Reactive Volatile Organic Compounds Research Articles

The impact of multi-decadal changes in VOC speciation on urban ozone chemistry: a case study in Birmingham, United Kingdom

Abstract. Anthropogenic non-methane volatile organic compounds (VOCs) in the United Kingdom have been substantially reduced since 1990, which is, in part, attributed to controls on evaporative and vehicle tailpipe emissions. Over time, other sources with a different speciation (for example, alcohols from solvent use and industry processes) have grown in both relative importance and, in some cases, in absolute terms. The impact of this change in speciation and the resulting photochemical reactivities of VOCs are evaluated using a photochemical box model constrained by observational data during a summertime ozone event (Birmingham, UK) and apportionment of sources based on the UK National Atmospheric Emission Inventory (NAEI) data over the period 1990–2019. Despite road transport sources representing only 3.3 % of UK VOC emissions in 2019, road transport continued being the sector with the largest influence on the local O3 production rate (P(O3)). Under case study conditions, the 96 % reduction in road transport VOC emissions that has been achieved between 1990 and 2019 has likely reduced daytime P(O3) by ∼ 1.67 ppbv h−1. Further abatement of fuel fugitive emissions was modeled to have had less impact on P(O3) reduction than abatement of VOCs from industrial processes and solvent use. The long-term trend of increased emissions of ethanol and methanol has somewhat weakened the benefits of reducing road transport emissions, increasing P(O3) by ∼ 0.19 ppbv h−1 in the case study. Abatement of VOC emissions from multiple sources has been a notable technical and policy success in the UK, but some future benefits (from an ozone perspective) of the phase-out of internal combustion engine passenger cars may be offset if domestic and commercial solvent use of VOCs continue to increase.

A better representation of volatile organic compound chemistry in WRF-Chem and its impact on ozone over Los Angeles

Abstract. The declining trend in vehicle emissions has underscored the growing significance of volatile organic compound (VOC) emissions from volatile chemical products (VCPs). However, accurately representing VOC chemistry in simplified chemical mechanisms remains challenging due to its chemical complexity including speciation and reactivity. Previous studies have predominantly focused on VOCs from fossil fuel sources, leading to an underrepresentation of VOC chemistry from VCP sources. We developed an integrated chemical mechanism, RACM2B-VCP, that is compatible with WRF-Chem and is aimed at enhancing the representation of VOC chemistry, particularly from VCP sources, within the present urban environment. Evaluation against the Air Quality System (AQS) network data demonstrates that our model configured with RACM2B-VCP reproduces both the magnitude and spatial variability of O3 and PM2.5 in Los Angeles. Furthermore, evaluation against comprehensive measurements of O3 and PM2.5 precursors from the Reevaluating the Chemistry of Air Pollutants in California (RECAP-CA) airborne campaign and the Southwest Urban NOx and VOC Experiment (SUNVEx) ground site and mobile laboratory campaign confirm the model's accuracy in representing NOx and many VOCs and highlight remaining biases. Although there exists an underprediction in the total VOC reactivity of observed VOC species, our model with RACM2B-VCP exhibits good agreement for VOC markers emitted from different sectors, including biogenic, fossil fuel, and VCP sources. Through sensitivity analyses, we probe the contributions of VCP and fossil fuel emissions to total VOC reactivity and O3. Our results reveal that 52 % of the VOC reactivity and 35 % of the local enhancement of MDA8 O3 arise from anthropogenic VOC emissions in Los Angeles. Significantly, over 50 % of this anthropogenic fraction of either VOC reactivity or O3 is attributed to VCP emissions. The RACM2B-VCP mechanism created, described, and evaluated in this work is ideally suited for accurately representing ozone for the right reasons in the present urban environment where mobile, biogenic, and VCP VOCs are all important contributors to ozone formation.

Multi-generation oxidation mechanism of M-xylene: Unexpected implications for secondary organic aerosol formation

Secondary organic aerosol (SOA) affects air quality, human health and climate. The multi-generation reactions of volatile organic compounds (VOCs) have become key process for explaining the SOA formation. M-xylene, as one of the most important VOCs in urban atmosphere, has got extensive study. However, the reaction mechanism of the first-generation products hydroperoxides (M-ROOH) and organonitrates (M-RONO2) remain unknown. In this work, the hydroxyl radicals (·OH) initiated reactions of M-ROOH and M-RONO2 were investigated by employing quantum chemical methods and kinetics modeling. The results show that new ring-retaining epoxides, a range of dialdehydes and less volatile hydroperoxides and organonitrates are formed, contributing to SOA formation. By adopting the unveiled new mechanism into the SOSAA box modeling, we found that the yield of SOA from m-xylene oxidation is up to 38%, which is comparable to the experimental value (36%). This work advances current understanding of multi-generation chemistry and elucidates the role of aromatic hydrocarbons oxidation in the formation of SOA.

A large role of missing volatile organic compound reactivity from anthropogenic emissions in ozone pollution regulation

Abstract. 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.

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 showed 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 were 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.

Modulating the Electronic States of Pt Nanoparticles on Reducible Metal-Organic Frameworks for Boosting the Oxidation of Volatile Organic Compounds.

The adsorption and activation of pollutant molecules and oxygen play a critical role in the oxidation reaction of volatile organic compounds (VOCs). In this study, superior adsorption and activation ability was achieved by modulating the interaction between Pt nanoparticles (NPs) and UiO-66 (U6) through the spatial position effect. Pt@U6 exhibits excellent activity in toluene, acetone, propane, and aldehyde oxidation reactions. Spectroscopic studies, 16O2/18O2 kinetic isotopic experiments, and density functional theory (DFT) results jointly reveal that the encapsulated Pt NPs of Pt@U6 possess higher electron density and d-band center, which is conducive for the adsorption and dissociation of oxygen. The toluene oxidation reaction and DFT results indicate that Pt@U6 is more favorable to activate the C-H of toluene and the C═C of maleic anhydride, while Pt/U6 with lower electron density and d-band center exhibits a higher oxygen dissociation temperature and higher reactant activation energy barriers. This study provides a deep insight into the architecture-performance relation of Pt-based catalysts for the catalytic oxidation of VOCs.

Composition and Reactivity of Volatile Organic Compounds and the Implications for Ozone Formation in the North China Plain

Enhanced ozone (O3) pollution has emerged as a pressing environmental concern in China, particularly for densely populated megacities and major city clusters. However, volatile organic compounds (VOCs), the key precursors to O3 formation, have not been routinely measured. In this study, we characterize the spatial and temporal patterns of VOCs and examine the role of VOCs in O3 production in five cities (Dongying (DY), Rizhao (RZ), Yantai (YT), Weihai (WH), and Jinan (JN)) in the North China Plain (NCP) for two sampling periods (June and December) in 2021 through continuous field observations. Among various VOC categories, alkanes accounted for the largest proportion of VOCs in the cities. For VOCs, chemical reactivities, aromatic hydrocarbons, and alkenes were dominant contributors to O3 formation potential (OFP). Unlike inland regions, the contribution to OFP from OVOCs increased greatly at high O3 concentrations in coastal regions (especially YT). Model simulations during the O3 episode show that the net O3 production rates were 27.87, 10.24, and 10.37 ppbv/h in DY, RZ, and JN. The pathway of HO2 + NO contributed the most to O3 production in JN and RZ, while RO2 + NO was the largest contributor to O3 production in DY. The relative incremental reactivity (RIR) revealed that O3 formation in DY was the transitional regime, while it was markedly the VOC-limited regime in JN and RZ. The O3 production response is influenced by NOx concentration and has a clear daily variation pattern (the sensitivity is greater from 15:00 to 17:00). The most efficiencies in O3 reduction could be achieved by reducing NOx when the NOx concentration is low (less than 20 ppbv in this study). This study reveals the importance of ambient VOCs in O3 production over the NCP and demonstrates that a better grasp of VOC sources and profiles is critical for in-depth O3 regulation in the NCP.

Pollution Characteristics，Source Analysis，and Activity Analysis of Atmospheric VOCs During Winter and Summer Pollution in Zhengzhou

In order to study the pollution characteristics of volatile organic compounds （VOCs）， continuous monitoring of VOCs in two pollution processes was conducted in June and December 2021 in Zhengzhou. Combined with meteorological conditions， the pollution characteristics， source contributions， and reactivity of VOCs in winter and summer were compared and analyzed. The results showed that the volume fraction of atmospheric VOCs in two episodes were （27.92±12.68）×10-9 and （24.30±5.93）×10-9， respectively. The volume fraction of atmospheric VOCs in the haze pollution process in winter was larger than that in the ozone pollution process in summer. The analysis results of winter sources were as follows： industrial source （27.0%）， motor vehicle source （22.5%）， combustion source （20.1%）， solvent use source （16.3%）， and oil and gas volatilization source （14.1%）. The analysis results of summer sources were as follows： motor vehicle source （24.8%）， industrial source （24.1%）， solvent source （17.4%）， oil and gas volatilization source （14.2%）， combustion source （11.2%）， and plant source （8.4%）. The results of the smog production model showed that the proportion of days in the synergistic control zone of VOCs during the two pollution processes in summer （66.7%） was smaller than that in winter （100.0%）. The secondary reaction activity results showed that the average ·OH loss rate （L·OH） values in winter and summer were 4.12 s-1 and 4.75 s-1， respectively. The average ozone formation potential （OFP） values in summer were 108.36 μg·m-3. The olefins were dominant in the top ten species due to L·OH and OFP contributions in summer. The total SOAFP values in winter in Zhengzhou were 54.38 μg·m-3. Among the top ten species contributing to SOAFP in winter， nine were aromatic hydrocarbons.

Total oxidation of propane using titania-supported platinum nanoparticles prepared through sol-immobilization

A set of mono-metallic nanoparticles catalysts, including palladium, platinum, and gold supported on titania, were prepared via the sol-immobilization technique, and evaluated for the total oxidation of propane as a model reaction of volatile organic compounds (VOCs) oxidation, which is a wide-ranging group of organic pollutants that contribute to serious atmospheric problems. The results showed that 1 wt.% Pt/TiO2 was the most active catalyst toward CO2, as the catalyst was very active, and the complete conversion of propane was achieved with full selectivity toward CO2. The effect of the support type was investigated through the immobilization of platinum nanoparticles on CeO2 and γ-Al2O3. The results indicated that the catalytic activity follows the order 1% Pt/TiO2 > 1% Pt/CeO2 > 1% Pt/Al2O3. For the Pt/TiO2 catalyst, the influence of the calcination temperature and metal loading on the catalytic activity was investigated. There is a slight increase in the Pt particle size when raising the calcination temperature from 300 °C to 500 °C, which enhances the catalytic activity of 1% Pt/TiO2 at 500 °C. Furthermore, increasing the metal loading from 0.1 to 1 wt.% enhances the catalytic activity as a result of the increase in particle size. Different characterization techniques were utilized, including XRD, TEM, XPS, and MP-AES, to determine the structure-activity relationship, and together they indicate that the catalytic activity is influenced more by the particle size of Pt nanoparticles than by the oxidation state.

Source characterization of volatile organic compounds at Carlsbad Caverns National Park

ABSTRACT Carlsbad Caverns National Park (CAVE), located in southeastern New Mexico, experiences elevated ground-level ozone (O3) exceeding the National Ambient Air Quality Standard (NAAQS) of 70 ppbv. It is situated adjacent to the Permian Basin, one of the largest oil and gas (O&G) producing regions in the US. In 2019, the Carlsbad Caverns Air Quality Study (CarCavAQS) was conducted to examine impacts of different sources on ozone precursors, including nitrogen oxides (NOx) and volatile organic compounds (VOCs). Here, we use positive matrix factorization (PMF) analysis of speciated VOCs to characterize VOC sources at CAVE during the study. Seven factors were identified. Three factors composed largely of alkanes and aromatics with different lifetimes were attributed to O&G development and production activities. VOCs in these factors were typical of those emitted by O&G operations. Associated residence time analyses (RTA) indicated their contributions increased in the park during periods of transport from the Permian Basin. These O&G factors were the largest contributor to VOC reactivity with hydroxyl radicals (62%). Two PMF factors were rich in photochemically generated secondary VOCs; one factor contained species with shorter atmospheric lifetimes and one with species with longer lifetimes. RTA of the secondary factors suggested impacts of O&G emissions from regions farther upwind, such as Eagle Ford Shale and Barnett Shale formations. The last two factors were attributed to alkenes likely emitted from vehicles or other combustion sources in the Permian Basin and regional background VOCs, respectively. Implications: Carlsbad Caverns National Park experiences ground-level ozone exceeding the National Ambient Air Quality Standard. Volatile organic compounds are critical precursors to ozone formation. Measurements in the Park identify oil and gas production and development activities as the major contributors to volatile organic compounds. Emissions from the adjacent Permian Basin contributed to increases in primary species that enhanced local ozone formation. Observations of photochemically generated compounds indicate that ozone was also transported from shale formations and basins farther upwind. Therefore, emission reductions of volatile organic compounds from oil and gas activities are important for mitigating elevated O3 in the region.

Catalytic Combustion of Volatile Organic Compounds (VOCs) over Perovskite Oxides: A Review

Volatile organic compounds (VOCs) are one of the crucial outdoor as well as indoor air pollutants. Recently, the elimination of volatile organic compounds is become more attractive due to its potentiality of long-term human health effects. Among the different existing methods for the removal of VOCs, the catalytic combustion is the best convenient method due to its operational simplicity, cost effectiveness, high efficiency and industrial acceptability. Various perovskite oxides have been widely studied as suitable catalysts for the removal of VOCs because of their tunable physico-chemical properties, compositional/structural exibility and high thermochemical stability. The morphology, material composition and surface as well as bulk properties of perovskite oxides is the key determining factors for catalytic efficiency. The suitable metal or non-metal doping, controlling morphology (nano-structuring, three-dimensional ordered microporous (3DOM) building) and hybrid construction (perovskite as support for other active catalysts and other oxides as support for active perovskite catalyst) may have a remarkable effect on the surface as well as bulk properties and consequently the catalytic efficiency for ther removal reactions of VOCs are also effected. In this review article, different aspects of the current development in perovskite oxides catalysts for VOCs combustion with a special highlighting on the material designing, like doping, morphology controlling, surface modication and hybrid construction are presented.

Removal of binary and ternary synergistic mixtures of ozone and VOCs by activated carbon filter: Mathematical modelling

Evaluating the activated carbon filter's performance in removing gaseous pollutants is essential to determining the filter maintenance schedule for indoor environments. This paper describes the development of a mathematical model to predict an activated carbon filter's performance for removing mixtures of ozone and volatile organic compounds (toluene and limonene) at their low-level concentrations in typical indoor environments. Mass transfer equations were employed to estimate the filter's dynamic behaviour by including the reaction rates of ozone with carbon surfaces and the reactive volatile organic compound, as well as the adsorption isotherm for a single volatile organic compound or binary mixtures of volatile organic compounds. The reaction rate constant for the ozone-limonene reaction was calculated by fitting the model to the experiment results of their binary mixture at 9 ppm of limonene and 0.1 ppm of ozone. Additionally, the ozone-exposed filters at 0.1 ppm were used to perform adsorption tests to determine the parameters of the Dubinin-Radushkevich isotherm using experimental results at 9, 30, 50, 70, and 90 ppm of volatile organic compounds. The Dubinin-Radushkevich isotherm was extended using the volume exclusion theory to consider the effect of by-products on the removal modelling of the binary mixture of ozone and limonene and the ternary mixture of ozone, limonene, and toluene.The model was able to show the reduced accessibility of the surface of activated carbon for reaction with ozone because of the adsorption of volatile organic compounds and generated by-products (keto-limonene and carvone). The initial influence is of minor magnitude; however, as the surface load intensifies, its significance can progressively amplify over time. Pre-exposing the filter to ozone prior to conducting adsorption tests was able to capture the average change in the adsorption properties of the filter. These considerations in the modelling result in a remarkable predictive capability in determining the breakthrough behaviour of the filter in removing the binary or ternary mixture of ozone and volatile organic compounds at various concentrations. The insignificant effect of the homogeneous reaction between ozone and limonene for the investigated experimental setup was confirmed by comparing the predictions made by the proposed model with those made by another model that considers the homogeneous reaction. Finally, the sensitivity analysis revealed that the model is more sensitive to adsorption isotherm parameters compared to the reaction kinetic parameter between ozone and limonene.

Composition Characteristics of VOCs in the Atmosphere of the Beibei Urban District of Chongqing: Insights from Long-Term Monitoring

Reducing anthropogenic volatile organic compounds (VOCs) is the most effective way to mitigate O3 pollution, which has increased over the past decades in China. From 2012 to 2017, special stainless-steel cylinders were used to collect ambient air samples from the urban area of Beibei district, Chongqing. Three-step pre-concentration gas chromatography–mass spectrometry was used to detect the collected air samples. The composition, concentration, photochemical reactivity, and sources of VOCs in Beibei were analyzed. During the observation period, the annual average VOC concentration was 31.3 ppbv, which was at an intermediate range compared to other cities in China. Alkanes (36.8%) and aromatics (35.6%) were the most abundant VOC groups, followed by halo-hydrocarbons (14.4%) and alkenes (12.6%). The overall trend of seasonal distribution of VOC concentration was high in summer and autumn, and low in winter and spring, with a statistically significant difference between summer and winter concentrations. The ozone formation potential (OFP) showed that alkenes were the most active species, followed by aromatics and alkanes, and summer was the season with the highest OFP (131.6 ppbv). Three major emission sources were identified through principal component analysis (PCA), i.e., vehicle exhaust emissions (66.2%), fuel oil evaporation (24.8%), and industrial sources (9.0%). To ameliorate the air quality within the study area, concerted efforts should be directed towards curtailing traffic emissions and mitigating the release of alkenes, particularly emphasizing more stringent interventions during the summer season.

Identification of priority pollutants at an integrated iron and steel facility based on environmental and health impacts in the Yangtze River Delta region, China

Emissions from the iron and steel industry are a major source of air pollution. To investigate the composition characteristics, estimate the secondary transformation potential, and assess the ecological risk and human health risks of air pollutants from iron and steel industry, field measurements of volatile organic compounds (VOCs) and trace metals (TMs) were conducted simultaneously from 2020 to 2022 in the Yangtze River Delta (YRD) region, China. The average mixing concentration of VOCs (Σ64VOCs) was 58.2 ppbv. Alkanes, alkenes and aromatics were the major components. Benzene and ethylene were the most abundant VOC species. In the O3 season, the calculated OH loss rates (LOH) and ozone formation potential (OFP) were 10.87 S−1 and 181.74 ppbv, respectively, which increased 39.54% and 21.51% compared to the non-O3 season. Furthermore, the O3-VOCs-NOx sensitivity indicated that O3 formation was under the VOCs-limited regime. The average concentration of total 10 trace metals (Σ10TMs) was 226.8 ng m−3, Zn, Pb and Mn were the top abundant TM species. The results also found that Se was extremely contaminated; Pb and Zn was heavily to extremely contaminated; Cu, As and Ni were moderately to heavily contaminated. For lifetime cancer risk, the cumulative carcinogenic risks were 1.84E-5 for children, 6.14E-5 for adults and 1.83E-5 for workers. The carcinogenic risks of individual chemicals cannot be ignored, especially for Cr, Ni, benzene and 1,3-butadiene. The hazard index values for workers and residents were 0.53 and 2.23, respectively, suggesting a high non-carcinogenic risks to the exposed population. These findings deepen the understanding of the pollutant character of the iron and steel industry, and provide theoretical support for policy development on O3 pollution treatment and human health in the YRD region, China. For the study area, we recommend utilizing high-quality raw coal, reducing the volatile hydrocarbon content in the sinter feed, and installing absorption device for highly reactive VOC components at the exhaust outlet.

Emission of volatile organic compounds from residential biomass burning and their rapid chemical transformations

Biomass combustion releases a complex array of Volatile Organic Compounds (VOCs) that pose significant challenges to air quality and human health. Although biomass burning has been extensively studied at ecosystem levels, understanding the atmospheric transformation and impact on air quality of emissions in urban environments remains challenging due to complex sources and burning materials. In this study, we investigate the VOC emission rates and atmospheric chemical processing of predominantly wood burning emissions in a small urban centre in Greece. Ioannina is situated in a valley within the Dinaric Alps and experiences intense atmospheric pollution accumulation during winter due to its topography and high wood burning activity. During pollution event days, the ambient mixing ratios of key VOC species were found to be similar to those reported for major urban centres worldwide. Positive matrix factorisation (PMF) analysis revealed that biomass burning was the dominant emission source (>50 %), representing two thirds of OH reactivity, which indicates a highly reactive atmospheric mixture. Calculated OH reactivity ranges from 5 s−1 to an unprecedented 278 s−1, and averages at 93 ± 66 s−1 at 9 PM, indicating the presence of exceptionally reactive VOCs. The highly pronounced photochemical formation of organic acids coincided with the formation of ozone, highlighting the significance of secondary formation of pollutants in poorly ventilated urban areas. Our findings underscore the pressing need to transition from wood burning to environmentally friendly sources of energy in poorly ventilated urban areas, in order to improve air quality and safeguard public health.

Atmospheric oxidation capacity and secondary pollutant formation potentials based on photochemical loss of VOCs in a megacity of the Sichuan Basin, China

Volatile organic compounds (VOCs) are significant precursors to photochemical pollution. However, reactive VOC species are easily oxidized during transportation, resulting in a systematic underestimate of the measured concentrations. To address this, we applied an improved calculation method to correct the measured VOC concentrations into photochemical initial concentrations (PICs) in Chengdu, a megacity in the Sichuan Basin, China, which is highly vulnerable to complex pollution. In this study, 56 VOC species on the Photochemical Assessment Monitor Station (PAMS) target list were quantitatively monitored throughout all four seasons. Comparing to directly measured values, photochemically initialized total mixing ratios of VOCs increased by 18.6 % in general. The photochemical loss percentages of alkenes and aromatics were prominent in summer (68.6 %, 28.7 %) and spring (65.9 %, 24.7 %), respectively. Furthermore, we examined contributions of VOCs to atmospheric oxidation capacity (AOC) depending on PICs and found that maximum daily total AOC showed a surge in spring and summer. Besides hydroxyl radicals, daytime O3 in spring and late-afternoon nitrate radicals in summer were essential for AOC with PICs. As expected, alkenes and aromatics dominated PIC-based ozone formation potentials (OFPs). Furthermore, contribution of alkenes to secondary organic aerosol formation potentials reached 15.5 % and 7.6 % in spring and summer, respectively. Using positive matrix factorization model, we identified five VOC sources including vehicular exhaust, industrial emissions, solvent usage, biogenic sources, and liquefied petroleum gas/natural gas use. Based on PICs, biogenic sources were significantly underestimated in spring and summer. Meanwhile, m,p-xylene from solvent usage and isoprene from biogenic sources were the primary contributors to OFPs. Consequently, these results emphasize the significance of photochemically oxidized VOC concentrations, especially for reactive species in typical seasons.

Source apportionment and ozone formation mechanism of VOCs considering photochemical loss in Guangzhou, China

Understanding the sources and impact of volatile organic compounds (VOCs) on ozone formation is challenging when the traditional method does not account for their photochemical loss. In this study, online monitoring of 56 VOCs was carried out in summer and autumn during high ozone pollution episodes. The photochemical age method was used to evaluate the atmospheric chemical loss of VOCs and to analyze the effects on characteristics, sources, and ozone formation of VOC components. The initial concentrations during daytime were 5.12 ppbv and 4.49 ppbv higher than the observed concentrations in the summer and autumn, respectively. The positive matrix factorization (PMF) model identified 5 major emission sources. However, the omission of the chemical loss of VOCs led to underestimating the contributions of sources associated with highly reactive VOC components, such as those produced by biogenic emissions and solvent usage. Conversely it resulted in overestimating the contributions from VOC components with lower chemical activity such as liquefied petroleum gas (LPG) usage, vehicle emissions, and gasoline evaporation. Furthermore, the estimation of ozone formation may be underestimated when the atmospheric photochemical loss is not taken into account. The ozone formation potential (OFP) method and propylene-equivalent concentration method both underestimated ozone formation by 53.24 ppbv and 47.25 ppbc, respectively, in the summer, and by 40.34 ppbv and 26.37 ppbc, respectively, in the autumn. The determination of the ozone formation regime based on VOC chemical loss was more acceptable. In the summer, the ozone formation regime changed from the VOC-limited regime to the VOC-NOx transition regime, while in the autumn, the ozone formation regime changed from the strong VOC-limited regime to the weak VOC-limited regime. To obtain more thorough and precise conclusions, further monitoring and analysis studies will be conducted in the near future on a wider variety of VOC species such as oxygenated VOCs (OVOCs).

Ambient Volatile Organic Compound Characterization, Source Apportionment, and Risk Assessment in Three Megacities of China in 2019.

In order to illustrate pollution characterization, source apportionment, and risk assessment of VOCs in Beijing, Baoding, and Shanghai, field observations of CO, NO, NO2, O3, and volatile organic compounds (VOCs) were conducted in 2019. Concentrations of VOCs were the highest in Beijing (105.4 ± 52.1 ppb), followed by Baoding (97.1 ± 47.5 ppb) and Shanghai (91.1 ± 41.3 ppb). Concentrations of VOCs were the highest in winter (120.3 ± 61.5 ppb) among the three seasons tested, followed by summer (98.1 + 50.8 ppb) and autumn (75.5 + 33.4 ppb). Alkenes were the most reactive VOC species in all cities, accounting for 56.0%, 53.7%, and 39.4% of ozone formation potential in Beijing, Baoding, and Shanghai, respectively. Alkenes and aromatics were the reactive species, particularly ethene, propene, 1,3,5-trimethylbenzene, and m/p-xylene. Vehicular exhaust was the principal source in all three cities, accounting for 27.0%, 30.4%, and 23.3% of VOCs in Beijing, Baoding, and Shanghai, respectively. Industrial manufacturing was the second largest source in Baoding (23.6%) and Shanghai (21.3%), and solvent utilization was the second largest source in Beijing (25.1%). The empirical kinetic modeling approach showed that O3 formation was limited by both VOCs and nitric oxides at Fangshan (the suburban site) and by VOCs at Xuhui (the urban site). Acrolein was the only substance with an average hazard quotient greater than 1, indicating significant non-carcinogenic risk. In Beijing, 1,2-dibromoethane had an R-value of 1.1 × 10-4 and posed a definite carcinogenic risk.

Closing the Reactive Carbon Flux Budget: Observations From Dual Mass Spectrometers Over a Coniferous Forest

AbstractWe use observations from dual high‐resolution mass spectrometers to characterize ecosystem‐atmosphere fluxes of reactive carbon across an extensive range of volatile organic compounds (VOCs) and test how well that exchange is represented in current chemical transport models. Measurements combined proton‐transfer reaction mass spectrometry (PTRMS) and iodide chemical ionization mass spectrometry (ICIMS) over a Colorado pine forest; together, these techniques have been shown to capture the majority of ambient VOC abundance and reactivity. Total VOC mass and associated OH reactivity fluxes were dominated by emissions of 2‐methyl‐3‐buten‐2‐ol, monoterpenes, and small oxygenated VOCs, with a small number of compounds detected by PTRMS driving the majority of both net and upward exchanges. Most of these dominant species are explicitly included in chemical models, and we find here that GEOS‐Chem accurately simulates the net and upward VOC mass and OH reactivity fluxes under clear sky conditions. However, large upward terpene fluxes occurred during sustained rainfall, and these are not captured by the model. Far more species contributed to the downward fluxes than are explicitly modeled, leading to a major underestimation of this key sink of atmospheric reactive carbon. This model bias mainly reflects missing and underestimated concentrations of depositing species, though inaccurate deposition velocities also contribute. The deposition underestimate is particularly large for assumed isoprene oxidation products, organic acids, and nitrates—species that are primarily detected by ICIMS. Net ecosystem‐atmosphere fluxes of ozone reactivity were dominated by sesquiterpenes and monoterpenes, highlighting the importance of these species for predicting near‐surface ozone, oxidants, and aerosols.

Crystal Plane Effect of Co3O4 on Styrene Catalytic Oxidation: Insights into the Role of Co3+ and Oxygen Mobility at Diverse Temperatures.

In the oxidation reaction of volatile organic compounds catalyzed by metal oxides, distinguishing the role of active metal sites and oxygen mobility at specific preferentially exposed crystal planes and diverse temperatures is challenging. Herein, Co3O4 catalysts with four different preferentially exposed crystal planes [(220), (222), (311), and (422)] and oxygen vacancy formation energies were synthesized and evaluated in styrene complete oxidation. It is demonstrated that the Co3O4 sheet (Co3O4-I) presents the highest C8H8 catalytic oxidation activity (R250°C = 8.26 μmol g-1 s-1 and WHSV = 120,000 mL h-1 g-1). Density functional theory studies reveal that it is difficult for the (311) and (222) crystal planes to form oxygen vacancies, but the (222) crystal plane is the most favorable for C8H8 adsorption regardless of the presence of oxygen vacancies. The combined analysis of temperature-programmed desorption and temperature-programmed surface reaction of C8H8 proves that Co3O4-I possesses the best C8H8 oxidation ability. It is proposed that specific surface area is vital at low temperature (below 250 °C) because it is related to the amount of surface-adsorbed oxygen species and low-temperature reducibility, while the ratio of surface Co3+/Co2+ plays a decisive role at higher temperature because of facile lattice oxygen mobility. In situ diffuse reflectance infrared Fourier spectroscopy and the 18O2 isotope experiment demonstrate that C8H8 oxidation over Co3O4-I, Co3O4-S, Co3O4-C, and Co3O4-F is mainly dominated by the Mars-van Krevelen mechanism. Furthermore, Co3O4-I shows superior thermal stability (57 h) and water resistance (1, 3, and 5 vol % H2O), which has the potential to be conducted in the actual industrial application.