Secondary Organic Aerosol Potential Research Articles

Manifesting the hidden pollutants: Quantifying emissions and environmental impact of petroleum refinery on PM2.5

This research thoroughly examined the emissions of primary fine particle and precursors of secondary particles (VOCs, SO2 and NOx) originating from the petroleum refinery operation. The central aim was to quantify the emission factors of fine particulate matter and analyze their spatial dispersion and source contributions, in order to evaluate their environmental impacts.The VOCs emission measurement appeared that the wastewater treatment plant unit was the most significant source of VOCs emissions, with pentane, cyclopentane, and propane being the dominant VOCs species released. The study employed the secondary organic aerosol potential (SOAP), sulfur oxidation ratio (SOR), and nitrogen oxidation ratio (NOR) methodologies to calculate the emissions of secondary PM2.5. The combustion stacks were the principal contributor to secondary PM2.5 emissions, with SO2 being the predominant secondary PM2.5 precursor species contributing to fine particulate matter, accounting for 82.5% of the total secondary PM2.5 emissions. The overall emission factor for the refinery was determined to be 0.31 g secondary PM2.5 per kg of refined crude oil. Furthermore, the analysis indicated that the combustion stacks were the primary contributors to PM2.5 concentrations at all receptor sites, accounting for 64.4%–80.8% of the total contribution, followed by the wastewater treatment unit and storage tanks. The study underscored the importance of focusing on secondary PM2.5 precursor emissions to effectively reduce emissions and environmental concentrations of PM2.5, highlighting the potential for more effective management and mitigation strategies targeting these precursors.

Seasonal and height dynamics of volatile organic compounds in rubber plantation: Impacts on ozone and secondary organic aerosol formation

Rubber trees emit a range of volatile organic compounds (VOCs), including isoprene, monoterpenes, and sesquiterpenes, as part of their natural metabolism. These VOCs can significantly influence air quality through photochemical reactions that produce ozone and secondary organic aerosols (SOAs). This study examines the impact of VOCs detected in a rubber tree plantation in Northeastern Thailand on air quality, highlighting their role in atmospheric reactions that lead to the formation of ozone and SOAs. VOCs were collected at varying heights and seasons using Tenax-TA tubes paired with an atmospheric sampler pump and identified by gas chromatography–mass spectrometry. In total, 100 VOCs were identified, including alkanes, alkenes, terpenes, aromatics, and oxygenated VOCs. Principal Coordinate Analysis (PCoA) revealed distinct seasonal VOC profiles, with hydrocarbons, peaking in summer and terpenes in the rainy season. The Linear Mixed-Effects (LME) model indicates that VOC concentrations are more influenced by seasonal changes than by sampling heights. Secondary organic aerosol potential (SOAP) and ozone formation potential (OFP) of selected VOC species were also determined. The total SOAP ranged from 67.24 μg/m3 in summer to 17.87 μg/m3 in winter, while the total OFP ranged from 377.87 μg/m3 in summer to 139.39 μg/m3 in winter. Additionally, positive matrix factorization (PMF) analysis identified four main VOC sources: gasoline combustion (18.3 %), microbial activity (38.6 %), monoterpene emissions during latex production (15.0 %), and industrial sources (28.1 %). These findings provide essential information for managing air pollution in rubber tree plantations. By adopting focused air quality management strategies, plantation operators can mitigate the adverse effects of VOCs, promoting a healthier and more sustainable future.

Elucidating the unexpected importance of intermediate-volatility organic compounds (IVOCs) from refueling procedure

Evaporative emissions release organic compounds comparable to gasoline exhaust in China. However, the measurement of intermediate volatility organic compounds (IVOCs) is lacking in studies focusing on gasoline evaporation. This study sampled organics from a real-world refueling procedure and analyzed the organic compounds using comprehensive two-dimensional gas chromatography coupled with a mass spectrometer (GC×GC-MS). The non-target analysis detected and quantified 279 organics containing 93 volatile organic compounds (VOCs, 64.9 ± 7.4 % in mass concentration), 182 IVOCs (34.9 ± 7.4 %), and 4 semivolatile organic compounds (SVOCs, 0.2 %). The refueling emission profile was distinct from that of gasoline exhaust. The b-alkanes in the B12 volatility bin are the most abundant IVOC species (1.9 ± 1.4 μg m−3) in refueling. A non-negligible contribution of 17.5 % to the ozone formation potential (OFP) from IVOCs was found. Although IVOCs are less in concentration, secondary organic aerosol potential (SOAP) from IVOCs (58.1 %) even exceeds SOAP from VOCs (41.6 %), mainly from b-alkane in the IVOC range. At the molecular level, the proportion of cyclic compounds in SOAP (12.1 %) indeed goes above its mass concentration (3.1 %), mainly contributed by cyclohexanes and cycloheptanes. As a result, the concentrations and SOAP of cyclic compounds (>50 %) could be overestimated in previous studies. Our study found an unexpected contribution of IVOCs from refueling procedures to both ozone and SOA formation, providing new insights into secondary pollution control policy.

Impact of emissions of volatile organic compounds from restaurants on ambient air quality and health: Case study in beijing

Cooking fumes are important sources of volatile organic compounds (VOCs). Compared with home cooking, commercial cooking uses a higher number of stoves, consumes more oil, operates for longer hours, and performs more complex cooking processes and usage of seasoning, resulting in more serious pollution. In this study, we collected samples of cooking fumes from six common types of restaurants in Beijing, and investigated their emission characteristics. We analyzed the secondary transformations of VOCs in cooking fumes and their impacts on human health. Results show that oxygenated VOCs (O–VOCs) accounted for the highest proportion of VOCs emitted by all types of restaurants (47.67–73.46%), with ethanol being their most significant component (27.04–62.31%). The ozone formation potential (OFP) were the highest from canteen emissions, and secondary organic aerosol potential (SOAP) were the highest from barbecue emissions. Among VOCs, aromatic hydrocarbons contributed the most to atmospheric SOA in all types of restaurants, exceeding 80%. The carcinogenic risks of the Class 1 carcinogens benzene and 1,3-butadiene in VOCs of barbecue emissions were the highest, and did not exceed acceptable levels. The non-carcinogenic risks were high from both barbecue and canteen without exceeding threshold values. This study can serve as an important basis for assessing the contribution of VOCs from restaurants in Beijing to secondary pollutants and their impacts on human health, and lead to the accurate determinations of the focus of pollution control.

Measurement report: Source apportionment and environmental impacts of volatile organic compounds (VOCs) in Lhasa, a highland city in China

Abstract. Hypoxia and adverse health outcomes might be affected by O3 pollution in the highland city of Lhasa. NOx emissions can amplify the role of volatile organic compounds (VOCs) in the secondary production of O3 under the conditions of high ultraviolet (UV) radiation levels and unfavourable dispersion patterns in the Lhasa River valley. Here, online C2–C11 VOC measurements, accompanied by other parameters concerning the O3 chemical budget, were first obtained and employed to identify the key VOC species and key sources of VOCs in terms of the loss rate against OH radicals (LOH), ozone formation potential (OFP), secondary organic aerosol potential (SOAP), and toxicity. Oxygenated VOCs (OVOCs) not only were the most abundant VOCs but also dominated LOH, OFP, and toxicity. Isoprene and anthropogenic VOCs were further identified as precursors of these OVOCs. Aromatics accounted for 5 % of the total VOCs (TVOCs) but contributed 88 % to the SOAP and 10 % to the toxicity. As the primary oxidative intermediates of aromatics were not well characterized by our measurements, the environmental impact of aromatics could be underestimated by our data. Source appointment and ternary analysis of benzene, toluene, and ethylbenzene confirmed the combined contribution of traffic emissions, solvent usage, and biomass burning. This suggests that O3 precursors are mainly from sources associated with residents' lives, except for solvent usage emissions which contribute to aromatics. Preliminary comparisons between source spectrums of transport sector emissions with positive matrix factorization (PMF)-decomposed ones and our measured ones suggest that vehicle emission patterns of VOCs at high altitude generally follow the ground-level impression. More quantitative data are required to further confirm this point though. Emission reduction strategy analysis for O3 pollution control highlighted multiple benefits of the simultaneous reduction in NOx originating from diesel vehicle emissions, biomass burning, and background sources (possibly dominated by incense burning). The notable biogenic emission contribution to the OFP was also first confirmed in our study, and this highlights the side effects of the government's pursuit of a greener city.

Spatiotemporal distribution, source apportionment and health risk assessment of atmospheric volatile organic compounds using passive air samplers in a typical coastal area, China

To fully understand source characteristics and human health effects of atmospheric volatile organic compounds (VOCs), it is of great importance to implement long-term measurements, precise source apportionment and simulation. In this study, a 12-month measurement of VOCs was conducted in a coastal area in East China by a novel passive air sampler (PAS). A total of 28 VOC species, mainly in groups of aromatics and halohydrocarbons were observed. The monthly average concentrations of TVOC were as follows: industrial sites (154.10–727.19 μg m−3) > business sites (65.83–86.96 μg m−3) > residential sites (59.63–60.05 μg m−3) > background site (57.62 μg m−3). Their seasonal variation characteristics were: winter > spring > autumn > summer, which was more apparent at industrial sites due to human activities. Six VOC sources including industrial processes, organic solvents, dyeing, plastic synthesis, traffic emissions, and pesticides identified by the positive matrix factorization model compared favorably with the local emissions at industrial sites. Bromoform, hexachloro-1,3-butadiene, C1–C3 halogenated alkanes and benzene homologs could be the important indicators of industrial VOC emissions. The halohydrocarbons and aromatics were the major contributors to the ozone formation potential (OFP) and secondary organic aerosol potential (SOAP) in industrial areas, respectively. Both of OFP and SOAP have their maximum values in winter due to high VOC concentrations. Health risk assessment indicated that a high probability of non-carcinogenic risk (HI > 1) was in the region at 10 m height and 50m radius, and minor carcinogenic risk (CR > 10−6) was in the region at 70 m height and 1000 m radius. Among all the compounds, 1,2-Dibromo-3-chloropropane was the largest contributor with the individual HI value (17.99) and carcinogenic risk (5.34 × 10−3) at the peak. In this study, the PAS as a sampling tool was proven to be reliable and efficient for long-term measurements in coastal areas. It is worth to have further studies to promote passive sampling as an alternative to VOCs monitoring methods.

Iron and Copper Alter the Oxidative Potential of Secondary Organic Aerosol: Insights from Online Measurements and Model Development.

The oxidative potential (OP) of particulate matter has been widely suggested as a key metric for describing atmospheric particle toxicity. Secondary organic aerosol (SOA) and redox-active transition metals, such as iron and copper, are key drivers of particle OP. However, their relative contributions to OP, as well as the influence of metal-organic interactions and particulate chemistry on OP, remains uncertain. In this work, we simultaneously deploy two novel online instruments for the first time, providing robust quantification of particle OP. We utilize online AA (OPAA) and 2,7-dichlorofluoroscein (ROSDCFH) methods to investigate the influence of Fe(II) and Cu(II) on the OP of secondary organic aerosol (SOA). In addition, we quantify the OH production (OPOH) from these particle mixtures. We observe a range of synergistic and antagonistic interactions when Fe(II) and Cu(II) are mixed with representative biogenic (β-pinene) and anthropogenic (naphthalene) SOA. A newly developed kinetic model revealed key reactions among SOA components, transition metals, and ascorbate, influencing OPAA. Model predictions agree well with OPAA measurements, highlighting metal-ascorbate and -naphthoquinone-ascorbate reactions as important drivers of OPAA. The simultaneous application of multiple OP assays and a kinetic model provides new insights into the influence of metal and SOA interactions on particle OP.

Characteristics of atmospheric non-methane hydrocarbon compounds (NMHCs) and their sources in urban typical secondary transformation in Beijing, China

Non-methane hydrocarbon compounds (NMHCs) paly the leading role in the formation of ozone (O3) and secondary organic aerosols (SOA), which can affect severely global climate change, air quality, and human health. NMHCs pollution became a meaningful and crucial research topic in Beijing. From the Eleventh Five-Year Plan to the present, volatile organic compounds (VOCs) have received widespread and great attention in environmental governance, especially the NMHCs. Due to successive stages to control air pollution, the concentration of NMHCs has dropped gradually nearly three years in Beijing. In this study, 54 NMHCs was measured from March 1 to March 30 in 2021. The mean concentration of NMHCs was 33.54 ± 16.69 ppbv during the whole observation period. The mean concentration of NMHCs was 40.69 ± 17.09 ppbv during the haze days, which was greater than non-haze days (26.68 ± 12.75 ppbv). Alkenes, alkanes, aromatics, and acetylene accounted for 34.22%, 33.02%, 32.60%, and 016% in total ozone formation potential (OFP), respectively. Aromatics accounted for 96.61% in total secondary organic aerosol potential (SOAP). All the sources of NMHCs (except for fuel evaporation) made non-negligible contribution to O3 formation. Solvent usage and gasoline exhaust contributed 52.19%, which were the largest contributor to SOAP. Therefore, Beijing should focus on the NMHCs pollution caused by the local emission (especially solvent usage and gasoline exhaust) to control and solve secondary pollution further in this study.

Marked impacts of transient conditions on potential secondary organic aerosol production during rapid oxidation of gasoline exhausts

Vehicle emission is a major source of atmospheric secondary organic aerosols (SOA). Driving condition is a critical influencing factor for vehicular SOA production, but few studies have revealed the dependence on rapid-changing real-world driving conditions. Here, a fast-response oxidation flow reactor system is developed and deployed to quantify the SOA formation potential under transient driving conditions. Results show that the SOA production factor varies by orders of magnitude, e.g., 20–1500 mg kg-fuel−1 and 12–155 mg kg-fuel−1 for China V and China VI vehicles, respectively. High speed, acceleration, and deceleration are found to considerably promote SOA production due to higher organic gaseous emissions caused by unburned fuel emission or incomplete combustion. In addition, China VI vehicles significantly reduce SOA formation potential, yield, and acceleration and deceleration peaks. Our study provides experimental insight and parameterization into vehicular SOA formation under transient driving conditions, which would benefit high time-resolved SOA simulations in the urban atmosphere.

Increasing volatile organic compounds emission from massive industrial coating consumption require more comprehensive prevention

Coating is an important raw material in industrial production. Global consumption of industrial coatings has approximated 28.84 Tg in 2019, with China accounting for more than half which generated plenty of Volatile Organic Compounds (VOCs). To learn the pollution characteristic and prevention strategy, we estimated the speciated VOCs emission of coating-consuming industries in China through field investigation, sample collection and analytical analysis. The environmental and health influences in 2019, 2025 and 2030 were then assessed based on scenario prediction with taking low-VOCs containing coating (LCC) application into consideration which was an important action in the ongoing prevention measures. Ozone formation potential (OFP), secondary organic aerosol potential (SOAP) and the newly established index of total health risks (THR) were employed to indicate the environmental influence and health threaten. Conclusions showed that (1) VOCs emissions would increase from 6.78 Tg to 10.46 Tg during 2019–2030 which result in a much higher OFP, SOAP and THR. (2) Replacing traditional organic coating (TOC) with LCC could effectively reduce VOCs emission. For every 1% increase in LCC proportion, VOCs emission, OFPs, SOAPs, and THRs decreased by 1.24%, 1.44%, 1.49%, and 1.70% on average, respectively. (3) Potential O3 and SOA yields approximated 25.61 Tg and 19.12 Tg (5.87% and 4.39% higher than 2019) even in the most stringent scenario for 2030 which meant continuous increases in industrial coating consumption could offset the positive effects produced by LCC substitution. (4) Esters, ethers, alcohols, and ketones are proposed as main composition of coatings to effectively reduce VOCs emission and their influence on account of better technical accessibility. These findings reveal that more innovative pollution prevention methods and production technologies are urgently needed to compensate for increased pollutant emissions derived from the growing demand for coating-associated commodities.

Characteristics, chemical transformation and source apportionment of volatile organic compounds (VOCs) during wintertime at a suburban site in a provincial capital city, east China

Based on the continuous online measurements of volatile organic compounds (VOCs) at a suburban site in Jinan, Shandong province in the wintertime of 2021, characteristics, chemical transformations and sources of VOCs were analyzed. The total mixing ratio of VOCs was 30.35 ± 19.9 ppbv, with alkanes being the most abundant species. Alkenes and aromatics were the major contributors to the hydroxyl radical loss rate (LOH) and the ozone formation potential (OFP), accounting for 44.9% and 32.7% to LOH, and 43.2% and 33.4% to OFP, respectively. Aromatics had the primary contribution (98.1%) to the secondary organic aerosol potential (SOAP), and the high correlation between SOAP and PM2.5 concentrations (R = 0.70) suggested that VOCs were critical precursors of PM2.5. Coal/biomass burning and motor vehicle emissions were the main sources of VOCs (24.6% and 23.8%, respectively), followed by petrochemical and fuel evaporation (19.9%), industrial sources (16.9%), and liquefied petroleum gas/natural gas use (14.8%). Backward trajectories and the potential source contribution function (PSCF) analysis results suggested that short-range transport from the southeast was the primary potential source of VOC concentrations in suburban Jinan. The results can provide theoretical support for local governments to develop VOC emission control strategies in suburban areas.

Emission characteristics and inventory of volatile organic compounds from the Chinese cement industry based on field measurements

Volatile organic compounds (VOCs) are major precursors of ozone (O3) and secondary organic aerosols (SOA), which degrade air quality and pose a serious risk to human health and ecological systems. Previous studies on the emission characteristics of VOCs have predominantly focused on petrochemical and solvent-using sources, while localized studies on the cement industry are scarce in China. Field measurements for four cement plants were carried out in this study to investigate the emission levels, source profiles, and secondary pollutant generation potential of 98 VOCs species emitted from rotary and shaft kilns in China. Furthermore, a species-differentiated VOCs emission inventory was compiled for the Chinese cement industry in 2019. The results demonstrated that the mass concentration of VOCs emitted from shaft kiln was more than 20-fold higher than that emitted from rotary kilns, and the alkanes was the dominant species (56%) in shaft kilns, while oxygenated VOCs (OVOCs) and halocarbons were the main species in rotary kilns. Moreover, alkenes & alkyne were the dominant contributors to ozone formation potential (OFP) in shaft kilns, whereas alkenes & alkyne and OVOCs were comparable and prominent contributors in rotary kilns. In contrast, secondary organic aerosol potential (SOAP) for the two types of kilns was dominated by aromatics. In 2019, approximately 18.18 kt VOCs were emitted from cement production and were found to be largely concentrated in the southeast and central provinces of China. Considering the influence on environmental conditions, high OFP-contributing species in cement kilns are suggested to be a priority in the pollution mitigation of O3. This study provides a new, comprehensive, and reasonable cognition of the current VOCs emissions from both rotary and shaft kilns in China, which will aid in a better understanding of VOCs emission characteristics and guide future policy-making.

Characteristics, Sources, and SOAP of VOCs During Winter in Jiyuan

Haze pollution events often occur in the heavy industry city of Jiyuan. Volatile organic compounds (VOCs) are the precursors of secondary organic aerosol (SOA), which accounts for 15%-20% of particulate matter (PM2.5). Here, PM2.5, O3, VOCs, and trace gases were monitored by using online instruments in Jiyuan from December 1st to 31st. The characteristics, sources, and secondary organic aerosol potential (SOAP) of VOCs were analyzed. The mean concentrations of TVOC were (54.3±27.5)×10-9. Alkanes, halocarbons, and alkynes were the predominant VOCs. The positive matrix factorization model was used to identify and apportion VOCs sources. Eight major sources of VOCs were identified, which included liquefied petroleum gas (LPG) or natural gas (NG), the polyvinyl chloride (PVC) industry, vehicular exhaust, the coking industry, solvent usage, industry, technological process, and fuel evaporation. The SOAP of aromatics was the largest. Among them, BTEXs were the dominant contributors to SOAP.

Characteristics and sources of volatile organic compounds during summertime in Tai'an, China

Continuous measurements of volatile organic compounds (VOCs) were conducted at an urban site in Tai'an, Shandong province of China from 15 May to 10 June 2019. The concentration of total VOCs (TVOCs) was 28.73 ± 15.20 ppbv, and oxygenated VOCs (OVOCs) comprised the dominant proportion (46.4%) among five VOC groups. The most abundant VOC species was formaldehyde, followed by propane, ethane, acetaldehyde, acetone and ethylene. Six VOC sources were identified by positive matrix factorization (PMF) model, including coal combustion (26.2%), OVOCs-related source (20.2%), liquefied petroleum gas (LPG) usage (18.9%), vehicle emission (17.1%), biogenic source (11.1%) and solvent usage (6.5%). The results of conditional bivariate probability function (CBPF) showed that LPG usage, vehicle exhaust and solvent usage were mainly affected by local emissions, while other three sources were greatly affected by regional transmission. Based on the China Ambient Air Quality Standard, O3 episode and non-O3 episode days were identified, and the concentrations of TVOCs were 32.80 ± 15.78 ppbv (O3 episode days) and 24.01 ± 14.47 ppbv (non-O3 episode days), respectively. During different O3 pollution episodes, OVOCs contributed the highest proportion to VOC concentration and ozone formation potential (OFP), while aromatics contributed the greatest potential for secondary organic aerosol potential (SOAP). Moreover, coal combustion and LPG usage were significantly associated with the increase in VOC pollution on O3 episode days.

Tower-based measurements of NMHCs and OVOCs in the Pearl River Delta: Vertical distribution, source analysis and chemical reactivity

Measurements of vertical distribution of volatile organic compounds (VOCs) have attracted wide attentions, which could help to understand atmospheric oxidation mechanism and provide implications for VOC control. This study measured the non-methane hydrocarbons (NMHCs) and oxygenated VOCs (OVOCs) simultaneously for the first time at three different heights, namely ground, 118 m and 488 m, in the Canton Tower located in the urban core of the Pearl River Delta (PRD). The results show that NMHCs decreased while some OVOC species such as formaldehyde and acetaldehyde increased with increasing height. It was mainly attributed to the dilution and chemical loss of NMHCs but secondary production of OVOCs during vertical transport. Ratio analysis and receptor modeling indicate that vehicle exhausts (47%) and fuel evaporation (39%) were major sources of the total NMHCs. Interestingly, industry contributed much more at 118 m, probably affected by organic gas discharge from the high chimney of industrial factories. The chemical reactivities in terms of OH radical loss rate (LOH), ozone formation potential (OFP) and secondary organic aerosol potential (SOAP) were lowest at 118 m, smaller than those influenced by high fresh NMHC emissions at ground and strong formation of secondary species (e.g. OVOCs) at 488 m. OH exposure estimated by isoprene and m,p-xylene/ethylbenzene was different depending on their time scale of vertical turbulent mixing and chemical loss. OVOC species measured at different heights were positively correlated with Ox (R = 0.48–0.87), indicating that OVOCs were largely contributed by secondary formation in photochemical process. The tower measurements of NMHCs and OVOCs provided a unique opportunity to investigate the VOC distribution and chemical behaviors, which could give important information for understanding O3 and PM2.5 pollution mechanism in the PRD region with fast developing urban setting and substantially changing air quality.

Emission characteristics and reactivity of volatile organic compounds from typical high-energy-consuming industries in North China

To effectively reduce the compound pollution of fine particulate matter (PM2.5) and ozone (O3), volatile organic compound (VOC) emission sources are being extensively studied. Studies on VOC emission characteristics have mainly focused on solvent-using and technological sources, while research on the combustion processes of high-energy-consuming industries remains limited. Here, we investigate the emission characteristics of 102 VOC species emitted from eight sources (sintering, pelletizing, steel smelting, a coke oven chimney, the topside of a coke oven, thermal power, and two types of cement kilns) used in four types of high-energy-consuming industries. Our results show significant differences among these sources. The average VOC mass concentrations varied from 0.14 to 7.08 mg/m3. Alkanes had the highest percentage contribution to VOCs from sintering (45.9%) and thermal power (44.6%), while aromatics had the highest percentage contribution from steel smelting (47.8%) and the topside of the coke oven (52.9%). Alkenes were abundant in the coke oven chimney (49.1%), and oxygenated VOCs accounted for 65.3% of the total VOCs from pelletizing. We also observed notable differences between the two types of cement kilns. In general, ethane, ethene, benzene, propane, acetaldehyde, and chloromethane were the dominant VOC species in all sources. The differences between the sources were due to factors such as the applied raw materials, calcination temperature, and end-of-pipe treatment. By reviewing studies from the past 20 years, we found that differences in the number of VOC species and the implementation of ultra-low emissions affect VOC emission characteristics. The coke oven chimney and cement kiln chimney-1 had the highest ozone formation potential and secondary organic aerosol potential, respectively. The VOC emissions from coking, iron and steel, thermal power, and cement industries were 1162.1, 289.9, 311.0, and 470.2 Gg, respectively. Our results highlight the need for more effective control measures to minimize VOC emissions from high-energy-consuming industries.

New Mechanistic Pathways for the Reactions of Formaldehyde with Formic Acid Catalyzed by Sulfuric Acid and Formaldehyde with Sulfuric Acid Catalyzed by Formic Acid: Formation of Potential Secondary Organic Aerosol Precursors

Formaldehyde (HCHO) plays an important role in the formation of secondary organic aerosols. Here, we report new mechanistic pathways for the reactions of formaldehyde with formic acid catalyzed by sulfuric acid and formaldehyde with sulfuric acid catalyzed by formic acid by using quantum chemical methods and reaction rate theory. We have found that sulfuric acid and formic acid have a strong catalytic role in the HCHO···HCOOH + H2SO4 and HCHO···H2SO4 + HCOOH reactions because the calculated energy barriers of the sulfuric acid-catalyzed reaction of formaldehyde with formic acid and formic acid-catalyzed reaction of formaldehyde with sulfuric acid are decreased by 21.17 and 14.81 kcal/mol, respectively. The calculated rates show that the reaction rate of HCHO···HCOOH + H2SO4 is faster than those of HCHO···H2SO4 + HCOOH and HCHO + HCOOH···H2SO4. Moreover, the HCHO + HCOOH + H2SO4 → H2C(OH)OCOH + H2SO4 reaction readily forms the carboxylic acid ester (H2C(OH)OCOH); this is a new mechanistic pathway for the reaction of formaldehyde with formic acid, which is expected to extend to other aldehydes’ reaction with carboxylic acids. Additionally, the present findings also suggest that formic acid-catalyzed formaldehyde and sulfuric acid reaction leads to the formation of an organosulfate as the nucleation precursor. The present results not only help understand the mechanisms for the initial processes of atmospheric nucleation but also are expected to extend other aldehydes and acids in the atmosphere.

Emissions of Volatile Organic Compounds (VOCs) from an Open-Circuit Dry Cleaning Machine Using a Petroleum-Based Organic Solvent: Implications for Impacts on Air Quality

Volatile organic compounds (VOCs) are known to play an important role in tropospheric chemistry, contributing to ozone and secondary organic aerosol (SOA) generation. Laundry facilities, using petroleum-based organic solvents, are one of the sources of VOCs emissions. However, little is known about the significance of VOCs, emitted from laundry facilities, in the ozone and SOA generation. In this study, we characterized VOCs emission from a dry-cleaning process using petroleum-based organic solvents. We also assessed the impact of the VOCs on air quality by using photochemical ozone creation potential and secondary organic aerosol potential. Among 94 targeted compounds including toxic organic air pollutants and ozone precursors, 36 compounds were identified in the exhaust gas from a drying machine. The mass emitted from one cycle of drying operation (40 min) was the highest in decane (2.04 g/dry cleaning). Decane, nonane, and n-undecane were the three main contributors to ozone generation (more than 70% of the total generation). N-undecane, decane, and n-dodecane were the three main contributors to the SOA generation (more than 80% of the total generation). These results help to understand VOCs emission from laundry facilities and impacts on air quality.

Source apportionment of VOCs in a typical medium-sized city in North China Plain and implications on control policy

Characteristics of atmospheric VOCs (volatile organic compounds) have been extensively studied in megacities in China, however, they are scarcely investigated in medium/small-sized cities in North China Plain (NCP). A comprehensive research on possible sources of VOCs was conducted in a medium-sized city of NCP, from May to September 2019. A total of 143 canister samples of 8 sites in Xuchang city were collected, and 57 VOC species were detected. The average VOC concentrations were 42.6 ± 31.6 μg/m3, with 53.7 ± 31.0 μg/m3 and 32.1 ± 27. 8 μg/m3, in the morning and afternoon, respectively. Alkenes and aromatics contributed 80% of the total ozone formation potential (OFP). Aromatics accounted for more than 95% of secondary organic aerosol potential (SOAP). VOCs were dominated by the local emission with significant transport from the southeast direction. PMF analysis extracted 6 sources, which were combustion (33.1%), LPG usage (19.3%), vehicular exhaust & fuel evaporation (15.8%), solvent usage (15.2%), industrial (9.11%) and biogenic (7.51%), respectively and they contributed 33.4%, 17.6%, 12.9%, 18.6%, 9.28% and 8.22% to the OFP, respectively. Combustion and LPG usage were the dominant VOC sources; and combustion, solvent usage and LPG usage were the main sources of OFP in Xuchang city, which were different to megacities in China with a high contribution from vehicular exhaust, solvent usage and industry, suggesting specific control strategies on VOCs need to be implemented in medium-sized city such as Xuchang city.

Characteristics, secondary transformation, and health risk assessment of ambient volatile organic compounds (VOCs) in urban Beijing, China

The long-term and high temporal resolution measurement of ambient volatile organic compounds (VOCs) was continuously performed in urban Beijing in 2016. Historical VOC data were compiled and compared with our results. A positive matrix factorization (PMF) model was used to determine potential emission sources. The backward trajectories and the concentration, ozone formation potential (OFP), and secondary organic aerosol potential (SOAP) of VOCs in the air masses from different regions were used to estimate the VOC chemical behaviour and transport-direction contributions. A health assessment, including the carcinogenic risk and non-carcinogenic risk of specific hazardous VOC species, was performed, while the point estimate approach was used for risk apportionment based on emission sources. In this study, the average (±standard deviation, Std) concentration of total observed VOCs (TVOCs) was 101.5 ± 65.2 μg/m3, ranging from 21.4 to 439.1 μg/m3. The VOC concentration in Beijing had decreased but was still higher than that in other Chinese cities according to compiled reported VOC data. Combustion-related sources were the primary sources of VOC pollution in urban Beijing. VOC contributions were increasingly coming from the northwestern regions instead of solely from regions to the south of Beijing according to the VOC concentration, OFP, and SOAP data. A potential health risk from VOCs should be considered for residents living in Beijing. The results of this study are expected to provide basic data for efficient VOC emission management and public health protection in Beijing.