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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 number 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 aims to investigate the emissions of ROGs from five industrial VCP sources in the Pearl River Delta (PRD) region of China, including the shoemaking, plastic surface coating, furniture coating, printing, and ship coating industries. A more comprehensive speciation of ROG emissions from these industrial VCP sources was developed by the combination of proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS) and the 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 industrial activities. Moreover, mass spectra similarity analysis revealed significant dissimilarities among the ROG emissions from industrial activities, 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, while the corresponding contributions of OVOCs in the ship coating industry are only 16 ± 3.5 % and 15 ± 3.6 %. 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 O 3 g -1 ROGs for the ship coating and furniture coating industries, primarily due to contributions from aromatics. We find that a few species can contribute the majority of the ROG emissions and also their OHR and OFP 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 ambient measurements in industrial areas have been significantly impacted by industrial VCP sources, and ROG pairs (e.g., methyl ethyl ketone (MEK) / C 8 aromatics ratio) can be utilized as reliable evidence by using high-time-resolution ROG measurements from PTR-ToF-MS. Our study demonstrated the importance of measuring a large number of ROGs using PTR-ToF-MS for characterizing ROG emissions from industrial VCP sources. [ABSTRACT FROM AUTHOR]

There are thousands of volatile organic compound (VOC) species in ambient air, while existing techniques can only detect a small part of them (approximately several hundred). The large number of unmeasured VOCs prevents us from understanding the photochemistry of ozone and aerosols in the atmosphere. The major sources and photochemical effects of these unmeasured VOCs in urban areas remain unclear. The missing VOC reactivity, which is defined as the total OH reactivity of the unmeasured VOCs, is a good indicator for constraining the photochemical effect of unmeasured VOCs. Here, we identified the dominant role of anthropogenic emission sources in the missing VOC reactivity (accounting for up to 70 %) by measuring missing VOC reactivity and tracer-based source analysis in a typical megacity in China. Omitting the missing VOC reactivity from anthropogenic emissions in model simulations will remarkably affect the diagnosis of sensitivity regimes for ozone formation, overestimating the degree of VOC-limited regimes by up to 46 %. Therefore, a thorough quantification of missing VOC reactivity from various anthropogenic emission sources is urgently needed for constraints of air quality models and the development of effective ozone control strategies. [ABSTRACT FROM AUTHOR]

To investigate the sources and formation mechanism of oxidized organic nitrogen (OON), field measurements of OON were conducted using an iodide-adduct chemical ionization mass spectrometer equipped with a Filter Inlet for Gases and AEROsols (FIGAERO-CIMS) during fall of 2018 in the megacity of Guangzhou, China. Using levoglucosan as a tracer of biomass burning emissions, the results show that biomass burning (49±23 %) and secondary formation (51±23 %) accounted for comparable fractions to the total particle-phase OON (pOON) but 24±25 % and 76±25 % to the gas-phase OON (gOON), respectively, signifying the important contribution of biomass burning to pOON and secondary formation to gOON in this urban area. Calculations of production rates of gOON indicated that hydroxyl radical (42 %) and nitrate radical (NO 3) (49 %) oxidation pathways potentially dominated the secondary formation of gOON. A high concentration of NO 3 radicals during the afternoon was observed, demonstrating that the daytime NO 3 oxidation might be more important than the previous recognition. Monoterpenes, found to be major precursors of secondary gOON, were mainly from anthropogenic emissions in this urban area. The ratio of secondary pOON to O x ([O x ] = [O 3 ] + [NO 2 ]) increased as a function of relative humidity and aerosol surface area, indicating that heterogeneous reaction might be an important formation pathway for secondary pOON. Finally, the highly oxidized gOON and pOON with 6 to 11 oxygen atoms were observed, highlighting the complex secondary reaction processes of OON in the ambient air. Overall, our results improve the understanding of the sources and dynamic variation of OON in the urban atmosphere. [ABSTRACT FROM AUTHOR]

Vehicular emission is an important source for volatile organic compounds (VOCs) in urban and downwind regions. In this study, we conducted a chassis dynamometer study to investigate VOC emissions from vehicles using gasoline, diesel, and liquefied petroleum gas (LPG) as fuel. Time-resolved VOC emissions from vehicles are chemically characterized by a proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF-MS) with high frequency. Our results show that emission factors of VOCs generally decrease with the improvement of emission standard for gasoline vehicles, whereas variations of emission factors for diesel vehicles with emission standards are more diverse. Mass spectra analysis of PTR-ToF-MS suggest that cold start significantly influence VOCs emission of gasoline vehicles, while the influences are less important for diesel vehicles. Large differences of VOC emissions between gasoline and diesel vehicles are observed with emission factors of most VOC species from diesel vehicles were higher than gasoline vehicles, especially for most oxygenated volatile organic compounds (OVOCs) and heavier aromatics. These results indicate quantification of heavier species by PTR-ToF-MS may be important in characterization of vehicular exhausts. Our results suggest that VOC pairs (e.g. C14 aromatics/toluene ratio) could potentially provide good indicators for distinguishing emissions from gasoline and diesel vehicles. The fractions of OVOCs in total VOC emissions are determined by combining measurements of hydrocarbons from canisters and online observations of PTR-ToF-MS. We show that OVOCs contribute 7.7% ± 6.2% of gasoline vehicles of the total VOC emissions, while the fractions are significantly higher for diesel vehicles (40-77%), highlighting the importance to detect these OVOC species in diesel emissions. Our study demonstrated that the large number of OVOC species measured by PTR-ToF-MS are important in characterization of VOC emissions from vehicles. [ABSTRACT FROM AUTHOR]

The comparative reactivity method (CRM) was developed more than a decade to measure OH reactivity (i.e., OH loss frequency) in both laboratory and field studies. However, accurate OH reactivity quantification remains challenging under real ambient conditions, especially for OH reactivity measurements in high- NOx (e.g., > 10 ppbv) environments, as ambient NO enhances the regeneration of OH radicals in the CRM reactor. To solve this problem, we design a new and improved CRM reactor (ICRM) and add NO into the system continuously so that the HO2 radical concentration is suppressed. We confirmed the appropriate level of NO by determining the maximum decrease in the pyrrole level caused by regenerated OH radicals from NO + HO2. RO2 radicals induced by volatile organic compounds (VOCs) in the ICRM reactor were also found to react with NO, which led to the regeneration of OH radicals and thus the underestimation of OH reactivity. This effect was quantified by the calibration of representative VOC species at different NO levels, and the correction coefficients obtained were used to correct the measured OH reactivity. All these efforts resulted in reducing the uncertainty of the NO-artifact correction by at least an order of magnitude compared to the original CRM system. Additionally, these technological improvements also considerably reduced the systematic errors from pyrrole photolysis in the original system. A new operation mode was proposed for the ICRM, which is able to avoid the interference resulting from OH radicals produced by photolysis of residual humidity and save time for ambient measurement. The ICRM system was employed in a field campaign to measure OH reactivity and performed well with ambient NO levels ranging from 0 to 50 ppbv , which are typically observed in the urban and suburban atmosphere. [ABSTRACT FROM AUTHOR]