Anchored Cobalt Nanoparticles on Layered Perovskites for Rapid Peroxymonosulfate Activation in Antibiotic Degradation.

In the Fenton-like reaction, revealing the dynamic evolution of the active sites is crucial to achieve the activity improvement and stability of the catalyst. This study reports a perovskite oxide in which atomic (Co0) in situ embedded exsolution occurs during the high-temperature phase transition. This unique anchoring strategy significantly improves the Co3+/Co2+ cycling efficiency at the interface and inhibits metal leaching during peroxymonosulfate (PMS) activation. The Co@L-PBMC catalyst exhibits superior PMS activation ability and could achieve 99% degradation of tetracycline within 5 min. The combination of experimental characterization and density functional theory (DFT) calculations elucidates that the electron-deficient oxygen vacancy accepts an electron from the Co 3d-orbital, resulting in a significant electron delocalization of the Co site, thereby facilitating the adsorption of the *HSO5/*OH intermediate onto the "metal-VO bridge" structure. This work provides insights into the PMS activation mechanism at the atomic level, which will guide the rational design of next-generation catalysts for environmental remediation.

Direct Measurement of Aerosol Liquid Water Content: A Case Study in Summer in Nanjing, China.

Aerosol liquid water content (ALWC) affects the mass loading, optical properties, and toxicity of aerosols. However, the measurement of ALWC is very rare due to its requirement of sophisticated instruments and its high operational costs. In this work, we improved on our previous simple, low-cost method by using a combination of one real-time fine particulate matter (PM2.5) monitor and two turbidimeters and successfully applied these for the direct measurement of ALWC in PM2.5 in Nanjing during the summer of 2023. The average ALWC during this measurement period occupied ~1/6 of the total PM2.5 mass, and this contribution was even greater with the elevation in the PM2.5 concentration. The ALWC was, as anticipated, closely related to the relative humidity (RH) and PM2.5 concentrations, but it did not always increase with the air quality index (AQI) due to the fact that polluted periods in summer were often governed by high O3 levels, not PM2.5 levels. The ALWC also had a great impact on visibility; it could decrease the visibility rapidly to hazy conditions when the dry PM2.5 was not high (~30 µg m-3) or the AQI was "good" (75~100), indicating that the air quality classified as "good" using the dry PM2.5 concentration might actually be "lightly polluted" if the ALWC is included. We also found that the air mass originating from Northeast China had the lowest PM2.5 mass concentration yet the highest ALWC values due to its high RH. Moreover, the quantification of ALWC levels can help us understand the solubility/bioavailability and thus the toxic effects of some specific components (for example, heavy metals or organics). Moreover, the influence of ALWC on air quality classifications should also be considered in the assessment of the health effects of air pollution and in public health early warning and protection.

Recent Advances in Iridium-based Electrocatalysts for Acidic Electrolyte Oxidation.

Ongoing research to develop advanced electrocatalysts for the oxygen evolution reaction (OER) is needed to address demand for efficient energy conversion and carbon-free energy sources. In the OER process, acidic electrolytes have higher proton concentration and faster response than alkaline ones, but their harsh strongly acidic environment requires catalysts with greater corrosion and oxidation resistance. At present, iridium oxide (IrO2 ) with its strong stability and excellent catalytic performance is the catalyst of choice for the anode side of commercial PEM electrolysis cells. However, the scarcity and high cost of iridium (Ir) and the unsatisfactory activity of IrO2 hinder industrial scale application and the sustainable development of acidic OER catalytic technology. This highlights the importance of further research on acidic Ir-based OER catalysts. In this review, recent advances in Ir-based acidic OER electrocatalysts are summarized, including fundamental understanding of the acidic OER mechanism, recent insights into the stability of acidic OER catalysts, highly efficient Ir-based electrocatalysts, and common strategies for optimizing Ir-based catalysts. The future challenges and prospects of developing highly effective Ir-based catalysts are also discussed.

[Characteristics of Light Absorption, Sources, and Seasonal Variation of Atmospheric Brown Carbon in Northern Nanjing].

Brown carbon (BrC) refers to a group of organic compounds in fine atmospheric particles (PM2.5) that are able to absorb light in the ultraviolet and visible range. They have a significant impact on the visibility of air and on the earth's climate. In this study, we used a black carbon analyzer (Model AE33) to conduct field measurements in northern suburban Nanjing from March 2021 to February 2022. We measured the light absorption coefficients of BrC in PM2.5 and quantified the contributions of primary (BrCpri) and secondary brown carbon (BrCsec) in BrC by using the minimum correlation method (MRS), combined with the backward trajectories,potential source contribution function (PSCF) analysis, and diurnal patterns to analyze the seasonal characteristics of BrC. The results showed that the annual average light absorption of BrC was(7.76±7.17)Mm-1 (at 370 nm), and its contribution to the total aerosol light absorption was (22.0±8.8)%. BrC light absorption at different wavelengths all showed a U-shape seasonal variation of high in spring and winter and low in summer and fall. MRS analysis showed that the annual average contributions of BrCpri and BrCsec were (62.9±21.4)% and (37.1±21.4)% (at 370 nm), respectively; however, the contribution of BrCsec increased with the increase in wavelength, and it became dominant in longer wavelengths such as 660 nm. Backward trajectory and PSCF analysis showed that BrC was heavily influenced by air masses from the sea in spring, summer, and fall but was influenced greatly by local and regional continental emissions in winter. Traffic emissions in spring, summer, and fall were more intense to contribute to BrCpri than that in winter, whereas coal and biomass combustion had a greater impact on BrCpri in winter. Detailed analysis revealed that gas-phase photochemistry and aqueous chemistry had different influences on BrCsec formation in different seasons. It was mainly from gas-phase photochemistry in summer but was dominated by aqueous process in winter; both processes, however, were important pathways to BrCsec in spring and fall.

Accelerated deprotonation with a hydroxy-silicon alkali solid for rechargeable zinc-air batteries.

Transition metal oxides are promising electrocatalysts for zinc-air batteries, yet surface reconstruction caused by the adsorbate evolution mechanism, which induces zinc-ion battery behavior in the oxygen evolution reaction, leads to poor cycling performance. In this study, we propose a lattice oxygen mechanism involving proton acceptors to overcome the poor performance of the battery in the OER process. We introduce a stable solid base, hydroxy BaCaSiO4, onto the surfaces of PrBa0.5Ca0.5Co2O5+δ perovskite nanofibers with a one-step exsolution strategy. The HO-Si sites on the hydroxy BaCaSiO4 significantly accelerate proton transfer from the OH* adsorbed on PrBa0.5Ca0.5Co2O5+δ during the OER process. As a proof of concept, a rechargeable zinc-air battery assembled with this composite electrocatalyst is stable in an alkaline environment for over 150 hours at 5 mA cm-2 during galvanostatic charge/discharge tests. Our findings open new avenues for designing efficient OER electrocatalysts for rechargeable zinc-air batteries.

Computational and experimental assessment of health risks of fine particulate matter in Nanjing and Yangzhou, China.

Fine particulate matter (PM2.5) is a major air pollutant in most cities of China, and poses great health risks to local residents. In this study, the health effects of PM2.5 in Nanjing and Yangzhou were compared using computational and experimental methods. The global exposure mortality model (GEMM), including the results of a cohort study in China, was used to estimate the disease-related risks. Premature mortality attributable to PM2.5 exposure were markedly higher in Nanjing than that in Yangzhou at comparable levels of PM2.5 (8191 95% CI, 6975-9994 vs. 6548 95% CI, 5599-8049 in 2015). However, the baseline mortality rate was on a country-level and the age distribution was on a province-level, traditional estimation method could not accurately represent the health burdens of PM2.5 on a city-level. We proposed a refined calculation method which based on the actual deaths of each city and the disease death rates. Conversely, similar concentrations of PM2.5 exposure resulted in higher actual deaths per million population in Yangzhou (1466 95% CI, 1266-1746) than that in Nanjing (1271 95% CI, 1098-1514). Health risks of PM2.5 are associated with the generation of reactive oxygen species, among which hydroxyl radial (·OH) is the most reactive one. We then collected these PM2.5 samples and quantified the induced ·OH. Consistently, average ·OH concentration in 2015 was higher in Yangzhou than that in Nanjing, again indicating that PM2.5 in Yangzhou was more toxic. The combination of computational and experimental methods demonstrated the complex relationship between health risks and PM2.5 concentrations. The refined estimation method could help us better estimate and interpret the risks caused by PM2.5 exposure on a city-level.

Nonagricultural emissions enhance dimethylamine and modulate urban atmospheric nucleation.

Gas-phase dimethylamine (DMA) has recently been identified as one of the most important vapors to initiate new particle formation (NPF), even in China's polluted atmosphere. Nevertheless, there remains a fundamental need for understanding the atmospheric life cycle of DMA, particularly in urban areas. Here we pioneered large-scale mobile observations of the DMA concentrations within cities and across two pan-region transects of north-to-south (∼700 km) and west-to-east (∼2000 km) in China. Unexpectedly, DMA concentrations (mean ± 1σ) in South China with scattered croplands (0.018 ± 0.010 ppbv, 1 ppbv=10-9 L/L) were over three times higher than those in the north with contiguous croplands (0.005 ± 0.001 ppbv), suggesting that nonagricultural activities may be an important source of DMA. Particularly in non-rural regions, incidental pulsed industrial emissions led to some of the highest DMA concentration levels in the world (>2.3 ppbv). Besides, in highly urbanized areas of Shanghai, supported by direct source-emission measurements, the spatial pattern of DMA was generally correlated with population (R2 = 0.31) due to associated residential emissions rather than vehicular emissions. Chemical transport simulations further show that in the most populated regions of Shanghai, residential DMA emissions can contribute for up to 78% of particle number concentrations. Shanghai is a case study for populous megacities, and the impacts of nonagricultural emissions on local DMA concentration and nucleation are likely similar for other major urban regions globally.

Machine Learning Explains Long-Term Trend and Health Risk of Air Pollution during 2015-2022 in a Coastal City in Eastern China.

Exposure to air pollution is one of the greatest environmental risks for human health. Air pollution level is significantly driven by anthropogenic emissions and meteorological conditions. To protect people from air pollutants, China has implemented clean air actions to reduce anthropogenic emissions, which has led to rapid improvement in air quality over China. Here, we evaluated the impact of anthropogenic emissions and meteorological conditions on trends in air pollutants in a coastal city (Lianyungang) in eastern China from 2015 to 2022 based on a random forest model. The annual mean concentration of observed air pollutants, including fine particles, inhalable particles, sulfur dioxide, nitrogen dioxide, and carbon monoxide, presented significant decreasing trends during 2015-2022, with dominant contributions (55-75%) by anthropogenic emission reduction. An increasing trend in ozone was observed with an important contribution (28%) by anthropogenic emissions. The impact of meteorological conditions on air pollution showed significant seasonality. For instance, the negative impact on aerosol pollution occurred during cold months, while the positive impact was in warm months. Health-risk-based air quality decreased by approximately 40% in 8 years, for which anthropogenic emission made a major contribution (93%).

Recent Progress in Atmospheric Chemistry Research in China: Establishing a Theoretical Framework for the "Air Pollution Complex".

Atmospheric chemistry research has been growing rapidly in China in the last 25 years since the concept of the "air pollution complex" was first proposed by Professor Xiaoyan TANG in 1997. For papers published in 2021 on air pollution (only papers included in the Web of Science Core Collection database were considered), more than 24 000 papers were authored or co-authored by scientists working in China. In this paper, we review a limited number of representative and significant studies on atmospheric chemistry in China in the last few years, including studies on (1) sources and emission inventories, (2) atmospheric chemical processes, (3) interactions of air pollution with meteorology, weather and climate, (4) interactions between the biosphere and atmosphere, and (5) data assimilation. The intention was not to provide a complete review of all progress made in the last few years, but rather to serve as a starting point for learning more about atmospheric chemistry research in China. The advances reviewed in this paper have enabled a theoretical framework for the air pollution complex to be established, provided robust scientific support to highly successful air pollution control policies in China, and created great opportunities in education, training, and career development for many graduate students and young scientists. This paper further highlights that developing and low-income countries that are heavily affected by air pollution can benefit from these research advances, whilst at the same time acknowledging that many challenges and opportunities still remain in atmospheric chemistry research in China, to hopefully be addressed over the next few decades.

Machine learning assesses drivers of PM2.5 air pollution trend in the Tibetan Plateau from 2015 to 2022.

The Tibetan Plateau (known as the Earth's Third Pole) has significant impact on climate. Fine particulate matter (PM2.5) is an important air pollutant in this region and has significant impact on health and climate. To mitigate PM2.5 air pollution over China, a series of clean air actions has been implemented. However, interannual trends in particulate air pollution and its response to anthropogenic emissions in the Tibetan Plateau are poorly understood. Here, we applied a random forest (RF) algorithm to quantify drivers of PM2.5 trends in six cities of the Tibetan Plateau from 2015 to 2022. The decreasing trends (-5.31 to -0.73 µg m-3 a-1) in PM2.5 during 2015-2022 were observed in all cities. The RF weather-normalized PM2.5 trends - which were driven by anthropogenic emissions - were -4.19 to -0.56 µg m-3 a-1, resulting in dominant contributions (65 %-83 %) to the observed PM2.5 trends. Relative to 2015, such anthropogenic emission driver was estimated to contribute -27.12 to -3.16 µg m-3 to declines in PM2.5 concentrations in 2022. However, the interannual changes in meteorological conditions only made a small contribution to the trends in PM2.5 concentrations. Potential source analysis suggested biomass burning from local residential sector and/or long-range transports originated from South Asia could significantly promote PM2.5 air pollution in this region. Based on health-risk air quality index (HAQI) assessment, the HAQI value was decreased by 15 %-76 % between 2015 and 2022 in these cities, with significant contributions (47 %-93 %) from anthropogenic emission abatements. Indeed, relative contribution of PM2.5 to the HAQI was decreased from 16 %-30 % to 11 %-18 %, while increasing and significant contribution from ozone was observed, highlighting that further effective mitigation of both PM2.5 and ozone air pollution could obtain more substantial health benefits in the Tibetan Plateau.

Concurrent dominant pathways of multifunctional products formed from nocturnal isoprene oxidation.

Determination of dominant chemical pathways toward the formation of nocturnal secondary organic aerosols (SOA) remains ambiguous by which nitrogen oxides (NOx) always affect oxidation of volatile alkenes. Here, comprehensive chamber simulations on dark isoprene ozonolysis were conducted under different nitrogen dioxides (NO2) mixing ratios to exam multiple functionalized isoprene oxidation products. Aside from that the oxidation processes were concurrently driven by nitrogen radical (NO3) and small hydroxyl radicals (OH), ozone (O3) cycloaddition at isoprene was launched initially regardless of NO2 to rapidly form first-generation oxidation products, i.e., carbonyls and Criegee intermediates (CI) referred to carbonyl oxides. They could further undergo complicated self- and cross-reactions to produce alkylperoxy radicals (RO2). Corresponding to yields of the C5H10O3 tracer, weak OH pathway at night was credited to ozonolysis of isoprene but suppressed by unique NO3 chemistry. Following the ozonolysis of isoprene, NO3 played a crucial supplementary role in nighttime SOA formation. The ensuing production of gas-phase nitrooxy carbonyls (the first-generation nitrates) became dominant in the production of a sizeable pool of organic nitrates (RO2NO2). By contrast, isoprene dihydroxy dinitrates (C5H10N2O8) were outstanding with the elevated NO2, related to typical second-generation nitrates. As such, the yielding number concentrations of dark SOA were promoted to approximately 1.8 × 104 cm-3 but presented a nonlinear relation with excess high-NO2 condition. This study provides valuable insights into importance of multifunctional organic compounds from alkene oxidation to constitute nighttime SOA.

Chemical Characteristics and Source-Specific Health Risks of the Volatile Organic Compounds in Urban Nanjing, China.

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

The interplays among meteorology, source, and chemistry in high particulate matter pollution episodes in urban Shanghai, China.

High particulate matter (PM) pollution episodes still occur occasionally in urban China, despite of improvements in recent years. Investigating the influencing factors of high-PM episodes is beneficial in the formulation of effective control measures. We herein present the effects of weather condition, emission source, and chemical conversion on the occurrence of high-PM episodes in urban Shanghai using multiple online measurements. Three high-PM episodes, i.e., locally-accumulated, regionally-transported, and dust-affected ones, as well as a clean period were selected. Stagnant air with temperature inversion was found in both locally-accumulated and regionally-transported high-PM episodes, but differences in PM evolution were observed. In the more complicated dust-affected episode, the weather condition interacted with the emission/transport sources and chemical conversion, resulting in consecutive stages with different PM characteristics. Specifically, there were (1) stronger local accumulation in the pre-dust period, (2) dust-laden air with aged organic aerosol (OA) upon dust arrival, (3) pollutants being swept into the ocean, and (4) back to the city with aged OA. Our results suggest that (a) local emissions could be rapidly oxidized in some episodes but not all, (b) aged OA from long-range transport (aged in space) had a similar degree of oxygenation compared to the prolonged local oxidation (aged in time), and (c) OA aged over land and over the ocean were similar in chemical characteristics. The findings help better understand the causes and evolution of high-PM episodes, which are manifested by the interplays among meteorology, source, and chemistry, providing a scientific basis for control measures.

Disentangling drivers of air pollutant and health risk changes during the COVID-19 lockdown in China.

The COVID-19 restrictions in 2020 have led to distinct variations in NO2 and O3 concentrations in China. Here, the different drivers of anthropogenic emission changes, including the effects of the Chinese New Year (CNY), China's 2018-2020 Clean Air Plan (CAP), and the COVID-19 lockdown and their impact on NO2 and O3 are isolated by using a combined model-measurement approach. In addition, the contribution of prevailing meteorological conditions to the concentration changes was evaluated by applying a machine-learning method. The resulting impact on the multi-pollutant Health-based Air Quality Index (HAQI) is quantified. The results show that the CNY reduces NO2 concentrations on average by 26.7% each year, while the COVID-lockdown measures have led to an additional 11.6% reduction in 2020, and the CAP over 2018-2020 to a reduction in NO2 by 15.7%. On the other hand, meteorological conditions from 23 January to March 7, 2020 led to increase in NO2 of 7.8%. Neglecting the CAP and meteorological drivers thus leads to an overestimate and underestimate of the effect of the COVID-lockdown on NO2 reductions, respectively. For O3 the opposite behavior is found, with changes of +23.3%, +21.0%, +4.9%, and -0.9% for CNY, COVID-lockdown, CAP, and meteorology effects, respectively. The total effects of these drivers show a drastic reduction in multi-air pollutant-related health risk across China, with meteorology affecting particularly the Northeast of China adversely. Importantly, the CAP's contribution highlights the effectiveness of the Chinese government's air-quality regulations on NO2 reduction.

Characteristics, formation, and sources of PM2.5 in 2020 in Suzhou, Yangtze River Delta, China.

Here we present seasonal chemical characteristics, formations, sources of PM2.5 in the year 2020 in Suzhou, Yangtze River Delta, China. Expectedly, organic matter (OM) found to be the most dominant component of PM2.5, with a year-average value of 10.3 ± 5.5 µg m-3, followed by NO3- (6.7 ± 6.5 µg m-3), SO42- (3.3 ± 2.5 µg m-3), NH4+ (3.2 ± 2.8 µg m-3), EC (1.1 ± 1.3 µg m-3), Cl- (0.57 ± 0.56 µg m-3), Ca2+ (0.55 ± 0.91 µg m-3), K+ (0.2 ± 1.0 µg m-3), Na+ (0.18 ± 0.45 µg m-3), and Mg2+ (0.09 ± 0.15 µg m-3). Seasonal variations of PM2.5 showed the highest average value in spring, followed by winter, fall, and summer. Meanwhile, the formation mechanisms of the major PM2.5 species (NO3-, SO42-, and OM) varied in seasons. Interestingly, NO2 may have the highest conversion rate to NO3- in spring, which might be linked with the nighttime chemistry due to the high relative humidity. Moreover, OM in summer was mainly produced by the daytime oxidation of volatile organic compounds, while local primary organic aerosols might play a significant role in other seasons. Source apportionment showed that the more-aged PM2.5 contributed significantly to the PM2.5 mass (42%), followed by the dust-related PM2.5 (38%) and the less-aged PM2.5 (21%). Potential contribution source function (PSCF) results indicated that aged PM2.5 were less affected by transportation than dust-related PM2.5.

Spatial and temporal characteristics of air pollutants and their health effects in China during 2019-2020.

This work presents the temporal and spatial characteristics of the major air pollutants and their associated health risks in China from 2019 to 2020, by using the monitoring data from 367 cities. The annual average PM2.5, PM10, NO2, SO2, CO, and O3 concentrations decreased by 10.9%, 13.2%, 9.3%, 10.1%, 9.4%, and 5.5% from 2019 to 2020. National average PM2.5 concentration in 2020 met the standard of 35 µg/m3, and that of O3 decreased from 2019. COVID-19 lockdown affected NO2 level dramatically, yet influences on PM2.5 and O3 were less clear-cut. Positive correlations between PM2.5 and O3 were found, even in winter in all five key regions, e.g., Jing-Jin-Ji (JJJ), FenWei Plain (FWP), Yangtze River Delta (YRD), Pearl River Delta (PRD) and Chengdu-Chongqing Region (CCR), indicating importance of secondary production for both PM2.5 and O3. Large seasonal variability of PM2.5-SO2 correlation indicates a varying role of SO2 to PM2.5 pollution in different seasons; and generally weak correlations in winter between PM2.5 and NO2 or SO2 reveal the complexity of secondary formation processes to PM2.5 pollution in winter. Multilinear regression analysis between PM2.5 and SO2, NO2 and CO demonstrates that PM2.5 is more sensitive to the change of NO2 than SO2 in JJJ, FWP, PRD and CCR, suggesting a priority of NOx emission control for future PM2.5 reduction. Furthermore, the new World Health Organization Air Quality Guidelines (WHO AQG2021) were adopted to calculate the excess health risks (ER) as well as the health-risk based air quality index (HAQIWHO) of the pollutants. Such assessment points out the severity of air pollution associated health risks under strict standards: 40.0% of days had HAQIWHO>100, while only 14.4% days had AQI>100. PM2.5 ER was generally larger than O3 ER, but O3 ER in low PM2.5 region (PRD) and during summer became more serious. Notably, NO2 ER became even more important than PM2.5 due to its strict limit of WHO AQG2021. Overall, our results highlight the increasing importance of O3 in both air quality evaluation and health risk assessment, and the importance of coordinated mitigation of multiple pollutants (mainly PM2.5, O3 and NO2) in protecting the public health.

Sources and processes of organic aerosol in non-refractory PM1 and PM2.5 during foggy and haze episodes in an urban environment of the Yangtze River Delta, China.

Organic aerosol (OA) generally accounts for a large fraction of fine particulate matter (PM2.5) in the urban atmosphere. Despite significant advances in the understanding their emission sources, transformation processes and optical properties in the submicron aerosol fraction (PM1), larger size fractions - e.g., PM2.5 - still deserve complementary investigations. In this study, we conducted a comprehensive analysis on sources, formation process and optical properties of OA in PM1 and PM2.5 under haze and foggy environments in the Yangtze River Delta (eastern China), using two aerosol chemical speciation monitors, as well as a photoacoustic extinctiometer at 870 nm. Positive matrix factorization analysis - using multilinear engine (ME2) algorithm - was conducted on PM1 and PM2.5 organic mass spectra. Four OA factors were identified, including three primary OA (POA) factors, i.e., hydrocarbon-like OA (HOA), cooking OA (COA), and biomass burning OA (BBOA), and a secondary OA (SOA) factor, i.e., oxidized oxygenated OA (OOA). An enhanced PM1-2.5 COA concentration was clearly observed during cooking peak hours, suggesting important contribution of fresh cooking emissions on large-sized particles (i.e., PM1-2.5). The oxidation state and concentration of PM2.5 HOA were higher than that in PM1, suggesting that large-sized HOA particles might be linked to oxidized POA. High contribution (44%) of large-sized OOA to non-refractory PM2.5 mass was observed during haze episodes. During foggy episodes, PM1 and PM2.5 OOA concentrations increased as a positive relationship over time, along with an exponential increase in the PM2.5-OOA to PM1-OOA ratio. Meanwhile, OOA loadings increased with the aerosol liquid water content (ALWC) during foggy episodes. Random forest cross-validation analysis also supported the important influence of ALWC on OOA variations, supporting substantial impact of aqueous process on SOA formation during haze and/or foggy episodes. Obtained results also indicated high OOA contributions (21%-36%) and low POA contributions (6%-14%) to the PM2.5 scattering coefficient during haze and foggy episodes, respectively. Finally, we could illustrate that atmospheric vertical diffusion and horizontal transport have important but different effects on the concentrations of different primary and secondary OA factors in different particle size fractions.

[Characteristics and Sources of Nitrated Phenols in Atmospheric Fine Particles of Northern Suburban Nanjing].

Nitrated phenols are a group of nitrogen-containing organics ubiquitously present in ambient air, which are also important components of atmospheric light-absorbing organic matter (brown carbon) that have significant impacts on climate change, air quality, and human health. In this study, we collected a total of 265 daily filter samples of fine particles (PM2.5) in northern suburban Nanjing from March 2019 to January 2020. We used ultra-high performance liquid chromatography-mass spectrometry (UHPLC-MS) to detect and quantify eight nitrated phenolic species. The results showed that the average annual concentration of total nitrated phenols in the sampling site was 18.77 ng·m-3, and the average concentrations in spring, summer, autumn, and winter were 16.82, 8.59, 17.28, and 44.79 ng·m-3, respectively. Such concentrations were obviously higher than those determined in other countries but were similar to those in domestic cities, such as Jinan. 4-Nitrophenol was the most abundant nitrated phenol, followed by 4-nitrocatechol and 2-methoxy-5-nitrophenol. Correlation analysis showed that 3-nitrosalicylic acid was from a specific source different from that of other species. Finally, we used a positive matrix factorization model to quantify the source contributions of nitrated phenols. The major sources were vehicle emissions (32%), mixed coal and biomass burning emissions (44%), and industrial emissions (24%). The mixed coal and biomass burning emissions were dominant in autumn and winter. The mass fraction of 3-nitrosalicylic acid in the factor of industrial emissions was>90%, consistent with the results of the correlation analysis. Overall, this study provides valuable insights into the understanding of concentrations, characteristics, and sources of atmospheric nitrated phenols in ambient air.

Chemical composition, sources and optical properties of nitrated aromatic compounds in fine particulate matter during winter foggy days in Nanjing, China.

Functionalized aromatic compounds are one of the most important light-absorbing organic chromophores - so-called brown carbon (BrC) - in fine particulate matter (PM2.5). In this study, we conducted a wintertime field campaign to measure eight nitrated aromatic compounds (NACs) in PM2.5 with offline analysis techniques, including liquid chromatograph mass spectrometer (LC-MS) and aerodyne high-resolution aerosol mass spectrometer (AMS) measurements, during foggy and nonfoggy days in suburban Nanjing in the Yangtze River Delta region, China. On average, 4-nitrophenol could be one of the most important light absorbing materials in the observed BrC, which accounted for over 40% of the mass concentration of identified chromophores. The mass concentration of 2-methyl-4-nitrophenol and 2,6-dimethyl-4-nitrophenol were evidently increased during foggy days, contribution of which to total NACs were increased by 10% and 5%, respectively. Positive matrix factorization analysis of combining LC-MS and AMS dataset was performed to identify the primary and secondary sources of NACs. Primary sources, e.g., traffic and solid-fuel combustion, accounted for 71% of the sum of 4-nitrophenol, 2,6-dimethyl-4-nitrophenol and 3-nitrosalicylic acid, suggesting important contribution of primary emissions to these NACs. The contribution of secondary sources, associated with two oxygenated organic aerosols, could contribute 66% to 4-nitrophenol, reflecting the link of such nitrated aromatic compounds to secondary organic aerosol source. Together with optical measurements, 4-nitrophenol presented a high contribution (>50%) to the identified BrC absorbance in the light range 250 and 550 nm was observed. This could highlight an important role of such NACs in ambient BrC light absorption, despite its mass contribution to total organic carbon was negligible. Our work could improve the understanding of the links between optical properties and chemical composition of BrC, and the difference between BrC chromophores from nonfoggy days and foggy days under the typical polluted atmospheric conditions.

Secondary organic aerosol formation from photooxidation of C3H6 under the presence of NH3: Effects of seed particles.

Frequently-occurred secondary organic aerosols (SOAs) under low-NOx conditions contribute to the winter haze episodes and remain unclear in the abundant presence of NH3. Here, the effects of CaCl2 seed particles on the photooxidation of low-molecular-weight C3H6 with co-existing NO2 and NH3 were highlighted and investigated through a chamber-simulation study equipped with high-resolution proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS). The influences of NH3 are often overestimated to exclusively enhance SOA yields under a low-[NO2]0 condition. Instead, the seeds played a central role in the heterogeneous formation of SOAs in this reaction with two orders of magnitudes higher than that in the absence of seeds at relative humidity (RH) of 82%. Interestedly, the O3 production was unchanged whether the seeds existed or not, small changes in the production of O3 were observed whether the seeds existed or not, indicating that the gas-phase conversions of C3H6 and NOx into C1-C3 oxygenated volatile organic compounds (OVOCs) and nitrogen-containing compounds (NOCs) were not affected by seed particles. Given that the ensuing formation of these low-volatile compounds was condensed into nucleation on the seeds, the explosive growth of C3H6 SOAs was then stimulated in the addition of NH3. Besides NO2 photolysis, the producing O3 was related to the formation of secondary carbonyls such as formaldehyde and then was consumed in the ·OH generation of approximately 3.40 × 10-12 molecules cm-3. This study provides a new insight to better understand the new gas-to-particle formation mechanisms when the haze pollution outbreaks in the complex air mixture.