科研成果 by Year: 2023

2023
Liu, W. ; Liao, K. ; Chen, Q. ; He, L. ; Liu, Y. ; Kuwata, M. Existence of Crystalline Ammonium Sulfate Nuclei Affects Chemical Reactivity of Oleic Acid Particles Through Heterogeneous Nucleation. Journal of Geophysical Research: Atmospheres 2023, 128, e2023JD038675. 访问链接Abstract
Organic aerosol particles are oxidized by atmospheric oxidants. These particles are occasionally internally mixed with solid materials such as soot and inorganic crystals. However, potential impacts of the particles' mixing states on chemical reactivity have rarely been investigated. This study investigated the influence of the existence of crystalline ammonium sulfate on chemical reactivity of oleic acid particles with ozone for the temperature range of −20°C to +35°C using an aerosol flow tube reactor. The chemical compositions of the resulting particles were monitored using online instruments for deriving the reactive uptake coefficients (γ) of ozone by oleic acid. The values of γ were not significantly influenced by the existence of ammonium sulfate when the temperature of the reactor was higher than the melting point of oleic acid (∼13°C). The values of γ were unmeasurably small for the lower temperature range when oleic acid particles were internally mixed with crystalline ammonium sulfate. No significant change in γ was observed for the temperature range down to −13°C when the inorganic salt was absent, likely due to the formation of supercooled liquid. The difference in chemical reactivity can be explained by the occurrence of heterogeneous nucleation induced by inorganic seed.
Li, Y. ; Hou, J. ; Wang, Z. ; Dai, X. ; Sun, Y. ; Liu, J. ; Liu, Y. Phthalate Levels in Chinese Residences: Seasonal and Regional Variations and the Implication on Human Exposure. National Science Open 2023, 2, 6. 访问链接Abstract
Indoor pollution of manmade semivolatile organic compounds (SVOCs) such as phthalates are a growing threat to human health. Herein we summarize the dust-phase phthalate concentrations in Chinese residences reported from 2011 to 2021 and simulate corresponding airborne concentrations based on equilibrium models. The simulation considers seasonal and regional variations in indoor temperature and PM2.5 concentration, in contrast to the common practice of using constant values. Results show that variations in these two environmental factors lead to up to ten- and six-fold variations in the monthly median gas- and particle-phase concentrations of phthalates, respectively, in residences in individual climate zones. For higher-vapor-pressure species di-n-butyl phthalate and di-isobutyl phthalate, the resultant seasonal and regional variations in aggregate non-diet intake can reach six- and three-fold, respectively. These results have important implications on exposure assessment of SVOCs and epidemiological evaluation of their health effects.
Qu, Y. ; Zou, Z. ; Weschler, C. J. ; Liu, Y. ; Yang, X. Quantifying Ozone-Dependent Emissions of Volatile Organic Compounds from the Human Body. Environmental Science & Technology 2023, 57, 13104–13113. 访问链接Abstract
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.
Kristensen, K. ; Lunderberg, D. M. ; Liu, Y. J. ; Misztal, P. K. ; Tian, Y. ; Arata, C. ; Nazaroff, W. W. ; Goldstein, A. H. Gas-Particle Partitioning of Semivolatile Organic Compounds in a Residence: Influence of Particles from Candles, Cooking, and Uutdoors. Environmental Science & Technology 2023, 57, 3260–3269. 访问链接Abstract
Semivolatile organic compounds (SVOCs) represent an important class of indoor pollutants. The partitioning of SVOCs between airborne particles and the adjacent air influences human exposure and uptake. Presently, little direct experimental evidence exists about the influence of indoor particle pollution on the gas–particle phase partitioning of indoor SVOCs. In this study, we present time-resolved gas- and particle-phase distribution data for indoor SVOCs in a normally occupied residence using semivolatile thermal desorption aerosol gas chromatography. Although SVOCs in indoor air are found mostly in the gas phase, we show that indoor particles from cooking, candle use, and outdoor particle infiltration strongly affect the gas–particle phase distribution of specific indoor SVOCs. From gas- and particle-phase measurements of SVOCs spanning a range of chemical functionalities (alkanes, alcohols, alkanoic acids, and phthalates) and volatilities (vapor pressures from 10–13 to 10–4 atm), we find that the chemical composition of the airborne particles influences the partitioning of individual SVOC species. During candle burning, the enhanced partitioning of gas-phase SVOCs to indoor particles not only affects the particle composition but also enhances surface off-gassing, thereby increasing the total airborne concentration of specific SVOCs, including diethylhexyl phthalate.
Qiu, J. ; Xie, D. ; Li, Y. ; Qu, Y. ; Liu, Y. ; Zhu, T. ; Xiong, J. ; Liu, Y. J. Temperature Dependence of Volatile Organic Compound Emissions from Surface Coatings: Inter-Species Difference Observed in Real Indoor Environments and Mechanistic Understanding. Building and Environment 2023, 229, 109954. 访问链接Abstract
Coatings often cover two-thirds of the surfaces in indoor environments and represent important sources of indoor volatile organic compounds (VOCs). Temperature is known to affect VOC emission rates from coatings, yet inter-species difference in the temperature dependence still needs to be understood. Based on time-resolved VOC measurements in an indoor air campaign conducted in residences in Beijing, China, we identified dibasic ester (DBE), a solvent mixture often used in coatings, and found that the concentration ratios of DBE components exhibited strong temperature dependence in an apartment when the indoor temperature declined stepwise over a multiweek period. To interpret the observational results, we developed a simplified mechanistic model relating the temperature dependence of VOC emission rates from coated surfaces to the temperature dependence of the diffusion coefficient of the emitted VOCs in the coating layer and further to a predicable molecular property of the emitted VOCs, molar volumes at 0 K, based on the free-volume theory. This correlation was quantitatively verified using the DBE data as well as using the data of alkanes, another set of VOCs that might be emitted from coatings, observed in two apartments in the same campaign. Given that indoor temperature varies considerably over seasons and across regions, the correlation proposed herein may help better predict indoor VOC emissions from coatings.