Identifying Driving Factors of Atmospheric N2O5 with Machine Learning.

Dinitrogen pentoxide (N2O5) plays an essential role in tropospheric chemistry, serving as a nocturnal reservoir of reactive nitrogen and significantly promoting nitrate formations. However, identifying key environmental drivers of N2O5 formation remains challenging using traditional statistical methods, impeding effective emission control measures to mitigate NOx-induced air pollution. Here, we adopted machine learning assisted by steady-state analysis to elucidate the driving factors of N2O5 before and during the 2022 Winter Olympics (WO) in Beijing. Higher N2O5 concentrations were observed during the WO period compared to the Pre-Winter-Olympics (Pre-WO) period. The machine learning model accurately reproduced ambient N2O5 concentrations and showed that ozone (O3), nitrogen dioxide (NO2), and relative humidity (RH) were the most important driving factors of N2O5. Compared to the Pre-WO period, the variation in trace gases (i.e., NO2 and O3) along with the reduced N2O5 uptake coefficient was the main reason for higher N2O5 levels during the WO period. By predicting N2O5 under various control scenarios of NOx and calculating the nitrate formation potential from N2O5 uptake, we found that the progressive reduction of nitrogen oxides initially increases the nitrate formation potential before further decreasing it. The threshold of NOx was approximately 13 ppbv, below which NOx reduction effectively reduced the level of night-time nitrate formations. These results demonstrate the capacity of machine learning to provide insights into understanding atmospheric nitrogen chemistry and highlight the necessity of more stringent emission control of NOx to mitigate haze pollution.

Health risks and sources of trace elements and black carbon in PM2.5 from 2019 to 2021 in Beijing.

A comprehensive health risk assessment of PM2.5 is meaningful to understand the current status and directions regarding further improving air quality from the perspective of human health. In this study, we evaluated the health risks of PM2.5 as well as highly toxic inorganic components, including heavy metals (HMs) and black carbon (BC) based on long-term observations in Beijing from 2019 to 2021. Our results showed that the relative risks of chronic obstructive pulmonary disease, lung cancer, acute lower respiratory tract infection, ischemic heart disease, and stroke decreased by 4.07%-9.30% in 2020 and 2.12%-6.70% in 2021 compared with 2019. However, they were still at high levels ranging from 1.26 to 1.77, in particular, stroke showed the highest value in 2021. Mn had the highest hazard quotient (HQ, from 2.18 to 2.56) for adults from 2019 to 2021, while Ni, Cr, Pb, As, and BC showed high carcinogenic risks (CR > 1.0×10-6) for adults. The HQ values of Mn and As and the CR values of Pb and As showed constant or slight upwards trends during our observations, which is in contrast to the downward trends of other HMs and PM2.5. Mn, Cr, and BC are crucial toxicants in PM2.5. A significant shrink of southern region sourcesof HMs and BCshrank suggests the increased importance of local sources. Industry, dust, and biomass burning are the major contributors to the non-carcinogenic risks, while traffic emissions and industry are the dominant contributors to the carcinogenic risks in Beijing.

Reactive Chlorine Species Advancing the Atmospheric Oxidation Capacities of Inland Urban Environments.

Chlorine (Cl) radicals from photolabile chlorine species are highly reactive and can affect the fate of air pollutants in the atmosphere. Although several campaigns have been conducted, typically in coastal environments, long-term observations of reactive chlorine species and their impacts on atmospheric oxidation capacities (AOCs) are lacking. Here, we report nearly full-year observations of Cl2 and ClNO2 levels in Beijing and evaluate their impacts on the AOC with a box model coupled with Cl chemistry. Cl radicals promote the circulation of OH-HO2-RO2 by accelerating the OH chain lengths by up to 12.6% on average, hence boosting the AOC, especially in the winter or spring. This promotion effect is nonlinearly dependent on the VOC and NOx concentrations, thus leading to a slight shift in ozone formation from a VOC-sensitive regime to a transition regime with seasonal differences. Given the ubiquitous reactive chlorines in polluted inland urban regions, the AOCs and the formation of secondary pollutants will be underestimated if the reactive chlorine species are neglected.

The role of NOx in Co-occurrence of O3 and PM2.5 pollution driven by wintertime east Asian monsoon in Hainan.

Clarifying the driving forces of O3 and fine particulate matter (PM2.5) co-pollution is important to perform their synergistic control. This work investigated the co-pollution of O3 and PM2.5 in Hainan Province using an observation-based model and explainable machine learning. The O3 and PM2.5 pollution that occurs in winter is affected by the wintertime East Asian Monsoon. The O3 formation shifts from a NOx-limited regime with a low O3 production rate (PO3) in the non-pollution season to a transition regime with a high PO3 in the pollution season due to an increase in NOx concentrations. Increased O3 and atmospheric oxidation capacity promote the conversion from gas-phase precursors to aerosols. Meanwhile, the high concentration of particulate nitrate favors HONO formation via photolysis, in turn facilitating O3 production. Machine learning reveals that NOx promotes O3 and PM2.5 co-pollution during the pollution period. The PO3 shows an upward trend at the observation site from 2018 to 2022 due to the inappropriate reduction of volatile organic compounds (VOCs) and NOx in the upwind areas. Our results suggest that a deep reduction of NOx should benefit both O3 and PM2.5 pollution control in Hainan and bring new insights into improving air quality in other regions of China in the future.

Emissions of Ammonia and Other Nitrogen-Containing Volatile Organic Compounds from Motor Vehicles under Low-Speed Driving Conditions.

Emissions of NH3 and nine nitrogen-containing volatile organic compounds (NVOCs) (C1-3-amines, C1-3-amides, and C1-3-imines) from motor vehicles powered by gasoline, diesel, and natural gas under low-speed driving conditions from roadside in situ measurements were characterized using a water-cluster chemical ionization mass spectrometer and trace gas monitors. The total emission strength of diesel trucks was the greatest followed by those of gasoline cars and natural gas cars. NH3 emission per vehicle was found to be 2-3 orders of magnitude greater than that of all NVOCs, regardless of the type of vehicle. Although much lower than the emissions of amides or imines, emissions of amines were sufficient to produce atmospheric concentrations exceeding the threshold level for amines to enhance atmospheric nucleation by several orders of magnitude. Different engine emission reduction technologies (e.g., three-way catalytic converter vs selective catalytic reduction) can lead to different NH3 and NVOC emission profiles. During the lifetime of a vehicle, its emission level was most likely to increase with its mileage. Source profiles of NH3 and NVOC emissions from the three types of vehicles were also obtained from the measurements. These profiles can be a valuable contribution to the air pollution management system in terms of source apportionment, elucidating the emission contributions from a specific type of vehicle.

Nontarget Screening Exhibits a Seasonal Cycle of PM2.5 Organic Aerosol Composition in Beijing.

The molecular composition of atmospheric particulate matter (PM) in the urban environment is complex, and it remains a challenge to identify its sources and formation pathways. Here, we report the seasonal variation of the molecular composition of organic aerosols (OA), based on 172 PM2.5 filter samples collected in Beijing, China, from February 2018 to March 2019. We applied a hierarchical cluster analysis (HCA) on a large nontarget-screening data set and found a strong seasonal difference in the OA chemical composition. Molecular fingerprints of the major compound clusters exhibit a unique molecular pattern in the Van Krevelen-space. We found that summer OA in Beijing features a higher degree of oxidation and a higher proportion of organosulfates (OSs) in comparison to OA during wintertime, which exhibits a high contribution from (nitro-)aromatic compounds. OSs appeared with a high intensity in summer-haze conditions, indicating the importance of anthropogenic enhancement of secondary OA in summer Beijing. Furthermore, we quantified the contribution of the four main compound clusters to total OA using surrogate standards. With this approach, we are able to explain a small fraction of the OA (∼11-14%) monitored by the Time-of-Flight Aerosol Chemical Speciation Monitor (ToF-ACSM). However, we observe a strong correlation between the sum of the quantified clusters and OA measured by the ToF-ACSM, indicating that the identified clusters represent the major variability of OA seasonal cycles. This study highlights the potential of using nontarget screening in combination with HCA for gaining a better understanding of the molecular composition and the origin of OA in the urban environment.

Key drivers of the oxidative potential of PM2.5 in Beijing in the context of air quality improvement from 2018 to 2022.

The mass concentration of atmospheric particulate matter (PM) has been continuously decreasing in the Beijing-Tianjin-Hebei region. However, health endpoints do not exhibit a linear correlation with PM mass concentrations. Thus, it is urgent to clarify the prior toxicological components of PM to further improve air quality. In this study, we analyzed the long-term oxidative potential (OP) of water-soluble PM2.5, which is generally considered more effective in assessing hazardous exposure to PM in Beijing from 2018 to 2022 based on the dithiothreitol assay and identified the crucial drivers of the OP of PM2.5 based on online monitoring of air pollutants, receptor model, and random forest (RF) model. Our results indicate that dust, traffic, and biomass combustion are the main sources of the OP of PM2.5 in Beijing. The complex interactions of dust particles, black carbon, and gaseous pollutants (nitrogen dioxide and sulfur dioxide) are the main factors driving the OP evolution, in particular, leading to the abnormal rise of OP in Beijing in 2022. Our data shows that a higher OP is observed in winter and spring compared to summer and autumn. The diurnal variation of the OP is characterized by a declining trend from 0:00 to 14:00 and an increasing trend from 14:00 to 23:00. The spatial variation in OP of PM2.5 was observed as the OP in Beijing is lower than that in Shijiazhuang, while it is higher than that in Zhenjiang and Haikou, which is primarily influenced by the distribution of black carbon. Our results are of significance in identifying the key drivers influencing the OP of PM2.5 and provide new insights for advancing air quality improvement efforts with a focus on safeguarding human health in Beijing.

A theoretical base for non-invasive prenatal paternity testing.

There is an increasing demand for prenatal paternity testing in the forensic applications, which identify biological fathers before the birth of children. Currently, one of the most effective and safe Non-Invasive Prenatal Paternity Testing (NIPPT) methods is high-throughput Next-Generation Sequencing (NGS)-based SNP genotyping of cell-free DNA in maternal peripheral blood. To the best of our knowledge, nearly all methods being used in such applications are based on traditional postnatal paternity tests and/or statistical models of conventional polymorphism sites. These methods have shown unsatisfactory performance due to the uncertainty of fetal genotype. In this study, we propose a cutting-edge methodology called the Prenatal paternity Test Analysis System (PTAS) for cell-free fetal DNA-based NIPPT using NGS-based SNP genotyping. With the implementation of our proposed PTAS methodology, 63 out of 64 early-pregnancy (i.e., less than seven weeks) samples can be precisely identified to determine paternity, except for one sample that does not meet quality control requirements. Although the fetal fraction of the non-identified sample is extremely low (0.51%), its paternity can still be detected by our proposed PTAS methodology through unique molecular identifier tagging. Paternity of the total 313 samples for mid-to-late pregnancy (i.e., more than seven weeks) can be accurately identified. Extensive experiments indicate that our methodology makes a significant breakthrough in the NIPPT theory and will bring substantial benefits to forensic applications.

Evolution of organic carbon during COVID-19 lockdown period: Possible contribution of nocturnal chemistry.

Carbonaceous aerosol is one of the main components of atmospheric particulate matter, which is of great significance due to its role in climate change, earth's radiation balance, visibility, and human health. In this work, carbonaceous aerosols were measured in Shijiazhuang and Beijing using the OC/EC analyzer from December 1, 2019 to March 15, 2020, which covered the Coronavirus Disease 2019 (COVID-19) pandemic. The observed results show that the gas-phase pollutants, such as NO, NO2, and aerosol-phase pollutants (Primary Organic Compounds, POC) from anthropogenic emissions, were significantly reduced during the lockdown period due to limited human activities in North China Plain (NCP). However, the atmospheric oxidation capacity (Ox/CO) shows a significantly increase during the lockdown period. Meanwhile, additional sources of nighttime Secondary Organic Carbon (SOC), Secondary Organic Aerosol (SOA), and babs, BrC(370 nm) are observed and ascribed to the nocturnal chemistry related to NO3 radical. The Potential Source Contribution Function (PSCF) analysis indicates that the southeast areas of the NCP region contributed more to the SOC during the lockdown period than the normal period. Our results highlight the importance of regional nocturnal chemistry in SOA formation.

Health threat of PM2.5-bound trace elements exposure on asthma hospital admission: A time-stratified case-crossover study.

Environmental pollution of trace elements has become of main concern due to the adverse effects. To estimate the impact of PM2.5-bound trace elements on human health, a time-stratified case-crossover study has been designed to examine the short-term associations between 28 elements and asthma hospitalizations from January 2019 to November 2021 in Xiamen, China. This research summarized the major components that pose health risks in different seasons and took risk assessment for different groups. We found that an inter-quartile range (IQR) increase of Ca, Fe, Mn, Pd, Si, and Ti was positively associated with the incidence of asthma in the lag of 0-4 days. In winter, the elements that predisposed the population to asthma attack were the most, such as Al, Ba, Ca, Cr, Cu, Fe, K, Mn, Pd, Si, and Ti, and these elements are at higher risk for longer periods of time. The discrepancy in risk levels and major elements of asthma diagnosis among various age groups were also found in this work. Our results provided insights into the development of specific policies to reduce the risk of asthma attacks due to exposure to PM2.5-bound trace elements.

Dust emission reduction enhanced gas-to-particle conversion of ammonia in the North China Plain.

Ammonium salt is an important component of particulate matter with aerodynamic diameter less than 2.5 µm (PM2.5) and has significant impacts on air quality, climate, and natural ecosystems. However, a fundamental understanding of the conversion kinetics from ammonia to ammonium in unique environments of high aerosol loading is lacking. Here, we report the uptake coefficient of ammonia (γNH3) on ambient PM2.5 varying from 2.2 × 10-4 to 6.0 × 10-4 in the North China Plain. It is significantly lower than those on the model particles under simple conditions reported in the literature. The probability-weighted γNH3 increases obviously, which is well explained by the annual decrease in aerosol pH due to the significant decline in alkali and alkali earth metal contents from the emission source of dust. Our results elaborate on the complex interactions between primary emissions and the secondary formation of aerosols and the important role of dust in atmospheric chemistry.

The impact of ammonium on the distillation of organic carbon in PM2.5.

Thermal desorption coupled with different detectors is an important analysis method for ambient carbonaceous aerosols. However, it is unclear how the compounds coexisting in both the gas and particle phases affect carbonaceous aerosol concentrations and measurements during thermal desorption. We observed matrix effects leading to a redistribution of different OC fractions (OC1 to OC4) during the thermal desorption process. These factors led to the formation of OC with low volatility (OC4), mainly from high-volatility OC (OC1 and OC2). Laboratory studies further indicated that ammonium promotes such matrix effects by transforming OC in the particle phase. Therefore, in addition to providing insights into the chemical evolution of OC during haze events, we argue that thermal-desorption-based OC measurements should be used with caution, which is an important step towards a more accurate measurement of OC in the ambient atmosphere.

Influence of Aerosol Chemical Composition on Condensation Sink Efficiency and New Particle Formation in Beijing.

Relatively high concentrations of preexisting particles, acting as a condensation sink (CS) of gaseous precursors, have been thought to suppress the occurrence of new particle formation (NPF) in urban environments, yet NPF still occurs frequently. Here, we aim to understand the factors promoting and inhibiting NPF events in urban Beijing by combining one-year-long measurements of particle number size distributions and PM2.5 chemical composition. Our results show that indeed the CS is an important factor controlling the occurrence of NPF events, with its chemical composition affecting the efficiency of the background particles in removing gaseous H2SO4 (effectiveness of the CS) driving NPF. During our observation period, the CS was found to be more effective for ammonium nitrate-rich (NH4NO3-rich) fine particles. On non-NPF event days, particles acting as CS contained a larger fraction of NH4NO3 compared to NPF event days under comparable CS levels. In particular, in the CS range from 0.02 to 0.03 s-1, the nitrate fraction was 17% on NPF event days and 26% on non-NPF event days. Overall, our results highlight the importance of considering the chemical composition of preexisting particles when estimating the CS and their role in inhibiting NPF events, especially in urban environments.

Unprecedented Ambient Sulfur Trioxide (SO3) Detection: Possible Formation Mechanism and Atmospheric Implications.

Sulfur trioxide (SO3) is a crucial compound for atmospheric sulfuric acid (H2SO4) formation, acid rain formation, and other atmospheric physicochemical processes. During the daytime, SO3 is mainly produced from the photo-oxidation of SO2 by OH radicals. However, the sources of SO3 during the early morning and night, when OH radicals are scarce, are not fully understood. We report results from two field measurements in urban Beijing during winter and summer 2019, using a nitrate-CI-APi-LTOF (chemical ionization-atmospheric pressure interface-long-time-of-flight) mass spectrometer to detect atmospheric SO3 and H2SO4. Our results show the level of SO3 was higher during the winter than during the summer, with high SO3 levels observed especially during the early morning (∼05:00 to ∼08:30) and night (∼18:00 to ∼05:00 the next day). On the basis of analysis of SO2, NO x , black carbon, traffic flow, and atmospheric ions, we suggest SO3 could be formed from the catalytic oxidation of SO2 on the surface of traffic-related black carbon. This previously unidentified SO3 source results in significant H2SO4 formation in the early morning and thus promotes sub-2.5 nm particle formation. These findings will help in understanding urban SO3 and formulating policies to mitigate secondary particle formation in Chinese megacities.