Combustion-Derived Pollutants Linked with Kidney Disease in Low-Lying Flood-Affected Areas in the Balkans.

Tens of thousands of people in southern Europe suffer from Balkan endemic nephropathy (BEN), and four times as many are at risk. Incidental ingestion of aristolochic acids (AAs), stemming from the ubiquitousAristolochia clematitis(birthwort) weed in the region, leads to DNA adduct-induced toxicity in kidney cells, the primary cause of BEN. Numerous cofactors, including toxic organics and metals, have been investigated, but all have shown small contributions to the overall BEN relative to non-BEN village distribution gradients. Here, we reveal that combustion-derived pollutants from wood and coal burning in Serbia also contaminate arable soil and test as plausible causative factors of BEN. Using a GC-MS screening method, biomass-burning-derived furfural and coal-burning-derived medium-chain alkanes were detected in soil samples from BEN endemic areas levels at up to 63-times and 14-times higher, respectively, than in nonendemic areas. Significantly higher amounts were also detected in colocated wheat grains. Coexposure studies with cultured kidney cells showed that these pollutants enhance DNA adduct formation by AA, - the cause of AA nephrotoxicity and carcinogenicity. With the coincidence of birthwort-derived AAs and the widespread practice of biomass and coal burning for household cooking and heating purposes and agricultural burning in rural low-lying flood-affected areas in the Balkans, these results implicate combustion-derived pollutants in promoting the development of BEN.

Phosphocholine-induced energy source shift alleviates mitochondrial dysfunction in lung cells caused by geospecific PM2.5 components.

Fine particulate matter (PM2.5) is globally recognized for its adverse implications on human health. Yet, remain limited the individual contribution of particular PM2.5 components to its toxicity, especially considering regional disparities. Moreover, prevention solutions for PM2.5-associated health effects are scarce. In the present study, we comprehensively characterized and compared the primary PM2.5 constituents and their altered metabolites from two locations: Taiyuan and Guangzhou. Analysis of year-long PM2.5 samples revealed 84 major components, encompassing organic carbon, elemental carbon, ions, metals, and organic chemicals. PM2.5 from Taiyuan exhibited higher contamination, associated health risks, dithiothreitol activity, and cytotoxicities than Guangzhou's counterpart. Applying metabolomics, BEAS-2B lung cells exposed to PM2.5 from both cities were screened for significant alterations. A correlation analysis revealed the metabolites altered by PM2.5 and the critical toxic PM2.5 components in both regions. Among the PM2.5-down-regulated metabolites, phosphocholine emerged as a promising intervention for PM2.5 cytotoxicities. Its supplementation effectively attenuated PM2.5-induced energy metabolism disorder and cell death via activating fatty acid oxidation and inhibiting Phospho1 expression. The highlighted toxic chemicals displayed combined toxicities, potentially counteracted by phosphocholine. Our study offered a promising functional metabolite to alleviate PM2.5-induced cellular disorder and provided insights into the geo-based variability in toxic PM2.5 components.

Unambiguous Analysis and Systematic Mapping of Oxygenated Aromatic Compounds in Atmospheric Aerosols Using Ultrahigh-Resolution Mass Spectrometry.

Compositional analysis of organic aerosols (OAs) at the molecular level has been a long-standing challenge in field and laboratory studies. In this work, we applied different extraction protocols to aerosol samples collected from the ambient atmosphere and biomass burning sources, followed by Orbitrap mass spectrometric analysis with a soft electrospray ionization source operating in both positive and negative ionization modes. To systematically map the distribution of mono- and dioxygenated aromatic compounds (referred to as aromatic CHO1 and CHO2 formulas) in OA, we developed a unique two-dimensional Kendrick mass defect (2D KMD) framework. Our analysis unveiled a total of (76, 64, 70) aromatic CHO1 formulas and (103, 110, 106) CHO2 formulas, corresponding to samples obtained from ambient air, rice straw burning, and sugarcane leaf burning, respectively. These results reveal a significant number of additional distinct formulas exclusively present in ambient samples, suggesting a significant chemical transformation of OAs in the atmosphere. The analytical approach can be further extended to incorporate multiple layers of 2D KMD, enabling systematic mapping of the unexplored chemical space for complex environmental samples.

[Chemical Composition and Characterization of Nitroaromatic Compounds in Urban Areas of Shanghai].

The compositional characteristics, concentration of nitroaromatic compounds(NACs) in PM2.5 in urban Shanghai, and their correlation with gaseous precursors were investigated. A total of 39 winter and 46 summer PM2.5 samples from 2020 to 2021 were collected using a high-flow sampler and analyzed via ultra-performance liquid chromatography coupled with ESI-Orbitrap high-resolution mass spectrometry(UPLC-Orbitrap-HRMS). Quantitative analysis was performed on 12 NACs compounds, combined with backward trajectory meteorological elements, molecular composition, and classification analysis of CHON substances. The results showed that a total of 12 NACs had an average concentration in winter of 17.1 ng·m-3, which was three times higher than that in summer(5.7 ng·m-3), mainly due to air masses in winter coming primarily from the northern part of China with more biomass burning, whereas more air masses in summer came from the cleaner southeastern ocean. 4-Nitrophenol was the most abundant species of NACs in winter, whereas 4-nitrophenol(clean days) and 4-hydroxy-3-nitrobenzoic acid(polluted days) were the most abundant species in summer. Qualitative analysis based on features such as aromatic ring equivalence number(Xc), O/C, and H/C values for the identification and characterization of monocyclic and polycyclic aromatic compounds showed that CHON compounds were mainly aromatic compounds in winter and summer in urban Shanghai. The number and abundance of CHON compounds detected on PM2.5 polluted days were 2 and 1.5 times higher(winter) and 2.5 and 2 times higher(summer) than that on clean days, respectively. Comparing the analysis results of clean and polluted days in winter and summer, it was found that 80% of the CHON compounds with a relative abundance in the top 10 had O/N ≥ 3 and RDBE values between 5 and 8. The results suggest that these highly abundant CHON analogs may have had mononitro- or dinitro-substituted benzene rings. Correlation analysis between gaseous precursors and NACs indicated that oxidative reactive formation of VOCs(benzene, toluene, etc.) from anthropogenic emissions was the main source of NACs in summer. By contrast, it was influenced by a combination of biomass combustion emissions and secondary formation of oxidative NOx from anthropogenic VOCs in winter.

Dissecting the contributions of organic nitrogen aerosols to global atmospheric nitrogen deposition and implications for ecosystems.

Atmospheric deposition of particulate organic nitrogen (ONp) is a significant process in the global nitrogen cycle and may be pivotally important for N-limited ecosystems. However, past models largely overlooked the spatial and chemical inhomogeneity of atmospheric ONp and were thus deficient in assessing global ONp impacts. We constructed a comprehensive global model of atmospheric gaseous and particulate organic nitrogen (ON), including the latest knowledge on emissions and secondary formations. Using this model, we simulated global atmospheric ONp abundances consistent with observations. Our estimated global atmospheric ON deposition was 26 Tg N yr-1, predominantly in the form of ONp (23 Tg N yr-1) and mostly from wildfires (37%), oceans (22%) and aqueous productions (17%). Globally, ONp contributed as much as 40% to 80% of the total N deposition downwind of biomass-burning regions. Atmospheric ONp deposition thus constituted the dominant external N supply to the N-limited boreal forests, tundras and the Arctic Ocean, and its importance may be amplified in a future warming climate.

Field observations of C2 and C3 organosulfates and insights into their formation mechanisms at a suburban site in Hong Kong.

Organosulfates (OSs) are formed from volatile organic compounds (VOCs) and their oxidation products in the presence of sulfate particles. While OSs represent an important component in secondary organic aerosol, the knowledge of their formation driving force, mechanisms, and environmental impact remain inadequately understood. In this study, we report ambient observations of C2-3 oxygenated VOCs derived OSs (C2-3 OSs) at a suburban location of Hong Kong during autumn 2016. The C2-3 OSs, including glycolaldehyde sulfate (GS), hydroxyacetone sulfate (HAS), glycolic acid sulfate (GAS), and lactic acid sulfate (LAS), were quantified/semi-quantified using offline liquid chromatography-mass spectrometry analysis of aerosol filter samples. The average sum concentration of C2-3 OSs was 36 ng/m3. Correlation analysis revealed that sulfate, surface area, and liquid water content were important factors influencing C2-3 OS formation. Online measurement with an iodide High-Resolution Time-of-Flight Chemical-Ionization Mass Spectrometer (HR-ToF-CIMS) coupled with the Filter Inlet for Gases and AEROsols (FIGAERO) was also conducted to monitor C2-3 OSs, and their potential oxygenated VOC precursors in both gas- and particle-phase, and aerosol acidity tracer simultaneously. Our measurements support that glycolaldehyde/glyoxal, hydroxyacetone, glycolic acid/glyoxal, and lactic acid/methylglyoxal are likely precursors for GS, HAS, GAS, and LAS, respectively. Additionally, we found strong correlation between C2-3 OSs and H3S2O8-, a marker for aerosol acidity, providing field observational evidence for acid-catalyzed formation of small OSs. Based on both online and offline measurements, acid-catalyzed formation mechanisms in particle/aqueous phase are proposed. Specifically, the unique structure of adjacent carbonyl and hydroxyl groups in the C2-3 oxygenated VOC precursors can facilitate the formation of (1) a five-member ring intermediate via intramolecular hydrogen bond to react with sulfur trioxide through heterogenous reaction or (2) cyclic sulfate intermediate via particle-phase reaction with sulfuric acid to generate C2-3 OSs. These proposed mechanisms provide an alternative pathway for the liquid-phase production of C2-3 OSs.

Abundance and sources of organic nitrogen in fine (PM2.5) and coarse (PM2.5-10) particulate matter in urban Hong Kong.

Organic nitrogen (ON) in atmospheric particles is much less monitored compared to inorganic nitrogen (IN), despite its significant contribution to atmospheric N deposition budget. In this study, we expanded a newly developed instrumental method for IN and ON in PM2.5 samples to PM10 samples. We determined the quantities of ON and IN for paired PM2.5 and PM10 samples collected at an urban coastal site in Hong Kong, southern China over a year. These measurements also allowed the determination of IN and ON abundance in the coarse PM (i.e., PM2.5-10) by taking the difference between PM10 and PM2.5. The measurement results show that ON accounted for 27.6 % and 21.1 % of total N in fine and coarse particles, respectively, and was mainly (87.7 %) distributed in the fine mode at the site. The seasonal variation of ON/total N was relatively small in PM2.5 (23.6-30.4 %) while considerably larger in coarse PM (4.3-42.1 %). Analysis aided by concurrently measured source indicators revealed that sea spray, biological particle emissions, and dust mixed with anthropogenic pollutants are potentially significant sources of ON in coarse particles. Positive matrix factorization (PMF) source apportionment further revealed that industrial emissions/coal combustion (43.6 %), soil dust emission (16.3 %), fresh sea salt emission (15.2 %), and aged sea salt (24.9 %) are major sources of PMcoarse-bound ON at the site. The contributions of industrial emissions/coal combustion and soil dust emission to ON were significantly higher in autumn and winter. Fresh sea salt emissions contributed greater proportions to ON in spring and summer, while ON associated with the aged sea salt source was higher in spring and autumn. These findings have advanced our quantitative understanding of the sources of PMcoarse-bound ON, which was scarcely determined in the past. Furthermore, the ON measurement data in fine and coarse particles helps estimate ON deposition, which has been previously under-evaluated.

Concurrent measurements of nitrate at urban and suburban sites identify local nitrate formation as a driver for urban episodic PM2.5 pollution.

Nitrate (NO3-) is often among the leading components of urban particulate matter (PM) during PM pollution episodes. However, the factors controlling its prevalence remain inadequately understood. In this work, we analyzed concurrent hourly monitoring data of NO3- in PM2.5 at a pair of urban and suburban locations (28 km apart) in Hong Kong for a period of two months. The concentration gradient in PM2.5 NO3- was 3.0 ± 2.9 (urban) vs. 1.3 ± 0.9 µg m-3 (suburban) while that for its precursors nitrogen oxides (NOx) was 38.1 vs 4.1 ppb. NO3- accounted for 45 % of the difference in PM2.5 between the sites. Both sites were characterized to have more available NH3 than HNO3. Urban nitrate episodes, defined as periods of urban-suburban NO3- difference exceeding 2 µg m-3, constituted 21 % of the total measurement hours, with an hourly NO3- average gradient of 4.2 and a peak value of 23.6 µg m-3. Our comparative analysis, together with 3-D air quality model simulations, indicates that the high NOx levels largely explain the excessive NO3- concentrations in our urban site, with the gas phase HNO3 formation reaction contributing significantly during the daytime and the N2O5 hydrolysis pathway playing a prominent role during nighttime. This study presents a first quantitative analysis that unambiguously shows local formation of NO3- in urban environments as a driver for urban episodic PM2.5 pollution, suggesting effective benefits of lowering urban NOx.

Face Mask as a Versatile Sampling Device for the Assessment of Personal Exposure to 54 Toxic Compounds in Environmental Tobacco Smoke.

Exposure to environmental tobacco smoke (ETS), which contains hundreds of toxic compounds, significantly increases the risk of developing many human diseases, including lung cancer. The most common method of assessing personal exposure to ETS-borne toxicants is by sampling sidestream smoke generated by a smoking machine through a sorbent tube or filter, followed by solvent extraction and instrumental analysis. However, the ETS sampled may not truly represent the ETS in the ambient environment, due to complicating factors from the smoke released by the burning end of the cigarette and from the absorption of the chemicals in the respiratory tract of the smoker. In this study, we developed and validated an alternative air sampling method involving breathing through a face mask to simultaneously determine personal exposure to 54 ETS-borne compounds, including polycyclic aromatic hydrocarbons, aromatic amines, alkaloids, and phenolic compounds in real smoking scenarios. The newly developed method was used to evaluate the risk associated with exposure to ETS released from conventional cigarettes (CCs) and that from novel tobacco products such as e-cigarettes (ECs) and heated tobacco products (HTPs), with the observation of cancer risk associated with exposure to ETS released from CCs significantly higher than that from ECs and HTPs. It is anticipated that this method offers a convenient and sensitive way to collect samples for assessing the health impacts of ETS exposure.

Development of an enhanced method for atmospheric carbonyls and characterizing their roles in photochemistry in subtropical Hong Kong.

Carbonyl compounds are ubiquitous and play vital roles in tropospheric photochemistry and oxidation capacity, particularly affecting radical cycling and ozone formation. An enhanced method based on ultra-high-performance liquid chromatography and electrospray ionization tandem mass spectrometry was developed to simultaneously quantify 47 carbonyl compounds with carbon (C) numbers from 1 to 13. Applying this new method to samples collected at ground and ship-borne field campaigns, we investigated the abundance, characteristic distribution, and photochemical activity of carbonyl species in the coastal atmosphere of Hong Kong. The total concentration of detected carbonyls ranged from 9.1 to 32.7 ppbv and exhibited distinct spatial variability. In addition to the usual abundant carbonyl species (formaldehyde, acetaldehyde, and acetone), aliphatic saturated aldehydes with C ≥ 5 (particularly hexaldehyde and nonanaldehyde), and di­carbonyls, exhibit significant abundance and photochemical reactivity in the coastal site and on the sea. The measured carbonyls could contribute to an estimated peroxyl radical formation rate of 1.88-8.43 ppb/h via OH oxidation and photolysis, greatly enhancing oxidation capacity and radical cycling. The ozone formation potential (OFP) estimated from the maximum incremental reactivity (MIR) was dominated (69 %-82 %) by formaldehyde and acetaldehyde, with significant contribution (4 %-13 %) from di­carbonyls. Furthermore, another dozens of long-chain carbonyls without MIR values, which were typically below detection or not included in the conventional analytical method, would increase the ozone formation rate by an additional 2 %-33 %. Additionally, the glyoxal, methylglyoxal, benzaldehyde and other α, ß-unsaturated aldehydes also exhibited considerable contribution to secondary organic aerosol (SOA) formation potential. This study highlights the importance of various reactive carbonyls in the atmospheric chemistry of urban and coastal regions. The newly developed method can effectively characterize more carbonyl compounds and advance our understanding of their roles in photochemical air pollution.

Important Roles and Formation of Atmospheric Organosulfates in Marine Organic Aerosols: Influence of Phytoplankton Emissions and Anthropogenic Pollutants.

Organosulfates (OSs) could be potentially important compounds in marine organic aerosols, while their formation in marine atmospheres is far from clear due to a lack of cruise observations. In this work, shipboard atmospheric observations were conducted over the Yellow Sea and Bohai Sea to investigate the abundance and formation of biogenic isoprene/monoterpene-OSs in marine aerosols. The quantified OSs and NOSs accounted for 0.04-6.9% of marine organic aerosols and were 0.07-2.2% of the non-sea-salt (nss) sulfate in terms of sulfur content. Isoprene-related (nitrooxy-)OSs occupied 27-87% of the total quantified OSs, following the abundance order of summer > autumn > spring or winter. This order was driven by the marine phytoplankton biomass and sea surface temperature (SST), which controlled the seawater and atmospheric isoprene concentration levels. Under the severe impacts of anthropogenic pollutants from the East Asia continent in winter, monoterpene nitrooxy-OSs, generated with NOx involved in, increased to 34.4 ± 35.5 ng/m3 and contributed 68% of the quantified (nitrooxy-)OSs. Our results highlight the notable roles of biogenic OSs in marine organic aerosols over regions with high biological activity and high SST. The formation of biogenic OSs and their roles in altering marine aerosol properties calls for elaboration through cruise observations in different marine environments.

Bayesian Inference Approach to Quantify Primary and Secondary Organic Carbon in Fine Particulate Matter Using Major Species Measurements.

The determination of primary organic carbon (POC) and secondary organic carbon (SOC) in fine particulate matter using ambient measurements is essential in atmospheric chemistry. A novel Bayesian inference (BI) approach is proposed to achieve such quantification using only major component measurement data and tested in two case studies. One case study composes of filter-based daily compositional data made in the Pearl River Delta region, China, during 2012, while the other uses online measurement data recorded at the Dianshan Lake monitoring site in Shanghai in wintertime 2019. Source-specific organic trace measurement data are available in both the cases so that positive matrix factorization (PMF) analysis is performed, where PMF-resolved POC and SOC are used as the best available reference values for model evaluation. Meanwhile, traditional techniques, i.e., minimum ratio value, minimum R squared, and multiple linear regression, are also employed and evaluated. For both the cases, the BI models have shown significant advantages in accurately estimating POC and SOC amounts over conventional methods. Further analysis suggests that using sulfate as the SOC tracer in BI model gives the best model performance. This methodological advance provides an improved and practical tool to derive POC and SOC levels for addressing PM-related environmental impacts.

Field Evidence for Asian Outflow and Fast Depletion of Total Gaseous Mercury in the Polluted Coastal Atmosphere.

Atmospheric mercury (Hg) cycling in polluted coastal atmosphere is complicated and not fully understood. Here, we present measurements of total gaseous mercury (TGM) monitored at a coastal mountaintop in Hong Kong downwind of mainland China. Sharp TGM peaks during cold front passages were frequently observed due to Asian pollution outflow with typical TGM/CO slopes of 6.8 ± 2.2 pg m-3 ppbv-1. Contrary to the daytime maximums of other air pollutants, TGM exhibited a distinct diurnal variation with a midday minimum. Moreover, we observed four cases of extremely fast TGM depletion after sunrise, during which TGM concentrations rapidly dipped to 0.3-0.6 ng m-3 accompanied by other pollutants on the rise. Simulated meteorological fields revealed that morning upslope flow transporting anthropogenically polluted but TGM-depleted air masses from the mixed layer caused morning TGM depletion at the mountaintop location. The TGM-depleted air masses were hypothesized to result mainly from fast photooxidation of Hg after sunrise with minor contributions from dry deposition (5.0%) and nocturnal oxidation (0.6%). A bromine-induced two-step oxidation mechanism involving abundant pollutants (NO2, O3, etc.) was estimated to play a dominant role, contributing 55%-60% of depleted TGM and requiring 0.20-0.26 pptv Br, an amount potentially available through sea salt aerosol debromination. Our findings suggest significant effects of the interaction between anthropogenic pollution and marine halogen chemistry on atmospheric Hg cycling in the coastal areas.

Ambient particle characteristics by single particle aerosol mass spectrometry at a coastal site in Hong Kong: a case study affected by the sea-land breeze.

The sea-land breeze (SLB) circulation plays a vital role in the transport of atmospheric pollutants in coastal cities. In this study, a single particle aerosol mass spectrometer (SPAMS) and combined bulk aerosol instruments were deployed to investigate the ambient particle characteristic at a suburban coastal site in Hong Kong from February 22 to March 10, 2013. Significant SLB circulations were captured from March 6-10, 2013, during the campaign. During the SLB periods, air quality worsened, with PM2.5 concentrations reaching a peak of 55.6 µg m-3 and an average value of 42.8 ± 4.5 µg m-3. A total of 235,894 particles were measured during the SLB stage. Eight major sources were identified by investigating the mixing states of the total particles, including the coal-burning related particles (48.1%), biomass burning particles (6.7%), vehicle emission-related particles (16.4%), sea salt (9.2%), ship emission particles (2.7%), dust/steeling industries (3.7%), waste incineration (6.3%), and road dust (3.9%). It was noteworthy that the PM2.5 concentrations and particle numbers increased sharply during the transition of land wind to the sea breeze. Meanwhile, the continental sourced pollutants recirculated back to land resulting in a cumulative increase in pollutants. Both individual and bulk measurements support the above results, with high contributions from coal burning, biomass burning, bulk K+, and NO3 -, which were probably from the regional transportation from the nearby area. In contrast, the ship and vehicle emissions increased during the SLB period, with a high sulfate concentration partially originating from the ship emission. In this study, field evidence of continental-source pollutants backflow to land with the evolution of sea breeze was observed and helped our current understanding of the effect of SLB on air quality in the coastal city.

Highly time-resolved measurements of elements in PM2.5 in Changzhou, China: Temporal variation, source identification and health risks.

The temporal variation, sources, and health risks of elemental composition in fine particles (PM2.5) were explored using online measurements of 19 elements with a time resolution of 1 h at an urban location in Changzhou, China, from December 10, 2020 to March 31, 2021. The mass concentration of PM2.5 was 50.1 ±â€¯32.6 µg m-3, with a range of 3-218 µg m-3. The total concentration of 19 elements (2568 ±â€¯1839 ng m-3) accounted for 5.1 % of PM2.5 mass concentration. S, Cl, Si, and Fe were the dominant elementary species, accounting for 90 % of total element mass concentrations during the whole campaign. Positive matrix factorization (PMF) model was applied to identify the major emission sources of elements in PM2.5. Seven factors, named secondary sulfate mixed with coal combustion, Cl-rich, traffic, iron and steel industry, soil dust, fireworks, and shipping, were identified. The major sources for elements were iron and steel industry, followed by soil dust and secondary sulfate mixed with coal combustion, explaining 32.0 %, 23.5 % and 16.7 % of the total source contribution, respectively. The total hazard index (HI) of elements was 3.01 for children and 1.18 for adults, much greater than the admissible level (HI = 1). The total carcinogenic risk (CR) in Changzhou was estimated to be 5.87 × 10-5, which was above the acceptable CR level (1 × 10-6). Among the calculated metal elements, Cr, Co and As have higher carcinogenic risk, and Co was found to trigger the highest noncarcinogenic risk to Children. Our results indicate that industrial emission is the dominant CR contributor, emphasizing the necessity for stringent regulation of industry sources. Overall, our study provides useful information for policymakers to reduce emissions and health risks from elements in the Yangtze River Delta region.

Hourly organic tracers-based source apportionment of PM2.5 before and during the Covid-19 lockdown in suburban Shanghai, China: Insights into regional transport influences and response to urban emission reductions.

During the Covid-19 outbreak, strict lockdown measures led to notable reductions in transportation-related emissions and significantly altered atmospheric pollution characteristics in urban and suburban areas. In this work, we compare comprehensive online measurements of PM2.5 major components and organic molecular markers in a suburban location in Shanghai, China before lockdown (Dec. 28, 2019 to Jan. 23, 2020) and during lockdown (Jan. 24 to Feb. 9, 2020). The NOx levels declined sharply by 59% from 44 to 18 ppb during the lockdown, while O3 rose two times higher to 42 ppb. The PM2.5 level dropped from 64 to 49 µg m-3 (-24%). The major components all showed reductions, with the reduction of nitrate most prominent at -58%, followed by organics at -19%, and sulfate at -17%. Positive matrix factorization analysis identifies fourteen source factors, including nine primary sources and five secondary sources. The secondary sources consist of sulfate-rich factor, nitrate-rich factor, and three secondary organic aerosol (SOA) factors, with SOA_I being anthropogenic SOA, SOA_II associated with later generation products of organic oxidation, and SOA_III being biogenic SOA. The combined secondary sources contributed to 69% and 63% (40 and 22 µg m-3) of PM2.5 before and during lockdown, respectively, among which the reductions in the nitrate-rich (-55%) factor was the most prominent. Among primary sources, large reductions (>80%) were observed in contributions from industrial, cooking, and vehicle emissions. Unlike some studies reporting that the restriction during the Covid-19 resulted in enhanced secondary sulfate and SOA formation, we observed decreases in both secondary inorganic and SOA formation despite the overall elevated oxidizing capacity in the suburban site. Our results indicate that the formation change in secondary inorganic and organic compounds in response to substantial reductions in urban primary precursors are different for urban and suburban environments.

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.

Polyurethane Foam Face Masks as a Dosimeter for Quantifying Personal Exposure to Airborne Volatile and Semi-Volatile Organic Compounds.

Airborne volatile organic compounds (VOCs) and semi-volatile organic compounds (SVOCs) are commonly quantitated by collecting the analytes on solid sorbent tubes or passive air samplers, followed by solvent extraction and instrumental analysis, or by grab bag/canister measurements. We report herein a user-friendly sampling method by breathing through polyurethane foam (PUF) face masks to collect airborne VOCs and SVOCs for chemical analysis. Specifically, dibasic esters, phthalate esters, polycyclic aromatic hydrocarbons, linalool, and nicotine trapped on PUF masks were quantitated by gas chromatography-mass spectrometry analysis as model VOCs and SVOCs. Results showed that the amount of these model VOCs and SVOCs trapped on PUF masks is proportional to the exposure duration. After cross-validation by parallel sampling using XAD-2 packed sorbent tubes, the method was used to quantitate VOCs and SVOCs in a variety of indoor and outdoor environments with varying air concentrations of analytes, temperature, humidity, and wind speed. Because air pollution is considered a major cause of many human diseases and premature deaths and the developed PUF mask sampling method showed high trapping efficiencies for both VOCs and SVOCs, it is believed that the developed sampling method will find wide application in assessing air pollution-associated disease risks with possible extension to more classes of VOCs and SVOCs when coupled with suitable instrumental detection methods.

[Characteristics of Nitroaromatic Compounds in PM2.5 in Urban Area of Shanghai].

Nitroaromatic compounds (NACs) are an important class of nitrogen-containing compounds in fine particles. The investigation of characteristics and seasonal variation of NACs in PM2.5 increases our knowledge about nitrogen-containing compounds and contributes to the scientific basis in formulating reduction policies of NOx in urban areas. In this study, we analyzed the chemical composition of PM2.5 samples collected from March 2018 to February 2019 in an urban location in Shanghai. A total of 2439-3695 organic molecular formulas were detected using UPLC-Orbitrap MS. Nine NACs were quantified using an internal standard method. In spring, ρ(NACs) ranged from 3.12 to 16.76 ng·m-3, and the average concentration was 9.31 ng·m-3. In summer, it ranged from 1.05 to 9.70 ng·m-3, and the average value was 4.16 ng·m-3. In autumn, it ranged from 2.87 to 36.27 ng·m-3, and its average was 9.84 ng·m-3. In winter, it ranged from 4.83 to 56.23 ng·m-3, and the average was 22.37 ng·m-3. 4-Nitrophenol accounted for more than 25% of the quantified NACs in different seasons. In summer, the concentration of 5-nitrosalicylic acid accounted for 36%, but it decreased to 19% in winter. NACs in summer mainly originated from secondary formation, as evidenced by their clear correlation with the oxidant level, whereas biomass burning became the main source of NACs in winter.

Modeling Secondary Organic Aerosol Tracers and Tracer-to-SOA Ratios for Monoterpenes and Sesquiterpenes Using a Chemical Transport Model.

The community multiscale air quality (CMAQ) model was modified to simulate secondary organic aerosol (SOA) formation from five explicit (α-pinene, ß-pinene, d-limonene, Δ3-carene, and sabinene) and one lumped monoterpene (MT) species and sesquiterpenes (SQTs). The contribution of each oxidation pathway [including OH, O3, NO3, and O(3P)] was explicitly tracked in the SOA module. Three MT SOA tracers (pinic acid, PA; pinonic acid, PNA; and 3-methyl-1,2,3-butanetricarboxylic acid, MBTCA) and one SQT SOA tracer (ß-caryophyllinic acid, BCARYA) were modeled to assess the tracer-to-SOA ratios (fSOA) for ambient SOA estimation. Good model performance for BCARYA and MBTCA and reasonable agreement between model predictions and observations of PA and PNA were achieved. The modeled daily fSOA showed significant variations, suggesting that using the chamber-derived constant fSOA could lead to large errors in estimating terpene SOA. Among the four tracers, MBTCA and BCARYA were more appropriate for tracking MT and SQT SOA due to their nonvolatility. Their fSOA values mainly depend on the organic aerosol loading and could be approximated using simple power-law equations. In addition, equations directly linking the tracer concentrations to the corresponding SOA concentrations were proposed and could lead to good SOA estimations. This work provides new insights into the formation of the key MT and SQT SOA tracers and would allow better assessments of the biogenic emissions to regional and global aerosol burden.