Atmospheric mercury in a developed region of eastern China: Interannual variation and gas-particle partitioning.

Atmospheric mercury plays a crucial role in the biogeochemical cycle of mercury. This study conducted an intensive measurement of atmospheric mercury from 2015 to 2018 at a regional site in eastern China. During this period, the concentration of particle-bound mercury (PBM) decreased by 13%, which was much lower than those of gaseous elemenral mercury (GEM, 30%) and reactive gaseous mercury (GOM, 62%). The gradual decrease in the correlation between PBM and CO, K, and Pb indicates that the influence of primary emissions on PBM concentration was weakening. Moreover, the value of the partitioning coefficient (Kp) increased gradually from 0.05 ± 0.076 m3/µg in 2015 to 0.16 ± 0.37 m3/µg in 2018, indicating that GOM was increasingly inclined to adsorb onto particulate matter. Excluding the influence of meteorological conditions and the primary emissions, the change in aerosol composition is designated as the main trigger factor for the increasing gas-particle partitioning of reactive mercury (RM). The increasing ratio of Cl-, NO3-, and organics (Org) in the chemical composition of particle matters (PM2.5), as well as the decrease in the proportion of SO42-, NH4+, and K+, are conducive to the adsorption of GOM onto particles, forming PBM, which led to an increase of Kp and a lag of PBM reduction compared to GEM and GOM under the continuous control measures of anthropogenic mercury emissions. The evolution of aerosol compositions in recent years affects the migration and transformation of atmospheric mercury, which in turn can affect the biogeochemical cycle of mercury.

Atmospheric saccharides over the East China Sea: Assessment of the contribution of sea-land emission and the aging of levoglucosan.

A one-year observation of aerosols on a remote island was conducted and saccharides were applied to reveal the behaviors of organic aerosol in the East China Sea (ECS). The seasonal fluctuations of total saccharides were relatively small, with annual mean concentration of 64.82 ± 26.88 ng/m3, contributing 10.20 % and 4.90 % to WSOC and OC, respectively. However, the individual species showed significant seasonal variations due to the differences in both the emission sources and the influencing factors between marine and terrestrial areas. Anhydrosugars was the highest species and showed little diurnal variation in air mass from land areas. Primary sugars and primary sugar alcohols showed higher concentrations in blooming spring and summer and were higher in daytime than nighttime due to intense biogenic emissions both in marine and mainland areas. Accordingly, secondary sugar alcohols showed obvious different diurnal variation with ratios of day/night reducing to 0.86 in summer but even increasing to 1.53 in winter, attributing to the additional impact of secondary transmission process. Source appointment suggested that biomass burning emission (36.41 %) and biogenic emission (43.17 %) were the main causes of organic aerosol, while anthropogenic related secondary process and sea salt injection accounted for 13.57 % and 6.85 %, respectively. We further elucidate that the biomass burning emission might be underestimated, as levoglucosan undergoes degradation processes in the atmosphere, which are affected by various atmospheric physicochemical factors, and the degradation degree is particularly severe in remote areas like the oceans. In addition, significantly low ratio of levoglucosan to mannosan (L/M) occurred in air mass from marine area, indicating that levoglucosan was likely be more fully aged after hovering over a large-scale of oceanic area.

Relationship between light absorption properties of black carbon and aerosol origin at a background coastal site.

As a potent climate forcer, black carbon (BC) optical properties can have significant impacts on the regional meteorology and climate. To unveil the seasonal differences of BC and its contribution by various emission sources, a one-year continuous monitoring of atmospheric aerosols was conducted at a background coastal site in Eastern China. By comparing the seasonal and diurnal patterns between BC and elemental carbon, we observed that BC were evidently aged with varying extents among all four seasons. The light absorption enhancement of BC (Eabs) was calculated as 1.89 ± 0.46, 2.40 ± 0.69, 1.91 ± 0.60, and 1.34 ± 0.28, from spring to winter, respectively, indicating that BC was more aged in summer. Contrary to the negligible impact of pollution levels on Eabs, the patterns of air masses arriving to the sampling site had a significant impact on the seasonal optical characteristics of BC. Sea breezes evidently exhibited higher Eabs than land-sourced breezes, and BC was more aged and light-absorbing with an increased contribution of marine airflows. By applying a receptor model, we resolved six emission sources as ship emission, traffic emission, secondary pollution, coal combustion, sea salt, and mineral dust. The mass absorption efficiency of BC for each source was estimated, showing the highest from the ship emission sector. This explained the highest Eabs observed in summer and sea breezes. Our study highlights that curbing emission from shipping activities is beneficial for reducing the warming effect of BC in coastal areas, particularly in the context of future rapid development of international shipping.

Seasonal source identification and formation processes of marine particulate water soluble organic nitrogen over an offshore island in the East China Sea.

Water soluble organic nitrogen (WSON) had great influences on the aerosol chemistry, hygroscopicity, marine primary productivity, as well as nitrogen biogeochemical cycles. Aerosol sampling was conducted over an offshore island in the East China Sea in four seasons of 2019, aiming to reveal the seasonal sources and secondary formation processes of marine WSON. The annual mean WSON concentration reached 1.05 ± 1.72 µg/m3 with a mean WSON/WSTN fraction of 27 %. In spring, WSON was associated with combustion emissions. The liquid-phase reaction of NH3/NH4+ with VOCs was a potential secondary formation process of WSON. In summer, WSON was mainly formed through the gaseous phase oxidation of marine biogenic precursors. In autumn, WSON showed miscellaneous sources from agricultural activities, biomass burning, and fossil fuel combustion. In addition to the contribution from primary urea, WSON could be also affected by the oxidation of biological proteinaceous matters. This explained the highest WSON concentrations and WSON/WSOC ratios in autumn. In winter, WSON was probably emitted from sea spray aerosols via the bubble-bursting processes. This study indicated that the sources of WSON over the coastal waters in the East China Sea were quite diverse, highlighting the need of more detailed characterization of marine WSON at the molecular level.

Response of PM2.5-bound elemental species to emission variations and associated health risk assessment during the COVID-19 pandemic in a coastal megacity.

The coronavirus (COVID-19) pandemic is disrupting the world from many aspects. In this study, the impact of emission variations on PM2.5-bound elemental species and health risks associated to inhalation exposure has been analyzed based on real-time measurements at a remote coastal site in Shanghai during the pandemic. Most trace elemental species decreased significantly and displayed almost no diel peaks during the lockdown. After the lockdown, they rebounded rapidly, of which V and Ni even exceeded the levels before the lockdown, suggesting the recovery of both inland and shipping activities. Five sources were identified based on receptor modeling. Coal combustion accounted for more than 70% of the measured elemental concentrations before and during the lockdown. Shipping emissions, fugitive/mineral dust, and waste incineration all showed elevated contributions after the lockdown. The total non-carcinogenic risk (HQ) for the target elements exceeded the risk threshold for both children and adults with chloride as the predominant species contributing to HQ. Whereas, the total carcinogenic risk (TR) for adults was above the acceptable level and much higher than that for children. Waste incineration was the largest contributor to HQ, while manufacture processing and coal combustion were the main sources of TR. Lockdown control measures were beneficial for lowering the carcinogenic risk while unexpectedly increased the non-carcinogenic risk. From the perspective of health effects, priorities of control measures should be given to waste incineration, manufacture processing, and coal combustion. A balanced way should be reached between both lowering the levels of air pollutants and their health risks.

Effects of rosmarinic acid on the inflammatory response in allergic rhinitis rat models after PM2.5 exposure.

BACKGROUND: Studies have shown the promising prospects of rosmarinic acid (RosA) for the prevention and treatment of allergic diseases. OBJECTIVE: The aim of this study was to investigate the effects of RosA on inflammatory reaction in rat models of allergic rhinitis (AR) after PM2.5 exposure. METHODS: Allergic rhinitis rat models were established by ovalbumin sensitization, and PM2.5 was applied at a concentration of 1000 µg/m3 , 3 h a day for 30 consecutive days. RosA was administered via intraperitoneal injection (20 mg/kg/d) for seven consecutive days. Allergic nasal symptoms were recorded. The expressions of interleukin (IL)-4, IL-13, interferon (INF)-γ, and OVA-sIgE were determined by ELISA. Histopathological changes in nasal mucosa were observed by HE staining. mRNA expressions of T-bet and GATA-3 in nasal mucosa were detected by RT-PCR. NF-κBp65 in cell nuclei and IκBα in cytoplasm were analyzed by Western blot. RESULTS: PM2.5 exposure worsened allergic nasal symptoms in AR rats, while RosA ameliorated these symptoms. Histopathologically, AR rats exhibited disorganized nasal mucosal epithelium, cell exfoliation, eosinophilic infiltration of lamina propria, gland swelling, and submucosal vascular congestion, which were aggravated by PM2.5 exposure and alleviated by RosA. RosA decreased the expressions of IL-4, IL-13, and increased the level of IFN-γ in PM2.5-exposed AR rats. After RosA intervention, the expressions of GATA-3 mRNA and NF-κBp65 in PM2.5-exposed AR rats were significantly reduced, while those of T-bet mRNA and IκBα were markedly increased. CONCLUSION: Rosmarinic acid may alleviate symptoms of AR rat models exposed to PM2.5 through the modulation of the NF-κB pathway and Th1/Th2 balance.

Airborne black carbon variations during the COVID-19 lockdown in the Yangtze River Delta megacities suggest actions to curb global warming.

Airborne black carbon is a strong warming component of the atmosphere. Therefore, curbing black carbon emissions should slow down global warming. The 2019 coronavirus pandemic (COVID-19) is a unique opportunity for studying the response of black carbon to the varied human activities, in particular due to lockdown policies. Actually, there is few knowledge on the variations of black carbon in China during lockdowns. Here, we studied the concentrations of particulate matter (PM2.5) and black carbon before, during, and after the lockdown in nine sites of the Yangtze River Delta in Eastern China. Results show 40-60% reduction of PM2.5 and 40-50% reduction of black carbon during the lockdown. The classical bimodal peaks of black carbon in the morning and evening rush hours were highly weakened, indicating the substantial decrease of traffic activities. Contributions from fossil fuels combustion to black carbon decreased about 5-10% during the lockdown. Spatial correlation analysis indicated the clustering of the multi-site black carbon concentrations in the Yangtze River Delta during the lockdown. Overall, control of emissions from traffic and industrial activities should be efficient to curb black carbon levels in the frame of a 'green public transit system' for mega-city clusters such as the Yangtze River Delta. SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s10311-021-01327-3.

Ursolic Acid Alleviates Mucus Secretion and Tissue Remodeling in Rat Model of Allergic Rhinitis After PM2.5 Exposure.

BACKGROUND: According to recent epidemiologic studies, exposure to fine particulate matter (particulate matter 2.5 ≤ µm [PM2.5]) in the air increases the incidence and severity of allergic rhinitis (AR). Ursolic acid (UA) has activities in immune regulation and anti-inflammatory. However, the role of UA intervention on PM2.5-exposed AR remains unknown. In this study, we investigated the effects of UA on tissue remodeling and mucus hypersecretion in a rat model of AR after PM2.5 exposure. METHODS: AR was induced in rats with ovalbumin (OVA) and they were exposed to ambient PM2.5(200 µg/m3) via a PM2.5 inhalation exposure system for 30 days(ARE group). Ursolic acid intervention was administrated in the AR model after PM2.5 exposure (UA group). Hyperplasia of goblet cells was detected by periodic acid-Schiff (PAS) staining and collagen deposition in the nasal mucosa was detected by Masson trichrome (MT) staining.MUC5AC expression was measured by immunohistochemistry. RESULTS: UA group showed reduced goblet cell hyperplasia and collagen deposition in the nasal mucosa which exacerbated after PM2.5 exposure, as reflected by PAS and MT staining when compared with the ARE group. Immunohistochemical results showed that the expression of MUC5AC in the UA group was lower than that in the ARE group. CONCLUSION: Analysis of our data indicated that UA could attenuate nasal remodeling and mucus hypersecretion in aggravation of AR after PM2.5 exposure, which may be the pathophysiologic mechanisms for the prevention of AR exacerbated by exposure to PM2.5.

Effects of N-acetylcysteine on oxidative stress and inflammation reactions in a rat model of allergic rhinitis after PM2.5 exposure.

Particulate matter 2.5 (PM2.5) exposure can increase the prevalence of allergic rhinitis (AR), the mechanism underlying which may include oxidative stress and inflammatory response. As a ROS quenching agent, N-acetylcysteine (NAC) can attenuate the accumulation of inflammatory cells and hyper-responsiveness in animal asthma models. To explore the effect of NAC on the oxidative stress and inflammatory reactions in AR rats exposed to PM2.5, we analyzed the components of PM2.5 and examined the nasal symptoms, redox level in nasal mucosa, Th1/Th2-related serum cytokines, nasal mucosal histopathology and ultrastructure in AR rat models with NAC intervention after PM2.5 exposure. The results showed that the high concentrations of metal cations and PAHs in PM2.5 could aggravate Th2-dominant allergic inflammation in AR model and cause redox imbalance, accompanied by nasal epithelial cell stripping and eosinophil infiltration, while NAC intervention could alleviate the clinical symptoms of AR model after PM2.5 exposure, correct the redox imbalance, reduce the Th2 cytokines, reduce eosinophil infiltration, and promote the moderate regeneration of epithelial cells. The mechanism of NAC reversing PM2.5-mediated action may be related to its anti-oxidant and anti-inflammatory effects, which may provide some new insights for the prevention of AR exacerbated by exposure to PM2.5.

Effects of Ursolic Acid on the Expression of Th1-Th2-related Cytokines in a Rat Model of Allergic Rhinitis After PM2.5 Exposure.

BACKGROUND: Allergic rhinitis (AR) is a global health problem and closely related to environmental factors. Ursolic acid (UA) has potential in the treatment of allergic inflammation. The effects of UA intervention on PM2.5-induced AR remain uncertain. OBJECTIVE: To assess the effects of UA on nasal symptoms and the expression of T-helper (Th)1-Th2-related cytokines in a rat model of AR after fine particulate matter (particulate matter ≤ 2.5 µm [PM2.5]) exposure. METHODS: A total of 40 healthy female Sprague-Dawley rats were randomly divided into 4 groups: normal control group (NC group), ovalbumin (OVA)- induced AR model (AR group), PM2.5-exposed AR group exposed to 200 g/m3 PM2.5 for 30 days via inhalation (ARE group), and a group with UA intervention to the AR model after PM2.5 exposure (UA group). UA intervention was adopted after PM2.5 exposure in the UA group. Nasal symptoms and levels of Th1-Th2 cytokines in the serum were detected in each individual rat. The pathological changes and expression of Eotaxin in the nasal mucosa of each individual rat were examined by histology. RESULTS: PM2.5 significantly increased the number of sneezes and nasal rubs in the rats with AR, and UA alleviated these symptoms. UA decreased interleukin (IL)-4, IL-5, IL-13, Eotaxin-1, and OVA Immunoglobulin E (IgE) protein levels. In the AR group, hematoxylin and eosin staining showed disordered arrangement of the nasal mucosa epithelium, cell shedding, eosinophilic infiltration, swelling of the glands, and submucosal vascular congestion. UA group showed reduced eosinophilic infiltration and orderly arrangement of the mucosal epithelium when compared with the ARE group. Immunohistochemical results showed that the expression of Eotaxin in the UA group was lower than that in the ARE group. CONCLUSION: UA could relieve nasal symptoms caused by PM2.5 exposure, the possible mechanism of which is to inhibit the expression of Th2 cytokines, eosinophilic infiltration, and specific IgE production.

Effect of PM2.5 on MicroRNA Expression and Function in Nasal Mucosa of Rats With Allergic Rhinitis.

BACKGROUND: Particulate matter 2.5 (PM2.5) refers to particulate matter with aerodynamic equivalent diameter less than or equal to 2.5 µm, which is an important component of air pollution. PM2.5 aggravates allergic rhinitis (AR) and promotes AR nasal mucosa inflammation. Therefore, the influence of PM2.5 inhalation exposure on microRNA (miRNA) expression profiles and function in the nasal mucosa of AR rats was investigated. METHODS: Female Sprague Dawley rats were distributed randomly to 2 groups: AR model PM2.5 exposure group (ARE group) and AR model PM2.5-unexposed control group (ARC group). The rats of ARE group were made to inhale PM2.5 at a concentration of 200 µg/m3, 3 h/day, for 30 days. miRNA expression profiles of the nasal mucosa from both groups were determined using an miRNA gene chip and were verified by quantitative real-time PCR (qRT-PCR). Gene function enrichment analysis was performed using bioinformatics analysis. RESULTS: The ARE group revealed 20 significantly differentially expressed miRNAs, including 4 upregulated and 16 downregulated miRNAs (fold change > 1.5 or < 0.66, P < .05). Of these, 9 selected miRNAs were verified by qRT-PCR, and the results of 8 miRNAs were in accordance with the miRNA gene chip results, with highly positive correlation (r = .8583, P = .0031). Numerous target genes of differentially expressed miRNAs were functionally enriched in high-affinity immunoglobulin E receptor signaling, ErbB signaling, mucin O-glycans biosynthesis, transforming growth factor ß signaling, mitogen-activated protein kinase signal transduction, phosphatidylinositol signaling, mucopolysaccharide biosynthesis, mammalian target of rapamycin signaling, T cell receptor signaling, Wnt signaling, chemokine signal transduction, and natural killer cell-mediated cytotoxicity pathways. CONCLUSIONS: PM2.5 causes significant changes in miRNA expression in the nasal mucosa of AR rats. miRNA plays an important role in regulating PM2.5 effects in AR rat biological behavior and mucosal inflammation. This study provides a theoretical basis for the prevention and treatment of AR from the effects of environmental pollution on the gene regulation mechanism.

Assessing Contributions of Agricultural and Nonagricultural Emissions to Atmospheric Ammonia in a Chinese Megacity.

Ammonia (NH3) is the predominant alkaline gas in the atmosphere contributing to formation of fine particles-a leading environmental cause of increased morbidity and mortality worldwide. Prior findings suggest that NH3 in the urban atmosphere derives from a complex mixture of agricultural (mainly livestock production and fertilizer application) and nonagricultural (e.g., urban waste, fossil fuel-related emissions) sources; however, a citywide holistic assessment is hitherto lacking. Here we show that NH3 from nonagricultural sources rivals agricultural NH3 source contributions in the Shanghai urban atmosphere. We base our conclusion on four independent approaches: (i) a full-year operation of a passive NH3 monitoring network at 14 locations covering urban, suburban, and rural landscapes; (ii) model-measurement comparison of hourly NH3 concentrations at a pair of urban and rural supersites; (iii) source-specific NH3 measurements from emission sources; and (iv) localized isotopic signatures of NH3 sources integrated in a Bayesian isotope mixing model to make isotope-based source apportionment estimates of ambient NH3. Results indicate that nonagricultural sources and agricultural sources are both important contributors to NH3 in the urban atmosphere. These findings highlight opportunities to limit NH3 emissions from nonagricultural sources to help curb PM2.5 pollution in urban China.

Characteristics of particulate-bound mercury at typical sites situated on dust transport paths in China.

The concentrations and seasonal variations of PBM (particulate-bound mercury) were observed at four dust source sites (Duolun, Yulin, Hetian, and Tazhong), two megacities (Shanghai and Beijing), and an island site (Huaniao Island) to obtain the spatiotemporal characteristics of PBM in dust transport path from desert area in China to the East China Sea. The highest annual mean concentrations of PBM in TSP (PBMTSP) were observed at megacity sites, reaching 146.7 pg/m3 and 274.7 pg/m3 in Shanghai and Beijing attributed primarily to anthropogenic emissions, while 39.7 pg/m3, 67.3 pg/m3, 61.0 pg/m3, 23.5 pg/m3 and 43.6 pg/m3 over Duolun, Yulin, Hetian, Tazhong, and Huaniao Island, respectively. PBM concentrations were higher in winter and autumn, while lower in spring and summer due to the variation of meteorological conditions (especially temperature and wind speed) together with the emission sources. Enrichment factors (EFs) of PBMTSP and PBM2.5 reached 158 and 1452 in Beijing, showing the serious anthropogenic emissions impacted on PBM pollution in megacities, and the profound high level of EFs of mercury in sand dust source sites (17-64 for TSP and 38-252 for PM2.5), suggesting the obvious mixing effect of dust and anthropogenic aerosols in dust source areas. Human activities played a major role in the increase of PBM concentrations and the enrichment factors during the long-range transport of air mass in China. The significant anthropogenic mercury emissions in the dust source areas and their long-range transport driven by the East Asian Monsoon might impact on the ecological cycle of mercury and should be taken into the mercury inventories. Coal combustion and smelting contributed 52-94% to PBM over all three types of sampling sites, and mining operations were additional sources of PBM in Yulin. In the coastal area, sea salt is an important source of PBM, and shipping could also contribute a certain proportion to PBM pollution which shouldn't be ignored.

Development and validation of a HPLC/FLD method combined with online derivatization for the simple and simultaneous determination of trace amino acids and alkyl amines in continental and marine aerosols.

A method was developed for simultaneous determination of 15 amino acids and 7 alkyl amines. The method was based on the employment of high performance liquid chromatography/fluorescence detection and online derivatization with o-phthaldiadehyde. The 22 derivatives were separated within 30 min including the equilibration time and detected by a fluorescence detector at an excitation wavelength of 230 nm and emission wavelength of 450 nm. The analysis procedure was satisfactorily validated by the reproducibility, recovery, linearity and detection limit of the analytes. The relative standard deviations (RSDs) of retention time and peak area for individual amino acids and alkyl amines were consistently less than 0.30% and 2.35%, respectively. Good recovery values ranging from 70% to 109% were obtained. The proposed method showed good linearity (R2≥0.99) in the range of 0.125-125 µM/L for amino acids and 2.5-5000 ng/L for alkyl amines. The detection limit ranged from 0.13 pM to 0.37 pM for individual amino acids and from 0.9 ng to 7.2 ng for individual alkyl amines. The developed and validated method was successfully applied to the quantitative analysis of amino acids and alkyl amines in continental and marine aerosols in China. Among the identified organic nitrogen compounds, 7 amino acids and 6 alkyl amines were detected in every aerosol sample. Glycine was the dominant amino acid, with the average of 130.93 pmol/m3 (accounting for 83% of the total amino acids) and 137.22 pmol/m3 (accounting for 66% of the total amino acids) in continental and marine aerosols in China, respectively. Methylamine and ethanolamine were the most abundant alkyl amines, contributing 87% and 64% to the total alkyl amines in continental and marine aerosols in China, respectively. This work provided an accurate, sensitive and simple method to determine simultaneously amino acids and alkyl amines, and applied the proposed method to the first investigation of amino acids in Shanghai and amino acids and alkyl amines in Huaniao Island in China. The finding of considerable amino acids and alkyl amines in continental and marine aerosols may exert significant implications on nitrogen cycling and atmospheric chemistry.

Effects of PM2.5 on mucus secretion and tissue remodeling in a rabbit model of chronic rhinosinusitis.

BACKGROUND: According to epidemiologic studies, fine particulate matter (particulate matter ≤2.5 µm, PM2.5) is closely associated with increases in the incidence and severity of chronic rhinosinusitis (CRS). However, the role of PM2.5 in the pathophysiology of CRS remains largely unknown. In this study, we investigated the effects of PM2.5 on nasal cilia, tissue remodeling, and mucus hypersecretion in a rabbit model of CRS. METHODS: CRS rabbits were exposed to ambient PM2.5 via a PM2.5 inhalation exposure system. The degree of ciliary damage was evaluated using scanning electron microscopy (SEM). Histopathologic changes were determined using periodic acid-Schiff (PAS) staining of goblet cells and Masson trichrome (MT) staining for collagen in the nasal mucosa. MUC5AC expression was assessed by immunohistochemistry. RESULTS: PM2.5 exposure substantially aggravated ciliary disruption in rabbits with CRS. PM2.5 also significantly increased goblet cell hyperplasia and collagen deposition, as reflected by PAS and MT staining. The nasal mucosa of CRS rabbits displayed markedly elevated MUC5AC expression after PM2.5 exposure. CONCLUSION: Increases in ciliary disruption, nasal remodeling, and mucus hypersecretion may be the pathophysiologic mechanisms underlying the PM2.5-induced aggravation of CRS.

Determination of atmospheric alkylamines by ion chromatography using 18-crown-6 as mobile phase additive.

An improved ion chromatographic method including two elution procedures was proposed for the quantitative determination of atmospheric alkylamines in field atmospheric samples involving high levels of inorganic cations by using 18-crown-6 as mobile phase additive. When 18-crown-6 was added to the mobile phase, the retention times increased significantly for Na+, NH4+, K+ and primary alkylamines but decreased for secondary and tertiary alkylamines due to the complexation with certain cations and interaction with both stationary and mobile phases of 18-crown-6. As a result, the separation of the cations was greatly promoted, which reduced the interference of peak distortion of overloaded inorganic cations on the quantitation of adjacent alkylamines. By using the presented method, five inorganic cations (Na+, NH4+, K+, Mg2+, Ca2+) and six alkylamines (dimethylamine (DMAH+), trimethylamine + diethylamine (TMAH+ + DEAH+), propylamine (MPAH+), triethylamine (TEAH+), ethanolamine (MEOAH+) and triethanolamine (TEOAH+)) were effectively separated and determined, and the relative standard derivations (RSDs) of objective cations were all less than 1% for retention time and 3.1% for peak area (n = 9), respectively. The linearity was excellent for each cation (R2 > 0.993) except for NH4+ and TEOAH+ showing a non-linear response (R2 > 0.998 for theoretical non-linear fitting), and the detection limit of these cations were 0.03-1.19 ng. The proposed method was successfully used in the determination of both alkylamines and inorganic cations in ambient particulate matters and gaseous alkylamines in ceiling duct exhaust. The annual average concentrations of DMAH+, TMAH+ + DEAH+ and TEAH+ were 15.56, 4.35 and 16.00 ng m-3 in PM2.5 over Shanghai in 2013. The concentrations of gaseous DMA and TMA + DEA in ceiling duct exhaust reached a maximum of 940.0 and 112.7 µg m-3, and were positively correlated with the human activity intensity, suggesting that human excreta emissions was a potential important source of atmospheric alkylamines in urban area of Shanghai.

First long-term detection of paleo-oceanic signature of dust aerosol at the southern marginal area of the Taklimakan Desert.

We firstly conducted a long-term in-situ field measurement at a marginal area (Hotan) of the southern Taklimakan Desert covering all four seasons. Detailed chemical characterization of dust aerosol over Hotan showed several unconventional features, including (1) ubiquity of high Na+ and Cl- abundances in the Taklimakan dust aerosol and its Cl-/Na+ ratio close to seawater; (2) high Ca content in the Taklimakan dust (7.4~8.0%) which was about two times of that in the natural crust; (3) high abundance of soluble sulfate concentrations and strong correlations between sulfate and Na+ and Cl- as well as typical mineral tracers such as Al and Ca. Our results collectively indicated that the dust aerosol from the Taklimakan Desert was characterized of evident paelo-oceanic signature as the Taklimakan Desert was found as an ocean in the ancient times from the perspective of paleogeology. It was estimated that primary sources dominated the total abundances of sulfate during the dust seasons while previous climate modeling works had seldom considered the cooling effects of sulfate from the Taklimakan Desert.

Nasal epithelial barrier disruption by particulate matter ≤2.5 µm via tight junction protein degradation.

Upper airway diseases including sinonasal disorders may be caused by exposure to fine particulate matter (≤2.5 µm; PM2.5), as proven by epidemiological studies. PM2.5 is a complex entity whose chemical constituents and physicochemical properties are not confined to a single, independent "particle" but which in this study means a distinctive environmental "toxin." The mechanism whereby PM2.5 induces nasal epithelial barrier dysfunction leading to sinonasal pathology remains unknown. In the present study, human nasal epithelial cells were exposed to non-cytotoxic doses of PM2.5 to examine how PM2.5 affects the nasal epithelial barrier. Tight junction (TJ) integrity and function were assessed by transepithelial electric resistance and paracellular permeability. The expression levels of TJ proteins such as zona occludens-1, occludin and claudin-1 were assessed by immunofluorescence staining and western blot. PM2.5 exposure induced epithelial barrier dysfunction as reflected by increased paracellular permeability and decreased transepithelial electric resistance. TJ proteins zona occludens-1, occludin and claudin-1 were found to be downregulated. Pretreatment with N-acetyl-l-cysteine alleviated PM2.5-mediated reactive oxygen species generation in RPMI 2650 cells, further preventing barrier dysfunction and attenuating the degradation of TJ proteins. These results suggest that PM2.5 induces nasal epithelial barrier disruption via oxidative stress, and N-acetyl-l-cysteine counteracts this PM2.5-mediated effect. Thus, nasal epithelial barrier disruption caused by PM2.5, which leads to sinonasal disease, may be prevented or treated through the inhibition of reactive oxygen species.

Insights into the characteristics and sources of primary and secondary organic carbon: High time resolution observation in urban Shanghai.

There is growing evidence suggesting that organic aerosols play an important role in the evolution of severe haze episodes. However, long-term investigations of the different characteristics of carbonaceous aerosols during haze and non-haze days are insufficient. In this work, hourly measurements of organic carbon (OC) and elemental carbon (EC) in PM2.5 were conducted in Shanghai, a megacity in Eastern China, over the course of a year from July 2013 to June 2014. Both OC and EC exhibited a bimodal diel pattern and were highly dependent on the wind speed and direction. The concentration-weighted trajectory (CWT) analysis illustrated that primary OC (POC) and EC were largely associated with regional and long-range transport. Secondary OC (SOC) formation was the strongest during the harvest season owing to significant biomass burning emissions from the adjacent Yangtze River Delta and farther agricultural regions. Compared to OC (6.7 µg m-3) and EC (2.0 µg m-3) in the non-haze days, higher levels of both OC (15.6 µg m-3) and EC (7.7 µg m-3) were observed in the haze days as expected, but with lower OC/EC ratios in the haze days (2.4) than in non-haze days (4.6). The proportion of POC and EC in PM2.5 remained relatively constant as a function of PM2.5 mass loadings, while that of SOC significantly decreased on the highly polluted days. It is concluded that the haze pollution in urban Shanghai was influenced more by the primary emissions (POC and EC), while the role of SOC in triggering haze was limited.

Signal Transductions of BEAS-2B Cells in Response to Carcinogenic PM2.5 Exposure Based on a Microfluidic System.

PM2.5 (particulate matter less than 2.5 µm in diameter) is considered as a harmful carcinogen. Determining the precise relationship between the chemical constituents of PM2.5 in the air and cancer progression could aid the treatment of environment related disease and establishing risk reduction strategies. Herein, we used transcriptomics (RNA-seq) and an integrated microfluidic system to identify the global gene expression and differential target proteins expression induced by ambient fine particles collected from the heavy haze in China. The results clearly indicated that cancer related pathways exhibited the strongest dysregulation. The ambient fine particles could be uptaken into the cells by pinocytosis, mainly promoting the PI3K-Akt pathway, FGF/FGFR/MAPK/VEGF signaling, and the JAK-STAT pathway, leading to evading apoptosis, sustained angiogenesis, and cell proliferation, which are the most important hallmarks of cancer. And fine particles also have been demonstrated to create intracellular reactive oxygen species (ROS) and mitochondrial ROS, change intracellular free Ca2+, and induce apoptosis, which are all key players in mediating cancer progression. It was observed by transmission electron microscopy (TEM) that the particles from the haze could enter the mitochondria, resulting in disturbance of the mitochondrial membrane and disruption of the mitochondria, and these particles can even enter inside the nucleus. It was also found in our study of organics (OC, PAHs) and metals (Zn, As, V) that compounds of fine particles were more closely associated with the exacerbation of cancer and secondary aerosols generated by traffic had the largest impact on cancer related signal transductions.