFAS present in the aqueous mixture. This finding supports the hypothesis that temperatures typical of these industrial furnaces may also induce chemical transformations within the fluorinated air emissions. Experiments using the two commercial fluoropolymer dispersions indicate air emissions of part-per-million by volume (ppmv) concentrations of heptafluoropropyl-1,2,2,2-tetrafluoroethyl ether (Fluoroether E1), as well as other PFAS at operationally relevant temperatures. We suspect that E1 is a direct thermal decomposition product (via decarboxylation) of 2,3,3,3-tetrafluoro-2-(heptafluoropropoxy)propanoic acid (commonly referred to as HFPO-DA) present in the dispersions. Other thermal decomposition products, including the monomer, tetrafluoroethene, may originate from the PFAS used to stabilize the dispersion or from the polymer particles in suspension. This study represents the first researcher-built coating application simulator to report nontargeted PFAS emission characterization, real-time analyses, and the quantification of 30 volatile target PFAS.Implications: Thermal processes used to affix fluoropolymers to fabrics are believed to be a source of PFAS air emissions. These coating operations are used by many large and small manufacturers and typically do not currently require any air emissions control. This research designed and constructed a bench-scale system that simulates these processes and used several off-line and advanced real-time mass spectroscopy techniques to characterize PFAS air emissions from two commercial fluoropolymer dispersions. Further, as the compositions of commercial dispersions are largely unknown, a model three-component solution containing a single PFAS was used to characterize emissions of multiple PFAS thermal transformation products at operationally relevant conditions. This research shows that fluoropolymer fabric coating facilities can be sources of complex mixtures of PFAS air emissions that include volatile and semivolatile PFAS present in the dispersions, as well as PFAS byproducts formed by the thermal transformation of fluorocarbon and hydrocarbon species present in these dispersions.

Impact of do-it-yourself air cleaner design on the reduction of simulated wildfire smoke in a controlled chamber environment.

During wildfire smoke events public health agencies release advisories to stay indoors, close doors and windows, and operate a portable air cleaner (PAC). The do-it-yourself (DIY) air cleaner consisting of a box fan and a furnace filter is a widely used low-cost alternative to commercial PACs because of its increased accessibility. In this study, we evaluate the clean air delivery rate (CADR) of different DIY air cleaner designs for reducing simulated wildfire smoke and identify operating parameters that may impact their performance and use. The simplest formulation of a DIY air cleaner (box fan with taped on minimum effectiveness reporting value - [MERV] 13 furnace filter) had a CADR of 111.2 ± 1.3 ft3 /min (CFM). Increasing the fan flow by changing the fan type, increasing the fan setting, or reducing the pressure drop across the filtering surface increased the CADR. Large increases in CADR could be obtained by using a shroud (40%), using a 4″ thick filter (123%) using two filters in a wedge shape (137%), or using four filters in a Corsi-Rosenthal (CR) box design (261%). The CADR was greatly reduced with filters heavily loaded with smoke, pointing to the need for frequent filter changes during smoke events.

Airborne Emission Rate Measurements Validate Remote Sensing Observations and Emission Inventories of Western U.S. Wildfires.

Carbonaceous emissions from wildfires are a dynamic mixture of gases and particles that have important impacts on air quality and climate. Emissions that feed atmospheric models are estimated using burned area and fire radiative power (FRP) methods that rely on satellite products. These approaches show wide variability and have large uncertainties, and their accuracy is challenging to evaluate due to limited aircraft and ground measurements. Here, we present a novel method to estimate fire plume-integrated total carbon and speciated emission rates using a unique combination of lidar remote sensing aerosol extinction profiles and in situ measured carbon constituents. We show strong agreement between these aircraft-derived emission rates of total carbon and a detailed burned area-based inventory that distributes carbon emissions in time using Geostationary Operational Environmental Satellite FRP observations (Fuel2Fire inventory, slope = 1.33 ± 0.04, r2 = 0.93, and RMSE = 0.27). Other more commonly used inventories strongly correlate with aircraft-derived emissions but have wide-ranging over- and under-predictions. A strong correlation is found between carbon monoxide emissions estimated in situ with those derived from the TROPOspheric Monitoring Instrument (TROPOMI) for five wildfires with coincident sampling windows (slope = 0.99 ± 0.18; bias = 28.5%). Smoke emission coefficients (g MJ-1) enable direct estimations of primary gas and aerosol emissions from satellite FRP observations, and we derive these values for many compounds emitted by temperate forest fuels, including several previously unreported species.

Fuel layer specific pollutant emission factors for fire prone forest ecosystems of the western U.S. and Canada.

Wildland fires are a major source of gases and aerosols, and the production, dispersion, and transformation of fire emissions have significant ambient air quality impacts and climate interactions. The increase in wildfire area burned and severity across the United States and Canada in recent decades has led to increased interest in expanding the use of prescribed fires as a forest management tool. While the primary goal of prescribed fire use is to limit the loss of life and property and ecosystem damage by constraining the growth and severity of future wildfires, a potential additional benefit of prescribed fire - reduction in the adverse impacts of smoke production and greenhouse gas (GHG) emissions - has recently gained the interest of land management agencies and policy makers in the United States and other nations. The evaluation of prescribed fire/wildfire scenarios and the potential mitigation of adverse impacts on air quality and GHGs requires fuel layer specific pollutant emission factors (EFs) for fire prone forest ecosystems. Our study addresses this need with laboratory experiments measuring EFs for carbon dioxide (CO2), carbon monoxide (CO), methane (CH4), ethyne (C2H2), formaldehyde (H2CO), formic acid (CH2O2), hydrogen cyanide (HCN), fine particulate matter (PM2.5), nitric oxide (NO), nitrogen dioxide (NO2), sulfur dioxide (SO2), and total reduced sulfur (TRS) for the burning of individual fuel components from three forest ecosystems which account for a large share of wildfire burned area and emissions in the western United States and Canada - Douglas fir, ponderosa pine, and black spruce/jack pine.

Ozone chemistry in western U.S. wildfire plumes.

Wildfires are a substantial but poorly quantified source of tropospheric ozone (O3). Here, to investigate the highly variable O3 chemistry in wildfire plumes, we exploit the in situ chemical characterization of western wildfires during the FIREX-AQ flight campaign and show that O3 production can be predicted as a function of experimentally constrained OH exposure, volatile organic compound (VOC) reactivity, and the fate of peroxy radicals. The O3 chemistry exhibits rapid transition in chemical regimes. Within a few daylight hours, the O3 formation substantially slows and is largely limited by the abundance of nitrogen oxides (NOx). This finding supports previous observations that O3 formation is enhanced when VOC-rich wildfire smoke mixes into NOx-rich urban plumes, thereby deteriorating urban air quality. Last, we relate O3 chemistry to the underlying fire characteristics, enabling a more accurate representation of wildfire chemistry in atmospheric models that are used to study air quality and predict climate.

Novel Analysis to Quantify Plume Crosswind Heterogeneity Applied to Biomass Burning Smoke.

We present a novel method, the Gaussian observational model for edge to center heterogeneity (GOMECH), to quantify the horizontal chemical structure of plumes. GOMECH fits observations of short-lived emissions or products against a long-lived tracer (e.g., CO) to provide relative metrics for the plume width (wi/wCO) and center (bi/wCO). To validate GOMECH, we investigate OH and NO3 oxidation processes in smoke plumes sampled during FIREX-AQ (Fire Influence on Regional to Global Environments and Air Quality, a 2019 wildfire smoke study). An analysis of 430 crosswind transects demonstrates that nitrous acid (HONO), a primary source of OH, is narrower than CO (wHONO/wCO = 0.73-0.84 ± 0.01) and maleic anhydride (an OH oxidation product) is enhanced on plume edges (wmaleicanhydride/wCO = 1.06-1.12 ± 0.01). By contrast, NO3 production [P(NO3)] occurs mainly at the plume center (wP(NO3)/wCO = 0.91-1.00 ± 0.01). Phenolic emissions, highly reactive to OH and NO3, are narrower than CO (wphenol/wCO = 0.96 ± 0.03, wcatechol/wCO = 0.91 ± 0.01, and wmethylcatechol/wCO = 0.84 ± 0.01), suggesting that plume edge phenolic losses are the greatest. Yet, nitrophenolic aerosol, their oxidation product, is the greatest at the plume center (wnitrophenolicaerosol/wCO = 0.95 ± 0.02). In a large plume case study, GOMECH suggests that nitrocatechol aerosol is most associated with P(NO3). Last, we corroborate GOMECH with a large eddy simulation model which suggests most (55%) of nitrocatechol is produced through NO3 in our case study.

Comparison of ozone measurement methods in biomass burning smoke: an evaluation under field and laboratory conditions.

In recent years wildland fires in the United States have had significant impacts on local and regional air quality and negative human health outcomes. Although the primary health concerns from wildland fires come from fine particulate matter (PM2.5), large increases in ozone (O3) have been observed downwind of wildland fire plumes (DeBell et al., 2004; Bytnerowicz et al., 2010; Preisler et al., 2010; Jaffe et al., 2012; Bytnerowicz et al., 2013; Jaffe et al., 2013; Lu et al., 2016; Lindaas et al., 2017; McClure and Jaffe, 2018; Liu et al., 2018; Baylon et al., 2018; Buysse et al., 2019). Conditions generated in and around wildland fire plumes, including the presence of interfering chemical species, can make the accurate measurement of O3 concentrations using the ultraviolet (UV) photometric method challenging if not impossible. UV photometric method instruments are prone to interferences by volatile organic compounds (VOCs) that are present at high concentrations in wildland fire smoke. Four different O3 measurement methodologies were deployed in a mobile sampling platform downwind of active prescribed grassland fire lines in Kansas and Oregon and during controlled chamber burns at the United States Forest Service, Rocky Mountain Research Station Fire Sciences Laboratory in Missoula, Montana. We demonstrate that the Federal Reference Method (FRM) nitric oxide (NO) chemiluminescence monitors and Federal Equivalent Method (FEM) gas-phase (NO) chemical scrubber UV photometric O3 monitors are relatively interference-free, even in near-field combustion plumes. In contrast, FEM UV photometric O3 monitors using solid-phase catalytic scrubbers show positive artifacts that are positively correlated with carbon monoxide (CO) and total gas-phase hydrocarbon (THC), two indicator species of biomass burning. Of the two catalytic scrubber UV photometric methods evaluated, the instruments that included a Nafion® tube dryer in the sample introduction system had artifacts an order of magnitude smaller than the instrument with no humidity correction. We hypothesize that Nafion®-permeating VOCs (such as aromatic hydrocarbons) could be a significant source of interference for catalytic scrubber UV photometric O3 monitors and that the inclusion of a Nafion® tube dryer assists with the mitigation of these interferences. The chemiluminescence FRM method is highly recommended for accurate measurements of O3 in wildland fire plume studies and at regulatory ambient monitoring sites frequently impacted by wildland fire smoke.

Investigation of factors controlling PM2.5 variability across the South Korean Peninsula during KORUS-AQ.

The Korea - United States Air Quality Study (May - June 2016) deployed instrumented aircraft and ground-based measurements to elucidate causes of poor air quality related to high ozone and aerosol concentrations in South Korea. This work synthesizes data pertaining to aerosols (specifically, particulate matter with aerodynamic diameters <2.5 micrometers, PM2.5) and conditions leading to violations of South Korean air quality standards (24-hr mean PM2.5 < 35 µg m-3). PM2.5 variability from AirKorea monitors across South Korea is evaluated. Detailed data from the Seoul vicinity are used to interpret factors that contribute to elevated PM2.5. The interplay between meteorology and surface aerosols, contrasting synoptic-scale behavior vs. local influences, is presented. Transboundary transport from upwind sources, vertical mixing and containment of aerosols, and local production of secondary aerosols are discussed. Two meteorological periods are probed for drivers of elevated PM2.5. Clear, dry conditions, with limited transport (Stagnant period), promoted photochemical production of secondary organic aerosol from locally emitted precursors. Cloudy humid conditions fostered rapid heterogeneous secondary inorganic aerosol production from local and transported emissions (Transport/Haze period), likely driven by a positive feedback mechanism where water uptake by aerosols increased gas-to-particle partitioning that increased water uptake. Further, clouds reduced solar insolation, suppressing mixing, exacerbating PM2.5 accumulation in a shallow boundary layer. The combination of factors contributing to enhanced PM2.5 is challenging to model, complicating quantification of contributions to PM2.5 from local versus upwind precursors and production. We recommend co-locating additional continuous measurements at a few AirKorea sites across South Korea to help resolve this and other outstanding questions: carbon monoxide/carbon dioxide (transboundary transport tracer), boundary layer height (surface PM2.5 mixing depth), and aerosol composition with aerosol liquid water (meteorologically-dependent secondary production). These data would aid future research to refine emissions targets to further improve South Korean PM2.5 air quality.

Ambient Nonmethane Hydrocarbon Levels Along Colorado's Northern Front Range: Acute and Chronic Health Risks.

Oil and gas (O&G) facilities emit air pollutants that are potentially a major health risk for nearby populations. We characterized prenatal through adult health risks for acute (1 h) and chronic (30 year) residential inhalation exposure scenarios to nonmethane hydrocarbons (NMHCs) for these populations. We used ambient air sample results to estimate and compare risks for four residential scenarios. We found that air pollutant concentrations increased with proximity to an O&G facility, as did health risks. Acute hazard indices for neurological (18), hematological (15), and developmental (15) health effects indicate that populations living within 152 m of an O&G facility could experience these health effects from inhalation exposures to benzene and alkanes. Lifetime excess cancer risks exceeded 1 in a million for all scenarios. The cancer risk estimate of 8.3 per 10 000 for populations living within 152 m of an O&G facility exceeded the United States Environmental Protection Agency's 1 in 10 000 upper threshold. These findings indicate that state and federal regulatory policies may not be protective of health for populations residing near O&G facilities. Health risk assessment results can be used for informing policies and studies aimed at reducing and understanding health effects associated with air pollutants emitted from O&G facilities.

Assessing a low-cost methane sensor quantification system for use in complex rural and urban environments.

Low-cost sensors have the potential to facilitate the exploration of air quality issues on new temporal and spatial scales. Here we evaluate a low-cost sensor quantification system for methane through its use in two different deployments. The first was a one-month deployment along the Colorado Front Range and included sites near active oil and gas operations in the Denver-Julesberg basin. The second deployment was in an urban Los Angeles neighborhood, subject to complex mixtures of air pollution sources including oil operations. Given its role as a potent greenhouse gas, new low-cost methods for detecting and monitoring methane may aid in protecting human and environmental health. In this paper, we assess a number of linear calibration models used to convert raw sensor signals into ppm concentration values. We also examine different choices that can be made during calibration and data processing, and explore cross-sensitivities that impact this sensor type. The results illustrate the accuracy of the Figaro TGS 2600 sensor when methane is quantified from raw signals using the techniques described. The results also demonstrate the value of these tools for examining air quality trends and events on small spatial and temporal scales as well as their ability to characterize an area - highlighting their potential to provide preliminary data that can inform more targeted measurements or supplement existing monitoring networks.

Ozone correlations between mid-tropospheric partial columns and the near-surface at two mid-atlantic sites during the DISCOVER-AQ campaign in July 2011.

The current network of ground-based monitors for ozone (O3) is limited due to the spatial heterogeneity of O3 at the surface. Satellite measurements can provide a solution to this limitation, but the lack of sensitivity of satellites to O3 within the boundary layer causes large uncertainties in satellite retrievals at the near-surface. The vertical variability of O3 was investigated using ozonesondes collected as part of NASA's Deriving Information on Surface Conditions from COlumn and VERtically Resolved Observations Relevant to Air Quality (DISCOVER-AQ) campaign during July 2011 in the Baltimore, MD/Washington D.C. metropolitan area. A subset of the ozonesonde measurements was corrected for a known bias from the electrochemical solution strength using new procedures based on laboratory and field tests. A significant correlation of O3 over the two sites with ozonesonde measurements (Edgewood and Beltsville, MD) was observed between the mid-troposphere (7-10 km) and the near-surface (1-3 km). A linear regression model based on the partial column amounts of O3 within these subregions was developed to calculate the near-surface O3 using mid-tropospheric satellite measurements from the Tropospheric Emission Spectrometer (TES) onboard the Aura spacecraft. The uncertainties of the calculated near-surface O3 using TES mid-tropospheric satellite retrievals and a linear regression model were less than 20 %, which is less than that of the observed variability of O3 at the surface in this region. These results utilize a region of the troposphere to which existing satellites are more sensitive compared to the boundary layer and can provide information of O3 at the near-surface using existing satellite infrastructure and algorithms.