Characterizing Volatile Emissions and Combustion Byproducts from Aqueous Film-Forming Foams Using Online Chemical Ionization Mass Spectrometry.

Aqueous film-forming foams (AFFFs) are used in firefighting applications and often contain per- and polyfluoroalkyl substances (PFAS), which can detrimentally impact environmental and biological health. Incineration is a potential disposal method for AFFFs, which may produce secondary PFAS and other air pollutants. We used online chemical ionization mass spectrometry (CIMS) to measure volatile PFAS emissions from incinerating AFFF concentrate solutions. We quantified perfluorinated carboxylic acids (PFCAs) during the incineration of legacy and contemporary AFFFs. These included trifluoroacetic acid, which reached mg m-3 quantities in the incinerator exhaust. These PFCAs likely arose as products of incomplete combustion of AFFF fluorosurfactants with lower peak furnace temperatures yielding higher PFCA concentrations. We also detected other short-chain PFAS, and other novel chemical products in AFFF combustion emissions. The volatile headspace above AFFF solutions contained larger (C ≥ 8), less oxidized PFAS detected by CIMS. We identified neutral PFAS resembling fluorotelomer surfactants (e.g., fluorotelomer sulfonamide alkylbetaines and fluorotelomer thioether amido sulfonates) and fluorotelomer alcohols in contemporary AFFF headspaces. Directly comparing the distinct chemical spaces of AFFF volatile headspace and combustion byproducts as measured by CIMS provides insight toward the chemistry of PFAS during thermal treatment of AFFFs.

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.

Summary of PM2.5 measurement artifacts associated with the Teledyne T640 PM Mass Monitor under controlled chamber experimental conditions using polydisperse ammonium sulfate aerosols and biomass smoke.

Particulate matter (PM) is a major primary pollutant emitted during wildland fires that has the potential to pose significant health risks to individuals/communities who live and work in areas impacted by smoke events. Limiting exposure is the principle measure available to mitigate health impacts of smoke and therefore the accurate determination of ambient PM concentrations during wildland fire events is critical to protecting public health. However, monitoring air pollutants in smoke impacted environments has proven challenging in that measurement interferences or sampling conditions can result in both positive and negative artifacts. The EPA has performed research on methods for the measurement of PM2.5 in a series of laboratory-based studies including evaluation in smoke. This manuscript will summarize the results of the laboratory-based evaluation of federal equivalent method (FEM) monitors for PM2.5 with particular attention being given to the Teledyne-API Model T640 PM Mass monitor, as compared to the filter-based federal reference method (FRM). The T640 is an optical-based PM monitor and has been gaining wide use by state and local agencies in monitoring for PM2.5 U.S. National Ambient Air Quality Standards (NAAQS) attainment. At present, the T640 (includes both T640 and T640×) comprises ~44% of the PM2.5 FEM monitors in U.S. regulatory monitoring networks. In addition, the T640 has increasingly been employed for the higher time resolution comparison/evaluation of low-cost PM sensors including during smoke impacted events. Results from controlled non-smoke laboratory studies using generated ammonium sulfate aerosols demonstrated a generally negative T640 measurement artifact that was significantly related to the PM2.5 concentration and particle size distribution. Results from biomass burning chamber studies demonstrated positive and negative artifacts significantly associated with PM2.5 concentration and optical wavelength-dependent absorption properties of the smoke aerosol.Implications: The results detailed in this paper will provide state and local air monitoring agencies with the tools and knowledge to address PM2.5 measurement challenges in areas frequently impacted by wildland fire smoke. The observed large positive and negative artifacts in the T640 PM mass determination have the potential to result in false exceedances of the PM2.5 NAAQS or in the disqualification of monitoring data through an exceptional event designation. In addition, the observed artifacts in smoke impacted air will have a detrimental effect on providing reliable public information when wildfires occur and also in identifying reference measurements for small sensor evaluation studies. Other PM2.5 FEMs such as the BAM-1022 perform better in smoke and are comparable to the filter-based FRM. Care must be taken in choosing high time resolution FEM monitors that will be operated at smoke impacted sites. Accurate methods, such as the FRM and BAM-1022 will reduce the burden of developing and reviewing exceptional event request packages, data loss/disqualification, and provide states with tools to adequately evaluate public exposure risks and provide accurate public health messaging during wildfire/smoke events.

Cytotoxicity and oxidative stress induced by atmospheric mono-nitrophenols in human lung cells.

Nitrophenols (NPs) are hazardous pollutants found in various environmental matrices, including ambient fine particulate matter (PM2.5), agricultural residues, rainwater, wildfires, and industrial wastes. This study showed for the first time the effect of three pure nitrophenols and their mixture on human lung cells to provide basic understanding of the NP influence on cell elements and processes. We identified NPs in ambient PM2.5 and secondary organic aerosol (SOA) particles generated from the photooxidation of monocyclic aromatic hydrocarbons in the U.S. EPA smog chamber. We assessed the toxicity of identified NPs and their equimolar mixture in normal bronchial epithelial (BEAS-2B) and alveolar epithelial cancer (A549) lung cell lines. The inhibitory concentration-50 (IC50) values were highest and lowest in BEAS-2B cells treated with 2-nitrophenol (2NP) and 4-nitrophenol (4NP), respectively, at 24 h of exposure. The lactate dehydrogenase (LDH) assay showed that 4NP, the most abundant NP we identified in PM2.5, was the most cytotoxic NP examined in both cell lines. The annexin-V/fluorescein isothiocyanate (FITC) analysis showed that the populations of late apoptotic/necrotic BEAS-2B and A549 cells exposed to 3NP, 4NP, and NP equimolar mixture increased between 24 and 48 h. Cellular reactive oxygen species (ROS) buildup led to cellular death post exposure to 3NP, 4NP and the NP mixtures, while 2NP induced the lowest ROS buildup. An increased mitochondrial ROS signal following NP exposure occurred only in BEAS-2B cells. The tetramethylrhodamine, methyl ester, perchlorate (TMRM) assay showed that exposed cells exhibited collapse of the mitochondrial membrane potential. TMRM signals decreased significantly only in BEAS-2B cells, and most strongly with 4NP exposures. Our results suggest that acute atmospheric exposures to NPs may be toxic at high concentrations, but not at ambient PM2.5 concentrations. Further chronic studies with NP and NP-containing PM2.5 are warranted to assess their contribution to lung pathologies.

Combustion of C1 and C2 PFAS: Kinetic modeling and experiments.

A combustion model, originally developed to simulate the destruction of chemical warfare agents, was modified to include C1-C3 fluorinated organic reactions and kinetics compiled by the National Institute of Standards and Technology (NIST). A simplified plug flow reactor version of this model was used to predict the destruction efficiency (DE) and formation of products of incomplete combustion (PICs) for three C1 and C2 per- and poly-fluorinated alkyl substances (PFAS) (CF4, CHF3, and C2F6) and compare predicted values to Fourier Transform Infrared spectroscopy (FTIR)-based measurements made from a pilot-scale EPA research combustor (40-64 kW, natural gas-fired, 20% excess air). PFAS were introduced through the flame, and at post-flame locations along a time-temperature profile allowing for simulation of direct flame and non-flame injection, and examination of the sensitivity of PFAS destruction on temperature and free radical flame chemistry. Results indicate that CF4 is particularly difficult to destroy with DEs ranging from ~60 to 95% when introduced through the flame at increasing furnace loads. Due to the presence of lower energy C-H and C-C bonds to initiate molecular dissociation reactions, CHF3 and C2F6 were easier to destroy, exhibiting DEs >99% even when introduced post-flame. However, these lower bond energies may also lead to the formation of CF2 and CF3 radicals at thermal conditions unable to fully de-fluorinate these species and formation of fluorinated PICs. DEs determined by the model agreed well with the measurements for CHF3 and C2F6 but overpredicted DEs at high temperatures and underpredicted DEs at low temperatures for CF4. However, high DEs do not necessarily mean absence of PICs, with both model predictions and limited FTIR measurements indicating the presence of similar fluorinated PICs in the combustion emissions. The FTIR was able to provide real-time emission measurements and additional model development may improve prediction of PFAS destruction and PIC formation.Implications: The widespread use of PFAS for over 70 years has led to their presence in multiple environmental matrixes including human tissues. While the chemical and thermal stability of PFAS are related to their desirable properties, this stability means that PFAS are very slow to degrade naturally and potentially difficult to destroy completely through thermal treatment processes often used for organic waste destruction. In this applied combustion study, model PFAS compounds were introduced to a pilot-scale EPA research furnace. Real-time FTIR measurements were performed of the injected compound and trace products of incomplete combustion (PICs) at operationally relevant conditions, and the results were successfully compared to kinetic model predictions of those same PFAS destruction efficiencies and trace gas-phase PIC constituents. This study represents a significant potential enhancement in available tools to support effective management of PFAS-containing wastes.

Inhalation of Simulated Smog Atmospheres Affects Cardiac Function in Mice.

The health effects of individual criteria air pollutants have been well investigated. However, little is known about the health effects of air pollutant mixtures that more realistically represent environmental exposures. The present study was designed to evaluate the cardiac effects of inhaled simulated smog atmospheres (SA) generated from the photochemistry of either gasoline and isoprene (SA-G) or isoprene (SA-Is) in mice. Four-month-old female mice were exposed for 4 h to filtered air (FA), SA-G, or SA-Is. Immediately and 20 h after exposure, cardiac responses were assessed with a Langendorff preparation using a protocol consisting of 20 min of global ischemia followed by 2 h of reperfusion. Cardiac function was measured by index of left-ventricular developed pressure (LVDP) and cardiac contractility (dP/dt) before ischemia. Pre-ischemic LVDP was lower in mice immediately after SA-Is exposure (52.2 ± 5.7 cm H2O compared to 83.9 ± 7.4 cm H2O after FA exposure; p = 0.008) and 20 h after SA-G exposure (54.0 ± 12.7 cm H2O compared to 79.3 ± 7.4 cm H2O after FA exposure; p = 0.047). Pre-ischemic left ventricular contraction dP/dtmax was lower in mice immediately after SA-Is exposure (2025 ± 169 cm H2O/sec compared to 3044 ± 219 cm H2O/sec after FA exposure; p < 0.05) and 20 h after SA-G exposure (1864 ± 328 cm H2O/sec compared to 2650 ± 258 cm H2O/sec after FA exposure; p = 0.05). In addition, SA-G reduced the coronary artery flow rate 20 h after exposure compared to the FA control. This study demonstrates that acute SA-G and SA-Is exposures decrease LVDP and cardiac contractility in mice, indicating that photochemically-altered atmospheres affect the cardiovascular system.

Size-Selective Sampling Performance of Six Low-Volume "Total" Suspended Particulate (TSP) Inlets.

Several low-volume inlets (flow rates ≤16.7 liters per minute (Lpm)) are commercially available as components of low-cost, portable ambient particulate matter samplers. Because the inlets themselves do not contain internal fractionators, they are often assumed to representatively sample "total" mass concentrations from the ambient air, independent of aerodynamic particle size and wind speed. To date, none of these so-called "TSP" inlets have been rigorously tested under controlled conditions. To determine their actual size-selective performance under conditions of expected use, wind tunnel tests of six commonly used omnidirectional, low-volume inlets were conducted using solid, polydisperse aerosols at wind speeds of 2, 8, and 24 km/hr. With the exception of axially-oriented, isokinetic sharp-edge nozzles operating at 5 and 10 Lpm, all low-volume inlets showed some degree of non-ideal sampling performance as a function of aerodynamic particle size and wind speed. Depending upon wind speed and assumed ambient particle size distribution, total mass concentration measurements were estimated to be negatively biased by as much as 66%. As expected from particle inertial considerations, inlet efficiency tended to degrade with increasing wind speed and particle size, although some exceptions were noted. The implications of each inlet's non-ideal behavior are discussed with regards to expected total mass concentration measurement during ambient sampling and the ability to obtain representative sampling for size ranges of interest, such as PM2.5 and PM10. Overall test results will aid in low-volume inlet selection and with proper interpretation of results obtained with their ambient field use.

Evaluation of an Air Quality Health Index for Predicting the Mutagenicity of Simulated Atmospheres.

No study has evaluated the mutagenicity of atmospheres with a calculated air quality health index (AQHI). Thus, we generated in a UV-light-containing reaction chamber two simulated atmospheres (SAs) with similar AQHIs but different proportions of criteria pollutants and evaluated them for mutagenicity in three Salmonella strains at the air-agar interface. We continuously injected into the chamber gasoline, nitric oxide, and ammonium sulfate, as well as either α-pinene to produce SA-PM, which had a high concentration of particulate matter (PM): 119 ppb ozone (O3), 321 ppb NO2, and 1007 µg/m3 PM2.5; or isoprene to produce SA-O3, which had a high ozone (O3) concentration: 415 ppb O3, 633 ppb NO2, and 55 µg/m3 PM2.5. Neither PM2.5 extracts, NO2, or O3 alone, nor nonphoto-oxidized mixtures were mutagenic or cytotoxic. Both photo-oxidized atmospheres were largely direct-acting base-substitution mutagens with similar mutagenic potencies in TA100 and TA104. The mutagenic potencies [(revertants/h)/(mgC/m3)] of SA-PM (4.3 ± 0.4) and SA-O3 (9.5 ± 1.3) in TA100 were significantly different ( P < 0.0001), but the mutation spectra were not ( P = 0.16), being ∼54% C → T and ∼46% C → A. Thus, the AQHI may have some predictive value for the mutagenicity of the gas phase of air.

Effects of Simulated Smog Atmospheres in Rodent Models of Metabolic and Immunologic Dysfunction.

Air pollution is a diverse and dynamic mixture of gaseous and particulate matter, limiting our understanding of associated adverse health outcomes. The biological effects of two simulated smog atmospheres (SA) with different compositions but similar air quality health indexes were compared in a nonobese diabetic rat model (Goto-Kakizaki, GK) and three mouse immune models (house dust mite (HDM) allergy, antibody response to heat-killed pneumococcus, and resistance to influenza A infection). In GK rats, both SA-PM (high particulate matter) and SA-O3 (high ozone) decreased cholesterol levels immediately after a 4-h exposure, whereas only SA-O3 increased airflow limitation. Airway responsiveness to methacholine was increased in HDM-allergic mice compared with nonallergic mice, but exposure to SA-PM or SA-O3 did not significantly alter responsiveness. Exposure to SA-PM did not affect the IgM response to pneumococcus, and SA-O3 did not affect virus titers, although inflammatory cytokine levels were decreased in mice infected at the end of a 7-day exposure. Collectively, acute SA exposures produced limited health effects in animal models of metabolic and immune diseases. Effects of SA-O3 tended to be greater than those of SA-PM, suggesting that gas-phase components in photochemically derived multipollutant mixtures may be of greater concern than secondary organic aerosol PM.

Photochemical Conversion of Surrogate Emissions for Use in Toxicological Studies: Role of Particulate- and Gas-Phase Products.

The production of photochemical atmospheres under controlled conditions in an irradiation chamber permits the manipulation of parameters that influence the resulting air-pollutant chemistry and potential biological effects. To date, no studies have examined how contrasting atmospheres with a similar Air Quality Health Index (AQHI), but with differing ratios of criteria air pollutants, might differentially affect health end points. Here, we produced two atmospheres with similar AQHIs based on the final concentrations of ozone, nitrogen dioxide, and particulate matter (PM2.5). One simulated atmosphere (SA-PM) generated from irradiation of ∼23 ppmC gasoline, 5 ppmC α-pinene, 529 ppb NO, and 3 µg m-3 (NH4)2SO4 as a seed resulted in an average of 976 µg m-3 PM2.5, 326 ppb NO2, and 141 ppb O3 (AQHI 97.7). The other atmosphere (SA-O3) generated from 8 ppmC gasoline, 5 ppmC isoprene, 874 ppb NO, and 2 µg m-3 (NH4)2SO4 resulted in an average of 55 µg m-3 PM2.5, 643 ppb NO2, and 430 ppb O3 (AQHI of 99.8). Chemical speciation by gas chromatography showed that photo-oxidation degraded the organic precursors and promoted the de novo formation of secondary reaction products such as formaldehyde and acrolein. Further work in accompanying papers describe toxicological outcomes from the two distinct photochemical atmospheres.

Development of Polydisperse Aerosol Generation and Measurement Procedures for Wind Tunnel Evaluation of Size-Selective Aerosol Samplers.

Accurate development and evaluation of inlets for representatively collecting ambient particulate matter typically involves use of monodisperse particles in aerosol wind tunnels. However, the resource requirements of using monodisperse aerosols for inlet evaluation creates the need for more rapid and less-expensive techniques to enable determination of size-selective performance in aerosol wind tunnels. The goal of recent wind tunnel research at the U.S. EPA was to develop and validate the use of polydisperse aerosols which provide more rapid, less resource-intensive test results which still meet data quality requirements necessary for developing and evaluating ambient aerosol inlets. This goal was successfully achieved through comprehensive efforts regarding polydisperse aerosol generation, dispersion, collection, extraction, and analysis over a wide range of aerodynamic particle sizes. Using proper experimental techniques, a sampler's complete size-selective efficiency curve can be estimated with polydisperse aerosols in a single test, as opposed to the use of monodisperse aerosols which require conducting multiple tests using several different particle sizes. While this polydisperse aerosol technique is not proposed as a regulatory substitute for use of monodisperse aerosols, the use of polydisperse aerosols is advantageous during an inlet's development where variables of sampling flow rate and inlet geometry are often iteratively evaluated before a final inlet design can be successfully achieved. Complete Standard Operating Procedures for the generation, collection, and analysis of polydisperse calibration aerosols are available from EPA as downloadable files. The described experimental methods will be of value to other researchers during development of ambient sampling inlets and size-selective evaluation of the inlets in aerosol wind tunnels.

Trends in the oxidation and relative volatility of chamber-generated secondary organic aerosol.

The relationship between the oxidation state and relative volatility of secondary organic aerosol (SOA) from the oxidation of a wide range of hydrocarbons is investigated using a fast-stepping, scanning thermodenuder interfaced with a high-resolution time-of-flight aerosol mass spectrometer (AMS). SOA oxidation state varied widely across the investigated range of parent hydrocarbons but was relatively stable for replicate experiments using a single hydrocarbon precursor. On average, unit mass resolution indicators of SOA oxidation (e.g., AMS f 43 and f 44) are consistent with previously reported values. Linear regression of H:C vs. O:C obtained from parameterization of f 43 and f 44 and elemental analysis of high-resolution spectra in Van Krevelen space both yield a slope of ~-0.5 across different SOA types. A similar slope was obtained for a distinct subset of toluene/NO x reactions in which the integrated oxidant exposure was varied to alter oxidation. The relative volatility of different SOA types displays similar variability and is strongly correlated with SOA oxidation state ( OS - ). On average, relatively low oxidation and volatility were observed for aliphatic alkene (including terpenes) and n-alkane SOA while the opposite is true for mono- and polycyclic aromatic hydrocarbon SOA. Effective enthalpy for total chamber aerosol obtained from volatility differential mobility analysis is also highly correlated with OS - c indicating a primary role for oxidation levels in determining the volatility of chamber SOA. Effective enthalpies for chamber SOA are substantially lower than those of neat organic standards but are on the order of those obtained for partially oligomerized glyoxal and methyl glyoxal.

Revisiting the size selective performance of EPA's high-volume total suspended particulate matter (Hi-Vol TSP) sampler.

Under the National Ambient Air Quality Standard (NAAQS) for airborne lead, measurements are conducted by means of a high-volume total suspended particulate matter (Hi-Vol TSP) sampler. In the decade between 1973 and 1983, there were 12 publications that explored the sampling characteristics and effectiveness of the Hi-Vol TSP, yet there persists uncertainty regarding its performance. This article presents an overview of the existing literature on the performance of the Hi-Vol TSP, and identifies the reported sampler effectiveness with respect to four factors: particle size (reported effectiveness of 7%-100%), wind speed (-36% to 100%), sampler orientation (7%-100%), and operational state (107%-140%). Effectiveness of the Hi-Vol TSP was evaluated with a solid, polydisperse aerosol in a controlled wind tunnel setting. Isokinetic samplers were deployed alongside the Hi-Vol TSP to investigate three wind speeds (2, 8, and 24 km h-1), three sampler orientations (0°, 45°, 90°), and two operational states (on, off) for aerosols with aerodynamic diameters from 5 to 35 µm. Results indicate that particle diameter was the largest determining factor of effectiveness followed by wind speed. Orientation of the sampler did not have a significant effect at 2 and 8 km h-1 but did at 24 km h-1. In a passive state, the Hi-Vol TSP was collected between 1% and 7% of available aerosol depending on particle size and wind speed. Results of this research do not invalidate results of previous studies but rather contribute to our overall understanding of the Hi-Vol TSP's size-selective performance. While results generally agreed with previous studies, the Hi-Vol TSP was found to exhibit less dependence on these four factors than previously reported.