Molecular characteristics, sources and influencing factors of isoprene and monoterpenes secondary organic aerosol tracers in the marine atmosphere over the Arctic Ocean.

Biogenic secondary organic aerosols (BSOA) are important components of the remote marine atmosphere. However, the response of BSOA changes to sea ice reduction over the Arctic Ocean remains unclear. Here we investigated isoprene and monoterpenes secondary organic aerosol (SOAI and SOAM) tracers in three years of summer aerosol samples collected from the Arctic Ocean atmosphere. The results indicated that methyltetrols were the most abundant SOAI tracers, while the main oxidation products of monoterpenes varied over the years owing to different aerosol aging. The results of the principal component analysis (PCA)-generalized additive model (GAM) combined with correlation analysis suggested that SOAI tracers were mainly generated by the oxidation of isoprene from marine emissions, while SOAM tracers were probably more influenced by terrestrial transport. Estimation of secondary organic carbon (SOC) indicated that monoterpenes oxidation contributed more than isoprene and that sea ice changes had a relatively small effect on biogenic SOC concentration levels. Our study quantified the contribution of influencing factors to the atmospheric concentration of BSOA tracers in the Arctic Ocean, and showed that there were differences in the sources of precursors for different BSOA. Hence, our findings have contributed to a better understanding of the characteristics, sources and formation of SOA in the atmosphere of the Arctic Ocean.

Occurrence and Risk Assessment of Dietary Exposure to Deoxynivalenol in Wheat-Based Products Based Different Wheat-Producing Area for the Inhabitants in Shanghai, China.

Deoxynivalenol (DON) is one of the major mycotoxins that contaminate cereals. In this study, we determined the DON level in wheat-based products from Chinese five main production areas collected in Shanghai and calculated the daily intake of DON for inhabitants using the point evaluation and the probabilistic evaluation based on Monte Carlo simulation. The results showed the positive rates of DON in the products were higher than 80.0%, with the concentrations ranging from 41.8 to 1110 µg/kg. The estimated mean daily intakes of DON for 7- to 10-year-old children and adults groups were below 1 µg/kg bw/day, the provisional maximum tolerable daily intake (PMTDI) set by the Joint FAO/WHO Expert Committee on Food Additives (JECFA), suggesting no health risks for the consumers. However, the 99th percentiles of dietary DON exposures for children and adults exceeded the PMTDI, indicating adverse health effects might occur if the two groups intake highly contaminated wheat-based products. The potential health risks for the two groups exposed to DON in the wheat-based products from the Middle and Lower Yangtze Valley (MLYV) were higher than those from the other areas in China.

Photocatalytic Degradation of Deoxynivalenol Using Cerium Doped Titanium Dioxide under Ultraviolet Light Irradiation.

Deoxynivalenol (DON) is a major mycotoxin with high toxicity that often contaminates grains, foods and feeds. The traditional approaches for DON removal are difficult to meet industry and agriculture demands due to the high stability of the DON molecule. Therefore, there is an urgent need to develop green and effective strategies for DON degradation. In this study, a batch of photocatalytic nanomaterials of cerium (Ce) doped titanium dioxide (TiO2) were successfully prepared by sol-gel method. The catalysts were systematically characterized by XRD, HRTEM, FT-IR, UV-Vis and XPS. The catalyst 0.5Ce-TiO2 showed superior photocatalytic activity for DON degradation in aqueous solution under ultraviolet light irradiation, better than that of traditional photocatalyst pure TiO2, and 96% DON with initial concentration of 5.0 mg/L could be degraded in 4 h. In addition, the two possible degradation intermediate products C5H8O3 and C17H18O6 were identified, the photocatalytic degradation mechanism and degradation pathway were studied. The results indicate that Ce doped TiO2 photocatalyst can be used to reduce DON effectively.

The observation of isotopic compositions of atmospheric nitrate in Shanghai China and its implication for reactive nitrogen chemistry.

The occurrence of PM2.5 pollution in China is usually associated with the formation of atmospheric nitrate, the oxidation product of nitrogen oxides (NOX = NO + NO2). The oxygen-17 excess of nitrate (Δ17O(NO3-)) can be used to reveal the relative importance of nitrate formation pathways and get more insight into reactive nitrogen chemistry. Here we present the observation of isotopic composition of atmospheric nitrate (Δ17O and δ15N) collected from January to June 2016 in Shanghai China. Concentrations of atmospheric nitrate ranged from 1.4 to 24.1 µg m-3 with the mean values being (7.6 ± 4.4 (1SD)), (10.2 ± 5.8) and (4.1 ± 2.4) µg m-3 in winter, spring and summer respectively. Δ17O(NO3-) varied from 20.5‰ to 31.9‰ with the mean value being (26.9 ± 2.8) ‰ in winter, followed by (26.6 ± 1.7) ‰ in spring and the lowest (23.2 ± 1.6) ‰ in summer. Δ17O(NO3-)-constrained estimates suggest that the conversion of NOX to nitrate is dominated by NO2 + OH and/or NO2 + H2O, with the mean possible contribution of 55-77% in total and even higher (84-92%) in summer. A diurnal variation of Δ17O(NO3-) featured by high values at daytime (28.6 ± 1.2‰) and low values (25.4 ± 2.8‰) at nighttime was observed during our diurnal sampling period. This trend is related to the atmospheric life of nitrate (τ) and calculations indicate τ is around 15 h during the diurnal sampling period. In terms of δ15N(NO3-), it changed largely in our observation, from -2.9‰ to 18.1‰ with a mean of (6.4 ± 4.4) ‰. Correlation analysis implies that the combined effect of NOX emission sources and isotopic fractionation processes are responsible for δ15N(NO3-) variations. Our observations with the aid of model simulation in future study will further improve the understanding of reactive nitrogen chemistry in urban regions.

The role of sulfate and its corresponding S(IV)+NO2 formation pathway during the evolution of haze in Beijing.

To better understand the role of stationary sources during the evolution of haze, we investigated sulfate formation characteristics at different stages of four haze events in Beijing, China. The mass fraction of sulfate in PM2.5 increased while that of nitrate declined slightly during the worsening process of most haze events, consistent with higher ratios of SO42-/NO3- on haze days (0.50 on average) than those on clean days (0.32 on average). Further calculations indicated that sulfate had a higher mass growth rate than nitrate during the haze-worsening process, probably due to regional transport of sulfate from heavy industrial areas accompanied by increased sulfate secondary transformation during polluted periods. We quantitatively evaluated the contribution of the S(IV) + NO2 reaction (pH-dependent) in sulfate formation during the haze evolution. The production rate (PS(IV)+NO2) of the S(IV) + NO2 pathway ranged from 1.97 × 10-4 to 5.91 (mean: 0.39) µg·m-3·h-1. Its proportion to sulfate total heterogeneous production rate (PS(IV)+NO2/Phet) was generally correlated positively with PM2.5 concentrations, indicating the relative importance of this pathway on haze days. Due to the mutual restriction between aerosol pH and aerosol liquid water content (ALWC) during haze evolution, the relative contribution of the S(IV) + NO2 pathway to sulfate heterogeneous formation was generally limited to 40%.

Composition and spatial distribution of elements and isotopes of a giant human bladder stone and environmental implications.

The composition and spatial distribution of minerals, trace elements, as well as carbon and nitrogen isotopes from the outer crust to inner nucleus of a 20-year old giant human bladder stone comprising thirteen layers were intensively investigated. Calcium oxalate monohydrate (COM) was found to concentrate in the inner and middle layers, struvite was concentrated in middle and outer layers, and fluorapatite occurred in almost all layers. The spatial distribution of minerals has the potential to provide preliminary knowledge regarding the long-term urine composition, or even the physiological condition of the patient. The stable carbon isotope ratio (δ13C) and stable nitrogen isotope ratio (δ15N) were measured in each layer and significant correlation was found between δ13C with calcium oxalate monohydrate content and between δ15N and struvite content. Nearly constant values of -23.2‰ and 7.1‰ for δ13C and δ15N, respectively, were found in the organic components of the stone. Both isotope ratios indicate a long-term fixed diet consisting mainly of C3 plants, such as rice and wheat, for the 20-year time period of the stone formation. In addition, eighteen elements (Ca, P, Mg, K, Na, Al, Fe, Zn, Pb, Cu, Sr, Ba, Ti, V, Cr, Ni, Mn and Co) were measured in all the layers. The trace elements Al, Fe, Cu, Zn, Pb, Sr, Ba and Ti showed a similar spatial distribution pattern from the outer crust to the inner core. Although there were complex correlations between elements and minerals, Factor Analysis suggests that the occurrence of these elements in stones may be mainly the result of environmental exposure to metals during the formation of the stone, indicating that urinary stones may serve as potential long-term biomonitors. In particular, Ni and Cr showed a distinct distribution pattern in the stone, which may relate to human metabolic activities.

δ(13)C-CH4 reveals CH4 variations over oceans from mid-latitudes to the Arctic.

The biogeochemical cycles of CH4 over oceans are poorly understood, especially over the Arctic Ocean. Here we report atmospheric CH4 levels together with δ(13)C-CH4 from offshore China (31°N) to the central Arctic Ocean (up to 87°N) from July to September 2012. CH4 concentrations and δ(13)C-CH4 displayed temporal and spatial variation ranging from 1.65 to 2.63 ppm, and from -50.34% to -44.94% (mean value: -48.55 ± 0.84%), respectively. Changes in CH4 with latitude were linked to the decreasing input of enriched δ(13)C and chemical oxidation by both OH and Cl radicals as indicated by variation of δ(13)C. There were complex mixing sources outside and inside the Arctic Ocean. A keeling plot showed the dominant influence by hydrate gas in the Nordic Sea region, while the long range transport of wetland emissions were one of potentially important sources in the central Arctic Ocean. Experiments comparing sunlight and darkness indicate that microbes may also play an important role in regional variations.

Systematic investigation of the toxic mechanism of PFOA and PFOS on bovine serum albumin by spectroscopic and molecular modeling.

Perfluorinated compounds (PFCs), an emerging class of globally environmental contaminations, pose a great threat to humans with wide exposure from food and other potential sources. The effects of perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) on bovine serum albumin (BSA) under normal physiological conditions were characterized by fluorescence, UV-Vis absorption, Fourier transform infrared (FT-IR) spectroscopy and molecular docking methods. The fluorescence study suggested that the fluorescence quenching of BSA by PFCs was a static procedure forming a PFCs-BSA complex. The negative values of enthalpy change (ΔH) and entropy change (ΔS) indicated that van der Waals forces and hydrogen bonds were the dominant intermolecular forces in the binding of PFCs to BSA. The displacement experiments of site markers and molecular docking revealed that the binding of PFOA to BSA took place in sub-domain IIA (Sudlow site I) whereas PFOS was mainly located in the sub-domain IIIA (Sudlow site II) and partially bound into site I. Furthermore, the results of UV-Vis and FT-IR spectra demonstrated that the microenvironment and the secondary structure of BSA were changed in the presence of PFCs. These results indicated that PFCs indeed impact the conformation of BSA and PFOS was more toxic than PFOA, which were supported by theoretical molecular modeling methods.

Potential toxicity of amphenicol antibiotic: binding of chloramphenicol to human serum albumin.

Antibiotics are widely used in daily life but their abuse has posed a potential threat to human health. To evaluate the toxicity of chloramphenicol (CAP) at the protein level, the interaction between CAP and human serum albumin (HSA) was investigated by fluorescence, Ultraviolet-visible (UV-Vis) absorption, Fourier transform infrared (FT-IR) spectroscopy and molecular docking methods. Fluorescence data revealed that the fluorescence quenching of HSA by CAP was the result of the formation of CAP-HSA complex, and the binding constant was determined to be 3.196 × 10(4) L mol(-1) at 310 K. The thermodynamic determination indicated that the interaction was driven by enthalpy change and entropy change together, where the multiple hydrogen bonds (CAP and the residues Arg 222 and His 242 of HSA) and van der Waals forces were the dominant binding force. The site marker competition revealed that CAP bound into sub-domain IIA of HSA. The binding of CAP induced the drastic reduction in α-helix conformation and the significant enhancement in ß-sheet conformation of HSA. Molecular docking study further confirmed the binding mode obtained by experimental study. This work provides a new quantitative evaluation method for antibiotics to cause the protein damage.