Oxygenated Volatile Organic Compounds Research Articles

A Year-Long Measurement and Source Contributions of Volatile Organic Compounds in Nanning, South China

Severe ozone (O3) pollution has been recorded in China in recent years. The key precursor, volatile organic compounds (VOCs), is still not well understood in Nanning, which is a less developed city compared to other megacities in China. In this study, a year-long measurement of VOCs was conducted from 1 October 2020 to 30 September 2021, to characterize the ambient variations and apportion the source contributions of VOCs. The daily-averaged concentration of VOCs was measured to be 26.4 ppb, ranging from 3.2 ppb to 136.2 ppb across the whole year. Alkanes and oxygenated VOCs (OVOCs) were major species, contributing 46.9% and 25.2% of total VOC concentrations, respectively. Propane, ethane, and ethanol were the most abundant in Nanning, which differed from the other significant species, such as toluene (3.7 ppb) in Guangzhou, ethylene (3.8 ppb) in Nanjing, and isopentane (5.5 ppb), in Chengdu. The positive matrix factorization (PMF) model resolved six source factors, including vehicular emission (contributing 33% of total VOCs), NG and LPG combustion (19%), fuel burning (17%), solvent use (16%), industry emission (10%), and biogenic emission (5%). This indicated that Nanning was less affected by industrial emission compared with other megacities of China, with industry contributing 12–50%. Ethylene, m/p-xylene, butane, propylene, and isoprene were key species determined by ozone formation potential (OFP) analysis, which should be priority-controlled. The variations in estimated OFP and observed O3 concentrations were significantly different, suggesting that VOC reactivity-based strategies as well as meteorological and NOx effects should be considered collectively in controlling O3 pollution. This study presents a year-long dataset of VOC measurements in Nanning, which gives valuable implications for VOC control in terms of key sources and reactive species and is also beneficial to the formulation of effective ozone control strategies in other less developed regions of China.

Molecular Characterization of Gaseous Organic Acids and Nitrogen‐Containing Compounds From Crop Straw and Wood Burning

AbstractBiomass burning serves as important sources of volatile organic compounds (VOCs), yet our understanding of the molecular characteristics of oxygenated volatile organic compounds (OVOCs) from fresh emissions remains limited. In this study, gaseous organic compounds in fresh smokes from burning typical Chinese crop straws and woods are measured using an iodide time‐of‐flight chemical ionization mass spectrometer. Approximately 750 molecular formulas are identified, with CHO compounds containing carbon, hydrogen and oxygen atoms accounting for 77%–95% of the total. C1–C3 organic acids and dicarboxylic acids dominate the total CHO signal intensities by 27%–48%, while well‐known molecular markers of biomass burning, such as monosaccharide, guaiacol and syringol derivatives, contribute 7%–17%. Notably, crop straw and wood burning emit a higher abundance of guaiacol than syringol derivatives by a factor of 5. Additionally, a variety of nitrogen‐containing compounds (mainly in the CHON group) is identified, including isocyanate, amide, amino acids, and pyridine. The mass spectral profiles of organic compounds are largely similar between crop straw and wood burning fuels, although wood burning produces higher contributions of compounds with carbon atoms numbers >10. The saturation concentrations of organic compounds are estimated using molecular formula‐based volatility parameterization, revealing that semi‐volatile and intermediate VOCs (S/intermediate volatility organic compounds (IVOCs)) predominate smoke releases by 35%–60% and 20%–43%, respectively, with only a small fraction of low‐volatility compounds. Given the widespread nature of biomass burning in winter China, our results may have significant implications for interpreting secondary organic aerosol formation through gas‐particle partitioning or aqueous‐phase reactions.

Vertical Features of Volatile Organic Compounds and Their Potential Photochemical Reactivities in Boundary Layer Revealed by In-Situ Observations and Satellite Retrieval

Based on in-situ vertical observations of volatile organic compounds (VOCs) in the lower troposphere (0–1.0 km) in Nanjing, China, during the summer and autumn, we analyzed the VOCs vertical profiles, diurnal variation, and their impact factors in meteorology and photochemistry. The results showed that almost all the concentrations of VOC species decreased with height, similar to the profiles of primary air pollutants, as expected. However, we found the ratios of inactive species (e.g., acetylene) and secondary VOCs (e.g., ketones and aldehydes) in total VOCs (TVOCs) increased with height. Combined with satellite-retrieved data, we found the average HCHO tropospheric column concentrations were 2.0 times higher in the summer than in the autumn. While the average of tropospheric NO2 column concentrations was 3.0 times lower in the summer than in the autumn, the seasonal differences in the ratio of oxygenated VOCs (OVOCs) to NO2 (e.g., HCHO/NO2) shown in TROPOMI satellite-retrieved data were consistent with in-situ observations (e.g., acetone/NO2). On average, during autumn daytime, the mixing layer (ML), stable boundary layer (SBL), and residual layer (RL) had OH loss rates (LOH) of 6.9, 6.3, and 5.5 s−1, respectively. The LOH of alkenes was the largest in the ML, while the LOH of aromatics was the largest in the SBL and RL. At autumn night, the NO3 loss rates (LNO3) in the SBL and RL were 2.0 × 10−2 and 1.6 × 10−2 s−1, respectively, and the LNO3 of aromatics was the largest in the SBL and RL. In the daytime of summer, the LOH of VOCs was ~40% lower than that in autumn in all layers, while there was no significant difference in LNO3 at night between the two seasons. This study provides data support and a theoretical basis for VOC composite pollution control in the Nanjing region.

Health Risk Assessment from Exposure to Ambient Volatile Organic Compounds (VOCs) at a Truck Tire Factory in the Yangtze River Delta, China

Occupational health risk assessments of exposure to VOCs still need to be extensively studied to improve the safety standards in the industry. Based on the monitoring of organic pollutants at various workstations in a truck tire factory in Jiangsu Province, both semi-quantitative and quantitative health risk assessment methods were employed to assess health risk levels. The findings indicated that VOCs were categorized into five classes, which included alkanes, aromatics, halocarbons, carbon disulfide, and oxygenated volatile organic compounds (OVOCs). The highest concentration of total volatile organic compounds (TVOCs) was found in shaping workshop; alkanes were the most abundant class (74.2%), followed by aromatics (24.02%) and OVOCs (1.96%). Although the results of the semi-quantitative risk assessment showed that most of the organic compounds had low R values, various kinds of VOCs were detected; particularly, many harmful organic compounds (such as toluene, ethyl benzene) were detected in all the sampling sites. The quantitative risk in the calendering and vulcanizing workshop exceeded the acceptable level; both the carcinogenic risk of ethylbenzene in the tire-strip storage room, and trichloroethylene and perchloroethylene in the calendering workshop were unacceptable. Thus, the calendering and vulcanizing processes in rubber tire manufacturing should be priority-controlled processes.

Measurement report: Bio-physicochemistry of tropical clouds at Maïdo (Réunion, Indian Ocean): overview of results from the BIO-MAÏDO campaign

Abstract. The BIO-MAÏDO (Bio-physicochemistry of tropical clouds at Maïdo: processes and impacts on secondary organic aerosols formation) campaign was conducted from 13 March to 4 April 2019 on the tropical island of Réunion. The main objective of the project was to improve understanding of cloud impacts on the formation of secondary organic aerosols (SOA) from biogenic volatile organic compound (BVOC) precursors in a tropical environment. Instruments were deployed at five sites: a receptor site, Maïdo Observatory (MO) at 2165 m a.s.l. and four sites along the slope of the Maïdo mountain. Observations include measurements of volatile organic compounds (VOCs) and characterization of the physical, chemical and biological (bacterial diversity and culture-based approaches) properties of aerosols and cloud water. Turbulent parameters of the boundary layer, radiative fluxes and emissions fluxes of BVOCs from the surrounding vegetation were measured to help interpret observed chemical concentrations in the different phases. Dynamical analyses showed two preferred trajectory routes for air masses arriving at MO during the daytime. Both trajectories correspond to return branches of the trade winds associated with upslope thermal breezes, where air masses likely encountered cloud processing. The highest mixing ratios of oxygenated VOCs (OVOCs) were measured above the site located in the endemic forest and the highest contribution of OVOCs to total VOCs at MO. Chemical compositions of particles during daytime showed higher concentrations of oxalic acid, a tracer of cloud processing and photochemical aging, and a more oxidized organic aerosol at MO than at other sites. Approximately 20 % of the dissolved organic compounds were analyzed. Additional analyses by ultra-high-resolution mass spectrometry will explore the complexity of the missing cloud organic matter.

Temporal evolution of speciated volatile organic compound (VOC) emissions from solvent use sources in the Pearl River Delta Region, China (2006–2019)

Volatile organic compounds (VOCs) emitted from solvent use sources constitute an important part of ozone (O3) and secondary organic aerosols (SOA) in the Pearl River Delta (PRD) region, China. While stringent control measures targeting VOCs have been implemented in recent years, an assessment of historical trends is imperative to evaluate their effectiveness. In this study, trends of VOC emissions, compositions, and reactivity from solvent use sources in the PRD region from 2006 to 2019 were estimated using a developed methodology, which considered the improvement of manufacturing equipment and removal efficiency. Results show that total VOC emissions from solvent use sources displayed an overall increase from 277 kt in 2006 to 400 kt in 2019 despites some fluctuations, with metal products contributing more than 20 % each year. Aromatics and oxygenated VOCs (OVOCs) accounted for over 70 % of total VOC emissions, increasing by 21 kt and 52 kt respectively. OFP and SOAFP increased by 40 % and 23 % respectively from 2006 to 2019. Specific aromatic species, including m/p-xylene, toluene, 1,2,3,5-tetramethylbenzene, o-xylene and ethylbenzene are identified as key species in both VOC emission amount and reactivity. This study aims to facilitate the understanding of VOC emission evolution from solvent use sources in the region and provide insights into the impact of enacted measures, aiding in the future development of more targeted and efficient strategies in the PRD region.

Characteristics of Volatile Organic Compounds Emitted from Airport Sources and Their Effects on Ozone Production.

In recent years, commercial air transport has increased considerably. However, the compositions and source profiles of volatile organic compounds (VOCs) emitted from aircraft are still not clear. In this study, the characteristics of VOCs (including oxygenated VOCs (OVOCs)) emitted from airport sources were measured at Shenzhen Bao'an International Airport. The results showed that the compositions and proportions of VOC species showed significant differences as the aircraft operating state changed. OVOCs were the dominant species and accounted for 63.17%, 58.44%, and 51.60% of the total VOC mass concentration during the taxiing, approach, and take-off stages. Propionaldehyde and acetone were the main OVOCs, and dichloromethane and 1,2-dichloroethane were the main halohydrocarbons. Propane had the highest proportion among all alkanes, while toluene and benzene were the predominant aromatic hydrocarbons. Compared with the source profiles of VOCs from construction machinery, the proportions of halogenated hydrocarbons and alkanes emitted from aircraft were significantly higher, as were those of propionaldehyde and acetone. OVOCs were still the dominant VOC species in aircraft emissions, and their calculated ozone formation potential (OFP) was much higher than that of other VOC species at all stages of aircraft operations. Acetone, propionaldehyde, formaldehyde, acetaldehyde, and ethylene were the greatest contributors to ozone production. This study comprehensively measured the distribution characteristics of VOCs, and its results will aid in the construction of a source profile inventory of VOCs emitted from aircraft sources in real atmospheric environments.

Spatiotemporal variations, sources, and atmospheric transformation potential of volatile organic compounds in an industrial zone based on high-resolution measurements in three plants

Industrial emissions are significant sources of volatile organic compounds (VOCs). This study conducted a field campaign at high temporal and spatial resolution to monitor VOCs within three plants in an industrial park in southern China. VOC concentrations showed significant spatial variability in this industrial zone, with median concentrations of 75.22, 40.53, and 29.41 μg/m3 for the total VOCs in the three plants, respectively, with oxygenated VOCs (OVOCs) or aromatics being the major VOCs. Spatial variability within each plant was also significant but VOC-dependent. Seasonal variations in the VOC levels were governed by their industrial emissions, meteorological conditions, and photochemical losses, and they were different for the four groups of VOCs. The temporal and spatial variations in the VOC compositions suggest similar sources of each class of VOCs during different periods of the year in each plant. The diurnal patterns of VOCs (unimodal or bimodal) clearly differed from those at most industrial/urban locations previously, reflecting a dependence on industrial activities. The secondary transformation potential of VOCs also varied temporally and spatially, and aromatics generally made the predominant contributions in this industrial park. The loss rate of OH radicals and ozone formation potential were highly correlated, but the linear relationship substantially changed in summer and autumn due to the intensive emissions of an OVOC species. The lifetime cancer and non-cancer risks via occupational inhalation of the VOCs in the plants were acceptable but merit attention. Taking the secondary transformation potential and health risks into consideration, styrene, xylene, toluene, trichloroethylene, and benzene were proposed to be the priority VOCs regulated in the plants.

Light oxygenated volatile organic compound concentrations in an Eastern Mediterranean urban atmosphere rivalling those in megacities

Highly resolved measurements of primary and secondary oxygenated volatile organic compounds (OVOCs) by proton-transfer-reaction mass spectrometry (PTR-MS) and the AMOVOC sampler (Airborne Measurements Of VOC) were performed in Beirut, Lebanon, during the ECOCEM (Emissions and Chemistry of Organic Carbon in the East Mediterranean) experiments. The OVOC concentrations (0.15–7.0 ppb) rival those reported for international megacities like Paris, Tokyo, or São Paulo (0.3–6.5 ppb). This study highlights the seasonal variability of OVOCs, the potential role of background pollution on OVOC concentrations, traffic emissions of OVOCs, and the secondary production of OVOCs during both summer and winter.The primary and secondary OVOC fractions were estimated using two methods based on the night-time emission ratio and photochemical age. Our calculations coupled with a correlation analysis revealed the following: firstly, background concentrations contributed significantly, especially for longer-lived OVOCs, such as methanol and acetone (30%–80%). Secondly, secondary production in summer increased up to 60%, except for methanol and isoprene oxidation products, i.e., for methacrolein and methyl vinyl ketone. Thirdly, the secondary production in the Eastern Mediterranean persisted in winter, and finally, strong primary traffic emissions dominated the primary biogenic emissions.Finally, the emission ratios were used to evaluate the global anthropogenic emission inventories downscaled to Lebanon. Although limited to two individual non-lumped species (formaldehyde and acetone), the emission ratios compared well, within a factor of 2. However, the emissions of aldehydes and ketones from the CAMS, Edgar, and MACCITY inventories showed discrepancies of up to three orders of magnitude. This demonstrates a need for improved OVOC representation in emission inventories, considering the atmospheric relevance and abundance of OVOCs and their use in volatile chemical products.

Salt-Supported Nickel Oxides for Boosted Hydrogen Production: The Critical Role of Halogen.

Hydrogen production from organic waste by gasification and reforming technologies offers major benefits to both the environment and climate. The long-term stability and regeneration of the reforming catalyst are still the biggest challenges because of carbon deposition. Here we report a recyclable salt-supported nickel oxide NiO/NaX (X: F, Cl, Br) catalyst for effective autothermal reforming of the oxygenated volatile organic compound (OVOC) ethyl acetate to hydrogen. The optimal hydrogen selectivity achieved 82.0% at 650 °C and the durability reached 43 h. Interestingly, with the decreasing of halogen electronegativity (F > Cl > Br) in NaX, the corresponding hydrogen selectivity of the catalysts decreased. Although NiO/NaX catalysts possess a very small specific surface area and a dense microstructure, their catalytic performance is better than that of normal Ni-based catalysts loaded on high-specific-surface-area supports. Detailed investigations revealed the critical roles played by halogen during the reforming reaction. First, the strong electronegative halogen in NaX induced the formation of hydrogen bonds with the reactants and reaction intermediates, which may prolong the surface residence time of such species, thus ensuring efficient hydrogen production over small-specific-surface-area catalysts under high-temperature conditions. Second, the halogen of the support NaX weakening the Ni-O bonds of the exposed Ni atoms in NiO/NaX made it easier for NiO to be reduced to Ni0, thus reducing the reaction activation energy and prompting the rapid catalytic reaction. The strength of such metal-support interaction can be easily modulated by varying the halogen electronegativity. This study provides a new prospect for the design of innovative recyclable heterogeneous catalysts with low specific surface area but high activity.

Study of secondary organic aerosol formation and aging using ambient air in an oxidation flow reactor during high pollution events over Delhi

Secondary aerosols constitute a significant fraction of atmospheric aerosols, yet our understanding of their formation mechanism and fate is very limited. In this work, the secondary organic aerosol (SOA) formation and aging of ambient air of Delhi are studied using a potential aerosol mass (PAM) reactor, an oxidation flow reactor (OFR), coupled with aerosol chemical speciation monitor (ACSM), proton transfer reaction time of flight mass spectrometer (PTR-ToF-MS), and scanning mobility particle sizer with counter (SMPS + C). The setup mimics atmospheric aging of up to several days with the generation of OH radicals. Variations in primary volatile organic compounds (VOCs) and oxygenated volatile organic compounds (OVOCs) as a function of photochemical age were investigated. Primary VOCs such as benzene, toluene, xylene, trimethyl benzene, etc. decrease and OVOCs like formic acid, formaldehyde, acetone, ethanol, etc. increase substantially upon oxidation in OFR. The highest organic aerosol (OA) enhancement was observed for the 4.2 equivalent photochemical days of aging i.e., 1.84 times the ambient concentration, and net OA loss was observed at very high OH exposure, typically after 8.4 days of photochemical aging due to heterogeneous oxidation followed by fragmentation/evaporation. In ambient air, OA enhancement is highest during nighttime due to the high concentrations of precursor VOCs in the atmosphere. SMPS + C results demonstrated substantial new particle formation upon aging and decrement in preexisting aerosol mass. This is the first experimental study conducting an in-situ evaluation of potential SOA mass generated from the ambient aerosols in India.

Revealing the Influencing Factors of an Oxygenated Volatile Organic Compounds (OVOCs) Source Apportionment Model: A Case Study of a Dense Urban Agglomeration in the Winter

AbstractUnderstanding sources of oxygenated volatile organic compounds (OVOCs) in the atmosphere still has large uncertainties. In this study, an improved OVOC source apportionment model was developed by principal component analysis and multiple linear regression based on the online monitoring of nonmethane hydrocarbons (NMHCs) and OVOCs in a dense urban agglomeration in the winter. The modeled concentrations were in good agreement with the measured concentrations (R2 = 0.56–0.97). The concentrations of major OVOCs, except for 2‐methylacrolein, were greatly affected by anthropogenic sources (15.8%–76.8%) and secondary generation (0.0%–51.7%), while transport and natural sources contributed to 0.0%–26.8% and 0.0%–32.0%, respectively. The selection of isoprene as the natural tracer led to an underestimation of the OVOC species from primary emission and an overestimation from natural sources. In addition, photochemical reactions significantly reduced the simulation accuracy of the model for NMHCs in the afternoon, with the R2 of 0.60 ± 0.23, which was lower than the overall value of 0.82 ± 0.11. However, the R2 for OVOCs (0.83 ± 0.14) did not decrease significantly in the afternoon due to the compensation of secondary oxidation. Furthermore, the concentration gradient distribution of the species gradually changes from a normal distribution to an exponential normal distribution with a decrease in concentration, the accuracy of the model was influenced by the degree of matching between tracer and species concentration gradient as species concentration change. Developing models with additional tracers at different concentration levels may enhance the robustness of the OVOC source apportionment model without increasing its complexity.

Characteristics and Source Apportionment of Volatile Organic Compounds in an Industrial Area at the Zhejiang–Shanghai Boundary, China

As “fuel” for atmospheric photochemical reactions, volatile organic compounds (VOCs) play a key role in the secondary generation of ozone (O3) and fine particulate matter (PM2.5, an aerodynamic diameter ≤ 2.5 μm). To determine the characteristics of VOCs in a high-level ozone period, comprehensive monitoring of O3 and its precursors (VOCs and NOx) was continuously conducted in an industrial area in Shanghai from 18 August to 30 September 2021. During the observation period, the average concentration of VOCs was 47.33 ppb, and alkanes (19.64 ppb) accounted for the highest proportion of TVOCs, followed by oxygenated volatile organic compounds (OVOCs) (13.61 ppb), alkenes (6.92 ppb), aromatics (4.65 ppb), halogenated hydrocarbons (1.60 ppb), and alkynes (0.91 ppb). Alkenes were the predominant components that contributed to the ozone formation potential (OFP), while aromatics such as xylene, toluene, and ethylbenzene contributed the most to the secondary organic aerosol production potential (SOAFP). During the study period, O3, NOx, and VOCs showed significant diurnal variations. Industrial processes were the main source of VOCs, and the second largest source of VOCs was vehicle exhaust. While the largest contribution to OFP was from vehicle exhaust, the second largest contribution was from liquid petroleum gas (LPG). High potential source contribution function (PSCF) values were observed in western and southeastern areas near the sampling sites. The results of a health risk evaluation showed that the Hazard Index was less than 1 and there was no non-carcinogenic risk, but 1,3-butadiene, benzene, chloroform, 1,2-dibromoethane, and carbon tetrachloride pose a potential carcinogenic risk to the population.

[Photochemical Mechanism and Control Strategy Optimization for Summertime Ozone Pollution in Yining City].

To explore the formation mechanism of the ozone （O3） and emission reduction strategy in a northwestern city， an extensive field campaign was conducted in summertime in 2021 in Yining City， in which the 0-D box model incorporating the latest explicit chemical mechanism （MCMv3.3.1） was applied for the first time to quantify the O3-NOx-VOCs sensitivity and formulate a precise O3 control strategy in this city. The results showed that： ① the three indicators ［i.e.， O3 formation potential （OFP）， ·OH reaction rate （k·OH）， and relative incremental reactivity （RIR）］ jointly indicated that alkenes， oxygenated volatile organic compounds （OVOCs）， and aromatics were the highest contributors among anthropogenic volatile organic compounds （AVOC） to O3 formation， and the contribution of biogenic volatile organic compounds （BVOC） also could not be ignored. Additionally， the results based on RIR calculation implied that that the acetaldehyde， ethylene， and propylene were the most sensitive individual VOCs species in Yining City. ② The in-situ photochemical O3 variations were primarily influenced by the local photochemical production and export process horizontally to downwind areas or vertically to the upper layer， and the reaction pathways of HO2·+ NO and ·OH + NO2 contributed the most to the gross Ox photochemical production （60%） and photochemical destruction production （53%）， respectively. Hence， the reduction in local emissions for O3 precursors was more essential to alleviate O3 pollution in this city. ③ The outcome based on RIR（NOx） / RIR（AVOC） and EKMA jointly suggested that the photochemical regime in this city can be considered a transitional regime that was also nearly a VOCs-limited regime. Detailed mechanism modeling based on multiple scenarios further suggested that the NOx and VOCs synergic emission reduction strategies was helpful to alleviate O3 pollution. These results are useful to provide policy-related guidance for other cities facing similar O3 pollution in northwest China.

Risk assessment of volatile organic compounds from aged asphalt: Implications for environment and human health

The recycling of aged asphalt offers significant economic benefits. However, its utilization may pose environmental and health risks. Limited research has been conducted to assess the health and environmental risks associated with volatile organic compounds (VOCs) emitted from aged asphalt. To investigate the environmental affects and health risks of VOCs from aged asphalt, this study conducted quantitative research through indoor simulation experiments, where different types of aged asphalt were prepared and analyzed for their VOCs release characteristics and associated risks. The findings of the study indicate noticeable differences in the VOCs release characteristics, environmental impacts, and health risks of aged asphalt, influenced by the asphalt type and aging method. Compared to the virgin asphalt, the concentration of VOCs in aged asphalt can be reduced by up to 88.38 %, resulting in a decreased impact on the environment and health. The content of alkanes, alkenes & alkynes, aromatics, and halogenated hydrocarbons in asphalt decreases, and oxygenated volatile organic compounds (OVOCs) became the primary components. In 70# and 90# virgin asphalt, alkanes, alkenes, and aromatics contribute 82.9 % and 87.3 %, respectively, to ozone generation, while in aged bitumen (except UV90#), OVOCs contribute more than 90 %. Alkanes and aromatics in the VOCs of the original asphalt contribute more than 90 % to the formation of secondary organic aerosols, while alkanes and OVOCs play this role in the aged asphalt. Although the release concentration of VOCs and the associated environmental and health risks are reduced after asphalt aging, they should not be disregarded. This study will contribute to accelerating the prevention and control of traffic pollution promoting green and sustainable development in transportation.

Comparative analysis for the impacts of VOC subgroups and atmospheric oxidation capacity on O3 based on different observation-based methods at a suburban site in the North China Plain

The persistent O3 pollution in the Beijing-Tianjin-Hebei (BTH) region remains unresolved, largely due to limited comprehension of O3-precursor relationship and photochemistry drivers. In this work, intraday O3 sensitivity evolution from VOC-limited (volatile organic compound) regime in the forenoon to transition regime in the late afternoon was inferred by relative incremental reactivity (RIR) in summer 2019 at Xianghe, a suburban site in BTH region, suggesting that VOC-focused control policy could combine with stringent afternoon NOx control. Then detailed impacts of VOC subgroups on O3 formation were further comprehensively quantified by parametric OH reactivity (KOH), O3 formation potential (OFP), as well as RIR weighted value and O3 formation path tracing (OFPT) approach based on photochemical box model. O3 episode days corresponded to stronger O3 formation, depicted by higher KOH (10.4 s−1), OFP (331.7 μg m−3), RIR weighted value (1.2), and F(O3)-OFPT (15.5 ppbv h−1). High proportions of isoprene and OVOCs (oxygenated VOCs) to the total KOH and the OFPT method were demonstrated whereas results of OFP and RIR-weighted presented extra great impacts of aromatics on O3 formation. The OFPT approach captured the process that has already happened and included final O3 response to the original VOC, thus reliable for replicating VOC impacts. The comparison results of the four methods showed similarities when utilizing KOH and OFPT methods, which reveals that the potential applicability of simple KOH for contingency VOC control and more complex OFPT method for detailed VOC- and source-oriented control during policy-making. To investigate propulsion of VOC-involved O3 photochemistry, atmospheric oxidation capacity (AOC) was quantified by two atmospheric oxidation indexes (AOI). Both AOIp_G (7.0 × 107 molec cm−3 s−1, potential AOC calculated by oxidation reaction rates) and AOIe_G (8.5 μmol m−3, estimated AOC given redox electron transfer for oxidation products) were stronger on O3 episode days, indicating that AOC promoted the radical cycling initiated from VOC oxidation and subsequent O3 production. Result-oriented AOIe_G reasonably characterized actual AOC inferred by good linear correlation between AOIe_G and O3 concentrations compared to process-oriented AOIp_G. Therefore, with continuous NOx abatement, AOIe_G should be considered to represent actual AOC, also O3-inducing ability.

Database of emission factors of volatile organic compound (VOC) species in motor vehicle exhaust in China

The synergistic strategy for fine particulate matter (PM2.5) and O3 pollution prevention and control has emerged as a pivotal approach in combating air pollution. Volatile organic compounds (VOCs) serve as crucial precursors to both O3 and secondary organic aerosols (SOAs), with motor vehicles representing one of their significant sources. In this study, a standard for establishing a database of VOC species emission factors for motor vehicles was developed, and a database containing 134 VOC species was constructed through field tests and literature surveys. The VOC emissions of light-duty gasoline passenger vehicles (LDGPVs) comprised primarily alkanes and aromatics. The VOC emissions of light-duty diesel trucks (LDDTs) comprised mostly alkanes. Regarding low-speed trucks, 3-wheel vehicles, medium-duty diesel trucks (MDDTs) and heavy-duty diesel trucks (HDDTs), their VOC emissions comprised mainly oxygenated volatile organic compounds (OVOCs). The update of emission standards resulted in a reduction in VOC species emission factors while altering the composition of VOCs. Attention should be directed toward isopentane, benzene and dichloromethane emitted by LDGPVs, dodecane, undecane, ethene and propene emitted by LDDTs, and acetaldehyde emitted by HDDTs. VOC species originating from LDGPVs were more dispersed than those originating from LDDTs and HDDTs. In addition, variations in VOC species were observed among motor vehicles with different fuel types. Toluene, ethene, benzene, m,p-xylene, isopentane, hexanal, ethyne and 1,2,4-trimethylbenzene were the predominant VOC species emitted by gasoline vehicles. Diesel vehicles emitted mainly dodecane, formaldehyde, propene, undecane, acetaldehyde, ethene, decane and benzene. The results could enhance our comprehension of the emission characteristics of VOC species originating from motor vehicles and provide data support and a scientific foundation for achieving synergistic PM2.5 and O3 pollution prevention and control.

A high-resolution (0.1° × 0.1°) emission inventory for the catering industry based on VOCs and PM2.5 emission characteristics of Chinese multi-cuisines

Catering enterprises gather in densely populated areas, whose pollutant emission has an important impact on human health and environmental quality. This study investigated detailed information of 5456 catering enterprises in a typical city, and analyzed PM2.5 and VOCs components of 15 catering cuisines and different scales. Based on the measured emission factors, the basic information of nationwide catering enterprises and the population density, this study established the national catering pollutant emission inventory with the spatial resolution of 0.1° × 0.1°. As the results showed, alkanes, alkenes and oxygenated volatile organic compounds (OVOCs) were the main components in VOCs of most catering cuisines, accounting for 36.6%–96.7%, while organic carbon (OC) was the dominant component in PM2.5, accounting for 55.4%–68.6%. The same cuisine of different scales also presented certain differences in emission characteristics. The total emissions of the ozone formation potential (OFP) and secondary organic aerosols formation potential (SOAFP) were 1737.8 kt and 76.4 kt, respectively, with alkanes and OVOCs being the main contributors, contributing 27.5% and 22.3%, respectively. Acetaldehyde, ethylene, propylene and the other top ten VOC species contribute 81.0% of the total OFP emissions, while toluene contributed much more to total SOAFP emissions than other VOC species, contributing 35.9%. The air pollutant emissions showed the highest correlation with the population, and the regions with prominent emissions were mainly concentrated in the Beijing-Tianjin-Hebei (BTH) region and coastal cities. This study is a systematic understanding of air pollutant emission characteristics of the catering industry in China, which has important supporting value for pollutant emission reduction planning in the catering industry.

Characteristics and sources of oxygenated VOCs in Hong Kong: Implications for ozone formation

To investigate the characteristics of oxygenated volatile organic compounds (OVOCs) and their potential contribution to ozone (O3) generation, we conducted 3-h high-resolution observations during the summertime of 2022 and the wintertime of 2021. This study focused on a total of 28 OVOCs in five different chemical classes, which were encompassed at two representative sites in Hong Kong, including a roadside and an urban area. During the summertime, the total concentrations of quantified OVOCs (∑OVOCs) were 45 ± 12 and 63 ± 20 μg m−3 at the roadside and urban sites, respectively, whereas the ∑OVOCs decreased by 31 ± 11 % and 38 ± 13 %, respectively, during the wintertime. Among the classes of OVOCs, carbonyls and alcohols were the two predominant at both sites, with relatively higher concentration levels of acetone, methanol, butanaldehyde, and acrolein. The sources of OVOCs have significant spatial and temporal characteristics. Spatially, OVOCs were predominately attributed to primary emission and background at the roadside site, whereas they were a combination of primary emission, secondary formation, and background at the urban site. Temporally, background sources dominated the summertime OVOCs, while the contribution of primary emissions increased for the wintertime OVOCs. The O3 formation potential (OFP) for the OVOCs was calculated. The OFPs were 67 ± 16 and 119 ± 31 μg m−3 at the roadside and urban sites during the summertime, whereas the winter OFPs declined 30 % at the roadside and 38 % at the urban site. The background sources of carbonyls and alcohols at the roadside and of carbonyls and acrylates in the urban area were the major contributors to the summer OFP. Controlling the OVOC sources from local non-combustion sources such as gasoline-fuel evaporation and volatile chemical-containing products could lead to a reduction of OVOCs in the background and subsequently mitigate the OFP. This is beneficial for local O3 reduction in Hong Kong and surrounding regions.

Origin and transformation of volatile organic compounds at a regional background site in Hong Kong: Varied photochemical processes from different source regions

Volatile organic compounds (VOCs) are important gaseous constituents in the troposphere, impacting local and regional air quality, human health, and climate. Oxidation of VOCs, with the participation of nitrogen oxides (NOx), leads to the formation of tropospheric ozone (O3). Accurately apportioning the emission sources and transformation processes of ambient VOCs, and effectively estimation of OH reactivity and ozone formation potential (OFP) will play an important role in reducing O3 pollution in the atmosphere and improving public health. In this study, field measurements were conducted at a regional background site (Hok Tsui; HT) in Hong Kong from October to November 2020 with proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF-MS). VOC data coupled with air mass back trajectory cluster analysis and receptor modelling were applied to reveal the pollution pattern, emission sources and transformation of ambient VOCs at HT in autumn 2020. Seven sources were identified by positive matrix factorization (PMF) analysis, namely vehicular + industrial, solvent usage, primary oxygenated VOCs (OVOCs), secondary OVOCs 1, secondary OVOCs 2 (aged), biogenic emissions, and background + biomass burning. Secondary formation and vehicular + industrial emissions are the vital sources of ambient VOCs at HT supersite, contributing to 20.8 % and 46.7 % of total VOC mixing ratios, respectively. Integrated with backward trajectory analysis and correlations of VOCs with their oxidation products, short-range transport of air masses from inland regions of southeast China brought high levels of total VOCs but longer-range transport of air masses brought more secondary OVOCs in aged air masses. Photolysis of OVOCs was the most important contributor to OH reactivity and OFP, among which aldehyde was the dominant contributor. The results of this study highlight the photochemical processing of VOCs from different source regions which should be considered in strategy making for pollution reduction.