Obscured Contribution of Oxygenated Intermediate-Volatility Organic Compounds to Secondary Organic Aerosol Formation from Gasoline Vehicle Emissions.

Secondary organic aerosol (SOA) formation from gasoline vehicles spanning a wide range of emission types was investigated using an oxidation flow reactor (OFR) by conducting chassis dynamometer tests. Aided by advanced mass spectrometric techniques, SOA precursors, including volatile organic compounds (VOCs) and intermediate/semivolatile organic compounds (I/SVOCs), were comprehensively characterized. The reconstructed SOA produced from the speciated VOCs and I/SVOCs can explain 69% of the SOA measured downstream of an OFR upon 0.5-3 days' OH exposure. While VOCs can only explain 10% of total SOA production, the contribution from I/SVOCs is 59%, with oxygenated I/SVOCs (O-I/SVOCs) taking up 20% of that contribution. O-I/SVOCs (e.g., benzylic or aliphatic aldehydes and ketones), as an obscured source, account for 16% of total nonmethane organic gas (NMOG) emission. More importantly, with the improvement in emission standards, the NMOG is effectively mitigated by 35% from China 4 to China 6, which is predominantly attributed to the decrease of VOCs. Real-time measurements of different NMOG components as well as SOA production further reveal that the current emission control measures, such as advances in engine and three-way catalytic converter (TWC) techniques, are effective in reducing the "light" SOA precursors (i.e., single-ring aromatics) but not for the I/SVOC emissions. Our results also highlight greater effects of O-I/SVOCs to SOA formation than previously observed and the urgent need for further investigation into their origins, i.e., incomplete combustion, lubricating oil, etc., which requires improvements in real-time molecular-level characterization of I/SVOC molecules and in turn will benefit the future design of control measures.

Insights into the Peroxide-Bicyclic Intermediate Pathway of Aromatic Photooxidation: Experimental Yields and NOx-Dependency of Ring-Opening and Ring-Retaining Products.

Aromatic hydrocarbons are important contributors to the formation of ozone and secondary organic aerosols in urban environments. The different parallel pathways in aromatic oxidation, however, remain inadequately understood. Here, we investigated the production yields and chemical distributions of gas-phase tracer products during the photooxidation of alkylbenzenes at atmospheric OH levels with NOx present using high-resolution mass spectrometers. The peroxide-bicyclic intermediate pathway emerged as the major pathway in aromatic oxidation, accounting for 52.1 ± 12.6%, 66.1 ± 16.6%, and 81.4 ± 24.3% of the total OH oxidation of toluene, m-xylene, and 1,3,5-trimethylbenzene, respectively. Notably, the yields of bicyclic nitrates produced from the reactions of bicyclic peroxy radicals (BPRs) with NO were considerably lower (3-5 times) than what the current mechanism predicted. Alongside traditional ring-opening products formed through the bicyclic pathway (dicarbonyls and furanones), we identified a significant proportion of carbonyl olefinic acids generated via the 1,5-aldehydic H-shift occurring in subsequent reactions of BPRs + NO, contributing 4-7% of the carbon flow in aromatic oxidation. Moreover, the observed NOx-dependencies of ring-opening and ring-retaining product yields provide insights into the competitive nature of reactions involving BPRs with NO, HO2, and RO2, which determine the refined product distributions and offer an explanation for the discrepancies between the experimental and model-based results.

Direct Observation of HONO Emissions from Real-World Residential Natural Gas Heating in China.

Atmospheric nitrous acid (HONO) is an important precursor of atmospheric hydroxyl radicals. Vehicle emissions and heterogeneous reactions have been identified as major sources of urban HONO. Here, we report on HONO emissions from residential natural gas (RNG) for water and space heating in urban areas based on in situ measurements. The observed HONO emission factors (EFs) of RNG heating vary between 6.03 and 608 mg·m-3 NG, which are highly dependent on the thermal load. The highest HONO EFs are observed at a high thermal load via the thermal NO homogeneous reaction. The average HONO EFs of RNG water heating in winter are 1.8 times higher than that in summer due to the increased thermal load caused by the lower inlet water temperatures in winter. The power-based HONO EFs of the traditional RNG heaters are 1085 times and 1.7 times higher than those of gasoline and diesel vehicles that meet the latest emission standards, respectively. It is estimated that the HONO emissions from RNG heaters in a typical Chinese city are gradually close to emissions from on-road vehicles when temperatures decline. These findings highlight that RNG heating is a non-negligible source of urban HONO emissions in China. With the continuous acceleration of coal-to-gas projects and the continuous tightening of NOx emission standards for vehicle exhaust, HONO emissions from RNG heaters will become more prominent in urban areas. Hence, it is urgently needed to upgrade traditional RNG heaters with efficient emission reduction technologies such as frequency-converted blowers, secondary condensers, and low-NOx combustors.

Enigma of Urban Gaseous Oxygenated Organic Molecules: Precursor Type, Role of NOx, and Degree of Oxygenation.

Oxidation of volatile organic compounds (VOCs) forms oxygenated organic molecules (OOMs), which contribute to secondary pollution. Herein, we present measurement results of OOMs using chemical ionization mass spectrometry with nitrate as the reagent ion in Shanghai. Compared to those in forests and laboratory studies, OOMs detected at this urban site were of relatively lower degree of oxygenation. This was attributed to the high NOx concentrations (∼44 ppb), which overall showed a suppression on the propagation reactions. As another result, a large fraction of nitrogenous OOMs (75%) was observed, and this fraction further increased to 84% under a high NO/VOC ratio. By applying a novel framework on OOM categorization and supported by VOC measurements, 50 and 32% OOMs were attributed to aromatic and aliphatic precursors, respectively. Furthermore, aromatic OOMs are more oxygenated (effective oxygen number, nOeff = 4-6) than aliphatic ones (nOeff = 3-4), which can be partly explained by the difference in initiation mechanisms and points to possible discrimination in termination reactions. This study highlights the roles of NOx in OOM formation in urban areas, as well as the formation of nitrogenous products that might show discrimination between aromatic and aliphatic VOCs.

Direct identification of total and missing OH reactivities from light-duty gasoline vehicle exhaust in China based on LP-LIF measurement.

Considerable efforts have been devoted to characterising the chemical components of vehicle exhaust. However, these components may not accurately reflect the contribution of vehicle exhaust to atmospheric reactivity because of the presence of species not accounted for ("missing species") given the limitations of analytical instruments. In this study, we improved the laser photolysis-laser-induced fluorescence (LP-LIF) technique and applied it to directly measure the total OH reactivity (TOR) in exhaust gas from light-duty gasoline vehicles in China. The TOR for China I to VI-a vehicles was 15.6, 16.3, 8.4, 2.6, 1.5, and 1.6 × 104 sec-1, respectively, reflecting a notable drop as emission standards were upgraded. The TOR was comparable between cold and warm starts. The missing OH reactivity (MOR) values for China I to IV vehicles were close to zero with a cold start but were much higher with a warm start. The variations in oxygenated volatile organic compounds (OVOCs) under different emission standards and for the two start conditions were similar to those of the MOR, indicating that OVOCs and the missing species may have similar production processes. Online measurement revealed that the duration of the stable driving stage was the primary factor leading to the production of OVOCs and missing species. Our findings underscore the importance of direct measurement of TOR from vehicle exhaust and highlight the necessity of adding OVOCs and other organic reactive gases in future upgrades of emission standards, such that the vehicular contribution to atmospheric reactivity can be more effectively controlled.

Observation-based sources evolution of non-methane hydrocarbons (NMHCs) in a megacity of China.

Both concentrations and emissions of many air pollutants have been decreasing due to implement of control measures in China, in contrast to the fact that an increase in emissions of non-methane hydrocarbons (NMHCs) has been reported. This study employed seven years continuous NMHCs measurements and the related activities data of Shanghai, a megacity in China, to explore evolution of emissions and effectiveness of air pollution control measures. The mixing ratio of NMHCs showed no statistical interannual changes, of which their compositions exhibited marked changes. This resulted in a decreasing trend of ozone formation potential by 3.8%/year (p < 0.05, the same below), which should be beneficial to ozone pollution mitigation as its production in Shanghai is in the NMHCs-limited regime. Observed alkanes, aromatics and acetylene changed by +3.7%/year, -5.9%/year and -7.4%/year, respectively, and alkenes showed no apparent trend. NMHCs sources were apportioned by a positive matrix factorization model. Accordingly, vehicular emissions (-5.9%/year) and petrochemical industry emissions (-7.1%/year) decreased significantly, but the decrease slowed down; significant reduction in solvent usage (-9.0%/year) appeared after 2010; however, emissions of natural gas (+12.6%/year) and fuel evaporation (with an increasing fraction) became more important. The inconsistency between observations and inventories was found in interannual trend and speciation as well as source contributions, emphasizing the need for further validation in NMHCs emission inventory. Our study confirms the effectiveness of measures targeting mobile and centralized emissions from industrial sources and reveals a need focusing on fugitive emissions, which provided new insights into future air policies in polluted region.

Upgrading Emission Standards Inadvertently Increased OH Reactivity from Light-Duty Diesel Truck Exhaust in China: Evidence from Direct LP-LIF Measurement.

Vehicular exhaust is an important source of reactive gases responsible for the formation of ozone and secondary organic aerosols (SOAs) in the atmosphere. Although significant efforts have been made to characterize the chemical compounds associated with vehicular exhaust, there is still a wealth of compounds that are unable to be detected, posing uncertainties in estimating their contribution to atmospheric reactivity. In this study, by improving laser-induced fluorescence techniques, we achieved the first-ever direct measurement of the total OH reactivity (TOR) from light-duty diesel truck (LDDT) exhaust with different emission standards. We found that the TOR from the LDDT exhaust was 80-130 times the TOR from the gasoline exhaust measured in Japan. Unexpectedly, we discovered increased TOR emissions along with upgrading emission standards, possibly as a collective result of high combustion temperature in the engine and the oxidation catalysts in the exhaust after-treatment that favor production of highly oxidized organics in the stricter emission standard. Most of these oxidized organics are unable to be speciated by routine measurements, resulting in the missing OH reactivity increasing rapidly from 1.91% for China III to 42.0% for China V LDDT. Upgrading the emission standard failed to reduce the TOR from LDDT exhaust, which may inadvertently promote the contribution of LDDT to the formation of ozone and SOA pollution in China.

Field Detection of Highly Oxygenated Organic Molecules in Shanghai by Chemical Ionization-Orbitrap.

Secondary organic aerosol, formed through atmospheric oxidation processes, plays an important role in affecting climate and human health. In this study, we conducted a comprehensive campaign in the megacity of Shanghai during the 2019 International Import Expo (EXPO), with the first deployment of a chemical ionization─Orbitrap mass spectrometer for ambient measurements. With the ultrahigh mass resolving power of the Orbitrap mass analyzer (up to 140,000 Th/Th) and capability in dealing with massive spectral data sets by positive matrix factorization, we were able to identify the major gas-phase oxidation processes leading to the formation of oxygenated organic molecules (OOM) in Shanghai. Nine main factors from three independent sub-range analysis were identified. More than 90% of OOM are of anthropogenic origin and >60% are nitrogen-containing molecules, mainly dominated by the RO2 + NO and/or NO3 chemistry. The emission control during the EXPO showed that even though the restriction was effectual in significantly lowering the primary pollutants (20-70% decrease), the secondary oxidation products responded less effectively (14% decrease), or even increased (50 to >200%) due to the enhancement of ozone and the lowered condensation sink, indicating the importance of a stricter multi-pollutant coordinated strategy in primary and secondary pollution mitigation.

Nocturnal atmospheric chemistry of NO3 and N2O5 over Changzhou in the Yangtze River Delta in China.

Comprehensive observations of the nocturnal atmospheric oxidation of NO3 and N2O5 were conducted at a suburban site in Changzhou in the YRD using cavity ring-down spectroscopy (CRDS) from 27 May to 24 June, 2019. High concentrations of NO3 precursors were observed, and the nocturnal production rate of NO3 was determined to be 1.7 ± 1.2 ppbv/hr. However, the nighttime NO3 and N2O5 concentrations were relatively low, with maximum values of 17.7 and 304.7 pptv, respectively, illustrating the rapid loss of NO3 and N2O5. It was found that NO3 dominated the nighttime atmospheric oxidation, accounting for 50.7%, while O3 and OH only contributed 34.1% and 15.2%, respectively. For the reactions of NO3 with volatile organic compounds (VOCs), styrene was found to account for 60.3%, highlighting its dominant role in the NO3 reactivity. In general, the contributions of the reactions between NO3 and VOCs and the N2O5 uptake to NO3 loss were found to be about 39.5% and 60.5%, respectively, indicating that N2O5 uptake also played an important role in the loss of NO3 and N2O5, especially under the high humidity conditions in China. The formation of nitrate at night mainly originated from N2O5 uptake, and the maximum production rate of NO3- reached 6.5 ppbv/hr. The average NOx consumption rate via NO3 and N2O5 chemistry was found to be 0.4 ppbv/h, accounting for 47.9% of the total NOx removal. The predominant roles of NO3 and N2O5 in nitrate formation and NOx removal in the YRD region was highlighted in this study.

Tracer-based characterization of source variations of PM2.5 and organic carbon in Shanghai influenced by the COVID-19 lockdown.

Air quality in megacities is significantly impacted by emissions from vehicles and other urban-scale human activities. Amid the outbreak of Coronavirus (COVID-19) in January 2020, strict policies were in place to restrict people's movement, bringing about steep reductions in pollution activities and notably lower ambient concentrations of primary pollutants. In this study, we report hourly measurements of fine particulate matter (i.e., PM2.5) and its comprehensive chemical speciation, including elemental and molecular source tracers, at an urban site in Shanghai spanning a period before the lockdown restriction (BR) (1 to 23 Jan. 2020) and during the restriction (DR) (24 Jan. to 9 Feb. 2020). The overall PM2.5 was reduced by 27% from 56.2 ± 40.9 (BR) to 41.1 ± 25.3 µg m-3 (DR) and the organic carbon (OC) in PM2.5 was similar, averaged at 5.45 ± 2.37 (BR) and 5.42 ± 1.75 µgC m-3 (DR). Reduction in nitrate was prominent, from 18.1 (BR) to 9.2 µg m-3 (DR), accounting for most of the PM2.5 decrease. Source analysis of PM2.5 using positive matrix factorization modeling of comprehensive chemical composition, resolved nine primary source factors and five secondary source factors. The quantitative source analysis confirms reduced contributions from primary sources affected by COVID-19, with vehicular emissions showing the largest drop, from 4.6 (BR) to 0.61 µg m-3 (DR) and the percentage change (-87%) in par with vehicle traffic volume and fuel sale statistics (-60% to -90%). In the same time period, secondary sources are revealed to vary in response to precursor reductions from the lockdown, with two sources showing consistent enhancement while the other three showing reductions, highlighting the complexity in secondary organic aerosol formation and the nonlinear response to broad primary precursor pollutants. The combined contribution from the two secondary sources to PM2.5 increased from 7.3 ± 6.6 (BR) to 14.8 ± 9.3 µg m-3 (DR), partially offsetting the reductions from primary sources and nitrate while their increased contribution to OC, from 1.6 ± 1.4 (BR) to 3.2 ± 2.0 µgC m-3 (DR), almost offset the decrease coming from the primary sources. Results from this work underscore challenges in predicting the benefits to PM2.5 improvement from emission reductions of common urban primary sources.

Ammonia Emission Measurements for Light-Duty Gasoline Vehicles in China and Implications for Emission Modeling.

Motor vehicle ammonia (NH3) emissions have attracted increasing attention for their potential to form secondary aerosols in urban atmospheres. However, vehicle NH3 emission factors (EFs) remain largely unknown due to a lack of measurements. Thus, we conducted detailed measurements of NH3 emissions from 18 Euro 2 to Euro 5 light-duty gasoline vehicles (LDGVs) in Shanghai, China. The distance- and fuel-based NH3 EFs average 29.2 ± 24.1 mg·km-1 and 0.49 ± 0.41 g·kg-1, respectively. The average NH3-to-CO2 ratio is 0.41 ± 0.34 ppbv·ppmv-1. The measurements reveal that NH3 emissions from LDGVs are strongly correlated with both vehicle specific power (VSP) and the modified combustion efficiency (MCE); these relationships were used to predict LDGV NH3 EFs via a newly developed model. The predicted LDGV NH3 EFs under urban and highway driving cycles are 23.3 mg·km-1 and 84.5 mg·km-1, respectively, which are consistent with field measurements. The NH3 EF has decreased by 32% in average since the implementation of vehicle emission control policies in China five years ago. The model presented herein more accurately predicts LDGV NH3 emissions, contributing substantially to the compilation of NH3 emission inventories and prediction of future motor vehicle emissions in China.

Intermediate Volatility Organic Compound Emissions from a Large Cargo Vessel Operated under Real-World Conditions.

Intermediate volatility organic compound (IVOC) emissions from a large cargo vessel were characterized under real-world operating conditions using an on-board measurement system. Test ship fuel-based emission factors (EFs) of total IVOCs were determined for two fuel types and seven operating conditions. The average total IVOC EF was 1003 ± 581 mg·kg-fuel-1, approximately 0.76 and 0.29 times the EFs of primary organic aerosol (POA) emissions from low-sulfur fuel (LSF, 0.38 wt % S) and high-sulfur fuel (HSF, 1.12 wt % S), respectively. The average total IVOC EF from LSF was 2.4 times that from HSF. The average IVOC EF under low engine load (15%) was 0.5-1.6 times higher than those under 36%-74% loads. An unresolved complex mixture (UCM) contributed 86.1 ± 1.9% of the total IVOC emissions. Ship secondary organic aerosol (SOA) production was estimated to be 546.5 ± 284.1 mg·kg-fuel-1; IVOCs contributed 98.9 ± 0.9% of the produced SOA on average. Fuel type was the dominant determinant of ship IVOC emissions, IVOC volatility distributions, and SOA production. The ship emitted more IVOC mass, produced higher proportions of volatile organic components, and produced more SOA mass when fueled with LSF than when fueled with HSF. When reducing ship POA emissions, more attention should be paid to commensurate control of ship SOA formation potential.

Size-resolved effective density of submicron particles during summertime in the rural atmosphere of Beijing, China.

Particle density is an important physical property of atmospheric particles. The information on high time-resolution size-resolved particle density is essential for understanding the atmospheric physical and chemical aging processes of aerosols particles. In the present study, a centrifugal particle mass analyzer (CPMA) combined with a differential mobility analyzer (DMA) was deployed to determine the size-resolved effective density of 50 to 350nm particles at a rural site of Beijing during summer 2016. The measured particle effective densities decreased with increasing particle sizes and ranged from 1.43 to 1.55g/cm3, on average. The effective particle density distributions were dominated by a mode peaked at around 1.5g/cm3 for 50 to 350nm particles. Extra modes with peaks at 1.0, 0.8, and 0.6g/cm3 for 150, 240, and 350nm particles, which might be freshly emitted soot particles, were observed during intensive primary emissions episodes. The particle effective densities showed a diurnal variation pattern, with higher values during daytime. A case study showed that the effective density of Aitken mode particles during the new particle formation (NPF) event decreased considerably, indicating the significant contribution of organics to new particle growth.

Chemical characteristics of fine particles and their impact on visibility impairment in Shanghai based on a 1-year period observation.

In this work, a one-year observation focusing on high time resolution characteristics of components in fine particles was conducted at an urban site in Shanghai. Contributions of different components on visibility impairment were also studied. Our research indicates that the major components of PM2.5 in Shanghai are water-soluble inorganic ions and carbonaceous aerosol, accounting for about 60% and 30% respectively. Higher concentrations of sulfate (SO42-) and organic carbon (OC) in PM2.5 occurred in fall and summer, while higher concentrations of nitrate (NO3-) were observed in winter and spring. The mass concentrations of Cl- and K+ were higher in winter. Moreover, NO3- increased significantly during PM2.5 pollution episodes. The high values observed for the sulfate oxidizing rate (SOR), nitrate oxidizing rate (NOR) and secondary organic carbon (SOC) in OC indicate that photochemical reactions were quite active in Shanghai. The IMPROVE (Interagency Monitoring of Protected Visual Environments) formula was used in this study to investigate the contributions of individual PM2.5 chemical components to the light extinction efficient in Shanghai. Both NH4NO3 and (NH4)2SO4 had close relationships with visibility impairment in Shanghai. Our results show that the reduction of anthropogenic SO2, NOx and NH3 would have a significant effect on the improvement of air quality and visibility in Shanghai.

Do vehicular emissions dominate the source of C6-C8 aromatics in the megacity Shanghai of eastern China?

The characteristic ratios of volatile organic compounds (VOCs) to i-pentane, the indicator of vehicular emissions, were employed to apportion the vehicular and non-vehicular contributions to reactive species in urban Shanghai. Two kinds of tunnel experiments, one tunnel with more than 90% light duty gasoline vehicles and the other with more than 60% light duty diesel vehicles, were carried out to study the characteristic ratios of vehicle-related emissions from December 2009 to January 2010. Based on the experiments, the characteristic ratios of C6-C8 aromatics to i-pentane of vehicular emissions were 0.53 ± 0.08 (benzene), 0.70 ± 0.12 (toluene), 0.41 ± 0.09 (m,p-xylenes), 0.16 ± 0.04 (o-xylene), 0.023 ± 0.011 (styrene), and 0.15 ± 0.02 (ethylbenzene), respectively. The source apportionment results showed that around 23.3% of C6-C8 aromatics in urban Shanghai were from vehicular emissions, which meant that the non-vehicular emissions had more importance. These findings suggested that emission control of non-vehicular sources, i.e. industrial emissions, should also receive attention in addition to the control of vehicle-related emissions in Shanghai. The chemical removal of VOCs during the transport from emissions to the receptor site had a large impact on the apportionment results. Generally, the overestimation of vehicular contributions would occur when the VOC reaction rate constant with OH radicals (kOH) was larger than that of the vehicular indicator, while for species with smaller kOH than the vehicular indicator, the vehicular contribution would be underestimated by the method of characteristic ratios.

Chemical and optical properties of aerosols and their interrelationship in winter in the megacity Shanghai of China.

A field campaign on air quality was carried out in Shanghai in winter of 2012. The concentrations of NO, NO2, NOx, SO2, CO, and PM2.5 increased during haze formation. The average masses of SO4(2-), NO3(-) and NH4(+) were 10.3, 11.7 and 6.7 µg/m(3) during the haze episodes, which exceeded the average (9.2, 7.9, and 3.4 µg/m(3)) of these components in the non-haze days. The mean values for the aerosol scattering coefficient (bsp), aerosol absorption coefficient (bap) and single scattering albedo (SSA) were 288.7, 27.7 and 0.91 Mm(-1), respectively. A bi-peak distribution was observed for the mass concentrations of CO, NO, NO2, and NOx. More sulfate was produced during daytime than that in the evening due to photochemical reactions. The mass concentration of NH4(+) achieved a small peak at noontime. NO3(-) showed lower concentrations in the afternoon and higher concentrations in the early morning. There were obvious bi-peak diurnal patterns for bsp and bap as well as SSA. bsp and bap showed a positive correlation with PM2.5 mass concentration. (NH4)2SO4, NH4NO3, organic mass, elemental carbon and coarse mass accounted for 21.7%, 19.3%, 31.0%, 9.3% and 12.3% of the total extinction coefficient during non-haze days, and 25.6%, 24.3%, 30.1%, 8.1% and 8.2% during hazy days. Organic matter was the largest contributor to light extinction. The contribution proportions of ammonium sulfate and ammonium nitrate to light extinction were significantly higher during the hazy time than during the non-haze days.

PM2.5 constituents and hospital emergency-room visits in Shanghai, China.

Although ambient PM2.5 has been linked to adverse health effects, the chemical constituents that cause harm are largely unclear. Few prior studies in a developing country have reported the health impacts of PM2.5 constituents. In this study, we examined the short-term association between PM2.5 constituents and emergency room visits in Shanghai, China. We measured daily concentrations of PM2.5, organic carbon (OC), elemental carbon (EC), and eight water-soluble ions between January 1, 2011 and December 31, 2012. We analyzed the data using overdispersed generalized linear Poisson models. During our study period, the mean daily average concentration of PM2.5 in Shanghai was 55 µg/m(3). Major contributors to PM2.5 mass included OC, EC, sulfate, nitrate, and ammonium. For a 1-day lag, an interquartile range increment in PM2.5 mass (36.47 µg/m(3)) corresponded to 0.57% [95% confidence interval (CI): 0.13%, 1.01%] increase of emergency room visits. In all the three models used, we found significant positive associations of emergency room visits with OC and EC. Our findings suggest that PM2.5 constituents from the combustion of fossil fuel (e.g., OC and EC) may have an appreciable influence on the health impact attributable to PM2.5.

Understanding secondary particles in a regional site of Yangtze River Delta: Insights from mass spectrometric measurement.

Submicron particulate matter (PM1) poses significant risks to health risks and global climate. In this study, secondary organic aerosols (SOA) and inorganic compositions were examined for their physicochemical characteristics and evolution using high-resolution aerosol instruments in Changzhou over one-month period. The results showed that transport accompanied by regional static conditions leaded to the occurrence of heavy pollution. In addition, regional generation and local emissions also leaded to the occurrence of light and moderate pollution during the observation period in Changzhou. Organic aerosols (OA) and nitrate (NO3-) accounted for 45 % and 23 % of PM1, respectively. The increase in PM1 was dominated by the contribution of NO3- and OA. SOA was dominance in OA (63 % with 40 % MO-OOA), which was higher than primary organic aerosols (POA). Besides, photochemical reactions and the high oxidizing nature of the urban atmosphere promoted the production of OA, especially MO-OOA in Changzhou. Our results highlight that secondary particles contribute significantly to PM pollution in Changzhou, underlining the importance of controlling emissions of gaseous precursors, especially under high oxidation conditions.

[Characteristics and Cause of PM2.5 During Haze Pollution in Winter 2022 in Zhoukou, China].

The characteristics and main factors of causes of haze in Zhoukou in January 2022 were analyzed. Six air pollutants, water-soluble ions, elements, OC, EC, and other parameters in fine particulate matter were monitored and analyzed using a set of online high-time-resolution instruments in an urban area. The results showed that the secondary inorganic aerosols(SNA), carbonaceous aerosols(CA, including organic carbon OC and inorganic carbon EC), and reconstructed crustal materials(CM, such as Al2O3, SiO2, CaO, and Fe2O3, etc.) were the three main components, accounting for 61.3%, 24.3%, and 9.72% in PM2.5, respectively. The concentrations of SNA, CA, CM, and SOA were increased, accompanied with higher AQI. The sulfur oxidation rate(SOR) and nitrogen oxidation rate(NOR) in January were 0.53 and 0.46, respectively. The growth rates[µg·(m3·h)] of sulfate and nitrate were 0.027(-5.89-9.47, range) and 0.051(-23.1-12.4), respectively. During the haze period, the growth rates of sulfate and nitrate were 0.13 µg·(m3·h)-1and 0.24 µg·(m3·h)-1, which were 4.8 and 4.7 times higher than the average value of January, respectively. Although the sulfur oxidation rate was greater than the nitrogen oxidation rate, the growth rate of nitrate was approximately 1.8 times that of sulfate owing to the difference in the concentration of gaseous precursors and the influence of relative humidity. The growth rates of nitrate in SNA were significantly higher than those of sulfate on heavily polluted days. The values of SOR, NOR, and concentrations of SNA and SOA during higher AQI and humidity periods were higher than those in lower AQI and humidity periods. The Ox(NO2+O3) decreased with the increase in relative humidity. The SOA was higher at nighttime, increasing faster with the humidity than that in daytime. Under the situation of lower temperature, higher humidity, and lower wind speed, the emission of gaseous precursors of SNA requires further attention in Zhoukou in winter. Advanced control strategies of emissions of SO2 and NO2, such as mobile sources and coal-burning sources, could reduce the peak of haze in winter efficiently.

Observation and simulation of HOx radicals in an urban area in Shanghai, China.

A continuous wintertime observation of ambient OH and HO2 radicals was first carried out in Shanghai, in 2019. This effort coincided with the second China International Import Expo (CIIE), during which strict emission controls were implemented in Shanghai, resulting in an average PM2.5 concentration of less than 35 µg/m3. The self-developed instrument based on the laser-induced fluorescence (LIF) technique reported that the average OH radical concentration at noontime (11:00-13:00) was 2.7 × 106 cm-3, while the HO2 concentration was 0.8 × 108 cm-3. A chemical box model utilizing the Regional Atmospheric Chemical Mechanism 2 (RACM2), which is used to simulate pollutant reactions and other processes in the troposphere and which incorporates the Leuven isoprene mechanism (LIM1), reproduced the OH concentrations on most days. The HO2 concentration was underestimated, and the observed-to-modelled ratio demonstrated poor performance by the model, especially during the elevated photochemistry period. Missing primary peroxy radical sources or unknown behaviors of RO2 for high-NOx regimes are possible reasons for the discrepancy. The daytime ROx production was controlled by various sources. HONO photolysis accounted for more than one half (0.83 ppb/h), and the contribution from formaldehyde, OVOCs and ozone photolysis was relatively similar. Active oxidation paths accelerated the rapid ozone increase in winter. The average ozone production rate was 15.1 ppb/h, which is comparable to that of a Beijing suburb (10 ppb/h for the 'BEST-ONE') but much lower than that of Beijing's center (39 ppb/h in 'PKU' and 71 ppb/h in 'APHH') in wintertime. Cumulative local ozone based on observed peroxy radicals was five times higher than the value simulated by the current model due to the underprediction of HO2 and RO2 under the high-NOx regime. This analysis provides crucial information for subsequent pollution control policies in Shanghai.