Modeling of spatial and temporal variations of ozone-NOx-VOC sensitivity based on photochemical indicators in China

Comprehensive air quality model with extensions (CAMx)-decoupled direct method (DDM) was used to simulate ozone-NO_x-VOCs sensitivity of for May–November in 2016–2018 in China. Based on the relationship between the simulated ozone (O₃) sensitivity values and the ratio of formaldehyde (HCHO) to NO₂ (FNR) and the ratio of production rate of hydrogen peroxide (H₂O₂) to production rate of nitric acid (HNO₃) ($P_{{\mathrm{H}}_2{\mathrm{O}}_2}/P_{\text{HN}{\mathrm{O}}_3}$), the localized range of FNR and $P_{{\mathrm{H}}_2{\mathrm{O}}_2}/P_{\text{HN}{\mathrm{O}}_3}$ thresholds in different regions in China were obtained. The overall simulated FNR values are about 1.640–2.520, and $P_{{\mathrm{H}}_2{\mathrm{O}}_2}/P_{\text{HN}{\mathrm{O}}_3}$ values are about 0.540–0.830 for the transition regime. Model simulated O₃ sensitivities or region specific FNR or $P_{{\mathrm{H}}_2{\mathrm{O}}_2}/P_{\text{HN}{\mathrm{O}}_3}$ thresholds should be applied to ensure the accurate local O₃ sensitivity regimes. Using the tropospheric column FNR values from ozone monitoring instrument (OMI) satellite data as an indicator with the simulated threshold values, the spatial distributions of O₃ formation regimes in China are determined. The O₃ sensitivity regimes from eastern to central China are gradually from VOC-limited, transition to NO_x-limited spatially, and moving toward to transition or NO_x-limited regime from 2005 to 2019 temporally.     

Vertical distribution and temporal evolution of formaldehyde and glyoxal derived from MAX-DOAS observations: The indicative role of VOC sources

Formaldehyde (HCHO) and glyoxal (CHOCHO) are important oxidization intermediates of most volatile organic compounds (VOCs), but their vertical evolution in urban areas is not well understood. Vertical profiles of HCHO, CHOCHO, and nitrogen dioxide (NO₂) were retrieved from ground-based Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) observations in Hefei, China. HCHO and CHOCHO vertical profiles prefer to occur at higher altitudes compared to NO₂, which might be caused by the photochemistry-oxidation of longer-lived VOCs at higher altitudes. Monthly means of HCHO concentrations were higher in summer, while enhanced amounts of NO₂ were mainly observed in winter. CHOCHO exhibited a hump-like seasonal variation, with higher monthly-averaged values not only occurred in warm months (July-August) but also in cold months (November-December). Peak values mainly occurred during noon for HCHO but emerged in the morning for CHOCHO and NO₂, suggesting that HCHO is stronger link to photochemistry than CHOCHO. We further use the glyoxal to formaldehyde ratio (GFR) to investigate the VOC sources at different altitudes. The lowest GFR value is almost found in the altitude from 0.2 to 0.4 km, and then rises rapidly as the altitude increases. The GFR results indicate that the largest contributor of the precursor VOC is biogenic VOCs at lower altitudes, while at higher altitudes is anthropogenic VOCs. Our findings provide a lot more insight into VOC sources at vertical direction, but more verification is recommended to be done in the future.