A mineral-based origin of Earth's initial hydrogen peroxide and molecular oxygen.

Terrestrial reactive oxygen species (ROS) may have played a central role in the formation of oxic environments and evolution of early life. The abiotic origin of ROS on the Archean Earth has been heavily studied, and ROS are conventionally thought to have originated from H2O/CO2 dissociation. Here, we report experiments that lead to a mineral-based source of oxygen, rather than water alone. The mechanism involves ROS generation at abraded mineral-water interfaces in various geodynamic processes (e.g., water currents and earthquakes) which are active where free electrons are created via open-shell electrons and point defects, high pressure, water/ice interactions, and combinations of these processes. The experiments reported here show that quartz or silicate minerals may produce reactive oxygen-containing sites (≡SiO•, ≡SiOO•) that initially emerge in cleaving Si-O bonds in silicates and generate ROS during contact with water. Experimental isotope-labeling experiments show that the hydroxylation of the peroxy radical (≡SiOO•) is the predominant pathway for H2O2 generation. This heterogeneous ROS production chemistry allows the transfer of oxygen atoms between water and rocks and alters their isotopic compositions. This process may be pervasive in the natural environment, and mineral-based production of H2O2 and accompanying O2 could occur on Earth and potentially on other terrestrial planets, providing initial oxidants and free oxygen, and be a component in the evolution of life and planetary habitability.

Generation of zero-valent sulfur from dissimilatory sulfate reduction in sulfate-reducing microorganisms.

Dissimilatory sulfate reduction (DSR) mediated by sulfate-reducing microorganisms (SRMs) plays a pivotal role in global sulfur, carbon, oxygen, and iron cycles since at least 3.5 billion y ago. The canonical DSR pathway is believed to be sulfate reduction to sulfide. Herein, we report a DSR pathway in phylogenetically diverse SRMs through which zero-valent sulfur (ZVS) is directly generated. We identified that approximately 9% of sulfate reduction was directed toward ZVS with S8 as a predominant product, and the ratio of sulfate-to-ZVS could be changed with SRMs' growth conditions, particularly the medium salinity. Further coculturing experiments and metadata analyses revealed that DSR-derived ZVS supported the growth of various ZVS-metabolizing microorganisms, highlighting this pathway as an essential component of the sulfur biogeochemical cycle.

Cosmogenic radiosulfur tracking of solar activity and the strong and long-lasting El Niño events.

Reconstruction of past solar activity or high-energy events of our space environment using cosmogenic radionuclides allows evaluation of their intensities, frequencies, and potential damages to humans in near space, modern satellite technologies, and ecosystems. This approach is limited by our understanding of cosmogenic radionuclide production, transformation, and transport in the atmosphere. Cosmogenic radiosulfur (35S) provides additional insights due to its ideal half-life (87.4 d), extensively studied atmospheric chemistry (gas and solid), and ubiquitous nature. Here, we report multiyear measurements of atmospheric 35S and show the sensitivity of 35S in tracking solar activity in Solar Cycle 24 and regional atmospheric circulation changes during the 2015/2016 El Niño. Incorporating 35S into a universal cosmogenic radionuclide model as an independent parameter facilitates better modeling of production and transport of other long-lived radionuclides with different atmospheric chemistries used for reconstructing past astronomical, geomagnetic, and climatic events.

Removal of contamination in helium for precise SF6 -based Δ36 S measurements.

RATIONALE: Quantifications of quadruple sulfur isotopic compositions (δ34 S, Δ33 S, and Δ36 S) of sulfur-bearing compounds in nature are valuable for providing new insights into the Earth's evolution such as the crust-mantle cycle, oxygenation of atmosphere and oceans, and the origin and evolution of early life. SF6 -based isotope ratio mass spectrometry is the most widely used method of quantification, but Δ36 S measurements at high precision and accuracy have always been technically difficult due to the low abundance of 36 S (~0.01%). In this paper, we identify a major source of isobaric interferences (i.e., contamination in helium carrier gas in the gas chromatography purification step) and propose a simple strategy to solve this problem. METHODS: An SF6 fluorination and purification system was built. Laboratory SF6 reference gas and international Ag2 S standard (IAEA-S1) were used as reference materials to test our method. Contamination from helium carrier gas (99.999%) was purified by a simple two-step cryogenic method to allow for accurate and precise measurements of Δ36 S using the SF6 -based isotope ratio mass spectrometry method. RESULTS: Without proper purification of helium carrier gas, large errors in Δ36 S measurements were found. Measured Δ36 S values of SF6 with trace contamination from helium were >10‰ higher than expected values. Using a newly developed purification strategy, the difference in Δ36 S values of SF6 before and after passing through the gas chromatography is less than instrumental errors (<0.2‰). Our improved method yielded an overall Δ36 S precision for IAEA-S1 of 0.12‰ (n = 6). This precision is comparable to that found by other laboratories around the world. CONCLUSION: Our simple two-step cryogenic method significantly improved the accuracy and precision of Δ36 S measurements and is therefore recommended for future determination of quadruple sulfur isotopic compositions in natural samples.

Atmospheric sulfur isotopic anomalies recorded at Mt. Everest across the Anthropocene.

Increased anthropogenic-induced aerosol concentrations over the Himalayas and Tibetan Plateau have affected regional climate, accelerated snow/glacier melting, and influenced water supply and quality in Asia. Although sulfate is a predominant chemical component in aerosols and the hydrosphere, the contributions from different sources remain contentious. Here, we report multiple sulfur isotope composition of sedimentary sulfates from a remote freshwater alpine lake near Mount Everest to reconstruct a two-century record of the atmospheric sulfur cycle. The sulfur isotopic anomaly is utilized as a probe for sulfur source apportionment and chemical transformation history. The nineteenth-century record displays a distinct sulfur isotopic signature compared with the twentieth-century record when sulfate concentrations increased. Along with other elemental measurements, the isotopic proxy suggests that the increased trend of sulfate is mainly attributed to enhancements of dust-associated sulfate aerosols and climate-induced weathering/erosion, which overprinted sulfur isotopic anomalies originating from other sources (e.g., sulfates produced in the stratosphere by photolytic oxidation processes and/or emitted from combustion) as observed in most modern tropospheric aerosols. The changes in sulfur cycling reported in this study have implications for better quantification of radiative forcing and snow/glacier melting at this climatically sensitive region and potentially other temperate glacial hydrological systems. Additionally, the unique Δ33S-δ34S pattern in the nineteenth century, a period with extensive global biomass burning, is similar to the Paleoarchean (3.6-3.2 Ga) barite record, potentially providing a deeper insight into sulfur photochemical/thermal reactions and possible volcanic influences on the Earth's earliest sulfur cycle.

Five-S-isotope evidence of two distinct mass-independent sulfur isotope effects and implications for the modern and Archean atmospheres.

The signature of mass-independent fractionation of quadruple sulfur stable isotopes (S-MIF) in Archean rocks, ice cores, and Martian meteorites provides a unique probe of the oxygen and sulfur cycles in the terrestrial and Martian paleoatmospheres. Its mechanistic origin, however, contains some uncertainties. Even for the modern atmosphere, the primary mechanism responsible for the S-MIF observed in nearly all tropospheric sulfates has not been identified. Here we present high-sensitivity measurements of a fifth sulfur isotope, stratospherically produced radiosulfur, along with all four stable sulfur isotopes in the same sulfate aerosols and a suite of chemical species to define sources and mechanisms on a field observational basis. The five-sulfur-isotope and multiple chemical species analysis approach provides strong evidence that S-MIF signatures in tropospheric sulfates are concomitantly affected by two distinct processes: an altitude-dependent positive 33S anomaly, likely linked to stratospheric SO2 photolysis, and a negative 36S anomaly mainly associated with combustion. Our quadruple stable sulfur isotopic measurements in varying coal samples (formed in the Carboniferous, Permian, and Triassic periods) and in SO2 emitted from combustion display normal 33S and 36S, indicating that the observed negative 36S anomalies originate from a previously unknown S-MIF mechanism during combustion (likely recombination reactions) instead of coal itself. The basic chemical physics of S-MIF in both photolytic and thermal reactions and their interplay, which were not explored together in the past, may be another ingredient for providing deeper understanding of the evolution of Earth's atmosphere and life's origin.

Decoupling Natural and Anthropogenic Mercury and Lead Transport from South Asia to the Himalayas.

Mercury (Hg) and lead (Pb) accumulation since the Industrial Revolution has been generally observed to increase concurrently in lake sedimentary records around the world. Located downwind during the monsoon season from the rapidly developing South Asia, the Himalayas and the Tibetan Plateau are expected to receive direct anthropogenic Hg and Pb loadings, yet the source, pathway, and effects of such transport remain poorly known due to logistic challenges in accessing this region. When studying the sediment record from Lake Gokyo (4750 m above sea level (a.s.l.)) in the Himalayas, we find remarkably different Hg and Pb accumulation trends over the past 260 years. Although Hg accumulation has continued to increase since the Industrial Revolution, Pb accumulation peaked during that time and has been decreasing since then. Stable isotope analysis reveals that the decoupling trends between these two elements are due to different sources and pathways of Hg and Pb in the region. Both δ202Hg and Δ199Hg have been increasing since the Industrial Revolution, suggesting that anthropogenic Hg emissions from South Asia have been continuously increasing and that the Indian monsoon-driven wet deposition of atmospheric Hg is the dominant pathway for Hg accumulation in the sediments. In contrast, analysis of 206Pb/207Pb and 208Pb/207Pb ratios suggests that Pb accumulation in the sediments originates primarily from natural sources and that the decreasing trend of Pb accumulation is most likely due to a weakening input of atmospheric mineral dust by the westerlies. These decoupling trends highlight the ongoing issue of transboundary Hg transport to the Himalayas and the Tibetan Plateau that are source waters for major freshwater systems in Asia and calls for regional and international collaborations on Hg emission controls in South Asia.

Detection of deep stratospheric intrusions by cosmogenic 35S.

The extent to which stratospheric intrusions on synoptic scales influence the tropospheric ozone (O3) levels remains poorly understood, because quantitative detection of stratospheric air has been challenging. Cosmogenic 35S mainly produced in the stratosphere has the potential to identify stratospheric air masses at ground level, but this approach has not yet been unambiguously shown. Here, we report unusually high 35S concentrations (7,390 atoms m-3; ∼16 times greater than annual average) in fine sulfate aerosols (aerodynamic diameter less than 0.95 µm) collected at a coastal site in southern California on May 3, 2014, when ground-level O3 mixing ratios at air quality monitoring stations across southern California (43 of 85) exceeded the recently revised US National Ambient Air Quality Standard (daily maximum 8-h average: 70 parts per billion by volume). The stratospheric origin of the significantly enhanced 35S level is supported by in situ measurements of air pollutants and meteorological variables, satellite observations, meteorological analysis, and box model calculations. The deep stratospheric intrusion event was driven by the coupling between midlatitude cyclones and Santa Ana winds, and it was responsible for the regional O3 pollution episode. These results provide direct field-based evidence that 35S is an additional sensitive and unambiguous tracer in detecting stratospheric air in the boundary layer and offer the potential for resolving the stratospheric influences on the tropospheric O3 level.

Use of Isotope Effects To Understand the Present and Past of the Atmosphere and Climate and Track the Origin of Life.

Stable isotope ratio measurements have been used as a measure of a wide variety of processes, including solar system evolution, geological formational temperatures, tracking of atmospheric gas and aerosol chemical transformation, and is the only means by which past global temperatures may be determined over long time scales. Conventionally, isotope effects derive from differences of isotopically substituted molecules in isotope vibrational energy, bond strength, velocity, gravity, and evaporation/condensation. The variations in isotope ratio, such as 18 O/16 O (δ18 O) and 17 O/16 O (δ17 O) are dependent upon mass differences with δ17 O/δ18 O=0.5, due to the relative mass differences (1 amu vs. 2 amu). Relations that do not follow this are termed mass independent and are the focus of this Minireview. In chemical reactions such as ozone formation, a δ17 O/δ18 O=1 is observed. Physical chemical models capture most parameters but differ in basic approach and are reviewed. The mass independent effect is observed in atmospheric species and used to track their chemistry at the modern and ancient Earth, Mars, and the early solar system (meteorites).

Accurate Quantification of Radiosulfur in Chemically Complex Atmospheric Samples.

An ultralow-level liquid scintillation counting (LSC) technique has been used in measuring radiosulfur (cosmogenic 35S) in natural samples. The ideal half-life of 35S (∼87 days) renders it a new way to examine various biogeochemical problems. A major limitation of the technique is that complex chemical compositions in atmospheric samples may lead to color quenching of LSC cocktails, a serious problem prolonging the pretreatment time (>1 week) and hampering the accurate determination of 35S. For application of the technique where many of the most important atmospheric chemical processes are examined, significant interferences arise and accurate analysis in small samples is not possible. In this study, we optimized the LSC method to minimize/eliminate color quenching in high-sensitivity 35S measurements. The analytical performance of this new method was evaluated using control laboratory experiments and natural aerosol samples. Results show that the new method offers comparable accuracy as the traditional method for normal environmental samples [bias: <±0.03 disintegrations per minute (DPM)] and significantly shortens the pretreatment time to less than 3 days. For samples that were heavily contaminated by color-quenching agents, the accuracy of this new method is notably higher than that of the traditional method (maximum bias: -0.3 vs -1.5 DPM). With the growing use of radiosulfur in the field of Earth and planetary sciences, the accurate determination of 35S would provide a reliable field-based constraint for modeling 35S production in the atmosphere and allow a wide range of atmospheric, hydrological, and biogeochemical applications.

Simple Method for High-Sensitivity Determination of Cosmogenic 35S in Snow and Water Samples Collected from Remote Regions.

Cosmogenic 35S is useful in understanding a wide variety of chemical and physical processes in the atmosphere, the hydrosphere, and the cryosphere. The 87.4-day half-life and the ubiquity of sulfur in natural environments renders it an ideal tracer of many phenomena. Measurements of 35S in snow and water samples are scarce as existing analytical methods require a large volume of sample (>20 L) due to their high analytical activity background and low counting efficiency. Here, we present a new set of snow/water sample collecting and handling procedures for high-sensitivity determination of cosmogenic 35S using a low-level liquid scintillation spectrometer. Laboratory experiments using diluted 35S standards (with activities of <5 disintegrations per minute) showed a 35S recovery percentage of ∼95%, demonstrating a relatively small deviation from the true value. Using this method, we successfully measured 35S in ∼1 L of fresh snow sample collected from a glacier on the Tibetan Plateau to be 47 ± 7 mBq/L. On the basis of 35S activities in 9 natural samples measured in this study, a first proof-of-concept approximation for age determinations and source attributions was presented. This new method will provide a powerful tool in studying 35S in small volumes of snow and water samples, especially those from remote but climatically important regions such as the polar regions and the Tibetan Plateau and Himalayas. The measurements are particularly important as the radioactive sulfur provides an actual clock of glacial melting processes. With the growing rate of glacial loss, the need for measurements from remote locations becomes all the more important.

Antihyperglycaemic action of diosmin, a citrus flavonoid, is induced through endogenous ß-endorphin in type I-like diabetic rats.

Diosmin is one of the flavonoids contained in citrus and has been demonstrated to improve glucose metabolism in diabetic disorders. However, the mechanism(s) of diosmin in glucose regulation remain obscure. Therefore, we investigated the potential mechanism(s) for the antihyperglycaemic action of diosmin in streptozotocin-induced diabetic rats (STZ-diabetic rats). Diosmin lowered hyperglycaemia in a dose-dependent manner in STZ-diabetic rats. This action was inhibited by naloxone at a dose sufficient to block opioid receptors. Additionally, we determined the changes in plasma ß-endorphin-like immunoreactivity (BER) using enzyme-linked immunosorbent assay (ELISA). Diosmin also increased BER dose-dependently in the same manner. Repeated treatment of STZ-diabetic rats with diosmin for 1 week resulted in an increase in the expression of the glucose transporter subtype 4 (GLUT 4) in the soleus muscle and a reduction in the expression of phosphoenolpyruvate carboxykinase (PEPCK) in the liver. These effects were also inhibited by naloxone at a dose sufficient to block opioid receptors. Bilateral adrenalectomy in STZ-diabetic rats eliminated the actions of diosmin, including both the reduction in hyperglycemia and the elevation of plasma BER. In conclusion, our results suggest that diosmin may act on the adrenal glands to enhance the secretion of ß-endorphin, which can stimulate the opioid receptors to attenuate hepatic gluconeogenesis and increase glucose uptake in soleus muscle, resulting in reduced hyperglycemia in STZ-diabetic rats.

Investigation of morin-induced insulin secretion in cultured pancreatic cells.

Morin is a flavonoid contained in guava that is known to reduce hyperglycemia in diabetes. Insulin secretion has been demonstrated to increase following the administration of morin. The present study is designed to investigate the potential mechanism(s) of morin-induced insulin secretion in the MIN6 cell line. First, we identified that morin induced a dose-dependent increase in insulin secretion and intracellular calcium content in MIN6 cells. Morin potentiated glucose-stimulated insulin secretion (GSIS). Additionally, we used siRNA for the ablation of imidazoline receptor protein (NISCH) expression in MIN6 cells. Interestingly, the effects of increased insulin secretion by morin and canavanine were markedly reduced in Si-NISCH cells. Moreover, we used KU14R to block imidazoline I3 receptor (I-3R) that is known to enhance insulin release from the pancreatic ß-cells. Without influence on the basal insulin secretion, KU14R dose-dependently inhibited the increased insulin secretion induced by morin or efaroxan in MIN6 cells. Additionally, effects of increased insulin secretion by morin or efaroxan were reduced by diazoxide at the dose sufficient to open KATP channels and attenuated by nifedipine at the dose used to inhibit L-type calcium channels. Otherwise, phospholipase C (PLC) is introduced to couple with imidazoline receptor (I-R). The PLC inhibitor dose-dependently inhibited the effects of morin in MIN6 cells. Similar blockade was also observed in protein kinase C (PKC) inhibitor-treated cells. Taken together, we found that morin increases insulin secretion via the activation of I-R in pancreatic cells. Therefore, morin would be useful to develop in the research and treatment of diabetic disorders.

Characteristics, sources and health risk assessment of toxic heavy metals in PM2.5 at a megacity of southwest China.

Twenty trace elements in fine particulate matters (i.e., PM2.5) at urban Chengdu, a southwest megacity of China, were determined to study the characteristics, sources and human health risk of particulate toxic heavy metals. This work mainly focused on eight toxic heavy metal elements (As, Cd, Cr, Cu, Mn, Ni, Pb and Zn). The average concentration of PM2.5 was 165.1 ± 84.7 µg m(-3) during the study period, significantly exceeding the National Ambient Air Quality Standard (35 µg m(-3) in annual average). The particulate heavy metal pollution was very serious in which Cd and As concentrations in PM2.5 significantly surpassed the WHO standard. The enrichment factor values of heavy metals were typically higher than 10, suggesting that they were mainly influenced by anthropogenic sources. More specifically, the Cr, Mn and Ni were slightly enriched, Cu was highly enriched, while As, Cd, Pb and Zn were severely enriched. The results of correlation analysis showed that Cd may come from metallurgy and mechanical manufacturing emissions, and the other metals were predominately influenced by traffic emissions and coal combustion. The results of health risk assessment indicated that As, Mn and Cd would pose a significant non-carcinogenic health risk to both children and adults, while Cr would cause carcinogenic risk. Other toxic heavy metals were within a safe level.

Short-lived natural radionuclides as tracers in hydrogeological studies - A review.

Fundamental approaches to the study of groundwater rely on investigating the spatial and temporal distribution of stable and radioactive isotopes and other anthropogenic compounds in natural waterbodies. The most often used tracers for estimating groundwater flow paths and residence times, groundwater/surface water interaction as well as tracing chemical (contamination) sources include stable isotopes of water (δ 18O and δ 2H), radiocarbon (14C; t1/2 = 5730 a), tritium (3H; t1/2 = 12.43 a) as well as unreactive fluorine-containing gases (e.g., chlorofluorocarbons CCl3F or CFC-11; CCl2F3 or CFC-12; C2Cl3F3 or CFC-113; and SF6). While gas tracers are usually referred to as transient tracers and are appropriate for investigating modern flow systems, the isotopic tracers are often used to investigated paleo or regional flow systems. Stable isotopes of water can also be used to investigate groundwater/surface water interactions. Another, thus far been less frequently used group of groundwater tracers, are cosmo- and geo- genic short-lived radioisotopes. These isotopes are uniquely suited for studying a wide range of groundwater problems that have short time scales including high aquifer vulnerability to quantitative and qualitative impacts and groundwater discharge to surface waters. Here, we discuss and compare the applications of radio­sulphur (35S; half-life t1/2 = 87 d), radio­beryllium (7Be; t1/2 = 53 d), radio­phosphorus (32/33P; combined t1/2 = 33 d), natural tritium (3H; t1/2 = 12.43 a), radon (222Rn; t1/2 = 3.8 d) and short-lived radium (224/223Ra; combined t1/2 = 5.2 d). The paper discusses the principles of the individual tracer methods, focusing on the isotopes' input functions or values, on sampling techniques, and on methods of analyses. Case studies that applied a combined use of the tracers are referred to for readers who wish to learn more about the application of the so far underused cosmo- and geo- genic radioisotopes as aquatic tracers.

Determining coefficients in a reconstructed aerosol concentrations model from observed visibility.

A model reconstructing aerosol loading from observed visibility was proposed by Rosenfeld et al. in 2007, and it has been adopted by many researchers. The validity of original coefficients of this model was examined by a correlation analysis between visibility and PM10 concentration. The results showed that the coefficients in this model are not applicable in the region studied and they needed to be adjusted. Optimized coefficients were determined using several approaches in this study. The authors suggest that the methodology put forward by this paper would be meaningful for not only the reconstruction of long-term aerosol concentration data but also the application of the model proposed by Rosenfeld et al.

Change of air quality and its impact on atmospheric visibility in central-western Pearl River Delta.

Ambient air quality data, including atmospheric visibility, of Foshan city, a highly polluted city in the Pearl River Delta (PRD), and data obtained by the On-line Air Pollutant Exhaust Monitoring Network (OAPEMN), recently established by the National Emission Monitoring and Control Network for major industrial enterprises, were analyzed and are reported here for the first time, revealing the change in air pollution patterns and its impact on visibility degradation in the last decade. Reduced visibility of less than 8 km (after elimination of rainy and foggy periods) was found 22% of the time from 1998 to 2008, accompanied by elevated levels of pollutants, especially SO2 and PM10, in comparison with that of other developed cities. However, PM10 showed a steady decreasing trend (0.004 mg m⁻³) year⁻¹) during 2001-2008, in contrast to the noticeable increase in ambient NO2 concentrations from ~0.020 mg m⁻³ before 2005 to above 0.050 mg m⁻³ afterward. Multiple regression analysis revealed that the percentage of reduced visibility strongly correlated with PM10 concentration, suggesting that visibility degradation was directly proportional to the loading of particles. Moreover, the fairly significant correlation between reduced visibility and NO2 concentration also implied that the impact of primary emissions of NO2 and enhanced secondary pollutants, formed via photochemical processes in the atmosphere, could not be ignored. The decreased PM10levels were obviously the predominant factor for the improvement in visibility (5.0% per 0.01 mg m⁻³) and were likely due to the implementation of stricter air pollution control measures for industrial exhaust, which also resulted in reduced SO2 pollution levels in the recent 2 years. In particular, the OAPEMN records showed an overall enhanced SO2 removal by 64% in major industrial sectors. The continuous increase in road traffic and lack of efficient NO(x) control strategies in the PRD region, however, caused an increase in ambient NO2 concentrations.

Etanercept Ameliorates Cardiac Fibrosis in Rats with Diet-Induced Obesity.

Diet-induced obesity (DIO) is considered the main risk factor for cardiovascular diseases. Increases in the plasma levels of tumor necrosis factor alpha (TNF-α) is associated with DIO. Etanercept, a TNF-α inhibitor, has been shown to alleviate cardiac hypertrophy. To investigate the effect of etanercept on cardiac fibrosis in DIO model, rats on high fat diet (HFD) were subdivided into two groups: the etanercept group and vehicle group. Cardiac injury was identified by classic methods, while fibrosis was characterized by histological analysis of the hearts. Etanercept treatment at 0.8 mg/kg/week twice weekly by subcutaneous injection effectively alleviates the cardiac fibrosis in HFD-fed rats. STAT3 activation seems to be induced in parallel with fibrosis-related gene expression in the hearts of HFD-fed rats. Decreased STAT3 activation plays a role in the etanercept-treated animals. Moreover, fibrosis-related genes are activated by palmitate in parallel with STAT3 activation in H9c2 cells. Etanercept may inhibit the effects of palmitate, but it is less effective than a direct inhibitor of STAT3. Direct inhibition of STAT3 activation by etanercept seems unlikely. Etanercept has the ability to ameliorate cardiac fibrosis through reduction of STAT3 activation after the inhibition of TNF-α and/or its receptor.

Isotopic constraints on the formation pathways and sources of atmospheric nitrate in the Mt. Everest region.

Inorganic particulate nitrate (p-NO3-), gaseous nitric acid (HNO3(g)) and nitrogen oxides (NOx = NO + NO2), as main atmospheric pollutants, have detrimental effects on human health and aquatic/terrestrial ecosystems. Referred to as the 'Third Pole' and the 'Water Tower of Asia', the Tibetan Plateau (TP) has attracted wide attention on its environmental changes. Here, we evaluated the oxidation processes of atmospheric nitrate as well as traced its potential sources by analyzing the isotopic compositions of nitrate (δ15N, δ18O, and Δ17O) in the aerosols collected from the Mt. Everest region during April to September 2018. Over the entire sampling campaigns, the average of δ15N(NO3-), δ18O(NO3-), and Δ17O(NO3-) was -5.1 ± 2.3‰, 66.7 ± 10.2‰, and 24.1 ± 3.9‰, respectively. The seasonal variation in Δ17O(NO3-) indicates the relative importance of O3 and HO2/RO2/OH in NOx oxidation processes among different seasons. A significant correlation between NO3- and Ca2+ and frequent dust storms in the Mt. Everest region indicate that initially, the atmospheric nitrate in this region might have undergone a process of settling; subsequently, it got re-suspended in the dust. Compared with the Δ17O(NO3-) values in the northern TP, our observed significantly higher values suggest that spatial variations in atmospheric Δ17O(NO3-) exist within the TP, and this might result from the spatial variations of the atmospheric O3 levels, especially the stratospheric O3, over the TP. The observed δ15N(NO3-) values predicted remarkably low δ15N values in the NOx of the sources and the N isotopic fractionation plays a crucial role in the seasonal changes of δ15N(NO3-). Combined with the results from the backward trajectory analysis of air mass, we suggest that the vehicle exhausts and agricultural activities in South Asia play a dominant role in determining the nitrate levels in the Mt. Everest region.