To contain the spread of coronavirus disease (COVID-19), many countries underwent large-scale lockdowns in 2020. Decreases in vehicle traffic, industrial activity, and power consumption led to reduced emissions of air pollutants and greenhouse gases. For example, reductions in nitrogen dioxide columns were detected over Asia, Europe and North America by space-based instruments (

Abstract. The outbreak of COVID-19 promoted strict restrictions to human activities in China, which led to a dramatic decrease in most air pollutant concentrations (e.g., PM2.5, PM10, NOx, SO2 and CO). However, an obvious increase in ozone (O3) concentrations was found during the lockdown period in most urban areas of China. In this study, we conducted field measurements targeting ozone and its key precursors by utilizing a novel proton transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS) in Changzhou, which is representative of the Yangtze River Delta (YRD) city cluster of China. We further applied the integrated methodology including machine learning, an observation-based model (OBM) and sensitivity analysis to obtain insights into the reasons causing the obvious increase in ozone. Major findings include the following: (1) by deweathered calculation, we found changes in precursor emissions contributed 1.46 ppbv to the increase in the observed O3 during the full-lockdown period in 2020, while meteorology constrained 3.0 ppbv of O3 in the full-lockdown period of 2019. (2) By using an OBM, we found that although a significant reduction in O3 precursors was observed during the full-lockdown period, the photochemical formation of O3 was stronger than that during the pre-lockdown period. (3) The NOx/VOC ratio dropped dramatically from 1.84 during the pre-lockdown to 0.79 in the full-lockdown period, which switched O3 formation from a VOC-limited regime to the boundary of a NOx- and VOC-limited regime. Additionally, box model results suggested that the decrease in the NOx/VOC ratio during the full-lockdown period could increase the mean O3 by 2.4 ppbv. Results of this study give insights into the relationship between O3 and its precursors in urban area and demonstrate reasons for the obvious increase in O3 in most urban areas of China during the COVID-19 lockdown period. This study also underlines the necessity of controlling anthropogenic oxygenated volatile organic compounds (OVOCs), alkenes and aromatics in the sustained campaign of reducing O3 pollution in China.

Abstract. Volatile organic compound (VOC) emissions and subsequent oxidation contribute to the formation of secondary pollutants and poor air quality in general. As more VOCs at lower mixing ratios have become the target of air quality investigations, their quantification has been aided by technological advancements in proton-transfer reaction time-of-flight mass spectrometry (PTR-TOF-MS). However, such quantification requires appropriate instrument background measurements and calibrations, particularly for VOCs without calibration standards. This study utilized a Vocus-PTR-TOF-MS to measure ambient VOCs in Boulder, Colorado during spring 2021. Fast, frequent calibrations were made every 2 h in addition to daily multipoint calibrations. Sensitivities derived from the fast calibrations were 5±6 % (average and one standard deviation) lower than those derived from the multipoint calibrations due to an offset between the calibrations and instrument background measurement. This offset was caused, in part, by incomplete mixing of the standard with diluent. These fast calibrations were used in place of a normalization correction to account for variability in instrument response and accounted for non-constant reactor conditions caused by a gradual obstruction of the sample inlet. One symptom of these non-constant conditions was a trend in fragmentation, although the greatest observed variability was 6 % (one relative standard deviation) for isoprene. A PTR Data Toolkit (PTR-DT) was developed to assess instrument performance and rapidly estimate the sensitivities of non-standard VOCs on the timescale of the fast calibrations using the measured sensitivities of standards, molecular properties, and simple reaction kinetics. Through this toolkit, the standards’ sensitivities were recreated within 1±8 % of the measured values. Three clean air sources were compared: a hydrocarbon trap, zero grade air and ultra-high purity nitrogen, and a catalytic zero-air generator. The catalytic zero-air generator yielded the lowest instrument background signals for the majority of ions, followed by the hydrocarbon trap. Depending on the ionization efficiency, product ion fragmentation, ion transmission, and instrument background, standards’ limits of detection (5-s measurement integration) derived from the catalytic zero-air generator and the fast calibration sensitivities ranged from 2 ppbv (methanol) to 1 pptv (decamethylcyclopentasiloxane; D5 siloxane) with most standards having detection limits below 20 pptv. Finally, applications of measurements with low detection limits are considered for a few low-signal species related to cooking emissions, volatile cyclic methyl siloxanes, and organosulfur compounds.