Ethylene Oxide in Southeastern Louisiana's Petrochemical Corridor: High Spatial Resolution Mobile Monitoring during HAP-MAP.

Ethylene oxide ("EtO") is an industrially made volatile organic compound and a known human carcinogen. There are few reliable reports of ambient EtO concentrations around production and end-use facilities, however, despite major exposure concerns. We present in situ, fast (1 Hz), sensitive EtO measurements made during February 2023 across the southeastern Louisiana industrial corridor. We aggregated mobile data at 500 m spatial resolution and reported average mixing ratios for 75 km of the corridor. Mean and median aggregated values were 31.4 and 23.3 ppt, respectively, and a majority (75%) of 500 m grid cells were above 10.9 ppt, the lifetime exposure concentration corresponding to 100-in-one million excess cancer risk (1 × 10-4). A small subset (3.3%) were above 109 ppt (1000-in-one million cancer risk, 1 × 10-3); these tended to be near EtO-emitting facilities, though we observed plumes over 10 km from the nearest facilities. Many plumes were highly correlated with other measured gases, indicating potential emission sources, and a subset was measured simultaneously with a second commercial analyzer, showing good agreement. We estimated EtO for 13 census tracts, all of which were higher than EPA estimates (median difference of 21.3 ppt). Our findings provide important information about EtO concentrations and potential exposure risks in a key industrial region and advance the application of EtO analytical methods for ambient sampling and mobile monitoring for air toxics.

Simulating indoor inorganic aerosols of outdoor origin with the inorganic aerosol thermodynamic equilibrium model ISORROPIA.

Outdoor aerosols can transform and have their composition altered upon transport indoors. Herein, IMAGES, a platform that simulates indoor organic aerosol with the 2-dimensional volatility basis set (2D-VBS), was extended to incorporate the inorganic aerosol thermodynamic equilibrium model, ISORROPIA. The model performance was evaluated by comparing aerosol component predictions to indoor measurements from an aerosol mass spectrometer taken during the summer and winter seasons. Since ammonia was not measured in the validation dataset, outdoor ammonia was estimated from aerosol measurements using a novel pH-based algorithm, while nitric acid was held constant. Modeled indoor ammonia sources included temperature-based occupant and surface emissions. Sensitivity to the nitric acid indoor surface deposition rate ß g , HNO 3 , g was explored by varying it in model runs, which did not affect modeled sulfate due to its non-volatile nature, though the fitting of a filter efficiency was required for good correlations of modeled sulfate with measurements in both seasons. Modeled summertime nitrate well-matched measured observations when ß g , HNO 3 , g = 2.75 h - 1 , but wintertime comparisons were poor, possibly due to missing thermodynamic processes within the heating, ventilating, and air-conditioning (HVAC) system. Ammonium was consistently overpredicted, potentially due to neglecting thirdhand smoke impacts observed in the field campaign, as well as HVAC impacts.

Improving Predictions of Indoor Aerosol Concentrations of Outdoor Origin by Considering the Phase Change of Semivolatile Material Driven by Temperature and Mass-Loading Gradients.

Outdoor aerosols experience environmental changes as they are transported indoors, including outdoor-to-indoor temperature and mass-loading gradients, which can reduce or enhance their indoor concentrations due to repartitioning driven by changes in thermodynamic equilibrium states. However, the complexity required to model repartitioning typically hinders its inclusion in studies predicting indoor exposure to ambient aerosols. To facilitate exposure predictions, this work used an explicit thermodynamic indoor aerosol model to simulate outdoor-to-indoor aerosol repartitioning typical for residential and office buildings across the 16 U.S. climate zones over an annual time horizon. Results demonstrate that neglecting repartitioning when predicting indoor concentrations can produce errors of up to 80-100% for hydrocarbon-like organic aerosol, 40-60% for total organic aerosol, 400% for ammonium nitrate, and 60% (typically 3 µg/m3) for the total PM2.5 aerosol. Underpredictions were more likely for buildings in hotter than colder regions, and for residences than offices, since both cooler indoor air and more meaningful residential organic aerosol concentrations encourage condensation of semivolatile organics. Furthermore, a method for computing correction factors to more easily account for thermodynamic repartitioning is provided. Applying these correction factors to mechanical-only aerosol predictions significantly reduced errors to <0.5 µg/m3 for the total indoor PM2.5 while bypassing explicit thermodynamic simulations.

Correction: Seasonal variation in aerosol composition and concentration upon transport from the outdoor to indoor environment.

Correction for 'Seasonal variation in aerosol composition and concentration upon transport from the outdoor to indoor environment' by Anita M. Avery et al., Environ. Sci.: Processes Impacts, 2019, 21, 528-547.

Human occupant contribution to secondary aerosol mass in the indoor environment.

Humans impact indoor air quality directly via emissions from skin, breath, or personal care products, and indirectly via reactions of oxidants with skin constituents, or with skin that has been shed. However, separating the influence of the many emissions and their oxidation products from the influence of outdoor-originated aerosols has been a challenge. Indoor and outdoor aerosols were alternatively sampled at 4 minute time resolution with a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) in a classroom with student occupants at regular intervals per university class schedule. Mass spectral analysis showed aerosol enhancements of oxidized and unoxidized hydrocarbon ion families during occupied periods, especially at ion fragments larger than m/z 100 and double bond equivalents consistent with squalene (C30H50) and its oxidized products from reaction with ozone, indicative of the secondary nature of the aerosol mass. Individual hydrocarbon mass fragments consistent with squalene fragmentation, including C5H9+, and C6H9+ were especially enhanced with room occupancy. Emissions of individual organic fragment ions were estimated using a model accounting for outdoor aerosols and air exchange. This showed occupancy related emissions at smaller fragments (C3H5+, C4H9+) that despite reflecting mostly outdoor-originated aerosols transported indoors, also show enhancements from occupant emissions indoors. Total emission of all fragments was 17.6 µg ß-1 h-1 above unoccupied levels, translating to approximately 25% increase in organic aerosol mass concentration in the classroom during an occupied hour with a median occupied ozone loss (ß). Human occupants, therefore, represent an additional mass burden of organic aerosol, especially in poorly ventilated or highly occupied indoor spaces.

Seasonal variation in aerosol composition and concentration upon transport from the outdoor to indoor environment.

Outdoor-originated aerosols are an important component impacting indoor air quality. Since outdoor aerosols vary over short (diurnal) and long (seasonal) timescales, we examined how the variation in outdoor aerosol concentration and composition impact indoor aerosol. Measurements of both indoor and outdoor aerosol composition in real time in an urban classroom in winter and summer seasons were performed using an aerosol mass spectrometer (AMS), aethalometer, and a suite of gas phase instruments. Factor analysis of the organic aerosol components identified three factors in common between seasons, including hydrocarbon-like, cooking, and oxidized organic aerosol (HOA, COA, and OOA). Since sulfate is non-volatile, we report a sulfate-normalized indoor-outdoor ratio (I/O)i/SO4 for measured aerosol i components, allowing us to estimate aerosol component-based effects of seasonal and other variations in ventilation and HVAC operation, indoor emission sources, and chemically-based loss processes between outdoor and indoor environments. These chemical loss processes are interpreted in terms of changes in temperature and relative humidity (RH) between environments, which fluctuate on a daily and seasonal basis. The degree to which any effect is observed depends on the particular outdoor aerosol population and the magnitude of temperature or RH change. In wintertime, when aerosols were warmed upon transport indoors and loss of volatile components is favored, median (I/O)i/SO4 values for nitrate, total organics, HOA, and BC were smaller (0.35, 1.00, 1.24, and 1.18, respectively) than summertime values (0.75, 1.17, 1.96, and 1.80). For COA and OOA, however, (I/O)i/SO4 values were higher in the winter than in summer. Calculated aerosol liquid water (ALW), which is a function of temperature and RH and the relative contribution of hygroscopic components, varied significantly by season. Summertime ALW indoors provides a medium for aqueous processing, which is necessary for some hydrophilic gas phase reaction products that are important to indoor air quality and occupant exposure. This work describes the linkages between seasonal variability in aerosol composition outdoors and the subsequent chemically-specific variation observed when that aerosol is brought indoors.

Thirdhand smoke uptake to aerosol particles in the indoor environment.

Aerosol composition measurements made in an indoor classroom indicate the uptake of thirdhand smoke (THS) species to indoor particles, a novel exposure route for THS to humans indoors. Chemical speciation of the organic aerosol fraction using mass spectrometric data and factor analysis identified a reduced nitrogen component, predominantly found in the indoor environment, contributing 29% of the indoor submicron aerosol mass. We identify this factor as THS compounds partitioning from interior surfaces to gas phase and then aerosol phase. Partitioning of THS vapors to aerosols requires an aqueous phase for reactive uptake of the reduced nitrogen species (RdNS), leading to seasonal differences in THS concentration indoors. RdNS protonate under the acidic conditions expected for indoor aerosols of outdoor origin. Controlled laboratory measurements performed using cigarette smoke deposited into a Pyrex vessel showed a similar partitioning behavior to aerosol of outdoor origin and mass spectral features comparable to the measured indoor THS factor after 1 week of residence time in the closed vessel. This study reports a new, potentially large THS exposure route from partitioning of surface volatile organic compounds into the aerosol phase and subsequent dispersion in a mechanically ventilated building.