Unraveling the O3-NOX-VOCs relationships induced by anomalous ozone in industrial regions during COVID-19 in Shanghai.

The COVID-19 pandemic promoted strict restrictions to human activities in China, which led to an unexpected increase in ozone (O3) regarding to nitrogen oxides (NOx) and volatile organic compounds (VOCs) co-abatement in urban China. However, providing a quantitative assessment of the photochemistry that leads to O3 increase is still challenging. Here, we evaluated changes in O3 arising from photochemical production with precursors (NOX and VOCS) in industrial regions in Shanghai during the COVID-19 lockdowns by using machine learning models and box models. The changes of air pollutants (O3, NOX, VOCs) during the COVID-19 lockdowns were analyzed by deweathering and detrending machine learning models with regard to meteorological and emission effects. After accounting for effects of meteorological variability, we find increase in O3 concentration (49.5%). Except for meteorological effects, model results of detrending the business-as-usual changes indicate much smaller reduction (-0.6%), highlighting the O3 increase attributable to complex photochemistry mechanism and the upward trends of O3 due to clear air policy in Shanghai. We then used box models to assess the photochemistry mechanism and identify key factors that control O3 production during lockdowns. It was found that empirical evidence for a link between efficient radical propagation and the optimized O3 production efficiency of NOX under the VOC-limited conditions. Simulations with box models also indicate that priority should be given to controlling industrial emissions and vehicle exhaust while the VOCs and NOX should be managed at a proper ratio in order to control O3 in winter. While lockdown is not a condition that could ever be continued indefinitely, findings of this study offer theoretical support for formulating refined O3 management in industrial regions in Shanghai, especially in winter.

High-resolution mapping of regional VOCs using the enhanced space-time extreme gradient boosting machine (XGBoost) in Shanghai.

The accurate estimation of highly spatiotemporal volatile organic compounds (VOCs) is of great significance to establish advanced early warning systems and regulate air pollution control. However, the estimation of high spatiotemporal VOCs remains incomplete. Here, the space-time extreme gradient boost model (STXGB) was enhanced by integrating spatiotemporal information to obtain the spatial resolution and overall accuracy of VOCs. To this end, meteorological, topographical and pollutant emissions, was input to the STXGB model, and regional hourly 300 m VOCs maps for 2020 in Shanghai were produced. Our results show that the STXGB model achieve good hourly VOCs estimations performance (R2 = 0.73). A further analysis of SHapley Additive exPlanation (SHAP) regression indicate that local interpretations of the STXGB models demonstrate the strong contribution of emissions on mapping VOCs estimations, while acknowledging the important contribution of space and time term. The proposed approach outperforms many traditional machine learning models with a lower computational burden in terms of speed and memory.

Virus-induced breath biomarkers: A new perspective to study the metabolic responses of COVID-19 vaccinees.

Coronavirus disease 2019 (COVID-19) vaccines can protect people from the infection; however, the action mechanism of vaccine-mediated metabolism remains unclear. Herein, we performed breath tests in COVID-19 vaccinees that revealed metabolic reprogramming induced by protective immune responses. In total, 204 breath samples were obtained from COVID-19 vaccinees and non-vaccinated controls, wherein numerous volatile organic compounds (VOCs) were detected by comprehensive two-dimensional gas chromatography and time-of-flight mass spectrometry system. Subsequently, 12 VOCs were selected as biomarkers to construct a signature panel using alveolar gradients and machine learning-based procedure. The signature panel could distinguish vaccinees from control group with a high prediction performance (AUC, 0.9953; accuracy, 94.42%). The metabolic pathways of these biomarkers indicated that the host-pathogen interactions enhanced enzymatic activity and microbial metabolism in the liver, lung, and gut, potentially constituting the dominant action mechanism of vaccine-driven metabolic regulation. Thus, our findings of this study highlight the potential of measuring exhaled VOCs as rapid, non-invasive biomarkers of viral infections. Furthermore, breathomics appears as an alternative for safety evaluation of biological agents and disease diagnosis.

Chemical drivers of ozone change in extreme temperatures in eastern China.

Surface ozone pollution has become the biggest issue in China's air pollution since particulate matters have been improved in the atmosphere. Compared with normal winter/summer, extremely cold/hot weather sustained several days and nights by unfavorable meteorology is more impactful in this regard. However, ozone changes in extreme temperatures and their driving processes remain rarely understood. Here, we combine comprehensive observational data analysis and 0-D box models to quantify the contributions of different chemical processes and precursors to ozone change in these unique environments. Analyses of radical cycling indicate that temperature accelerates OH-HO2-RO2, optimizing ozone production efficiency in higher temperatures. The HO2 + NO → OH + NO2 reaction was the most influenced by temperature change, followed by OH + VOCs → HO2/RO2. Although most reactions in ozone formation increased with temperature, the increase in ozone production rates was greater than the rate of ozone loss, leading to a fast net ozone accumulation in heat waves. Our results also show that the ozone sensitivity regime is VOC-limited in extreme temperatures, highlighting the significance of volatile organic compound (VOC) control (particularly the control of alkenes and aromatics). In the context of global warming and climate change, this study helps us deeply understand ozone formation in extreme environments and design abatement policies for ozone pollution in such conditions.

On-line trace monitoring of volatile halogenated compounds in air by improved thermal desorption-gas chromatography-mass spectrometry.

Volatile halogenated compounds (VHCs) are important industrial chemicals and play a crucial role in potential stratospheric ozone-depletion and global warming. Profiling of VHCs is of great significance but replete with challenges due to the species' richness and diversity. In this study, we developed a novel method employing water removal mode combined with thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS) for on-line measurement of VHCs at the ultratrace level. By removing water with Nafion dryer tandem cold trap device, VHCs could achieve better separation and identification, and detection precision of VHCs lower than 10%. The proposed method exhibited limits of detection for VHCs ranging from 0.1 to 6.2 pptv. Benefiting from the improved trapping efficiency due to water removal, we successfully quantified 34 VHCs at the Shangdianzi background station and achieved a comprehensive assessment of VHCs in ambient air.

Attributing Increases in Ozone to Accelerated Oxidation of Volatile Organic Compounds at Reduced Nitrogen Oxides Concentrations.

Surface ozone (O3) is an important secondary pollutant affecting climate change and air quality in the atmosphere. Observations during the COVID-19 lockdown in urban China show that the co-abatement of nitrogen oxides (NOx) and volatile organic compounds (VOCs) caused winter ground-level O3 increases, but the chemical mechanisms involved are unclear. Here we report field observations in the Shanghai lockdown that reveals increasing photochemical formation of O3 from VOC oxidation with decreasing NOx. Analyses of the VOC profiles and NO/NO2 indicate that the O3 increases by the NOx reduction counteracted the O3 decreases through the VOC emission reduction in the VOC-limited region, and this may have been the main mechanism for this net O3 increase. The mechanism may have involved accelerated OH-HO2-RO2 radical cycling. The NOx reductions for increasing O3 production could explain why O3 increased from 2014 to 2020 in response to NOx emission reduction even as VOC emissions have essentially remained unchanged. Model simulations suggest that aggressive VOC abatement, particularly for alkenes and aromatics, should help reverse the long-term O3 increase under current NOx abatement conditions.

Associations of acute exposure to airborne pollutants with COVID-19 infection: evidence from China.

The outbreak of COVID-19, caused by SARS-CoV-2, has spread across many countries globally. Greatly, there are limited studies concerned with the effect of airborne pollutants on COVID-19 infection, while exposure to airborne pollutants may harm human health. This paper aimed to examine the associations of acute exposure to ambient atmospheric pollutants to daily newly COVID-19 confirmed cases in 41 Chinese cities. Using a generalized additive model with Poisson distribution controlling for temperature and relative humidity, we evaluated the association between pollutant concentrations and daily COVID-19 confirmation at single-city level and multicity levels. We observed a 10-µg/m3 rise in levels of PM2.5 (lag 0-14), O3 (lag 0-1), SO2 (lag 0), and NO2 (lag 0-14) were positively associated with relative risks of 1.050 (95% CI: 1.028, 1.073), 1.011 (1.007, 1.015), 1.052 (1.022, 1.083), and 1.094 (1.028, 1.164) of daily newly confirmed cases, respectively. Further adjustment for other pollutants did not change the associations materially (excepting in the model for SO2). Our results indicated that COVID-19 incidence may be susceptible to airborne pollutants such as PM2.5, O3, SO2, and NO2, and mitigation strategies of environmental factors are required to prevent spreading.