Ozone Chemistry on Greasy Glass Surfaces Affects the Levels of Volatile Organic Compounds in Indoor Environments.

The chemistry of ozone (O3) on indoor surfaces leads to secondary pollution, aggravating the air quality in indoor environments. Here, we assess the heterogeneous chemistry of gaseous O3 with glass plates after being 1 month in two different kitchens where Chinese and Western styles of cooking were applied, respectively. The uptake coefficients of O3 on the authentic glass plates were measured in the dark and under UV light irradiation typical for indoor environments (320 nm < λ < 400 nm) at different relative humidities. The gas-phase product compounds formed upon reactions of O3 with the glass plates were evaluated in real time by a proton-transfer-reaction quadrupole-interface time-of-flight mass spectrometer. We observed typical aldehydes formed by the O3 reactions with the unsaturated fatty acid constituents of cooking oils. The formation of decanal, 6-methyl-5-hepten-2-one (6-MHO), and 4-oxopentanal (4-OPA) was also observed. The employed dynamic mass balance model shows that the estimated mixing ratios of hexanal, octanal, nonanal, decanal, undecanal, 6-MHO, and 4-OPA due to O3 chemistry with authentic grime-coated kitchen glass surfaces are higher in the kitchen where Chinese food was cooked compared to that where Western food was cooked. These results show that O3 chemistry on greasy glass surfaces leads to enhanced VOC levels in indoor environments.

Emissions of Volatile Organic Compounds from Human Occupants in a Student Office: Dependence on Ozone Concentration.

Human occupants themselves constitute an important source of volatile organic compounds (VOCs) in indoor environments through breath and dermal emissions. In order to quantify VOC emissions from occupants under real-world settings, previous indoor observational studies often determined emission factors (i.e., average emission rates per person). However, the values obtained across these studies exhibited large variability, and the causes of this variability still need to be understood. Herein we report 10-day real-time VOC measurements in a university student office, using a proton transfer reaction-quadrupole interface-time-of-flight mass spectrometer. A method was developed to identify VOCs of primary human origin and to quantify the corresponding emission factors, accounting for the dynamically changing occupancy level and ventilation rate in the assessed office. We found that the emission factors of many dermally emitted VOCs strongly increased as the ozone concentration increased from <3 to 10-15 ppb. These VOCs include geranyl acetone, 6-methyl-5-hepten-2-one (6-MHO), and C10-C12 saturated aldehydes, which align with characteristic first-generation ozonolysis products of skin oil. The strongest increase occurred for 6-MHO, from 113 to 337 µg/h/p. In comparison, acetone and isoprene, which are primarily emitted from human breath, varied little with the ozone level. In light of this finding, we conducted an integrated analysis of emission factors reported in the literature for two frequently reported species, namely, 6-MHO and decanal. Ozone concentration alone can explain 94-97% of the variation in their emission factors across previous studies, and the best-estimated ozone dependence obtained using the literature data is consistent with those obtained in the current study. These results suggest that the ozone concentration is a key factor regulating emission factors of many dermally emitted VOCs in real indoor environments, which has to be considered when reporting or using the emission factors.

Quantifying Ozone-Dependent Emissions of Volatile Organic Compounds from the Human Body.

Ozone reactions on human body surfaces produce volatile organic compounds (VOCs) that influence indoor air quality. However, the dependence of VOC emissions on the ozone concentration has received limited attention. In this study, we conducted 36 sets of single-person chamber experiments with three volunteers exposed to ozone concentrations ranging from 0 to 32 ppb. Emission fluxes from human body surfaces were measured for 11 targeted skin-oil oxidation products. For the majority of these products, the emission fluxes linearly correlated with ozone concentration, indicating a constant surface yield (moles of VOC emitted per mole of ozone deposited). However, for the second-generation oxidation product 4-oxopentanal, a higher surface yield was observed at higher ozone concentrations. Furthermore, many VOCs have substantial emissions in the absence of ozone. Overall, these results suggest that the complex surface reactions and mass transfer processes involved in ozone-dependent VOC emissions from the human body can be represented using a simplified parametrization based on surface yield and baseline emission flux. Values of these two parameters were quantified for targeted products and estimated for other semiquantified VOC signals, facilitating the inclusion of ozone/skin oil chemistry in indoor air quality models and providing new insights on skin oil chemistry.