Trifluoroacetic acid (TFA) in the atmosphere is produced by degradation of hydrochlorofluorocarbons and hydrofluorocarbons. In recent years, TFA has attracted global attention because of increased environmental concentrations, biological toxicity and accumulation in aqueous environments. This study focused on the mechanisms underlying the adsorption of TFA by particulate matter to identify the appropriate descriptive model for this process and thus improve estimation of TFA adsorption in future environmental monitoring. Onsite gas and particle phase sampling in Beijing, China, and subsequent measurement of TFA concentrations indicated that the TFA concentration in the gas phase (1396 ± 225 pg m−3) was much higher than that in the particle phase (62 ± 8 pg m−3) and that monthly concentrations varied seasonally with temperature. Based on the field results and analysis, an adsorption experiment of TFA on soot was then conducted at three different temperatures (293, 303, and 313 K) to provide parameters for kinetic and thermodynamic modelling. The proportion of atmospheric TFA concentration in the gas phase increased with temperature, indicating that temperature affected the phase distribution of TFA. The subsequent kinetic and thermodynamic modelling showed that the adsorption of TFA by soot could be described well by the Bangham kinetic model. The adsorption was controlled by diffusion, and the key mechanism was physical adsorption. The adsorption behavior can be well described by the Langmuir isotherm model. The calculated thermodynamic parameters ΔG° (−2.34, −1.25, and −0.15 kJ mol−1 at 293, 303, and 313 K, respectively), ΔH° (−34.34 kJ mol−1), and ΔS° (−109.22 J mol−1. K−1) for TFA adsorption by soot were negative, indicating that adsorption was a spontaneous, exothermic process.
Stratabound massive sulfide deposits are widespread along the Middle-Lower Yangtze Metallogenic Belt (MLYMB) and serve as an important copper producer in China. Two contrasting genetic models have been proposed, interpreting the stratabound massive sulfide deposits as a Carboniferous SEDEX protore overprinted by Cretaceous magmatic-hydrothermal system or an Early Cretaceous carbonate replacement deposit. These two contrasting models have been applied to the Xinqiao stratabound Cu-Au sulfide deposit, which is dominated by massive sulfide ores hosted in marine carbonates of the Carboniferous Chuanshan and Huanglong Formations, with minor Cu-Au skarn ores localized in the contact zone between the Cretaceous diorite Jitou stock and the Carboniferous carbonate rocks. New SIMS zircon U-Pb dating suggests that the Jitou stock formed at 138.5 +/- 1.1 Ma (2 sigma, MSWD = 0.6). Pyrite Re-Os dating yields an imprecise date of 142 +/- 47 Ma (2 sigma, MSWD = 7.8). The geochronological data thus constrain the mineralization of the Xinqiao deposit at Early Cretaceous.Fluid inclusions in prograde skarn diopside have homogenization temperatures of 450-600 degrees C and calculated salinities of 13-58 wt.% NaCl equiv. Quartz from the stratabound ores and pyrite-quartz vein networks beneath the stratabound ores have homogenization temperatures of 290-360 and 200-300 degrees C, with calculated salinities of 5-12 and 2-10 wt.% NaCl equiv., respectively. Quartz from the skarn ores and veins beneath the stratabound ores have delta O-18 values of 12.32 +/- 0.55 (2 SD, n = 22) and 15.57 +/- 1.92 parts per thousand (2 SD, n = 60), respectively, corresponding to calculated delta O-18 values of 622 +/- 1.59 (2 sigma) and 6.81 +/- 2.76 parts per thousand (2 sigma) for the equilibrated ore-forming fluids. The fluid inclusion and oxygen isotope data thus support a magmatic-hydrothermal origin rather than a SEDEX system for the stratabound ores, with the hydrothermal fluids most likely being derived from the Jitou stock or associated concealed intrusion. Results from this study have broad implications for the genesis and exploration of other stratabound massive sulfide deposits along the MLYMB. (C) 2016 Elsevier B.V. All rights reserved.
The effect of calcium hydroxide (Ca(OH)(2)), a promising additive to control the pollutants released during sludge pyrolysis, on the pyrolysis behavior and kinetics of sewage sludge was investigated in detail in this study. The obtained thermograms of Ca(OH)(2)-blended sludge showed that the addition of Ca(OH)(2) influenced the thermogravimetric characteristics of sludge, especially in the temperature range of 340-700 degrees C where the decomposition of Ca(OH)(2) happens. An increasing addition of Ca(OH)(2) improved the pyrolysis conversion of sludge at temperatures of more than 600 degrees C, which was verified by the increase of the process heat flow. Importantly, the transformation of elements in sludge was promoted, resulting in a lesser content of impurities, which existed mostly in the thermally stable forms, in the remaining char. Kinetic analysis revealed that the pyrolysis behavior of sludge was influenced by the addition of Ca(OH)(2) and reaction temperature. At low temperatures, Ca(OH)(2) acted as the source of nuclei required for the establishment of reaction interface and then induced the secondary cracking of the pyrolytic compounds in the sludge matrix when the reaction came to high temperatures. A retrofitted kinetic model, overcoming the drawback faced by most Arrhenius-derived models that the integral of temperature-induced item was resolved by approximation, is developed and exhibits superiority in describing the reaction characteristics of sludge pyrolysis.
This paper presents the effect of NaCl on aerobic denitrification by a novel aerobic denitrifier strain Achromobacter sp. GAD-3. Results indicated that the aerobic denitrification process was inhibited by NaCl concentrations ae<yen>20 g L-1, leading to lower nitrate removal rates (1.67 +/- 4.0 mg L-1 h(-1)), higher nitrite accumulation (50.2 +/- 87.4 mg L-1), and increasing N2O emission ratios (13 +/- 72 mg L-1/mg L-1). Poor performance of aerobic denitrification at high salinity was attributed to the suppression of active microbial biomass and electron donating capacity of strain GAD-3. Further studies on the corresponding inhibition of the denitrifying gene expression by higher salinities revealed the significant sensitivity order of nosZ (for N2O reductase) > cnorB (for NO reductase) ae nirS (for cytochrome cd(1) nitrite reductase) > napA (for periplasmic nitrate reductase), accompanied with a time-lapse expression between nosZ and cnorB based on reverse transcription and real-time quantitative polymerase chain reaction (RT-qPCR) analysis. The insights into the effect of NaCl on aerobic denitrification are of great significance to upgrade wastewater treatment plants (WWTPs) containing varying levels of salinity.
Sulfamethoxazole (SMX), as a common sulfonamide antibiotic, was reported to affect conventional anaerobic denitrification. This study presented effects of SMX on aerobic denitrification by an aerobic denitrifier strain Pseudomonas stutzeri PCN-1. Results demonstrated serious inhibition of N2O reduction as SMX reached 4 mu g/L, leading to higher N2O emission ratio (251-fold). Increase of SMX (similar to 8 mu g/L) would induce highest nitrite accumulation (95.3 mg/L) without reduction, and severe inhibition of nitrate reduction resulted in lower nitrate removal rate (0.15 mg/L/h) as SMX reached 20 mu g/L. Furthermore, corresponding inhibition of SMX on denitrifying genes expression (nosZ > nirS > cnorB > napA) was found with a time-lapse expression between nosZ and cnorB. Meanwhile, the decline in electron transport activity and active microbial biomass of strain PCN-1 was revealed. The insight into mechanism of SMX influence on aerobic denitrifier is of particular significance to upgrade nitrogen removal process in antibiotics-containing wastewater treatment plant. (C) 2017 Elsevier Ltd. All rights reserved.
Background & aims: As important virological markers, serum hepatitis B surface antigen (HBsAg) and hepatitis B virus (HBV) DNA levels show large fluctuations among chronic hepatitis B patients. The aim of this study was to reveal the potential impact and mechanisms of amino acid substitutions in small hepatitis B surface proteins (SHBs) on serum HBsAg and HBV DNA levels.
Methods: Serum samples from 230 untreated chronic hepatitis B patients with genotype C HBV were analyzed in terms of HBV DNA levels, serological markers of HBV infection and SHBs sequences. In vitro functional analysis of the identified SHBs mutants was performed.
Results: Among 230 SHBs sequences, there were 39 (16.96%) sequences with no mutation detected (wild-type) and 191 (83.04%) with single or multiple mutations. SHBs consist of 226 amino acids, of which 104 (46.02%) had mutations in our study. Some mutations (e.g., sE2G, sL21S, sR24K, sT47A/K, sC69stop (sC69∗), sL95W, sL98V, and sG145R) negatively correlated with serum HBsAg levels. HBsAg and HBV DNA levels from this group of patients had a positive correlation (r=0.61, p<0.001). In vitro analysis showed that these mutations reduced extracellular HBsAg and HBV DNA levels by restricting virion secretion and antibody binding capacity. Virion secretion could be rescued for sE2G, sC69∗, and sG145R by co-expression of wild-type HBsAg.
Conclusion: The serum HBsAg levels were lower in untreated CHB patients with novel SHBs mutations outside the major antigenic region than those without mutations. Underlying mechanisms include impairment of virion secretion and lower binding affinity to antibodies used for HBsAg measurements.
Semivolatile organic compounds (SVOCs) represent a dominant category of secondary organic aerosol precursors that are increasingly included in air quality models. In the present study, an experimental system was developed and applied to a light-duty diesel engine to determine the emission factors of particulate SVOCs (pSVOCs) and nonvolatile particulate matter (PM) components at dilution ratios representative of ambient conditions. The engine was tested under three steady-state operation modes, using ultra-low-sulfur diesel (ULSD), three types of pure biodiesels and their blends with ULSD. For ULSD, the contribution of pSVOCs to total particulate organic matter (POM) mass in the engine exhaust ranged between 21 and 85%. Evaporation of pSVOCs from the diesel particles during dilution led to decreases in the hydrogen to carbon ratio of POM and the PM number emission factor of the particles. Substituting biodiesels for ULSD could increase pSVOCs emissions but brought on large reductions in black carbon (BC) emissions. Among the biodiesels tested, tallow/used cooking oil (UCO) biodiesel showed advantages over soybean and canola biodiesels in terms of both pSVOCs and nonvolatile PM emissions. It is noteworthy that PM properties, such as particle size and BC mass fraction, differed substantially between emissions from conventional diesel and biodiesels. (C) 2017 Elsevier Ltd. All rights reserved.
Although organic compounds in marine atmospheric aerosols have significant effects on climate and marine ecosystems, they have rarely been studied, especially in the coastal regions of East China. To assess the origins of the organic aerosols in the East China coastal atmosphere, PM2.5 samples were collected from the atmospheres of the Yellow Sea, the East China Sea, and Changdao Island during the CAPTAIN (Campaign of Air PolluTion At INshore Areas of Eastern China) field campaign in the spring of 2011. The marine atmospheric aerosol samples that were collected were grouped based on the backward trajectories of their air masses. The organic carbon concentrations in the PM2,5 samples from the marine and Changdao Island atmospheres were 5.5 +/- 3.1 mu gC/m(3) and 6.9 +/- 2.4 mu gC/m(3), respectively, which is higher than in other coastal water atmospheres. The concentration of polycyclic aromatic hydrocarbons (PAHs) in the marine atmospheric PM2.5 samples was 17.0 +/- 20.2 ng/m(3), indicating significant continental anthropogenic influences. The influences of fossil fuels and biomass burning on the composition of organic aerosols in the coastal atmosphere of East China were found to be highly dependent on the origins of the air masses. Diesel combustion had a strong impact on air masses from the Yangtze River Delta (YRD), and gasoline emissions had a more significant impact on the "North China" marine atmospheric samples. The "Northeast China" marine atmospheric samples were most impacted by biomass burning. Coal combustion contributed significantly to the compositions of all of the atmospheric samples. The proportions of secondary compounds increased as samples aged in the marine atmosphere indicating that photochemical oxidation occured during transport. Our results quantified ecosystem effects on marine atmospheric aerosols and highlighted the uncertainties that arise when modeling marine atmospheric PM2.5 without considering high spatial resolution source data and meteorological parameters. (C) 2017 Published by Elsevier Ltd.
Although organic compounds in marine atmospheric aerosols have significant effects on climate and marine ecosystems, they have rarely been studied, especially in the coastal regions of East China. To assess the origins of the organic aerosols in the East China coastal atmosphere, PM2.5 samples were collected from the atmospheres of the Yellow Sea, the East China Sea, and Changdao Island during the CAPTAIN (Campaign of Air PolluTion At INshore Areas of Eastern China) field campaign in the spring of 2011. The marine atmospheric aerosol samples that were collected were grouped based on the backward trajectories of their air masses. The organic carbon concentrations in the PM2,5 samples from the marine and Changdao Island atmospheres were 5.5 +/- 3.1 mu gC/m(3) and 6.9 +/- 2.4 mu gC/m(3), respectively, which is higher than in other coastal water atmospheres. The concentration of polycyclic aromatic hydrocarbons (PAHs) in the marine atmospheric PM2.5 samples was 17.0 +/- 20.2 ng/m(3), indicating significant continental anthropogenic influences. The influences of fossil fuels and biomass burning on the composition of organic aerosols in the coastal atmosphere of East China were found to be highly dependent on the origins of the air masses. Diesel combustion had a strong impact on air masses from the Yangtze River Delta (YRD), and gasoline emissions had a more significant impact on the "North China" marine atmospheric samples. The "Northeast China" marine atmospheric samples were most impacted by biomass burning. Coal combustion contributed significantly to the compositions of all of the atmospheric samples. The proportions of secondary compounds increased as samples aged in the marine atmosphere indicating that photochemical oxidation occured during transport. Our results quantified ecosystem effects on marine atmospheric aerosols and highlighted the uncertainties that arise when modeling marine atmospheric PM2.5 without considering high spatial resolution source data and meteorological parameters. (C) 2017 Published by Elsevier Ltd.
Effects of heavy metals on aerobic denitrification have been poorly understood compared with their impacts on anaerobic denitrification. This paper presented effects of four heavy metals (Cd(II), Cu(II), Ni(II), and Zn(II)) on aerobic denitrification by a novel aerobic denitrifying strain Pseudomonas stutzeri PCN-1. Results indicated that aerobic denitrifying activity decreased with increasing heavy metal concentrations due to their corresponding inhibition on the denitrifying gene expression characterized by a time lapse between the expression of the nosZ gene and that of the cnorB gene by PCN-1, which led to lower nitrate removal rate (1.67 similar to 6.67 mg L-1 h(-1)), higher nitrite accumulation (47.3 similar to 99.8 mg L-1), and higher N2O emission ratios (5 similar to 283 mg L-1/mg L-1). Specially, promotion of the nosZ gene expression by increasing Cu(II) concentrations (0 similar to 0.05 mg L-1) was found, and the absence of Cu resulted in massive N2O emission due to poor synthesis of N2O reductase. The inhibition effect for both aerobic denitrifying activity and denitrifying gene expression was as follows from strongest to least: Cd(II) (0.5 similar to 2.5 mg L-1) > Cu(II) (0.5 similar to 5 mg L-1) > Ni(II) (2 similar to 10 mg L-1) > Zn(II) (25 similar to 50 mg L-1). Furthermore, sensitivity of denitrifying gene to heavy metals was similar in order of nosZ > nirS ae cnorB > napA. This study is of significance in understanding the potential application of aerobic denitrifying bacteria in practical wastewater treatment.
