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This work comprehensively investigated the constituents, sources, and associated health risks of ambient volatile organic compounds (VOCs) sampled during the autumn of 2020 in urban Nanjing, a megacity in the densely populated Yangtze River Delta region in China. The total VOC (TVOC, sum of 108 species) concentration was determined to be 29.04 ± 14.89 ppb, and it was consisted of alkanes (36.9%), oxygenated VOCs (19.9%), halogens (19.1%), aromatics (9.9%), alkenes (8.9%), alkynes (4.9%), and others (0.4%). The mean TVOC/NOx (ppbC/ppbv) ratio was only 3.32, indicating the ozone control is overall VOC-limited. In terms of the ozone formation potential (OFP), however, the largest contributor became aromatics (41.9%), followed by alkenes (27.6%), and alkanes (16.9%); aromatics were also the dominant species in secondary organic aerosol (SOA) formation, indicative of the critical importance of aromatics reduction to the coordinated control of ozone and fine particulate matter (PM2.5). Mass ratios of ethylbenzene/xylene (E/X), isopentane/n-−pentane (I/N), and toluene/benzene (T/B) ratios all pointed to the significant influence of traffic on VOCs. Positive matrix factorization (PMF) revealed five sources showing that traffic was the largest contributor (29.2%), particularly in the morning. A biogenic source, however, became the most important source in the afternoon (31.3%). The calculated noncarcinogenic risk (NCR) and lifetime carcinogenic risk (LCR) of the VOCs were low, but four species, acrolein, benzene, 1,2-dichloroethane, and 1,2-dibromoethane, were found to possess risks exceeding the thresholds. Furthermore, we conducted a multilinear regression to apportion the health risks to the PMF-resolved sources. Results show that the biogenic source instead of traffic became the most prominent contributor to the TVOC NCR and its contribution in the afternoon even outpaced the sum of all other sources. In summary, our analysis reveals the priority of controls of aromatics and traffic/industrial emissions to the efficient coreduction of O3 and PM2.5; our analysis also underscores that biogenic emissions should be paid special attention if considering the direct health risks of VOCs. [ABSTRACT FROM AUTHOR]

High loads of fine particulate matter (PM2.5) and ozone (O3) pollution occurred frequently since early spring and led to an increasing contribution of secondary organic aerosols (SOA) in organic aerosols. However, the characteristics of precursor volatile organic compounds (VOCs) have rarely been studied. In this study, the continuous observation of VOCs was performed by an offline VOC monitoring system and gas chromatography-mass/flame ionization detector from 1 April 2020 to 31 July 2020; the characterization of VOCs and their contribution to SOA was explored. The results showed that during the observation period, the average mixing ratio of TVOCs was 42.6 ± 11.2 ppbv, and the major VOCs species were OVOCs, followed by alkanes, halocarbons, aromatics, alkenes and acetylene. When the west circulation pattern functioned, the value of aromatics increased, and the relation between PM2.5, O3 and VOCs increased when the high-pressure system controlled by anticyclone functioned. In combination with the results of positive matrix factorization, the main emission sources of ambient VOCs were complex, and the fuel combustion, industry-related emission, vehicle emission, biogenic emission and solvent volatilization accounted for 27.1%, 24.4%, 24.3%, 12.1% and 12.0%, respectively. Moreover, the industry-related emission contributed the greatest to the generation of SOA. This result indicated that the restrictions on aromatics during the industrial process are vital to reducing SOA formation. [ABSTRACT FROM AUTHOR]

Nitrogen-containing organic compounds (NOCs), a type of important reactive-nitrogen species, are abundant in organic aerosols in haze events observed in Northern China. However, due to the complex nature of NOCs, the sources, formation, and influencing factors are still ambiguous. Here, the molecular composition of organic matters (OMs) in hourly PM 2.5 samples collected during a haze event in Northern China was characterized using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). We found that CHON compounds (formulas containing C, H, O, and N atoms) dominated the OM fractions during the haze and showed high chemodiversity and transformability. Relying on the newly developed revised-workflow and oxidation-hydrolyzation knowledge for CHON compounds, 64% of the major aromatic CHON compounds (>80%) could be derived from the oxidization or hydrolyzation processes. Results from FT-ICR MS data analysis further showed that the aerosol liquid water (ALW)-involved aqueous-phase reactions are important for the molecular distribution of aromatic-CHON compounds besides the coal combustion, and the ALW-involved aromatic-CHON compound formation during daytime and nighttime was different. Our results improve the understanding of molecular composition, sources, and potential formation of CHON compounds, which can help to advance the understanding for the formation, evolution, and control of haze.

To investigate the formation of secondary organic aerosol (SOA) under current atmospheric conditions, we conducted a field observation of SOA precursors in the downwind region of the Yangtze River Delta (YRD) in winter 2019 using a variety of offline and online instruments. During the entire observation period, the averaged fine particulate SOA was 7.9 ± 2.3 μg m -3 , with precursor concentrations of 31 ± 11 ppbv for the measured volatile organic compounds (VOCs) and 16 ± 12 ppbv for NOx. Compared to those on the clean days, SOA on the haze days increased by a factor of 1.6, while the VOC and NOx increased by a factor of 1.3 and 2.0, respectively. Aerosol liquid water content (ALWC) and oxygenated VOCs (OVOCs, including acetaldehyde, formic acid, acetone, acetic acid, methyl ethyl ketone, and methylglyoxal) relationships suggested that the gasSOA and aqSOA occurred simultaneously on Chongming Island in winter. The gasSOA was primarily formed by the oxidation of aromatics and NOx at low RH (RH < 80%) conditions. In contrast, the aqSOA was formed under higher RH (RH > 80%) conditions via a combination of daytime photochemical aqueous phase processes of water-soluble OVOCs and nocturnal dark aqueous phase processes of primary emissions from biomass. The inversed higher mass ratio of NACs to (benzene + toluene) and nitrogen oxidation ratio (NOR) in the daytime during the gasSOA-dominated haze periods indicated that gasSOA could be transformed to aqSOA at high NOx levels. Our results also suggested the importance of NOx and VOC reduction measures in directly mitigating gasSOA and indirectly mitigating aqSOA during winter haze pollution., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Automotive painting plants are important emission sources of volatile organic compounds (VOCs) that contribute significantly to ground-level ozone (O₃) pollution in atmosphere. Here, we investigated process-specified emission characteristics of VOCs, without or with advanced adsorption/incineration after-treatments, from an ultra-low-emission (ULE) waterborne painting process in a modernized automotive plant. Overall, more than 80 VOCs species were identified and sorted into seven main categories. In the stack emissions without after-treatments, oxygenated VOCs (alcohols, esters, ketones, ethers, etc.) were found to be the most abundant components (48.8%), followed by aromatic (30.9%), alkanes (16.9%) and alkenes (1.2%). Among the different VOCs species discharged to atmosphere (i.e. after adsorption/incineration after-treatments), aromatics demonstrated a predominant contribution (by 60.6%) to the total O₃ formation potentials (OFPs) despite their relatively lower abundance. Trimethylbenzene was identified to have the highest OFPs, and thus should be controlled with peculiar priority. As compared to traditional organic solvent-based painting process, the ULE waterborne process implemented in the target plant allows to reduce the OFPs from 10.7 mg m -3 to 3 mg m -3 (or by 72%). Additional monitoring by unmanned aerial vehicle (over more than 3000 sampling points in the plant) confirmed that the instantaneous concentrations of fugitive VOCs were well below the regulated limit value during typical working and non-working days. These findings may provide important reference for reduction of VOCs emissions and O 3 pollution from automotive painting processes., (Copyright © 2022 Elsevier Ltd. All rights reserved.)