A Rat Dry Eye Model with Lacrimal Gland Dysfunction Induced by Scopolamine.

Aqueous-deficient dry eye (ADDE) is a type of dry eye disease that can result in the reduction of tear secretion quantity and quality. Prolonged abnormal tear production can lead to a disturbance in the ocular surface environment, including corneal damage and inflammation. In severe cases, ADDE can cause vision loss or even blindness. Currently, dry eye treatment is limited to eye drops or physical therapy, which can only alleviate eye discomfort symptoms and cannot fundamentally cure dry eye syndrome. To restore the function of the lacrimal gland in dry eye, we have created an animal model of lacrimal gland dysfunction in rats induced by scopolamine. Through the comprehensive evaluation of the lacrimal gland, corneas, conjunctivas, and other factors, we aim to provide a full understanding of the pathological changes of ADDE. Compared with the current dry eye mouse model, this ADDE animal model includes a functional evaluation of the lacrimal gland, providing a better platform for studying lacrimal gland dysfunction in ADDE.

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.

Nitrate Radicals Suppress Biogenic New Particle Formation from Monoterpene Oxidation.

Highly oxygenated organic molecules (HOMs) are a major source of new particles that affect the Earth's climate. HOM production from the oxidation of volatile organic compounds (VOCs) occurs during both the day and night and can lead to new particle formation (NPF). However, NPF involving organic vapors has been reported much more often during the daytime than during nighttime. Here, we show that the nitrate radicals (NO3), which arise predominantly at night, inhibit NPF during the oxidation of monoterpenes based on three lines of observational evidence: NPF experiments in the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber at CERN (European Organization for Nuclear Research), radical chemistry experiments using an oxidation flow reactor, and field observations in a wetland that occasionally exhibits nocturnal NPF. Nitrooxy-peroxy radicals formed from NO3 chemistry suppress the production of ultralow-volatility organic compounds (ULVOCs) responsible for biogenic NPF, which are covalently bound peroxy radical (RO2) dimer association products. The ULVOC yield of α-pinene in the presence of NO3 is one-fifth of that resulting from ozone chemistry alone. Even trace amounts of NO3 radicals, at sub-parts per trillion level, suppress the NPF rate by a factor of 4. Ambient observations further confirm that when NO3 chemistry is involved, monoterpene NPF is completely turned off. Our results explain the frequent absence of nocturnal biogenic NPF in monoterpene (α-pinene)-rich environments.

[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.

[Characteristics and Cause of PM2.5 During Haze Pollution in Winter 2022 in Zhoukou, China].

The characteristics and main factors of causes of haze in Zhoukou in January 2022 were analyzed. Six air pollutants, water-soluble ions, elements, OC, EC, and other parameters in fine particulate matter were monitored and analyzed using a set of online high-time-resolution instruments in an urban area. The results showed that the secondary inorganic aerosols(SNA), carbonaceous aerosols(CA, including organic carbon OC and inorganic carbon EC), and reconstructed crustal materials(CM, such as Al2O3, SiO2, CaO, and Fe2O3, etc.) were the three main components, accounting for 61.3%, 24.3%, and 9.72% in PM2.5, respectively. The concentrations of SNA, CA, CM, and SOA were increased, accompanied with higher AQI. The sulfur oxidation rate(SOR) and nitrogen oxidation rate(NOR) in January were 0.53 and 0.46, respectively. The growth rates[µg·(m3·h)] of sulfate and nitrate were 0.027(-5.89-9.47, range) and 0.051(-23.1-12.4), respectively. During the haze period, the growth rates of sulfate and nitrate were 0.13 µg·(m3·h)-1and 0.24 µg·(m3·h)-1, which were 4.8 and 4.7 times higher than the average value of January, respectively. Although the sulfur oxidation rate was greater than the nitrogen oxidation rate, the growth rate of nitrate was approximately 1.8 times that of sulfate owing to the difference in the concentration of gaseous precursors and the influence of relative humidity. The growth rates of nitrate in SNA were significantly higher than those of sulfate on heavily polluted days. The values of SOR, NOR, and concentrations of SNA and SOA during higher AQI and humidity periods were higher than those in lower AQI and humidity periods. The Ox(NO2+O3) decreased with the increase in relative humidity. The SOA was higher at nighttime, increasing faster with the humidity than that in daytime. Under the situation of lower temperature, higher humidity, and lower wind speed, the emission of gaseous precursors of SNA requires further attention in Zhoukou in winter. Advanced control strategies of emissions of SO2 and NO2, such as mobile sources and coal-burning sources, could reduce the peak of haze in winter efficiently.

High serum interleukin-6 concentration upon admission is predictive of disease severity in paediatric trauma patients.

BACKGROUND: Trauma is the leading cause of death among children worldwide. The inflammatory response of paediatric patients to multiple injuries can be monitored using serum interleukin-6 (IL-6) levels. This study aimed to assess the value of IL-6 levels in predicting the severity of paediatric trauma and its clinical association with disease activity. METHOD: We prospectively tested serum IL-6 levels and evaluated the Paediatric Trauma Score (PTS) and other clinical data among 106 paediatrics trauma patients from January 2022 to May 2023 at the Emergency Department of the Xi'an Children's Hospital in China. The relationship between IL-6 and trauma severity levels by PTS was analyzed statistically. RESULTS: IL-6 levels were elevated in 76 (71.70%) of the 106 paediatric patients with trauma. Spearman's test showed a significant negative linear correlation between IL-6 and PTS (rs = - 0.757, p < 0.001). IL-6 levels were moderate positively correlated with alanine aminotransferase, aspartate aminotransferase, white blood cells, blood lactic acid and interleukin 10 (rs = 0.513, 0.600, 0.503, 0.417, 0.558, p < 0.01). IL-6 levels were positively correlated with hypersensitive C-reactive protein and glucose (rs = 0.377, rs = 0.389, respectively, p < 0.001). IL-6 levels were negatively correlated with fibrinogen and PH (rs = - 0.434, p < 0.001; rs = - 0.382, respectively, p < 0.001). Binary scatter plots further demonstrated higher levels of IL-6 correlated with lower PTS scores. CONCLUSION: Serum IL-6 levels significantly increased with increasing severity of paediatric trauma. Serum levels of IL-6 can function as important indicators for predicting disease severity and activity in paediatric trauma patients.

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.

Thrombocytosis and eosinophilia in 32 Chinese neonatal incontinentia pigmenti.

INTRODUCTION: Incontinentia pigmenti (IP) is a rare X-linked dominant genetic disease affecting ectodermal tissue and often misdiagnosed in the neonatal period. The aim of this study was to highlight sequential clinical features and evaluate prognosis of the 32 neonatal IP patients. MATERIAL AND METHODS: A retrospective descriptive analysis was performed, using the clinical, blood analytical, pathological, radiological, genetic, and followed-up data of neonatal patients diagnosed with IP from 2010 to 2021, in Xi'an, China. RESULTS: Of the 32 patients, two (6.25%) were male. Thirty babies (93.75%) had eosinophilia (eosinophilic granulocyte count: 0.31-19.9 × 109 , mean proportion of white blood cells: 20.98 ± 15.21%). Twenty babies (62.5%) had thrombocytosis (thrombocyte count: 139-975 × 109 , mean count: 416.76 ± 176.82). Thirty-one babies (96.88%) exhibited the first three cutaneous lesion stages characterized by erythema and superficial vesicles on inflammatory bases in a linear distribution in the first week of age. Thirteen babies (40%) combined nervous system abnormalities, and nine babies (28.13%) had retinopathy. Two types of genetic mutations were detected in the NEMO gene. Nineteen babies were followed up. According to the follow-up, four babies displayed psychomotor retardation, and five babies developed a decrease in vision with astigmatism and amblyopia. CONCLUSION: It is important that 30 babies (93.75%) had eosinophilia and 20 babies (62.5%) had thrombocytosis. Therefore, we speculate that the mechanism of the injury may be related to the platelet aggregation on the basis of the increase in eosinophil cells and the release of inflammatory factors.

[Spatial and Temporal Distribution Characteristics of Ozone Concentration and Population Health Benefit Assessment in the Yangtze River Delta Region from 2017 to 2020].

In recent years, the ozone (O3) concentration has showed a rising trend in China, becoming second only to PM2.5 as an important factor affecting air quality. To grasp the spatial-temporal variations characteristics of O3 and the associated health impacts during the implementation of the three-year plan on defending the blue sky in the Yangtze River Delta (YRD) region, data collected from 210 monitoring stations in the YRD from 2017 to 2020 were analyzed using the global Moran's index and Getis-Ord Gi* index methods, and the associated health benefits of reduced O3 exposure were evaluated using the health risk and environmental value assessment methods. The results showed that during the study period, the interquartile range (IQR) of the annual average O3 concentration and that of the warm season both presented a declining trend. The average O3 concentrations in both warm and cold seasons showed a similar spatial distribution pattern, with the northern part exhibiting the higher concentrations and the southern part showing the lower concentrations. Furthermore, the O3 concentrations in the warm season were characterized by high O3 concentrations clustering in the northern and central part of the region. The proportion of the population exposure to annual average O3 concentration over 160 µg·m-3 decreased from 72.3% in 2017 to 34.8% in 2020 in the YRD. Although the population-weighted annual mean O3 concentration in the whole YRD region showed a downward trend, some cities in western Anhui province, northern Jiangsu province, and central Jiangsu province showed fluctuations and even an increasing trend. In terms of health benefits, there were 3782 cases (95% CI:2050-5511 cases) of avoided premature deaths associated with reduced O3 concentrations in the warm season in 2020 compared to 2017. The total health benefit was 26198 million yuan (95% CI:14201-38175 million yuan). Compared to the cost of the main O3 precursor emission reduction, the cost-benefits ratio was 1:1.67 to 3.23.

Investigation of a haze-to-dust and dust swing process at a coastal city in northern China part I: Chemical composition and contributions of anthropogenic and natural sources.

The long retention of dust air masses in polluted areas, especially in winter, may efficiently change the physicochemical properties of aerosols, causing additional health and ecological effects. A large-scale haze-to-dust weather event occurred in the North China Plain (NCP) region during the autumn-to-winter transition period in 2018, affecting the coastal city Qingdao several times between Nov. 27th and Dec. 1st. To study the evolution of the pollution process, we analyzed the chemical characteristics of PM2.5 and PM10-2.5 and source apportionments of PM2.5 and PM10, The dust stagnated around NCP and moved out and back to the site, noted as dust swing process, promoting SO42- formation in PM2.5 and NO3- formation in PM10-2.5. Source apportionments were analyzed using the Positive Matrix Factorization (PMF) receptor model and weighted potential source contribution function (WPSCF). Before the dust invasion, Qingdao was influenced by severe haze; waste incineration and coal burning were the major contributors (~80 %) to PM2.5, and the source region was in the southwest of Shandong Province. During the initial dust event, mineral dust and the mixed factor of dust and sea salt were the major contributors (46.0 % of PM2.5 and 86.5 % of PM10). During the polluted dust period, the contributions of regional transported biomass burning (22.3 %), vehicle emissions (20.8 %), and secondary aerosols (33.8 %) to PM2.5 from the Beijing-Tianjin-Hebei region significantly increased. The secondary aerosols source was more regional than that of vehicle emissions and biomass burning and contributed considerably to PM10 (30.8 %) during the dust swing process. Our findings demonstrate that environmental managers should consider the possible adverse effects of winter dust on regional and local pollution.

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.

Field Detection of Highly Oxygenated Organic Molecules in Shanghai by Chemical Ionization-Orbitrap.

Secondary organic aerosol, formed through atmospheric oxidation processes, plays an important role in affecting climate and human health. In this study, we conducted a comprehensive campaign in the megacity of Shanghai during the 2019 International Import Expo (EXPO), with the first deployment of a chemical ionization─Orbitrap mass spectrometer for ambient measurements. With the ultrahigh mass resolving power of the Orbitrap mass analyzer (up to 140,000 Th/Th) and capability in dealing with massive spectral data sets by positive matrix factorization, we were able to identify the major gas-phase oxidation processes leading to the formation of oxygenated organic molecules (OOM) in Shanghai. Nine main factors from three independent sub-range analysis were identified. More than 90% of OOM are of anthropogenic origin and >60% are nitrogen-containing molecules, mainly dominated by the RO2 + NO and/or NO3 chemistry. The emission control during the EXPO showed that even though the restriction was effectual in significantly lowering the primary pollutants (20-70% decrease), the secondary oxidation products responded less effectively (14% decrease), or even increased (50 to >200%) due to the enhancement of ozone and the lowered condensation sink, indicating the importance of a stricter multi-pollutant coordinated strategy in primary and secondary pollution mitigation.

[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.

Abundance of organosulfates derived from biogenic volatile organic compounds: Seasonal and spatial contrasts at four sites in China.

Atmospheric organosulfates (OSs) derived from biogenic volatile organic compounds (BVOCs) encode chemical interaction strength between anthroposphere and biosphere. We report BVOC-derived OSs in the summer of 2016 and the winter of 2017 at four locations in China (i.e., Hong Kong (HK), Guangzhou (GZ), Shanghai (SH), and Beijing (BJ)). The spatial coverage of three climatic zones from the south to the north in China is accompanied with a wide range of aerosol inorganic sulfate (4.9-13.8 µg/m3). We employed a combined targeted and untargeted approach using high-performance liquid chromatography-Orbitrap mass spectrometry to quantify/semi-quantify ~200 OSs and nitrooxy OSs derived from four types of precursors, namely C2-C3 oxygenated VOCs, isoprene, monoterpenes (MT), and sesquiterpenes (ST). The seasonal averages of the total quantified OSs across the four sites are in the range of 201-545 (summer) and 123-234 ng/m3 (winter), with the isoprene-derived OSs accounting for more than 80% (summer) and 57% (winter). The C2-3 OSs and isoprene-derived OSs share the same seasonality (summer >winter) and the same south-north spatial gradient as those of isoprene emissions. In contrast, the MT- and ST-derived OSs are of either comparable abundance or slightly higher abundance in winter at the four sites. The spatial contrasts for MT- and ST-derived OSs are not clearly discernable among GZ, SH, and BJ. HK is noted to have invariably lower abundances of all groups of OSs, in line with its aerosol inorganic sulfate being the lowest. These results indicate that BVOC emissions are the driving factor regulating the formation of C2-3 OSs and isoprene-derived OSs. Other factors, such as sulfate abundance, however, play a more important role in the formation of MT- and ST-derived OSs. This in turn suggests that the formation kinetics and/or pathways differ between these two sub-groups of BVOCs-derived OSs.

Comparative Assessment of Cooking Emission Contributions to Urban Organic Aerosol Using Online Molecular Tracers and Aerosol Mass Spectrometry Measurements.

Cooking organic aerosol (COA) is an important source of particulate pollutants in urbanized regions. Yet, the diversity and complexity of COA components make direct identification and quantification of COA difficult. In this study, we conducted collocated OA measurements with an aerosol mass spectrometer (AMS) and a thermal desorption aerosol gas chromatography-mass spectrometer (TAG) in Shanghai. Cooking molecular tracers (e.g., C18 fatty acids, azelaic acid) measured by TAG provide unambiguous source information for evaluating the tracer ion (C6H10O+, m/z 98) used for identification and apportionment of COA in AMS analysis. Based on the collocated AMS and TAG measurements, two COA factors, namely, a primary COA (PCOA) and an oxygenated COA (OCOA) produced from rapid oxygenation of freshly emitted PCOA, were identified. Criteria for identifying COA factors from AMS analysis with different oxygenation levels are proposed, i.e., characteristic mass spectra, temporal variations, etc. Furthermore, two positive matrix factorization approaches, namely, AMS-PMF and the molecular marker (MM)-PMF, were compared for COA quantification, where high consistency was found with the contribution of COA to total PM2.5 mass estimated to be 9 ± 7% by AMS-PMF and 6 ± 5% by the MM-PMF. Our study highlights the important impacts of cooking activities on air quality in urban areas. We also demonstrate the advantage of conducting collocated measurements using multiple high time resolution mass spectrometric techniques in advancing our understanding of atmospheric OA chemistry and improving the accuracy of source apportionment.

Polycyclic aromatic hydrocarbons in leaves of Cinnamomum camphora along the urban-rural gradient of a megacity: Distribution varies in concentration and potential toxicity.

Rapid urbanization and industrialization have precipitated the significant urban-rural gradient involving various aspects of human-related activities especially in megacities. Anthropogenic activities are the main source of polycyclic aromatic hydrocarbon (PAH) contamination, and the rising awareness concerning PAH potential toxicity to human health promotes a further understanding of its spatial distribution pattern in cities. Whether the distribution of PAH concentration and potential toxicity respond to the urban-rural gradient still requires investigation. This study applied a grid sampling method to investigate PAH concentration using Cinnamomum camphora leaves as bioindicators which were obtained from 84 sampling sites in a megacity, Shanghai. The potential toxicity of PAHs in leaves was calculated by toxicity factor equivalent method. Results revealed the patterns of PAH distribution in the city varied in concentration and potential toxicity: the total concentration of PAHs in leaves decreased along the urban-rural gradient, while the potential toxicity peaked at junction areas. The trend of PAH concentration along the distance from urban center corresponded to that of population density. The spatial distribution of potential toxicity did not correspond with the gradient but was influenced by high benzo(a)pyrene concentration originated from the industry districts nearby. Higher potential toxicity of PAHs was observed at the urban-suburban-rural junction areas of megacities, advocating health-risk attention and appropriate plan for land use of these transition areas in cities.

[Exposure Levels, Sources, and Health Risks of Heavy Metal Components of PM2.5 in Housewives in Rural Shanghai].

To investigate exposure characteristics and potential health risk of PM2.5-bound heavy metals in housewives in rural areas, 265 personal exposure samples from 143 subjects were collected in the Songjiang district, Shanghai from February 2017 to June 2018. Mass concentrations of 13 elements in PM2.5 were determined by energy-dispersive X-ray fluorescence spectrometry (ED-XRF). The sources of heavy metal components in PM2.5 were analyzed using positive matrix factorization (PMF). The inhalation health risks of exposure to Ni, V, Cr, Mn, As, and Pb were analyzed using the US EPA health risk assessment model. The results showed that the average concentration of personal exposure to PM2.5 was 40.61 µg·m-3 in housewives, which was higher than the concentration at peripheral monitoring stations. The carcinogenic risks of Cr(Ⅵ)and As exceeded the acceptable risk level (10-6). The non-carcinogenic risks of V, Cr(Ⅵ), Mn, Ni, and As were all below the safety threshold, while the total non-carcinogenic risks of these five elements were higher than the safety threshold (>1). The results of PMF indicated that resuspended dust and indoor dust(43.8%), the metallurgy industry(34.6%), coal combustion(14.5%), and fossil-fuel combustion(7.2%)were the major sources of ten elements (Al, Ti, V, Cr, Mn, Fe, Ni, Zn, As, and Pb) in PM2.5. Based on the results of health risk assessment of pollution sources, control measures on the metallurgy industry and fossil-fuel combustion should be further strengthened.

Nitrite-Mediated Photooxidation of Vanillin in the Atmospheric Aqueous Phase.

Nitrite (NO2-) and its conjugate acid, nitrous acid (HNO2), have long been recognized as a ubiquitous atmospheric pollutant as well as an important photochemical source of hydroxyl radicals (·OH) and reactive nitrogen species (·NO, ·NO2, ·N2O3, etc.) in both the gas phase and aqueous phase. Although NO2-/HNO2 plays an important role in atmospheric chemistry, our understanding on its role in the chemical evolution of organic components in atmospheric waters is rather incomplete and is still in dispute. In this study, the nitrite-mediated photooxidation of vanillin (VL), a phenolic compound abundant in biomass burning emissions, was investigated under pH conditions relevant for atmospheric waters. The influence of solution pH, dissolved oxygen, and ·OH scavengers on the nitrite-mediated photooxidation of VL was discussed in detail. Our study reveals that the molecular composition of the products is dependent on the molar ratio of NO2-/VL in the solution and that nitrophenols are the major reaction products. We also found that the light absorbance of the oxidative products increases with increasing pH in the visible region, which can be attributed to the deprotonation of the nitrophenols formed. These results contribute to a better understanding of methoxyphenol photooxidation mediated by nitrite as a source of toxic nitrophenols and climatically important brown carbon in atmospheric waters.

Monoterpene and Sesquiterpene α-Hydroxy Organosulfates: Synthesis, MS/MS Characteristics, and Ambient Presence.

Organosulfates (OSs) derived from biogenic volatile organic compounds are important compounds signifying interactions between anthropogenic sulfur pollution and natural emission. In this work, we substantially expand the OS standard library through the chemical synthesis of 26 α-hydroxy OS standards from eight monoterpenes (i.e., α- and ß-pinene, limonene, sabinene, Δ3-carene, terpinolene, and α- and γ-terpinene) and two sesquiterpenes (i.e., α-humulene and ß-caryophyllene). The sulfation of unsymmetrically substituted 1,2-diol intermediates produced a regioisomeric mixture of two OSs. The major regioisomeric OSs were isolated and purified for full NMR characterization, while the minor regioisomers could only be determined by liquid chromatograph-mass spectrometer (MS). The tandem mass spectra of the molecular ion formed through electrospray ionization confirmed the formation of abundant bisulfate ion fragments (m/z 97) and certain minor ion fragments characteristic of the carbon backbone. A knowledge of the MS/MS spectra and chromatographic retention times for authentic standards allows us to identify α-hydroxy OSs derived from six monoterpenes and ß-caryophyllene in ambient samples. Notably, among two possible regioisomers of α-hydroxy OSs, we only detected the isomers with the sulfate group at the less substituted carbon position derived from α-pinene, limonene, sabinene, Δ3-carene, and terpinolene in the ambient samples. This observation sheds light on the atmospheric OS formation mechanisms.