Impact of Biomass Burning Organic Aerosol Volatility on Smoke Concentrations Downwind of Fires.

Biomass burning particulate matter (BBPM) affects regional air quality and global climate, with impacts expected to continue to grow over the coming years. We show that studies of North American fires have a systematic altitude dependence in measured BBPM normalized excess mixing ratio (NEMR; ΔPM/ΔCO), with airborne and high-altitude studies showing a factor of 2 higher NEMR than ground-based measurements. We report direct airborne measurements of BBPM volatility that partially explain the difference in the BBPM NEMR observed across platforms. We find that when heated to 40-45 °C in an airborne thermal denuder, 19% of lofted smoke PM1 evaporates. Thermal denuder measurements are consistent with evaporation observed when a single smoke plume was sampled across a range of temperatures as the plume descended from 4 to 2 km altitude. We also demonstrate that chemical aging of smoke and differences in PM emission factors can not fully explain the platform-dependent differences. When the measured PM volatility is applied to output from the High Resolution Rapid Refresh Smoke regional model, we predict a lower PM NEMR at the surface compared to the lofted smoke measured by aircraft. These results emphasize the significant role that gas-particle partitioning plays in determining the air quality impacts of wildfire smoke.

Reactive Chlorine Emissions from Cleaning and Reactive Nitrogen Chemistry in an Indoor Athletic Facility.

Indoor gas-phase radical sources are poorly understood but expected to be much different from outdoors. Several potential radical sources were measured in a windowless, light-emitting diode (LED)-lit room in a college athletic facility over a 2 week period. Alternating measurements between the room air and the supply air of the heating, ventilation, and air-conditioning system allowed an assessment of sources. Use of a chlorine-based cleaner was a source of several photolabile reactive chlorine compounds, including ClNO2 and Cl2. During cleaning events, photolysis rates for these two compounds were up to 0.0023 pptv min-1, acting as a source of chlorine atoms even in this low-light indoor environment. Unrelated to cleaning events, elevated ClNO2 was often observed during daytime and lost to ventilation. The nitrate radical (NO3), which is rapidly photolyzed outdoors during daytime, may persist in low-light indoor environments. With negligible photolysis, loss rates of NO3 indoors were dominated by bimolecular reactions. At times with high NO2 and O3 ventilated from outdoors, N2O5 was observed. Elevated ClNO2 measured concurrently suggests the formation through heterogeneous reactions, acting as an additional source of reactive chlorine within the athletic facility and outdoors.

Understanding the Evolution of Smoke Mass Extinction Efficiency Using Field Campaign Measurements.

Aerosol mass extinction efficiency (MEE) is a key aerosol property used to connect aerosol optical properties with aerosol mass concentrations. Using measurements of smoke obtained during the Fire Influence on Regional to Global Environments and Air Quality (FIREX-AQ) campaign we find that mid-visible smoke MEE can change by a factor of 2-3 between fresh smoke (<2 hr old) and one-day-old smoke. While increases in aerosol size partially explain this trend, changes in the real part of the aerosol refractive index (real(n)) are necessary to provide closure assuming Mie theory. Real(n) estimates derived from multiple days of FIREX-AQ measurements increase with age (from 1.40 - 1.45 to 1.5-1.54 from fresh to one-day-old) and are found to be positively correlated with organic aerosol oxidation state and aerosol size, and negatively correlated with smoke volatility. Future laboratory, field, and modeling studies should focus on better understanding and parameterizing these relationships to fully represent smoke aging.

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.

Quantification and source characterization of volatile organic compounds from exercising and application of chlorine-based cleaning products in a university athletic center.

Humans spend approximately 90% of their time indoors, impacting their own air quality through occupancy and activities. Human VOC emissions indoors from exercise are still relatively uncertain, and questions remain about emissions from chlorine-based cleaners. To investigate these and other issues, the ATHLETic center study of Indoor Chemistry (ATHLETIC) campaign was conducted in the weight room of the Dal Ward Athletic Center at the University of Colorado Boulder. Using a Vocus Proton-Transfer-Reaction Time-of-Flight Mass Spectrometer (Vocus PTR-TOF), an Aerodyne Gas Chromatograph (GC), an Iodide-Chemical Ionization Time-of-Flight Mass Spectrometer (I-CIMS), and Picarro cavity ringdown spectrometers, we alternated measurements between the weight room and supply air, allowing for determination of VOC, NH3 , H2 O, and CO2 emission rates per person (emission factors). Human-derived emission factors were higher than previous studies of measuring indoor air quality in rooms with individuals at rest and correlated with increased CO2 emission factors. Emission factors from personal care products (PCPs) were consistent with previous studies and typically decreased throughout the day. In addition, N-chloraldimines were observed in the gas phase after the exercise equipment was cleaned with a dichlor solution. The chloraldimines likely originated from reactions of free amino acids with HOCl on gym surfaces.

Real-time organic aerosol chemical speciation in the indoor environment using extractive electrospray ionization mass spectrometry.

Understanding the sources and composition of organic aerosol (OA) in indoor environments requires rapid measurements, since many emissions and processes have short timescales. However, real-time molecular-level OA measurements have not been reported indoors. Here, we present quantitative measurements, at a time resolution of five seconds, of molecular ions corresponding to diverse aerosol-phase species, by applying extractive electrospray ionization mass spectrometry (EESI-MS) to indoor air analysis for the first time, as part of the highly instrumented HOMEChem field study. We demonstrate how the complex spectra of EESI-MS are screened in order to extract chemical information and investigate the possibility of interference from gas-phase semivolatile species. During experiments that simulated the Thanksgiving US holiday meal preparation, EESI-MS quantified multiple species, including fatty acids, carbohydrates, siloxanes, and phthalates. Intercomparisons with Aerosol Mass Spectrometer (AMS) and Scanning Mobility Particle Sizer suggest that EESI-MS quantified a large fraction of OA. Comparisons with FIGAERO-CIMS shows similar signal levels and good correlation, with a range of 100 for the relative sensitivities. Comparisons with SV-TAG for phthalates and with SV-TAG and AMS for total siloxanes also show strong correlation. EESI-MS observations can be used with gas-phase measurements to identify co-emitted gas- and aerosol-phase species, and this is demonstrated using complementary gas-phase PTR-MS observations.

Measurements and modeling of absorptive partitioning of volatile organic compounds to painted surfaces.

Partitioning to surfaces is an important sink for volatile organic compounds (VOCs) indoors, but the mechanisms are not well understood or quantified. Here, a mass spectrometer was coupled to a portable surface reactor and a flow tube to measure partitioning of VOCs into paint films coated onto glass or wallboard, and their subsequent diffusion. A model was developed to extract values of the effective absorbing organic mass concentration of the film, Cw , which is a measure of absorption capacity, and VOC diffusion coefficients, Df , from VOC time profiles measured during film passivation and depassivation. Values of Cw agreed well with the value estimated from the paint film mass and flow tube air volume, and Df values (also measured using attenuated total reflectance-Fourier transform infrared spectroscopy) correlated well with VOC vapor saturation concentrations, C*, estimated using a group contribution method. The value of these relationships for estimating key parameters that control VOC partitioning into paint and the fate of VOCs indoors was demonstrated using a house model, which indicated that >50% of VOCs with C* ≤108  µg/m3 (C* of octane, hexanone, and propanol) that contacted a paint film of typical thickness fully permeated the film regardless of emission duration.

Budgets of Organic Carbon Composition and Oxidation in Indoor Air.

The chemical composition of indoor air at the University of Colorado, Boulder art museum was measured by a suite of gas- and particle-phase instruments. Over 80% of the total observed organic carbon (TOOC) mass (100 µg m-3) consisted of reduced compounds (carbon oxidation state, OSC < -0.5) with high volatility (log10 C* > 7) and low carbon number (nC < 6). The museum TOOC was compared to other indoor and outdoor locations, which increased according to the following trend: remote < rural ≤ urban < indoor ≤ megacity. The museum TOOC was comparable to a university classroom and 3× less than residential environments. Trends in the total reactive flux were remote < indoor < rural < urban < megacity. High volatile organic compound (VOC) concentrations compensated low oxidant concentrations indoors to result in an appreciable reactive flux. Total hydroxyl radical (OH), ozone (O3), nitrate radical (NO3), and chlorine atom (Cl) reactivities for each location followed a similar trend to TOOC. High human occupancy events increased all oxidant reactivities in the museum by 65-125%. The lifetimes of O3, NO3, OH, and Cl reactivities were 13 h, 15 h, 23 days, and 189 days, respectively, corresponding to over 88% of indoor VOC oxidant reactivity being consumed outdoors after ventilation.

A Library of Proton-Transfer Reactions of H3O+ Ions Used for Trace Gas Detection.

We have collected data on the proton-transfer reactions with H3O+ ions for trace gas detection into an online and publicly available library. The library allows users of proton-transfer-reaction mass spectrometry (PTR-MS) and selected-ion flow-tube mass spectrometry (SIFT-MS) to look up at which m/z a trace gas of interest is detected. Vice versa, the library also allows looking up what trace gas may have been responsible for a product ion detected in PTR-MS and SIFT-MS. Finally, the library may serve as a dataset for further research on calculating instrument sensitivity and product-ion fragmentation, improving identification and quantification of newly detectable compounds as advances in instrumentation continue. To demonstrate the utility of the library, we present a brief analysis of product-ion fragmentation. We show that oxygenated organic compounds exhibit trends in neutral loss according to their functionality, and that on average neutral losses decrease the carbon number and increase the extent of unsaturation of product ions. Graphical Abstract.

Time-Resolved Measurements of Indoor Chemical Emissions, Deposition, and Reactions in a University Art Museum.

A 6-week study was conducted at the University of Colorado Art Museum, during which volatile organic compounds (VOCs), carbon dioxide (CO2), ozone (O3), nitric oxide (NO), nitrogen dioxide (NO2), other trace gases, and submicron aerosol were measured continuously. These measurements were then analyzed using a box model to quantify the rates of major processes that transformed the composition of the air. VOC emission factors were quantified for museum occupants and their activities. The deposition of VOCs to surfaces was quantified across a range of VOC saturation vapor concentrations ( C*) and Henry's Law constants ( H) and determined to be a major sink for VOCs with C* < 108 µg m-3 and H > 102 M atm-1. The reaction rates of VOCs with O3, OH radicals, and nitrate (NO3) radicals were quantified, with unsaturated and saturated VOCs having oxidation lifetimes of >5 and >15 h, making deposition to surfaces and ventilation the dominant VOC sinks in the museum. O3 loss rates were quantified inside a museum gallery, where reactions with surfaces, NO, occupants, and NO2 accounted for 62%, 31%, 5%, and 2% of the O3 sink. The measured concentrations of acetic acid, formic acid, NO2, O3, particulate matter, sulfur dioxide, and total VOCs were below the guidelines for museums.

Hygroscopicity of Organic Compounds as a Function of Carbon Chain Length and Carboxyl, Hydroperoxy, and Carbonyl Functional Groups.

The albedo and microphysical properties of clouds are controlled in part by the hygroscopicity of particles serving as cloud condensation nuclei (CCN). Hygroscopicity of complex organic mixtures in the atmosphere varies widely and remains challenging to predict. Here we present new measurements characterizing the CCN activity of pure compounds in which carbon chain length and the numbers of hydroperoxy, carboxyl, and carbonyl functional groups were systematically varied to establish the contributions of these groups to organic aerosol apparent hygroscopicity. Apparent hygroscopicity decreased with carbon chain length and increased with polar functional groups in the order carboxyl > hydroperoxy > carbonyl. Activation diameters at different supersaturations deviated from the -3/2 slope in log-log space predicted by Köhler theory, suggesting that water solubility limits CCN activity of particles composed of weakly functionalized organic compounds. Results are compared to a functional group contribution model that predicts CCN activity of organic compounds. The model performed well for most compounds but underpredicted the CCN activity of hydroperoxy groups. New best-fit hydroperoxy group/water interaction parameters were derived from the available CCN data. These results may help improve estimates of the CCN activity of ambient organic aerosols from composition data.

Quantification of Gas-Wall Partitioning in Teflon Environmental Chambers Using Rapid Bursts of Low-Volatility Oxidized Species Generated in Situ.

Partitioning of gas-phase organic compounds to the walls of Teflon environmental chambers is a recently reported phenomenon than can affect the yields of reaction products and secondary organic aerosol (SOA) measured in laboratory experiments. Reported time scales for reaching gas-wall partitioning (GWP) equilibrium (τGWE) differ by up to 3 orders of magnitude, however, leading to predicted effects that vary from substantial to negligible. A new technique is demonstrated here in which semi- and low-volatility oxidized organic compounds (saturation concentration c* < 100 µg m(-3)) were photochemically generated in rapid bursts in situ in an 8 m(3) environmental chamber, and then their decay in the absence of aerosol was measured using a high-resolution chemical ionization mass spectrometer (CIMS) equipped with an "inlet-less" NO3(-) ion source. Measured τGWE were 7-13 min (rel. std. dev. 33%) for all compounds. The fraction of each compound that partitioned to the walls at equilibrium follows absorptive partitioning theory with an equivalent wall mass concentration in the range 0.3-10 mg m(-3). Measurements using a CIMS equipped with a standard ion-molecule reaction region showed large biases due to the contact of compounds with walls. On the basis of these results, a set of parameters is proposed for modeling GWP in chamber experiments.