Measuring short-chain per- and polyfluoroalkyl substances in Central New Jersey air using chemical ionization mass spectrometry.

Real-time measurements of short-chain (C < 8) per- and polyfluoroalkyl substances (PFAS) were performed in Central New Jersey air using chemical ionization mass spectrometry (CIMS). The CIMS was calibrated for C2 - C6 perfluorinated carboxylic acids, and 4:2 and 6:2 fluorotelomer alcohols. Of these, only trifluoroacetic acid (TFA) was detected in ambient air above instrumental detection limits. However, instrumental sensitivities (and thus ambient mixing ratios) were estimated for other detected PFAS including C3H2F6O and C6HF11O3. TFA mixing ratios reached up to 0.7 parts-per-trillion by volume (pptv). Estimated C3H2F6O and C6HF11O3 mixing ratios reached the single pptv level. These latter two formulas are consistent with hexafluoroisopropanol (HFIP) and hexafluoropropylene oxide dimer acid (HFPO-DA) respectively, though they may potentially represent multiple isomers. Diel profiles of detected PFAS, along with local meteorological data can provide information on potential local sources of these compounds. However, only limited discussion of potential sources was provided here given the sparse detection of these compounds above instrument detection limits. These results demonstrate the potential of online CIMS instrumentation for measuring certain PFAS in ambient outdoor air in real time at or below the pptv level. This technique also has potential for fenceline monitoring and other near-source applications.Implications: Online chemical ionization mass spectrometry (CIMS) has potential for fast, real-time measurements of certain airborne per- and polyfluoroalkyl substances (PFAS). Three short-chain (C < 8) PFAS were detected by CIMS in Central New Jersey ambient air near or above the parts-per-trillion by volume (pptv) level. This technique also has potential for fenceline monitoring and other near-source applications for airborne PFAS.

A review of sample collection and analytical methods for detecting per- and polyfluoroalkyl substances in indoor and outdoor air.

Per- and polyfluoroalkyl substances (PFAS) are a unique class of chemicals synthesized to aid in industrial processes, fire-fighting products, and to benefit consumer products such as clothing, cosmetics, textiles, carpets, and coatings. The widespread use of PFAS and their strong carbon-fluorine bonds has led to their ubiquitous presence throughout the world. Airborne transport of PFAS throughout the atmosphere has also contributed to environmental pollution. Due to the potential environmental and human exposure concerns of some PFAS, research has extensively focused on water, soil, and organismal detection, but the presence of PFAS in the air has become an area of growing concern. Methods to measure polar PFAS in various matrices have been established, while the investigation of polar and nonpolar PFAS in air is still in its early development. This literature review aims to present the last two decades of research characterizing PFAS in outdoor and indoor air, focusing on active and passive air sampling and analytical methods. The PFAS classes targeted and detected in air samples include fluorotelomer alcohols (FTOHs), perfluoroalkane sulfonamides (FASAs), perfluoroalkane sulfonamido ethanols (FASEs), perfluorinated carboxylic acids (PFCAs), and perfluorinated sulfonic acids (PFSAs). Although the manufacturing of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) has been largely phased out, these two PFAS are still often detected in air samples. Additionally, recent estimates indicate that there are thousands of PFAS that are likely present in the air that are not currently monitored in air methods. Advances in air sampling methods are needed to fully characterize the atmospheric transport of PFAS.

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.

Tubing material considerably affects measurement delays of gas-phase oxygenated per- and polyfluoroalkyl substances.

Per- and polyfluoroalkyl substances (PFAS) are persistent environmental pollutants associated with negative health impacts. Assessments of tubing-related measurement bias for volatile PFAS are lacking, as gas-wall interactions with tubing can delay quantification of gas-phase analytes. We use online iodide chemical ionization mass spectrometry measurements to characterize tubing delays for three gas-phase oxygenated PFAS - 4:2 fluorotelomer alcohol (4:2 FTOH), perfluorobutanoic acid (PFBA), and hexafluoropropylene oxide dimer acid (HFPO-DA). Perfluoroalkoxy alkane and high-density polyethylene tubing yielded relatively short absorptive measurement delays, with no clear dependence on tubing temperature or sampled humidity. Sampling through stainless steel tubing led to prolonged measurement delays due to reversible adsorption of PFAS to the tubing surface, with strong dependence on tubing temperature and sample humidification. Silcosteel tubing afforded shorter measurement delays than stainless steel due to diminished surface adsorption of PFAS. Characterizing and mitigating these tubing delays is crucial for reliable quantification of airborne PFAS.Implications: Per- and polyfluoroalkyl substances (PFAS) are persistent environmental contaminants. Many PFAS are sufficiently volatile to exist as airborne pollutants. Measurements and quantification of airborne PFAS can be biased from material-dependent gas-wall interactions with sampling inlet tubing. Thus, characterizing these gas-wall interactions are crucial for reliably investigating emissions, environmental transport, and fates of airborne PFAS.

Detailed Investigation of the Contribution of Gas-Phase Air Contaminants to Exposure Risk during Indoor Activities.

Analytical capabilities in atmospheric chemistry provide new opportunities to investigate indoor air. HOMEChem was a chemically comprehensive indoor field campaign designed to investigate how common activities, such as cooking and cleaning, impacted indoor air in a test home. We combined gas-phase chemical data of all compounds, excluding those with concentrations <1 ppt, with established databases of health effect thresholds to evaluate potential risks associated with gas-phase air contaminants and indoor activities. The chemical composition of indoor air is distinct from outdoor air, with gaseous compounds present at higher levels and greater diversity─and thus greater predicted hazard quotients─indoors than outdoors. Common household activities like cooking and cleaning induce rapid changes in indoor air composition, raising levels of multiple compounds with high risk quotients. The HOMEChem data highlight how strongly human activities influence the air we breathe in the built environment, increasing the health risk associated with exposure to air contaminants.

Behavior of Isocyanic Acid and Other Nitrogen-Containing Volatile Organic Compounds in The Indoor Environment.

Isocyanic acid (HNCO) and other nitrogen-containing volatile chemicals (organic isocyanates, hydrogen cyanide, nitriles, amines, amides) were measured during the House Observation of Microbial and Environmental Chemistry (HOMEChem) campaign. The indoor HNCO mean mixing ratio was 0.14 ± 0.30 ppb (range 0.012-6.1 ppb), higher than outdoor levels (mean 0.026 ± 0.15 ppb). From the month-long study, cooking and chlorine bleach cleaning are identified as the most important human-related sources of these nitrogen-containing gases. Gas oven cooking emits more isocyanates than stovetop cooking. The emission ratios HNCO/CO (ppb/ppm) during stovetop and oven cooking (mean 0.090 and 0.30) are lower than previously reported values during biomass burning (between 0.76 and 4.6) and cigarette smoking (mean 2.7). Bleach cleaning led to an increase of the HNCO mixing ratio of a factor of 3.5 per liter of cleaning solution used; laboratory studies indicate that isocyanates arise via reaction of nitrogen-containing precursors, such as indoor dust. Partitioned in a temperature-dependent manner to indoor surface reservoirs, HNCO was present at the beginning of HOMEChem, arising from an unidentified source. HNCO levels are higher at the end of the campaign than the beginning, indicative of occupant activities such as cleaning and cooking; however the direct emissions of humans are relatively minor.

Contrasting Chemical Complexity and the Reactive Organic Carbon Budget of Indoor and Outdoor Air.

Reactive organic carbon (ROC) comprises a substantial fraction of the total atmospheric carbon budget. Emissions of ROC fuel atmospheric oxidation chemistry to produce secondary pollutants including ozone, carbon dioxide, and particulate matter. Compared to the outdoor atmosphere, the indoor organic carbon budget is comparatively understudied. We characterized indoor ROC in a test house during unoccupied, cooking, and cleaning scenarios using various online mass spectrometry and gas chromatography measurements of gaseous and particulate organics. Cooking greatly impacted indoor ROC concentrations and bulk physicochemical properties (e.g., volatility and oxidation state), while cleaning yielded relatively insubstantial changes. Additionally, cooking enhanced the reactivities of hydroxyl radicals and ozone toward indoor ROC. We observed consistently higher median ROC concentrations indoors (≥223 µg C m-3) compared to outdoors (54 µg C m-3), demonstrating that buildings can be a net source of reactive carbon to the outdoor atmosphere, following its removal by ventilation. We estimate the unoccupied test house emitted 0.7 g C day-1 from ROC to outdoors. Indoor ROC emissions may thus play an important role in air quality and secondary pollutant formation outdoors, particularly in urban and suburban areas, and indoors during the use of oxidant-generating air purifiers.

Modeling the Removal of Water-Soluble Trace Gases from Indoor Air via Air Conditioner Condensate.

Water-soluble trace gas (WSTG) loss from indoor air via air conditioning (AC) units has been observed in several studies, but these results have been difficult to generalize. In the present study, we designed a box model that can be used to investigate and estimate WSTG removal due to partitioning to AC coil condensate. We compared the model output to measurements of a suite of organic acids cycling in an indoor environment and tested the model by varying the input AC parameters. These tests showed that WSTG loss via AC cycling is influenced by Henry's law constant of the compound in question, which is controlled by air and water temperatures and the condensate pH. Air conditioning unit specifications also impact WSTG loss through variations in the sensible heat ratio, the effective recirculation rate of air through the unit, and the timing of coil and fan operation. These findings have significant implications for indoor modeling. To accurately model the fate of indoor WSTGs, researchers must either measure or otherwise account for these unique environmental and operational characteristics.

Spatial and temporal scales of variability for indoor air constituents.

Historically air constituents have been assumed to be well mixed in indoor environments, with single point measurements and box modeling representing a room or a house. Here we demonstrate that this fundamental assumption needs to be revisited through advanced model simulations and extensive measurements of bleach cleaning. We show that inorganic chlorinated products, such as hypochlorous acid and chloramines generated via multiphase reactions, exhibit spatial and vertical concentration gradients in a room, with short-lived ⋅OH radicals confined to sunlit zones, close to windows. Spatial and temporal scales of indoor constituents are modulated by rates of chemical reactions, surface interactions and building ventilation, providing critical insights for better assessments of human exposure to hazardous pollutants, as well as the transport of indoor chemicals outdoors.

Secondary organic aerosol formation from evaporated biofuels: comparison to gasoline and correction for vapor wall losses.

With an ongoing interest in displacing petroleum-based sources of energy with biofuels, there is a need to measure and model the formation and composition of secondary organic aerosol (SOA) from organic compounds present in biofuels. We performed chamber experiments to study SOA formation from four recently identified biofuel molecules and mixtures and commercial gasoline under high NOx conditions: diisobutylene, cyclopentanone, an alkylfuran mixture, and an ethanol-to-hydrocarbon (ETH) mixture. Cyclopentanone and diisobutylene had a significantly lower potential to form SOA compared to commercial gasoline, with SOA mass yields lower than or equal to 0.2%. The alkylfuran mixture had an SOA mass yield (1.6%) roughly equal to that of gasoline (2.0%) but ETH had an average SOA mass yield (11.5%) that was six times higher than that of gasoline. We used a state-of-the-science model to parameterize or simulate the SOA formation in the chamber experiments while accounting for the influence of vapor wall losses. Simulations performed with vapor wall losses turned off and at atmospherically relevant conditions showed that the SOA mass yields were higher than those measured in the chamber at the same photochemical exposure and were also higher than those estimated using a volatility basis set that was fit to the chamber data. The modeled SOA mass yields were higher primarily because they were corrected for vapor wall losses to the Teflon® chamber.

Surface reservoirs dominate dynamic gas-surface partitioning of many indoor air constituents.

Human health is affected by indoor air quality. One distinctive aspect of the indoor environment is its very large surface area that acts as a poorly characterized sink and source of gas-phase chemicals. In this work, air-surface interactions of 19 common indoor air contaminants with diverse properties and sources were monitored in a house using fast-response, on-line mass spectrometric and spectroscopic methods. Enhanced-ventilation experiments demonstrate that most of the contaminants reside in the surface reservoirs and not, as expected, in the gas phase. They participate in rapid air-surface partitioning that is much faster than air exchange. Phase distribution calculations are consistent with the observations when assuming simultaneous equilibria between air and large weakly polar and polar absorptive surface reservoirs, with acid-base dissociation in the polar reservoir. Chemical exposure assessments must account for the finding that contaminants that are fully volatile under outdoor air conditions instead behave as semivolatile compounds indoors.

Multiphase Chemistry Controls Inorganic Chlorinated and Nitrogenated Compounds in Indoor Air during Bleach Cleaning.

We report elevated levels of gaseous inorganic chlorinated and nitrogenated compounds in indoor air while cleaning with a commercial bleach solution during the House Observations of Microbial and Environmental Chemistry field campaign in summer 2018. Hypochlorous acid (HOCl), chlorine (Cl2), and nitryl chloride (ClNO2) reached part-per-billion by volume levels indoors during bleach cleaning-several orders of magnitude higher than typically measured in the outdoor atmosphere. Kinetic modeling revealed that multiphase chemistry plays a central role in controlling indoor chlorine and reactive nitrogen chemistry during these periods. Cl2 production occurred via heterogeneous reactions of HOCl on indoor surfaces. ClNO2 and chloramine (NH2Cl, NHCl2, NCl3) production occurred in the applied bleach via aqueous reactions involving nitrite (NO2-) and ammonia (NH3), respectively. Aqueous-phase and surface chemistry resulted in elevated levels of gas-phase nitrogen dioxide (NO2). We predict hydroxyl (OH) and chlorine (Cl) radical production during these periods (106 and 107 molecules cm-3 s-1, respectively) driven by HOCl and Cl2 photolysis. Ventilation and photolysis accounted for <50% and <0.1% total loss of bleach-related compounds from indoor air, respectively; we conclude that uptake to indoor surfaces is an important additional loss process. Indoor HOCl and nitrogen trichloride (NCl3) mixing ratios during bleach cleaning reported herein are likely detrimental to human health.

Interpretation of detections of volcanic activity at Ioto Island obtained from in situ seismometers and remote hydrophones of the International Monitoring System.

In-situ seismic observations identified that volcanic activity of Ioto (formerly Iwojima), a volcanic island offshore Japan, increased in early September 2018. Observations of discolored nearshore waters and a splash reported by a local flyover provided evidence for a connection between undersea eruptions and recorded seismic activity. However there remain uncertainties as to when the undersea eruption series commenced and how much of the in-situ seismic activity recorded on the island was associated with volcanic earthquakes versus undersea eruptions. During this period, a large number of underwater acoustic (hydroacoustic) signals were recorded by the Comprehensive Nuclear-Test-Ban Treaty (CTBT) International Monitoring System (IMS) hydroacoustic station HA11, at Wake Island (U.S. Territory), in the northwestern Pacific Ocean with signals with directions of arrival consistent with sources located at Ioto. The analysis presented here interprets signal features of the remote hydroacoustic recordings provided by HA11 in order to attempt to distinguish between volcanic earthquake signals and undersea eruption signals originating from Ioto. Histograms of hydroacoustic events interpreted as originating from Ioto correlate well with the in-situ seismic observations at Ioto in the early stage of volcanic activity. The results presented suggest that around 75% of the signals detected at HA11 with directions of arrival consistent with Ioto as their origin could be associated with undersea eruptions, supporting the conclusion that the IMS hydroacoustic stations can contribute to volcanic event remote monitoring.

Emission of formic and acetic acids from two Colorado soils.

A 'missing source' of atmospheric formic acid is consistently observed during model-measurement comparisons, and evidence from multiple environments suggests a near-surface source. Soil emissions are considered to be a small formic acid source, but estimates are based on a single study from a tropical site. Here, we investigate soil emissions of organic acids from two soils - a ponderosa pine forest (Manitou Experimental Forest Observatory), and a managed lawn (Colorado State University) using a laboratory chamber. Both soils are a source of formic and acetic acids. Under ambient conditions, formic acid emissions are 0.11 (pine forest) and 0.15 (lawn) nmol m-2 s-1, and acetic acid emissions are 0.05 (pine forest) and 0.71 (lawn) nmol m-2 s-1. Only acetic acid emissions from the forest site correlate with CO2 fluxes, but all formic and acetic acid emissions increase exponentially with temperature. Increasing soil moisture only enhances acetic acid emissions from the forest. Considering this temperature and moisture dependence, we hypothesize that while equilibrium partitioning may contribute to the forest emissions, organic acid emissions from the lawn are likely driven by microbial activity. Lactic acid was emitted from both soils, but not quantified. The observed formic acid emissions are higher than previous measurements, but still low enough that soils are unlikely the 'missing source' of atmospheric organic acids, although the variability in the soil source is substantial. We contrast observations to previous parameterizations used in models, and present recommendations for modified parameterizations for formic and acetic acid emission.