Deciphering the seasonal dynamics of multifaceted aerosol-ozone interplay: Implications for air quality management in Eastern China.

We employed an enhanced WRF-Chem to investigate the discrete mechanisms of aerosol-radiation-feedback (ARF), extinction-photochemistry (AEP), and heterogeneous-reactions (AHR) across different seasons in eastern China, aiming to assess the synergistic effects arising from the simultaneous operation of multiple processes on O3 and PM2.5. Our findings demonstrated that ARF fostered the accumulation of pollutants and moisture, initiating two distinct feedback mechanisms concerning O3. The elevation in the NO/NO2 ratio amplified O3 consumption. Increased near-surface moisture diminished upper-level cloud formation, thereby enhancing photolysis rates and O3 photochemical production. The pronounced impact of heightened NO/NO2 on O3 led to a decrease of 0.1-2.7 ppb. When decoupled from ARF, AEP led to a more significant reduction in photolysis rates, resulting in declines in both O3 and PM2.5, except for an anomalous increase observed in summer, with O3 increasing by 1.6 ppb and PM2.5 by 2.5 µg m-3. The heterogeneous absorption of hydroxides in spring, autumn, and winter predominantly governed the AHR-induced variation of O3, leading to a decrease in O3 by 0.7-1 ppb. Conversely, O3 variations in summer were primarily dictated by O3-sensitive chemistry, with heterogeneous absorption of NOy catalyzing a decrease of 2.4 ppb in O3. Furthermore, AHR accentuated PM2.5 by facilitating the formation of fine sulfates and ammonium while impeding nitrate formation. In summer, the collective impact of ARF, AEP, and AHR (ALL) led to a substantial reduction of 6.2 ppb in O3, alleviating the secondary oxidation of PM2.5 and leading to a decrease of 0.3 µg m-3 in PM2.5. Conversely, albeit aerosol substantially depleted O3 by 0.4-4 ppb through their interactions except for summer, aerosol feedback on PM2.5 was more pronounced, resulting in a significant increase of 1.7-6.1 µg m-3 in PM2.5. Our study underscored the seasonal disparities in the ramifications of multifaceted aerosol-ozone interplay on air quality.

Significantly underestimated traffic-related ammonia emissions in Chinese megacities: Evidence from satellite observations during COVID-19 lockdowns.

Ammonia (NH3) plays an important role in the formation of atmospheric particulate matter, but the contribution of traffic-related emissions remains unclear, particularly in megacities with a large number of vehicles. Taking the opportunity of the stringent COVID-19 lockdowns implemented in Beijing and Shanghai in 2022, this study aims to estimate the traffic-related NH3 emissions in these two megacities based on satellite observations. Differences between urban and suburban areas during the lockdown and non-lockdown periods are compared. It was found that despite different dominating sources, the overall NH3 concentrations in urban and suburban areas were at a similar level, and the lockdown resulted in a more prominent decrease in urban areas, where traffic activities were most heavily affected. The traffic-related contribution to the total emission was estimated to be ∼30% in megacities, and ∼40% in urban areas, which are about 2-10 times higher than that in previous studies. The findings indicate that the traffic-related NH3 emissions have been significantly underestimated in previous studies and may play a more critical role in the formation of air pollution in megacities, especially in winter, when agricultural emissions are relatively low. This study highlights the importance of traffic-related NH3 emissions in Chinese megacities and the need to reassess the emissions and their impacts on air quality.

Application of machine learning to analyze ozone sensitivity to influencing factors: A case study in Nanjing, China.

Ground-level ozone (O3) has been an emerging concern in China. Due to its complicated formation mechanisms, understanding the effects of influencing factors is critical for making effective efforts on the pollution control. This study aims to present and demonstrate the practicality of a data-driven technique that applies a machine learning (ML) model coupled with the SHapley Additive exPlanations (SHAP) approach in O3 simulation and sensitivity analysis. Based on hourly measured concentrations of O3 and its major precursors, as well as meteorological factors in a northern area of Nanjing, China, a Light Gradient Boosting Machine (LightGBM) model was established to simulate O3 concentrations in different seasons, and the SHAP approach was applied to conduct in-depth analysis on the impacts of influencing factors on O3 formation. The results indicated a reliable performance of the ML model in simulating O3 concentrations, with the coefficient of determination (R2) between the measured and simulated larger than 0.80, and the impacts of influencing factors were reasonably evaluated by the SHAP approach on both seasonal and diurnal time scales. It was found that although volatile organic compounds (VOCs) and nitrogen oxides (NOx), as well as temperature and relative humidity, were generally the main influencing factors, their sensitivities to O3 formation varied significantly in different seasons and with time of the day. This study suggests that the data-driven ML model is a practicable technique and may act as an alternative way to perform mechanism analysis to some extent, and has immense potential to be applied in both problem research and decision-making for air pollution control.

Multi-timescale variation characteristics of PM2.5 in different regions of China during 2014-2022.

Over the past decade, China has achieved a significant reduction in PM2.5 concentrations. Due to the diversity of natural and artificial factors, regional differences are remarkable in the variation characteristics and have not been well addressed in previous studies. Based on hourly observed PM2.5 concentrations from 2014 to 2022, this study conducted a comprehensive analysis of variation characteristics on annual, seasonal, and diurnal scales, with a special focus on differences across major regions. Driving factors of the variations, the effectiveness of air pollution control efforts as well as future priorities were discussed. The annual PM2.5 concentrations in all regions showed an overall downward trend from 2014 to 2022, but the decline rates differed notably across the regions, with the maximum value nearly two times higher than the minimum value. The seasonal decline rates also differ from region to region, which could be partially attributed to the burning of crop residues and dust events. Northeast China was significantly affected by the burning of crop residues and experienced a big drop in the number of fire points in autumn, but a remarkable increase in spring. The spring dust events may greatly contribute to PM2.5 concentrations in northern and western China. For diurnal variation, nighttime concentrations were generally greater than daytime concentrations, and the nighttime concentrations were likely to increase in eastern regions and decrease in western regions. Furthermore, the daytime and nighttime ratios (calculated by daytime/nighttime concentration divided by the daily-mean concentration) exhibited different interannual trends, with the daytime ratios decreasing and nighttime ratios increasing, especially in the northeastern and western regions. The findings indicate that the air pollution control efforts have been generally successful, but with large regional disparities, and highlight the importance of controlling crop residue burning, dust events, and nighttime emissions for specific seasons and regions.

[Pollution Characteristics and Source Apportionment of Volatile Organic Compounds in Lishui Area of Nanjing].

To understand the changes in the components of volatile organic compounds(VOCs), the contribution proportion of each component to ozone, and the VOCs sources, we monitored the VOCs for a year in Lishui. The results showed that theρ(TVOC) was 223.46 µg·m-3, ρ(alkanes) was 49.45 µg·m-3(22.3%), ρ(OVOCs) was 50.63 µg·m-3(22.66%), ρ(halogenated hydrocarbons) was 64.73 µg·m-3(28.95%), ρ(aromatic hydrocarbons) was 35.46 µg·m-3(15.87%), ρ(alkenes) was 18.26 µg·m-3(8.19%), and ρ(others) was 4.9 µg·m-3(2.2%). ρ(TVOC) was higher in summer(263.75 µg·m-3) and lower in winter(187.2 µg·m-3), with 246.11 µg·m-3 in spring and 204.77 µg·m-3 in autumn. The daily concentration of VOCs showed two peaks, one from 9:00 to 10:00 and another from 14:00 to 15:00, and the high concentration was mainly found in the urban main road area with dense human activities. The ozone formation potential(OFP) was 278.92 µg·m-3, and those of olefin and aromatic hydrocarbon were 114.47 µg·m-3(41.1%) and 113.49 µg·m-3(40.8%), respectively, contributing over 80%, which was an important precursor of ozone. On the other hand, the ratio of characteristic compounds to toluene/benzene(T/B) was 4.13, which indicated that it was greatly affected by the solvent usage. In the end, the results of positive matrix factorization(PMF) source apportionment showed that VOCs mainly came from solvent usage, industrial production, and traffic emissions. The VOCs pollution had a great influence on ozone, so it was necessary to strengthen the treatment of industrial production, solvent usages, and traffic emissions.

Size-resolved light-absorbing organic carbon and organic molecular markers in Nanjing, east China: Seasonal variations and sources.

Owing to the potential influence of light-absorbing organic carbon (OC), also termed "brown carbon" (BrC), on the planetary radiation budget, many studies have focused on its absorption in single-sized ranges of particulate matter (PM). However, the size distribution and organic tracer-based source apportionment of BrC absorption have not been extensively investigated. In this study, size-resolved PM samples were collected using multi-stage impactors from eastern Nanjing during each season in 2017. The light absorption of methanol-extractable OC at 365 nm (Abs365, Mm-1) was determined using spectrophotometry, and a series of organic molecular markers (OMMs) was measured using a gas chromatography-mass spectrometer. Fine PM with an aerodynamic diameter <2.1 µm (PM2.1) dominated Abs365 (79.8 ± 10.4%) of the total size ranges with maxima and minima in winter and summer, respectively. The distributions of Abs365 shifted to larger PM sizes from winter to spring and summer due to lower primary emissions and increased BrC chromophores in dust. Except for low-volatility (po,*L < 10-10 atm) polycyclic aromatic hydrocarbons (PAHs), the non-polar OMMs, including n-alkanes, PAHs, oxygenated PAHs, and steranes, showed a bimodal distribution pattern. Secondary products of biogenic precursors and biomass burning tracers presented a unimodal distribution peaking at 0.4-0.7 µm, while sugar alcohols and saccharides were enriched in coarse PM. Their seasonal variations in average concentrations reflected intense photochemical reactions in summer, more biomass burning emissions in winter, and stronger microbial activity in spring and summer. Positive matrix factorization was used for the source apportionment of Abs365 in fine and coarse PM samples. Biomass burning contributed an average of 53.9% to the Abs365 of PM2.1 extracts. The Abs365 of coarse PM extracts was associated with various dust-related sources where the aging processes of aerosol organics could occur.

[Seasonal Variations, Size Distributions, and Sources of Chemical Components of Submicron Particulate Matter in Nanjing].

Size-segregated particulate matter (PM) samples were collected in different seasons from 2016 to 2017 at the Xianlin Campus of Nanjing University. Mass concentrations of water-soluble inorganic ions, carbonaceous components, and elements were analyzed for PM with an aerodynamic diameter ≤ 1.1 µm (PM1.1; <0.4 µm, 0.4-0.7 µm, and 0.7-1.1 µm). The results showed that PM1.1, OC, NO3-, SO42-, and NH4+ exhibited higher ambient levels in fall-winter than those in spring-summer, which was attributed to the changes in local diffusion conditions, evaporation, and decomposition of non-refractory components. Elemental carbon (EC) reached its maximum concentration[(1.87±0.98) µg·m-3]in spring due to the increase in industrial and road dust resuspension. According to the characteristic ratio between bulk components, the anions in PM1.1 were dominated by NO3-, SO42-, and Cl- in Nanjing, and the carbonaceous components were mainly from fossil fuel combustions and associated aging processes. As the ambient temperature increased, the size distributions of thermo-unstable components including NH4+, NO3-, and OC shifted towards finer particles, whereas EC became more enriched in coarse particles, possibly due to the increase in emission intensity of motor vehicles and fugitive dust contributions. Since high relative humidity (>70%) is often accompanied by high temperature (>20℃) and improved diffusion conditions, a relative humidity of 60%-70% was more conducive to the formation of secondary inorganic ions in PM1.1. Source apportionment results based on the speciation data of PM1.1 showed that secondary formation processes[(66.6±18.3)%]and dust resuspension[(16.8±14.8)%]were the main contributors to PM1.1 in Nanjing, and further control of the emissions of gaseous precursors and dust is necessary.

[Evolution of PM2.5 Chemical Composition and Sources in Nanjing During the Implementation of the APPCAP].

To acquire a deeper understanding about the impact of the Air Pollution Prevention and Control Action Plan (APPCAP) on ambient fine particulate matter (PM2.5), measurements of PM2.5 chemical components were conducted in the urban area of Nanjing during the implementation of the APPCAP. Evolution characteristics of several properties of the PM2.5 were studied, including the concentrations, proportions, and enrichment factors of major PM2.5 components and the acidity of the PM2.5. In addition, the source apportion of the PM2.5 was analyzed using the positive matrix factorization (PMF) model. The results showed that during the implementation of the APPCAP, the proportion of sulfate (SO42-) in PM2.5 decreased, whereas the proportions of nitrate (NO-3) and ammonium (NH+4) increased significantly together, from 25.58% in 2014 to 37.15% in 2017. The concentrations of carbon components (OC and EC) decreased in the early stage of the APPCAP; however, the decreasing trend slowed down in the later stage. In particular, the proportion of organic carbon (OC) increased, especially for the secondary organic carbon (SOC). The acidity of the PM2.5 decreased significantly, with the molar equivalent ratio of cations and anions increasing from 0.83 in 2014 to 1.13 in 2017. The contributions of coal combustion and the metallurgical and petrochemical industry to the PM2.5 generally showed a downward trend, whereas the contribution of vehicle emissions increased rapidly, from 8.78% in 2014 to 13.92% in 2017. The contribution of general fugitive dust fluctuated greatly, but that of soil fugitive dust showed an upward trend. This study suggested that the direct PM2.5 emissions, such as those from coal combustion and industries, were effectively controlled during the implementation of the APPCAP; however, the contribution of secondary aerosols became increasingly prominent, which indicates that future policies of PM2.5 pollution control should focus on emission reduction of the precursors such as NOx, NH3, and VOCs. In addition, the effects of increasing alkalization of the PM2.5 and enhanced oxidizability of the atmosphere on the PM2.5 pollution also require further attention.

Improved atmospheric mercury simulation using updated gas-particle partition and organic aerosol concentrations.

The gaseous or particulate forms of divalent mercury (HgII) significantly impact the spatial distribution of atmospheric mercury concentration and deposition flux (FLX). In the new nested-grid GEOS-Chem model, we try to modify the HgII gas-particle partitioning relationship with synchronous and hourly observations at four sites in China. Observations of gaseous oxidized Hg (GOM), particulate-bound Hg (PBM), and PM2.5 were used to derive an empirical gas-particle partitioning coefficient as a function of temperature (T) and organic aerosol (OA) concentrations under different relative humidity (RH). Results showed that with increasing RH, the dominant process of HgII gas-particle partitioning changed from physical adsorption to chemical desorption. And the dominant factor of HgII gas-particle partitioning changed from T to OA concentrations. We thus improved the simulated OA concentration field by introducing intermediate-volatility and semi-volatile organic compounds (I/SVOCs) emission inventory into the model framework and refining the volatile distributions of I/SVOCs according to new filed tests in the recent literatures. Finally, normalized mean biases (NMBs) of monthly gaseous element mercury (GEM), GOM, PBM, WFLX were reduced from -33%-29%, 95%-300%, 64%-261%, 117%-122% to -13%-0%, -20%-80%, -31%-50%, -17%-23%. The improved model explains 69%-98% of the observed atmospheric Hg decrease during 2013-2020 and can serve as a useful tool to evaluate the effectiveness of the Minamata Convention on Mercury.

Seasonal variations, temperature dependence, and sources of size-resolved PM components in Nanjing, east China.

Size-segregated ambient particulate matter (PM) samples were collected seasonally in suburban Nanjing of east China from 2016 to 2017 and chemically speciated. In both fine (< 2.1 µm, PM2.1) and coarse (> 2.1 µm, PM>2.1) PM, organic carbon (OC) accounted for the highest fractions (26.9% ± 10.9% and 23.1% ± 9.35%) of all measured species, and NO3- lead in average concentrations of water-soluble inorganic ions (WSIIs). The size distributions of measured components were parameterized using geometric mean diameter (GMD). GMD values of NO3-, Cl-, OC, and PM for the whole size range varied from < 2.1 µm in winter to > 2.1 µm in warm seasons, which was due to the fact that the size distributions of semi-volatile components (e.g., NH4NO3, NH4Cl, and OC) had a dependency on the ambient temperature. Unlike OC, elemental carbon (EC), and elements, NH4+, NO3-, and SO42- exhibited an increase trend in GMD values with relative humidity, indicating that the hygroscopic growth might also play a role in driving seasonal changes of PM size distributions. Positive matrix factorization was performed using compositional data of fine and coarse particles, respectively. The secondary formation of inorganic salts contributing to the majority (> 70%) of fine PM and 20.2% ± 19.9% of speciated coarse PM. The remaining coarse PM content was attributed to a variety of dust sources. Considering that coarse and fine PM had comparable mass concentrations, more attention should be paid to local dust emissions in future air quality plans.

Secondary organic aerosol formation and source contributions over east China in summertime.

Various precursor emissions and chemical mechanisms for secondary organic aerosol (SOA) formation were incorporated into a regional air quality model system (RAQMS) and applied to investigate the distribution, composition, and source contribution of SOA over east China in summer 2018. Model comparison against a variety of observations at a national scale demonstrated that the model was able to reasonably reproduce meteorological variables, O3 and PM2.5 concentrations, and the model simulated SOA concentration generally agreed with observations, with the overall NMB of 7.0% and R of 0.4 in 10 cities over east China. The simulated period-mean SOA concentrations of 4-15 µg m-3 were mainly distributed over the North China Plain (NCP), the middle and lower reaches of the Yangtze River and Chongqing district. SOA dominated organic aerosol (OA) over China in summertime (90%). The percentage contributions to SOA from ASOA (SOA produced from anthropogenic volatile organic compounds (AVOC)), BSOA (SOA produced from biogenic volatile organic compounds (BVOC)), DSOA (SOA produced from aqueous uptake of glyoxal and methylglyoxal) and S/I-SOA (SOA produced from semi-volatile and intermediate volatile organic compounds) were estimated to be 48.3%, 28.6%, 14.3%, and 8.8% respectively, over east China in summertime. In terms of domain and period average, ASOA contributed most to SOA (59%) in north China, while BSOA contributed most to SOA (37.3%) in northeast China. The percentage contribution of DSOA to SOA reached 21.5% in southwest China. S/I-SOA accounted for approximately 10% of SOA in most areas of east China. This study reveals that while AVOC dominates SOA formation on average over east China, the SOA source contributions differ considerably in different regions of China. BVOC makes the same contribution to SOA formation as AVOC in northeast China and southwest China, where forest coverage and BVOC emission are higher and anthropogenic emissions are relatively low, highlighting the significant role of BVOC in summer SOA formation in China.

Inflammatory responses of urban air PM modulated by chemical composition and different air quality situations in Nanjing, China.

The health risks of air pollutants and ambient particulate matter (PM) are widely known. PM composition and toxicity have shown substantial spatiotemporal variability. Yet, the connections between PM composition and toxicological and health effects are vaguely understood. This is a crucial gap in knowledge that needs to be addressed in order to establish air quality guidelines and limit values that consider the chemical composition of PM instead of the current assumption of equal toxicity per inhaled dose. Here, we demonstrate further evidence for varying toxicological effects of urban PM at equal mass concentrations, and estimate how PM composition and emission source characteristics influenced this variation. We exposed a co-culture model mimicking alveolar epithelial cells and macrophages with size-segregated urban ambient PM collected before, during, and after the Nanjing Youth Olympic Games 2014. We measured the release of a set of cytokines, cell cycle alterations, and genotoxicity, and assessed the spatiotemporal variations in these responses by factorial multiple regression analysis. Additionally, we investigated how a previously identified set of emission sources and chemical components affected these variations by mixed model analysis. PM-exposure induced cytokine signaling, most notably by inducing dose-dependent increases of macrophage-regulating GM-CSF and proinflammatory TNFα, IL-6, and IL-1ß concentrations, modest dose-dependent increase for cytoprotective VEGF-A, but very low to no responses for anti-inflammatory IL-10 and immunoregulatory IFNγ, respectively. We observed substantial differences in proinflammatory cytokine production depending on PM sampling period, location, and time of day. The proinflammatory response correlated positively with cell cycle arrest in G1/G0 phase and loss of cellular metabolic activity. Furthermore, PM0.2 caused dose-dependent increases in sub-G1/G0 cells, suggesting increased DNA degradation and apoptosis. Variations in traffic and oil/fuel combustion emissions contributed substantially to the observed spatiotemporal variations of toxicological responses.

High time-resolved PM2.5 composition and sources at an urban site in Yangtze River Delta, China after the implementation of the APPCAP.

In this study, hourly concentrations of PM2.5 water-soluble inorganic ions, bulk organic carbon (OC), and elemental carbon (EC) were monitored from 1/1/2017 to 12/31/2017 and validated using filter-based offline analysis at an urban site in Nanjing, China. Compared with 2013 or before, the annual average of PM2.5 concentration (36.5 ± 32.9 µg m-3) in 2017 decreased by more than 40%, NO3- (12.8 ± 11.4 µg m-3) became the most abundant water-soluble ion instead of SO42- (9.29 ± 6.07 µg m-3), and the relative contribution of OC (5.92 ± 3.40 µg m-3) and EC (2.95 ± 1.53 µg m-3) to bulk PM2.5 (24.9 ± 9.31%) increased substantially, indicating the effectiveness of the control policy for reducing gaseous precursor emissions. Based on the diurnal variations of water-soluble ions and gaseous pollutants, NH4+, SO42-, and NO3- were secondarily formed and NH4NO3 dominated the composition of ammonium salts in PM2.5. The diurnal changes of OC, EC, and OC/EC ratios reflected prominent influences from local traffic patterns. Positive matrix factorization was performed using hourly data of PM2.5 components (PMF1-h), of which the results were justified by comparing to those using 23-h averaged data (PMF23-h). Given that the secondary ion formation was still the dominant source (68.2%) of PM2.5, and the average PM2.5 concentration in urban Nanjing remained higher than Tier II limit (35 µg m-3) of the Chinese National Ambient Air Quality Standard, controlling emissions of PM2.5 precursor gases should be continued after the completion of Air Pollution Prevention and Control Action Plan in 2017.

Particulate matter exposure disturbs inflammatory cytokine homeostasis associated with changes in trace metal levels in mouse organs.

Few studies have focused on the impact of particulate matter (PM) exposure with respect to the relationship between PM-induced inflammation and the levels of trace metals in tissues and organs. In this study, C57BL/6 male mice were exposed to ambient air alongside control mice breathing air filtered through a high-efficiency particulate air (HEPA) filter. In both groups, mRNA levels of pro- and anti-inflammatory cytokines were measured after 4, 8 and 12 weeks together with the trace metal contents of the lungs, heart, liver, hippocampus and blood. PM exposure resulted in a general upward trend in the levels of pro-inflammatory cytokines in lung, heart, liver and hippocampus. By contrast, IL-10 mRNA expression varied depending on the organ, with a continuous upward trend in heart and liver and an up-regulation at 8 weeks followed by a down-regulation at 12 weeks in lung and hippocampus. The disturbed homeostasis of inflammatory cytokines was accompanied by changes in trace metal levels in the mice. These alterations may have constituted a compensatory effect conferring protection from inflammatory damage. However, prolonged PM exposure finally resulted in the deficiency of several essential trace metals in the lungs and hippocampus, which may have contributed to the observed histological changes typical of an inflammatory response.

Air quality intervention during the Nanjing youth olympic games altered PM sources, chemical composition, and toxicological responses.

Ambient particulate matter (PM) is a leading global environmental health risk. Current air quality regulations are based on airborne mass concentration. However, PM from different sources have distinct chemical compositions and varied toxicity. Connections between emission control measures, air quality, PM composition, and toxicity remain insufficiently elucidated. The current study assessed the composition and toxicity of PM collected in Nanjing, China before, during, and after an air quality intervention for the 2014 Youth Olympic Games. A co-culture model that mimics the alveolar epithelium with the associated macrophages was created using A549 and THP-1 cells. These cells were exposed to size-segregated inhalable PM samples. The composition and toxicity of the PM samples were influenced by several factors including seasonal variation, emission sources, and the air quality intervention. For example, we observed a size-dependent shift in particle mass concentrations during the air quality intervention with an emphasized proportion of smaller particles (PM2.5) present in the air. The roles of industrial and fuel combustion and traffic emissions were magnified during the emission control period. Our analyses revealed that the PM samples demonstrated differential cytotoxic potencies at equal mass concentrations between sampling periods, locations, and time of day, influenced by variations in the predominant emission sources. Coal combustion and industrial emissions were the most important sources affecting the toxicological responses and displayed the least variation in emission contributions between the sampling periods. In conclusion, emission control mitigated cytotoxicity and oxidative stress for particles larger than 0.2 µm, but there was inadequate evidence to determine if it was the key factor reducing the harmful effects of PM0.2.

Chemical composition, structures, and light absorption of N-containing aromatic compounds emitted from burning wood and charcoal in household cookstoves.

N-containing aromatic compounds (NACs) are an important group of light-absorbing molecules in the atmosphere. They are often observed in combustion emissions, but their chemical formulas and structural characteristics remain uncertain. In this study, red oak wood and charcoal fuels were burned in cookstoves using the standard water boiling test (WBT) procedure. Submicron aerosol particles in the cookstove emissions were collected using quartz (Q f ) and polytetrafluoroethylene (PTFE) filter membranes positioned in parallel. A back-up quartz filter (Q b ) was also installed downstream of the PTFE filter to evaluate the effect of sampling artifact on NACs measurements. Liquid chromatography-mass spectroscopy (LC-MS) techniques identified seventeen NAC chemical formulas in the cookstove emissions. The average concentrations of total NACs in Q b samples (0.37 ± 0.31 - 1.79 ± 0.77 µg m-3) were greater than 50% of those observed in the Q f samples (0.51 ± 0.43 - 3.91 ± 2.06 µg m-3), and the Q b to Q f mass ratios of individual NACs had a range of 0.02 - 2.71, indicating that the identified NACs might have substantial fractions remaining in the gas-phase. In comparison to other sources, cookstove emissions from red oak or charcoal fuels did not exhibit unique NAC structural features, but had distinct NACs composition. However, before identifying NACs sources by combining their structural and compositional information, the gas-particle partitioning behaviors of NACs should be further investigated. The average contributions of total NACs to the light absorption of organic matter at λ = 365 nm (1.10 - 2.57%) in Q f and Q b samples (10.7 - 21.0%) are up to 10 times larger than their mass contributions (Q f 0.31 - 1.01%, Q b 1.08 - 3.31%), so the identified NACs are mostly strong light absorbers. To explain more sample extracts absorption, future research is needed to understand the chemical and optical properties of high molecular weight (e.g., MW > 500 Da) entities in particulate matter.

PM2.5 elements at an urban site in Yangtze River Delta, China: High time-resolved measurement and the application in source apportionment.

Elemental concentrations of ambient aerosols are commonly sampled over 12-24 h, and the low time resolution puts a great limit on current understanding about the temporal variations and source apportionment based on receptor models. In this work, hourly-resolved concentrations of eighteen elements in PM2.5 at an urban site in Nanjing, a megacity in Yangtze River Delta of east China, were obtained by using a Xact 625 ambient metals monitor from 12/12/2016 to 12/31/2017. The influence of traffic activities was clearly reflected by the spikes of crustal elements (e.g., Fe, Ca, and Si) in the morning rush hour, and the firework burning and sandstorm events during the sampling periods were tracked by sharp enrichment of Ba, K and Fe, Ca, Si, Ti in PM2.5, respectively. To evaluate the advantage of hourly-resolved elements data in identifying impacts from specific emission sources, positive matrix factorization (PMF) analysis was performed with the 1-h data set (PMF1-h) and 23-h averaged data (PMF23-h), respectively. The 4- and 6-factor PMF23-h solutions had similar factor profiles and consistent factor contributions as the corresponding PMF1-h solutions. However, due to the limit in inter-sample variability, PMF analysis with 23-h average data misclassified some major (e.g., K, Fe, Zn, Ca, and Si) and trace (e.g., Pb) elements in factor profiles, resulting in different absolute factor contributions between PMF23-h and PMF1-h solutions. These results suggested the use of high time-resolved data to obtain valid and robust source apportionment results.

Emissions and atmospheric processes influence the chemical composition and toxicological properties of urban air particulate matter in Nanjing, China.

Ambient inhalable particulate matter (PM) is a serious health concern worldwide, but especially so in China where high PM concentrations affect huge populations. Atmospheric processes and emission sources cause spatial and temporal variations in PM concentration and chemical composition, but their influence on the toxicological characteristics of PM are still inadequately understood. In this study, we report an extensive chemical and toxicological characterization of size-segregated urban air inhalable PM collected in August and October 2013 from Nanjing, and assess the effects of atmospheric processes and likely emission sources. A549 human alveolar epithelial cells were exposed to day- and nighttime PM samples (25, 75, 150, 200, 300 µg/ml) followed by analyses of cytotoxicity, genotoxicity, cell cycle, and inflammatory response. PM10-2.5 and PM0.2 caused the greatest toxicological responses for different endpoints, illustrating that particles with differing size and chemical composition activate distinct toxicological pathways in A549 cells. PM10-2.5 displayed the greatest oxidative stress and genotoxic responses; both were higher for the August samples compared with October. In contrast, PM0.2 and PM2.5-1.0 samples displayed high cytotoxicity and substantially disrupted cell cycle; August samples were more cytotoxic whereas October samples displayed higher cell cycle disruption. Several components associated with combustion, traffic, and industrial emissions displayed strong correlations with these toxicological responses. The lower responses for PM1.0-0.2 compared to PM0.2 and PM2.5-1.0 indicate diminished toxicological effects likely due to aerosol aging and lower proportion of fresh emission particles rich in highly reactive chemical components in the PM1.0-0.2 fraction. Different emission sources and atmospheric processes caused variations in the chemical composition and toxicological responses between PM fractions, sampling campaigns, and day and night. The results indicate different toxicological pathways for coarse-mode particles compared to the smaller particle fractions with typically higher content of combustion-derived components. The variable responses inside PM fractions demonstrate that differences in chemical composition influence the induced toxicological responses.

Particulate Matter Triggers Depressive-Like Response Associated With Modulation of Inflammatory Cytokine Homeostasis and Brain-Derived Neurotrophic Factor Signaling Pathway in Mice.

Particulate matter (PM) exposure may contribute to depressive-like response in mice. However, few studies have evaluated the adaptive impacts of long-term PM exposure on depressive-like response associated with systemic inflammation and brain-derived neurotrophic factor (BDNF) signaling pathway. We studied the association among depressive-like behaviors, mRNA levels of pro and anti-inflammatory cytokines, and the expression of BDNF signaling pathway in mice by long-term PM exposure. C57BL/6 male mice were exposed to ambient air alongside control mice breathing air filtered through a high-efficiency air PM (HEPA) filter. Depressive-like behaviors were assessed together with proinflammatory, anti-inflammatory cytokine mRNA levels and the modulation of BDNF pathway in hippocampus and olfactory-bulb of mice exposed to PM for 4, 8, and 12 weeks. Exposure to HEPA-filtered air for 4 weeks may exert antidepressant like effects in mice. Proinflammatory cytokines were up-regulated while the expression of BDNF, its high-affinity receptor tropomyosin-related kinase B (TrkB), and the transcription factor (cyclic adenosine monophosphate)-response element-binding protein (CREB) were down-regulated in ambient air mice. However, after 8 weeks, there was no significant difference in the rate of depressive-like behaviors between the 2 groups. After 12 weeks, mice exposed to ambient air again had a higher rate of depressive-like behaviors, significant up-regulation of proinflammatory cytokines, down-regulation of interleukin-10, BDNF, TrkB, and CREB than HEPA mice. Ultrafine PM in brain tissues of mice exposed to ambient air was observed. Our results suggest continuous high-level PM exposure alters the depressive-like response in mice and induces a damage-repair-imbalance reaction.

Magnetic Properties as a Proxy for Predicting Fine-Particle-Bound Heavy Metals in a Support Vector Machine Approach.

The development of a reasonable statistical method of predicting the concentrations of fine-particle-bound heavy metals remains challenging. In this study, daily PM2.5 samples were collected within four different seasons from a Chinese mega-city. The annual average PM2.5 concentrations determined in industrial, city center, and suburban areas were 90, 81, and 85 µg m-3, respectively. Environmental magnetic measurements, including magnetic susceptibility, anhysteretic remanent magnetization, isothermal remanent magnetization, hysteresis loops, and thermomagnetism, indicated that the main magnetic mineral of PM2.5 is low-coercivity pseudosingle domain (PSD) magnetite. Using a support vector machine (SVM), both the volume- and mass-related concentrations of heavy metals were predicted by the PM2.5 mass concentrations and meteorological factors, with or without magnetic properties as input variables. The inclusion of magnetic variables significantly improved the prediction results for most heavy metals. Predictions based on models that included the magnetic properties of the metals Al, Fe, Mn, Ni, and Ti were promising, with R values of >0.8 in both the training and the test stages as well as relatively low errors. Our results demonstrate that the inclusion of environmental magnetism in a SVM approach aids in the effective monitoring and assessment of airborne heavy-metal contamination in cities.