Volatile organic compounds (VOCs) play crucial roles in regulating the formation of tropospheric ozone. However, limited knowledge on the interactions between vertical VOC variations and photochemical ozone formation in the planetary boundary layer (PBL) has hindered effective ozone control strategies, especially in large cities. In this study, we investigated the vertical changes in concentrations, compositions, and key driving factors of a large suite of VOCs using online gradient measurements taken from a 325 m tall tower in urban Beijing. The impacts of these vertical VOC variations on photochemical ozone formation were also analyzed using box model simulations. Our results indicate that VOCs exhibited distinct vertical variation patterns due to their differences in sources and chemical reactivities, along with the diurnal evolution of the PBL. During daytime, reactive VOCs (e.g., hydrocarbons) are rapidly oxidized as they mix upward, accompanied by the formation and accumulation of oxygenated VOCs (OVOCs) in the middle and upper layers. In addition, the photochemical formation of ozone responds positively to changes in both NOx and VOCs. As a result, the production rate of ozone declines with height due to the simultaneous decreases in concentrations of reactive VOCs and NOx but remains high in the middle and upper layers. The strong production of ozone aloft is primarily driven by the presence of high OVOC concentrations. Therefore, careful consideration should be given to the vertical variations in both photochemical ozone production rates and formation regimes in the whole PBL when developing regional ozone control strategies.

Understanding the near-ground vertical and temporal photochemical O3 formation mechanism is important to mitigate O3 pollution. Here, we measured the vertical profiles of O3 and its precursors at six different heights, ranging from 5 to 335 m, using a newly built vertical observation system in the Pearl River Delta (PRD) region of China. The net photochemical ozone production rate (P(O3)net) and O3 formation sensitivities at various heights were diagnosed using an observation-based model coupled with the Master Chemical Mechanism (MCM v3.3.1). Moreover, to assess model performance and identify the causative factors behind O3 pollution episodes, the P(O3)net was measured at 5 m above ground level with a custom-built detection system. In total, three O3 pollution episodes and two non-episodes were captured. The identified O3 pollution episodes were found to be jointly influenced by both photochemical production and physical transport, with local photochemical reactions playing a major role. The high index of agreement (IOA) calculated by comparing the modelled and measured P(O3)net values indicated the rationality of investigating the vertical and temporal variability in O3 formation mechanisms using model results. However, the measured P(O3)net values were generally higher than the modelled P(O3)net values, particularly under high-NOx conditions, which may indicate a potential underestimation of total RO2 by the model. Throughout the measurement period, the contribution of different reaction pathways to O3 production remained consistent across various heights, with HO2 + NO as the major O3 production pathway, followed by RO2 + NO. We observed that P(O3)net decreased with an increase in measurement height, which was primarily attributed to the reduction in O3 precursors, such as oxygenated volatile organic compounds (OVOCs) and non-methane hydrocarbons (NMHCs). The O3 formation regimes were similar at different heights during both episodes and non-episodes, either being located in the VOC-sensitive regime or in the transition regime that is more sensitive to VOCs. Diurnally, photochemical O3 formation typically remained in the VOC-sensitive regime during the morning and noon, but it transitioned to the transition regime and was more sensitive to VOCs in the afternoon at around 16:00 LT (local time). Vertical and temporal photochemical O3 formation is most sensitive to OVOCs, suggesting that targeting specific VOCs for control measures is more practical and feasible at the observation site. The vertical temporal analysis of O3 formation mechanisms near the ground surface in this study provides critical foundational knowledge that can be used to formulate effective short-term emergency and long-term control strategies to combat O3 pollution in the PRD region of China.

Abstract. Volatile chemical products (VCPs) have become an important source of reactive organic gases (ROGs) in urban areas worldwide. Industrial activities can also utilize a large amount of VCPs and emit many organic gases into the atmosphere. Due to multiple sampling and measurement challenges, only a subset of ROG species is usually measured for many industrial VCP sources. This study aimed to investigate the emissions of ROGs from five industrial VCP sources in China, including shoemaking, plastic surface coating, furniture coating, printing, and ship coating industries. More comprehensive speciation of ROG emissions from these industrial VCP sources was developed by the combination of the proton transfer reaction time-of-flight mass spectrometer (PTR-ToF-MS) along with gas chromatography-mass spectrometer/flame ionization detector (GC-MS/FID). Our study identified oxygenated ROG species (OVOCs) as representative ROGs emitted from these sources, which are highly related to specific chemicals used during the industrial activities. Moreover, mass spectra similarity analysis revealed significant dissimilarities among the ROG emission sources, indicating substantial variations between different industrial VCP sources. Except for the ship coating industry utilizing solvent-borne coatings, the proportions of OVOCs range from 67 % to 96 % in total ROG emissions and 72 % to 97 % in total OH reactivity (OHR) for different industrial sources. The industrial VCP sources associated with solvent-borne coatings exhibited a higher ozone formation potential (OFP), reaching as high as 5.5 and 2.7 g O3·g-1 ROGs for ship coating and furniture coating industries, primarily due to contributions from aromatics. The fractions of the ten most abundant species in total ROG emissions, OHR, and OFP indicated a highly centralized of ROG emissions from various industrial VCP sources. Our results suggest that ROG treatment devices may have limited effectiveness for all ROGs, with treatment efficiencies ranging from -12 % to 68 %. Furthermore, we found that ROG pairs (e.g., methyl ethyl ketone (MEK) /C8 aromatics ratio) could serve as effective indicators for distinguishing industrial VCP sources, particularly for measurements in industrial areas. Our study demonstrated the importance of measuring a large number of ROGs using PTR-ToF-MS for characterizing ROG emissions from industrial VCP sources.

As an emerging source for organic compounds in the atmosphere, volatile chemical products (VCPs) emissions can strongly affect regional air quality. However, the emission characteristics and strengths of VCPs is not understood well in China. In this presentation, I will introduce recent experimental and modelling activities in our group to characterize organic compounds from the most important VCPs. Using this information, an updated gridded emission inventory of VCPs in China is compiled and emission patterns will be analyzed. In the end, the contributions of VCPs emissions to organic compounds and secondary formation of ozone and organic aerosols will be investigated.

The vertical variations and key drivers of ozone and its precursors, namely NOx and VOCs, in the atmospheric boundary layer, have vital impacts on surface ozone budgets but are poorly understood so far. Using online gradient measurements from a 356 m tower, we obtained continuous vertical profiles of ozone and its precursors, which exhibited strong gradients throughout the day. In the daytime, the vertical gradients of ozone precursors are significantly regulated by reactions with OH radicals. At night, our observations confirmed more intense VOC reactions with NO3 radicals in the residual layer than in the boundary layer. Additionally, we found that residual layer entrainment could contribute to over half of the boundary-layer ozone enhancements in the morning periods. Our results underscore the importance of considering vertical changes of ozone and its precursors in the atmospheric boundary layer when developing future ozone mitigation strategies.

Current process-based research mainly uses box models to evaluate photochemical ozone production and destruction rates, and it is unclear to what extent the photochemical reaction mechanisms are elucidated. Here, we modified and improved a net photochemical ozone production rate (NPOPR, P(O3)net) detection system based on the current dual-channel reaction chamber technique, which makes the instrument applicable to different ambient environments, and its various operating indicators were characterized, i.e., “airtightness”, light transmittance, wall losses of the reaction and reference chambers, conversion rate of O3 to NO2, air residence time, and performance of the reaction and reference chambers. The limits of detection of the NPOPR detection system were determined to be 0.07, 1.4, and 2.3 ppbv h−1 at sampling flow rates of 1.3, 3, and 5 L min−1, respectively. We further applied the NPOPR detection system to field observations at an urban site in the Pearl River Delta (China). During the observation period, the maximum value of P(O3)net was 34.1 ppbv h−1, which was ∼ 0 ppbv h−1 at night within the system detection error and peaked at approximately noon local time. The daytime (from 06:00–18:00 LT) average value of P(O3)net was 12.8 (± 5.5) ppbv h−1. We investigated the detailed photochemical O3 formation mechanism in the reaction and reference chambers of the NPOPR detection system using a zero-dimensional box model. We found that the photochemical reactions in the reaction chamber were very close to those in ambient air, but there was not zero chemistry in the reference chamber because the reaction related to the production and destruction of RO2 (= HO2 + RO2) continued in the reference chamber, which led to a small amount of P(O3)net. Therefore, the P(O3)net measured here can be regarded as the lower limit of the real P(O3)net in the atmosphere; however, the measured P(O3)net was still ∼ 7.5 to 9.3 ppbv h−1 higher than the modeled P(O3)net value depending on different modeling methods, which may be due to the inaccurate estimation of HO2 / RO2 radicals in the modeling study. Short-lived intermediate measurements coupled with direct P(O3)net measurements are needed in the future to better understand O3 photochemistry. Our results show that the NPOPR detection system can achieve high temporal resolution and continuous field observations, which helps us to better understand photochemical O3 formation and provides a key scientific basis for continuous improvement of air quality in China.

Volatile organic compounds (VOCs) are key components of tropospheric chemistry, of which industrial emissions are an important source of atmospheric VOCs. In this study, online measurements of 74 VOCs were made in a typical industrial area of the Pearl River Delta in southern China during the early summer of 2021. The mean volume mixing ratio of total volatile organic compounds (TVOC) was (81.9±45.4)×10-9 during the campaign. Among them, oxygenated volatile organic compounds (OVOCs) accounted for the largest fraction of TVOC, with an average of 51.5%, followed by aromatics, accounting for 19.4% of TVOC. The proportion of OVOCs in TVOC gradually increased with the increase in TVOC concentration. Industry-related emissions were the main contributors to aromatics and OVOCs in this region. Aromatics and OVOCs were the two major contributors to the ozone formation potential (OFP), accounting for 56.4% and 26.7%, respectively. Furthermore, OVOCs also contributed 40.0% of the total ·OH reactivity from VOCs. Xylenes, toluene, acrolein, and ethyl acetate had a greater contribution to the formation of secondary pollution; thus, these species should be given priority for controlling secondary pollution. Our results underscore the severity of OVOCs pollution in industrial areas and the important roles of OVOCs in secondary pollution.

Negligible losses were observed for many atmospheric trace species after traversing the PFA Teflon tubing that was hundreds of meters in length.

Cycloalkanes are important trace hydrocarbons existing in the atmosphere, and they are considered a major class of intermediate volatile organic compounds (IVOCs). Laboratory experiments showed that the yields of secondary organic aerosols (SOAs) from oxidation of cycloalkanes are higher than acyclic alkanes with the same carbon number. However, measurements of cycloalkanes in the atmosphere are still challenging at present. In this study, we show that online measurements of cycloalkanes can be achieved using proton transfer reaction time-of-flight mass spectrometry with NO+ chemical ionization (NO+ PTR-ToF-MS). Cyclic and bicyclic alkanes are ionized with NO+ via hydride ion transfer, leading to major product ions of CnH2n-1+ and CnH2n-3+, respectively. As isomers of cycloalkanes, alkenes undergo association reactions with major product ions of CnH2n ⚫ (NO)+, and concentrations of 1-alkenes and trans-2-alkenes in the atmosphere are usually significantly lower than cycloalkanes (about 25 % and <5 %, respectively), as a result inducing little interference with cycloalkane detection in the atmosphere. Calibrations of various cycloalkanes show similar sensitivities associated with small humidity dependence. Applying this method, cycloalkanes were successfully measured at an urban site in southern China and during a chassis dynamometer study of vehicular emissions. Concentrations of both cyclic and bicyclic alkanes are significant in urban air and vehicular emissions, with comparable cyclic alkanes / acyclic alkanes ratios between urban air and gasoline vehicles. These results demonstrate that NO+ PTR-ToF-MS provides a new complementary approach for the fast characterization of cycloalkanes in both ambient air and emission sources, which can be helpful to fill the gap in understanding the importance of cycloalkanes in the atmosphere.

Here we present a field measurement of ClNO2 (nitryl chloride) and N2O5 (dinitrogen pentoxide) by a time-of-flight chemical ionization mass spectrometer (ToF-CIMS) with the Filter Inlet for Gas and AEROsols (FIGAERO) at a regional site in the Pearl River Delta during a photochemical pollution season from 26 September to 17 November 2019. Three patterns of air masses are sampled during this campaign, including the dominating air masses from the north and northeast urban regions (Type A), the southeast coast (Type B), and the South China Sea (Type C). The concentration of ClNO2 and N2O5 was observed to be much higher in Type A and B than in Type C, indicating that the urban nighttime chemistry is more active than the background marine regions. The N2O5 uptake coefficient and ClNO2 production yield were estimated based on the field measurement, and the performance of the previously derived parameterizations was assessed. The nighttime ClNO2 correlated with particulate chloride and the mass concentration of fine particles (most likely due to aerosol surface area) suggested that the ClNO2 formation was limited by the N2O5 uptake at this site. By examining the relationship between particulate chloride and other species, we implied that anthropogenic emissions (e.g., biomass burning) rather than sea salt particles dominate the origin of particulate chloride, although the site was only about 100 km away from the ocean. A box model with detailed chlorine chemistry is used to investigate the impacts of ClNO2 chemistry on atmospheric oxidation. Model simulations showed that the chlorine radical liberated by ClNO2 photolysis during the next day had a slight increase in concentrations of OH, HO2, and RO2 radicals, as well as minor contributions to RO2 radical and O3 formation (< 5 %, on daytime average), in all the three types of air masses. Relatively high contributions were observed in Type A and B. The overall low contributions of ClNO2 to atmospheric oxidation are consistent with those reported recently from wintertime observations in China (including Shanghai, Beijing, Wangdu, and Mt. Tai). This may be attributed to the following: (1) relatively low particle mass concentration limited ClNO2 formation; (2) other reactions channels, like nitrous acid (HONO), oxygenated volatile organic compounds (OVOCs, including formaldehyde), and ozone photolysis had a more significant radical formation rate during the ozone pollution episodes and weakened the ClNO2 contribution indirectly. The results provided scientific insights into the role of nighttime chemistry in photochemical pollution under various scenarios in coastal areas.