Aqueous production of secondary organic aerosol from fossil-fuel emissions in winter Beijing haze.

Secondary organic aerosol (SOA) produced by atmospheric oxidation of primary emitted precursors is a major contributor to fine particulate matter (PM2.5) air pollution worldwide. Observations during winter haze pollution episodes in urban China show that most of this SOA originates from fossil-fuel combustion but the chemical mechanisms involved are unclear. Here we report field observations in a Beijing winter haze event that reveal fast aqueous-phase conversion of fossil-fuel primary organic aerosol (POA) to SOA at high relative humidity. Analyses of aerosol mass spectra and elemental ratios indicate that ring-breaking oxidation of POA aromatic species, leading to functionalization as carbonyls and carboxylic acids, may serve as the dominant mechanism for this SOA formation. A POA origin for SOA could explain why SOA has been decreasing over the 2013-2018 period in response to POA emission controls even as emissions of volatile organic compounds (VOCs) have remained flat.

An unexpected catalyst dominates formation and radiative forcing of regional haze.

Although regional haze adversely affects human health and possibly counteracts global warming from increasing levels of greenhouse gases, the formation and radiative forcing of regional haze on climate remain uncertain. By combining field measurements, laboratory experiments, and model simulations, we show a remarkable role of black carbon (BC) particles in driving the formation and trend of regional haze. Our analysis of long-term measurements in China indicates declined frequency of heavy haze events along with significantly reduced SO2, but negligibly alleviated haze severity. Also, no improving trend exists for moderate haze events. Our complementary laboratory experiments demonstrate that SO2 oxidation is efficiently catalyzed on BC particles in the presence of NO2 and NH3, even at low SO2 and intermediate relative humidity levels. Inclusion of the BC reaction accounts for about 90-100% and 30-50% of the sulfate production during moderate and heavy haze events, respectively. Calculations using a radiative transfer model and accounting for the sulfate formation on BC yield an invariant radiative forcing of nearly zero W m-2 on the top of the atmosphere throughout haze development, indicating small net climatic cooling/warming but large surface cooling, atmospheric heating, and air stagnation. This BC catalytic chemistry facilitates haze development and explains the observed trends of regional haze in China. Our results imply that reduction of SO2 alone is insufficient in mitigating haze occurrence and highlight the necessity of accurate representation of the BC chemical and radiative properties in predicting the formation and assessing the impacts of regional haze.

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.

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.

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.

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, 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.

Changes of air quality and its associated health and economic burden in 31 provincial capital cities in China during COVID-19 pandemic.

With outbreak of the novel coronavirus disease (COVID-19), immediate prevention and control actions were imposed in China. Here, we conducted a timely investigation on the changes of air quality, associated health burden and economic loss during the COVID-19 pandemic (January 1 to May 2, 2020). We found an overall improvement of air quality by analyzing data from 31 provincial cities, due to varying degrees of NO2, PM2.5, PM10 and CO reductions outweighing the significant O3 increase. Such improvement corresponds to a total avoided premature mortality of 9410 (7273-11,144) in the 31 cities by comparing the health burdens between 2019 and 2020. NO2 reduction was the largest contributor (55%) to this health benefit, far exceeding PM2.5 (10.9%) and PM10 (23.9%). O3 instead was the only negative factor among six pollutants. The period with the largest daily avoided deaths was rather not the period with strict lockdown but that during February 25 to March 31, due to largest reduction of NO2 and smallest increase of O3. Southwest, Central and East China were regions with relatively high daily avoided deaths, while for some cities in Northeast China, the air pollution was even worse, therefore could cause more deaths than 2019. Correspondingly, the avoided health economic loss attributable to air quality improvement was 19.4 (15.0-23.0) billion. Its distribution was generally similar to results of health burden, except that due to regional differences in willingness to pay to reduce risks of premature deaths, East China became the region with largest daily avoided economic loss. Our results here quantitatively assess the effects of short-term control measures on changes of air quality as well as its associated health and economic burden, and such information is beneficial to future air pollution control.

Comparison of air pollutants and their health effects in two developed regions in China during the COVID-19 pandemic.

Air pollution attributed to substantial anthropogenic emissions and significant secondary formation processes have been reported frequently in China, especially in Beijing-Tianjin-Hebei (BTH) and Yangtze River Delta (YRD). In order to investigate the aerosol evolution processes before, in, and after the novel coronavirus (COVID-19) lockdown period of 2020, ambient monitoring data of six air pollutants were analyzed from Jan 1 to Apr 11 in both 2020 and 2019. Our results showed that the six ambient pollutants concentrations were much lower during the COVID-19 lockdown due to a great reduction of anthropogenic emissions. BTH suffered from air pollution more seriously in comparison of YRD, suggesting the differences in the industrial structures of these two regions. The significant difference between the normalized ratios of CO and NO2 during COVID-19 lockdown, along with the increasing PM2.5, indicated the oxidation of NO2 to form nitrate and the dominant contribution of secondary processes on PM2.5. In addition, the most health risk factor was PM2.5 and health-risked based air quality index (HAQI) values during the COVID-19 pandemic in YRD in 2020 were all lower than those in 2019. Our findings suggest that the reduction of anthropogenic emissions is essential to mitigate PM2.5 pollution, while O3 control may be more complicated.

COVID-19 Impact on the Concentration and Composition of Submicron Particulate Matter in a Typical City of Northwest China.

In this study, we evaluated the variations of air quality in Lanzhou, a typical city in Northwestern China impacted by the COVID-19 lockdown. The mass concentration and chemical composition of non-refractory submicron particulate matter (NR-PM1) were determined by a high-resolution aerosol mass spectrometer during January-March 2020. The concentration of NR-PM1 dropped by 50% from before to during control period. The five aerosol components (sulfate, nitrate, ammonium, chloride, and organic aerosol [OA]) all decreased during the control period with the biggest decrease observed for secondary inorganic species (70% of the total reduction). Though the mass concentration of OA decreased during the control period, its source emissions varied differently. OA from coal and biomass burning remained stable from before to during control period, while traffic and cooking related emissions were reduced by 25% and 50%, respectively. The low concentration during the control period was attributed to the lower production rate for secondary aerosols.

Puzzling Haze Events in China During the Coronavirus (COVID-19) Shutdown.

It is a puzzle as to why more severe haze formed during the New Year Holiday in 2020 (NYH-20), when China was in an unprecedented state of shutdown to contain the coronavirus (COVID-19) outbreak, than in 2019 (NYH-19). We performed a comprehensive measurement and modeling analysis of the aerosol chemistry and physics at multiple sites in China (mainly in Shanghai) before, during, and after NYH-19 and NYH-20. Much higher secondary aerosol fraction in PM2.5 were observed during NYH-20 (73%) than during NYH-19 (59%). During NYH-20, PM2.5 levels correlated significantly with the oxidation ratio of nitrogen (r 2 = 0.77, p < 0.01), and aged particles from northern China were found to impede atmospheric new particle formation and growth in Shanghai. A markedly enhanced efficiency of nitrate aerosol formation was observed along the transport pathways during NYH-20, despite the overall low atmospheric NO2 levels.

Characterization of Size-Resolved Hygroscopicity of Black Carbon-Containing Particle in Urban Environment.

The hygroscopic properties of BC-containing particles (BCc) are important to determine their wet scavenging, atmospheric lifetime, and interactions with clouds. Such information is still lacking in the real world because of the challenges in isolating BCc from other aerosols to be directly characterized. In this study, the size-resolved chemical components of BCc including the refractory BC core and associated coatings were measured by a soot particle-aerosol mass spectrometer in suburban Nanjing. The size-resolved hygroscopicity parameter of BCc (κBCc) was obtained based on this full chemical characterization of BCc. We found increased inorganic fraction and more oxidized organic coatings with thicker coatings, which modified κBCc besides the determinant of particle size. The bulk κBCc was observed to range from 0.11 to 0.34. The size-resolved κBCc consistently showed minima at coated diameter (Dcoated) of 100 nm, parametrized as κ(x) = 0.28-0.35 × exp(-0.004 × x), x = Dcoated. Under critical supersaturations (SS) of 0.1% and 0.2%, the D50 values of BCc were 200 ± 20 and 135 ± 18 nm, respectively. On average 33 ± 16% and 59 ± 20% of BCc in number could be activated at SS = 0.1% and 0.2%, respectively. These results provide constraints on surface CCN sources for the light-absorbing BC-containing particles.

Chemical pyrolysis of E-waste plastics: Char characterization.

This work studied the disposal of the non-metallic fraction from waste printed circuit board (NMF-WPCB) via the chemical pretreatments followed by pyrolysis. As a main heavy metal, the metallic Cu could be significantly removed by 92.4% using the HCl leaching process. Subsequently, the organic-Br in the brominated flame retardants (BFRs) plastics could be converted into HBr by pyrolysis. The alkali pretreatment was benefit for the Br fixation in the solid char. The Br fixation efficiency could reach up to 53.6% by the NaOH pretreatment followed by the pyrolysis process. The formed HBr could react with NaOH/KOH to generate the stabilized NaBr/KBr. Therefore, the integrated chemical pretreatment could be used for the eco-friendly disposal of the NMF-WPCB via pyrolysis.

First Chemical Characterization of Refractory Black Carbon Aerosols and Associated Coatings over the Tibetan Plateau (4730 m a.s.l).

Refractory black carbon (rBC) aerosol is an important climate forcer, and its impacts are greatly influenced by the species associated with rBC cores. However, relevant knowledge is particularly lacking at the Tibetan Plateau (TP). Here we report, for the first time, highly time-resolved measurement results of rBC and its coating species in central TP (4730 m a.s.l), using an Aerodyne soot particle aerosol mass spectrometer (SP-AMS), which selectively measured rBC-containing particles. We found that the rBC was overall thickly coated with an average mass ratio of coating to rBC (RBC) of ∼7.7, and the coating species were predominantly secondarily formed by photochemical reactions. Interestingly, the thickly coated rBC was less oxygenated than the thinly coated rBC, mainly due to influence of the transported biomass burning organic aerosol (BBOA). This BBOA was relatively fresh but formed very thick coating on rBC. We further estimated the "lensing effect" of coating semiquantitatively by comparing the measurement data from a multiangle absorption photometer and SP-AMS, and found it could lead to up to 40% light absorption enhancement at RBC > 10. Our findings highlight that BBOA can significantly affect the "lensing effect", in addition to its relatively well-known role as light-absorbing "brown carbon."

Air pollution characteristics and health risks in Henan Province, China.

Events of severe air pollution occurred frequently in China recently, thus understanding of the air pollution characteristics and its health risks is very important. In this work, we analyzed a two-year dataset (March 2014 - February 2016) including daily concentrations of six criteria pollutants (PM2.5, PM10, CO, SO2, NO2, and O3) from 18 cities in Henan province. Results reveal the serious air pollution status in Henan province, especially the northern part, and Zhengzhou is the city with the worst air quality. Annual average PM2.5 concentrations exceed the second grade of Chinese Ambient Air Quality Standard (75µg/m3) at both 2014 and 2015. PM2.5 is typically the major pollutant, but ozone pollution can be significant during summer. Furthermore, as the commonly used air quality index (AQI) neglects the mutual health effects from multiple pollutants, we introduced the aggregate air quality index (AAQI) and health-risk based air quality index (HAQI) to evaluate the health risks. Results show that based on HAQI, the current AQI system likely significantly underestimate the health risks of air pollution, highlighting that the general public may need stricter health protection measures. The population-weighted two-year average HAQI data further demonstrates that all population in the studied cities in Henan province live with polluted air - 72% of the population is exposed to air that is unhealthy for sensitive people, while 28% of people is exposed to air that can be harmful to healthy people; and the health risks are much greater during winter than during other seasons. Future works should further improve the HAQI algorithm, and validate the links between the clinical/epidemiologic data and the HAQI values.

Regional Influence of Aerosol Emissions from Wildfires Driven by Combustion Efficiency: Insights from the BBOP Campaign.

Wildfires are important contributors to atmospheric aerosols and a large source of emissions that impact regional air quality and global climate. In this study, the regional and nearfield influences of wildfire emissions on ambient aerosol concentration and chemical properties in the Pacific Northwest region of the United States were studied using real-time measurements from a fixed ground site located in Central Oregon at the Mt. Bachelor Observatory (∼2700 m a.s.l.) as well as near their sources using an aircraft. The regional characteristics of biomass burning aerosols were found to depend strongly on the modified combustion efficiency (MCE), an index of the combustion processes of a fire. Organic aerosol emissions had negative correlations with MCE, whereas the oxidation state of organic aerosol increased with MCE and plume aging. The relationships between the aerosol properties and MCE were consistent between fresh emissions (∼1 h old) and emissions sampled after atmospheric transport (6-45 h), suggesting that biomass burning organic aerosol concentration and chemical properties were strongly influenced by combustion processes at the source and conserved to a significant extent during regional transport. These results suggest that MCE can be a useful metric for describing aerosol properties of wildfire emissions and their impacts on regional air quality and global climate.

Quantum control of electron wave packet during high harmonic process of H2(+) in a combination of a circularly polarized laser field and a Terahertz field.

By solving a two-dimensional time-dependent Schrödinger equation we investigate high harmonic generation (HHG) and isolated attosecond pulse generation for the H2+ molecular ion in a circularly polarized laser pulse combined with a Terahertz (THz) field. The harmonic intensity can be greatly enhanced and a continuum spectrum can be obtained when a THz field is added. The HHG process is studied by the semi-classical three-step model and the time-frequency analysis. Our studies show that only short trajectories contribute to HHG. Furthermore, we present the temporal evolution of the probability density of electron wave packet, which perfectly shows a clear picture of the electron's two-time recombination when a THz field is added, and it is the main mechanism of HHG. By superposing the harmonics in the range of 216-249 eV, an isolated attosecond pulse with a duration of about 69 attoseconds can be generated.

Toward understanding amines and their degradation products from postcombustion CO2 capture processes with aerosol mass spectrometry.

Amine-based postcombustion CO2 capture (PCCC) is a promising technique for reducing CO2 emissions from fossil fuel burning plants. A concern of the technique, however, is the emission of amines and their degradation byproducts. To assess the environmental risk of this technique, standardized stack sampling and analytical methods are needed. Here we report on the development of an integrated approach that centers on the application of a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) for characterizing amines and PCCC-relevant species. Molecular characterization is achieved via ion chromatography (IC) and electrospray ionization high-resolution mass spectrometry (ESI-MS). The method has been optimized, particularly, by decreasing the AMS vaporizer temperature, to gain quantitative information on the elemental composition and major nitrogen-containing species in laboratory-degraded amine solvents commonly tested for PCCC applications, including ethanolamine (MEA), methyldiethanolamine (MDEA), and piperazine (PIP). The AMS-derived nitrogen-to-carbon (N/C) ratios for the degraded solvent and product mixtures agree well with the results from a total organic carbon and total nitrogen (TOC/TN) analyzer. In addition, marker ions identified in the AMS spectra are used to estimate the mass contributions of individual species. Overall, our results indicate that this new approach is suitable for characterizing PCCC-related mixtures as well as organic nitrogen species in other sample types. As an online instrument, AMS can be used for both real-time characterization of emissions from operating PCCC plants and ambient particles in the vicinity of the facilities.

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.