This study presents new insight into the photochemical degradation of polybrominated diphenyl ethers (PBDEs), and it provides details about the structures and properties of 27 PBDE congeners in the electronically excited state using the time-dependent density functional theory method. Each PBDE congener exhibited remarkably different geometries in the ground state and the excited state. The significant lengthening of C-Br bond in each PBDE congener was observed in the excited state for the first time by theoretical calculation, which is directly involved in the photochemistry reductive debromination of n-BDE to (n−1)-BDE. Generally, the lengthening of C-Br bonds cannot occur at the para position. Furthermore, the calculated results demonstrated that the photoreactivity of PBDEs increased with an increase of bromination degree. It was also found that the pattern of Br substituents had an effect upon the photoreactivity of PBDEs. These findings suggest that the information obtained in the excited state is crucial to the mechanism explanation of the photochemical degradation of PBDEs. 相似文献
Human activities have increased anthropogenic CO2 emissions, which are believed to play important roles in global warming. The spatiotemporal variations of CO2 concentration and flux at fine spatial scales in aquaculture ponds remain unclear, particularly in China, the country with the largest aquaculture. In this study, the plot-scale spatiotemporal variations of water CO2 concentration and flux, both within and among ponds, were researched in shrimp ponds in Shanyutan Wetland, Min River Estuary, Southeast China. The average water CO2 concentration and flux across the water–air interface in the shrimp ponds over the shrimp farming period varied from 22.79?±?0.54 to 186.66?±?8.71 μmol L?1 and from ??0.50?±?0.04 to 2.87?±?0.78 mol m?2 day?1, respectively. There was no remarkable difference in CO2 concentration and flux within the ponds, but significantly spatiotemporal differences in CO2 flux were observed between shrimp ponds. Chlorophyll a, pH, salinity, air temperature, and morphometry were the important factors driving the spatiotemporal patterns of CO2 flux in the shrimp ponds. Our findings highlighted the importance and spatiotemporal variations of CO2 flux in the important coastal ecosystems.
Occurrence and removal efficiencies of fifteen pharmaceuticals were investigated in a conventional municipal wastewater treatment plant in Michigan. Concentrations of these pharmaceuticals were determined in both wastewater and sludge phases by a high-performance liquid chromatograph coupled to a tandem mass spectrometer. Detailed mass balance analysis was conducted during the whole treatment process to evaluate the contributing processes for pharmaceutical removal. Among the pharmaceuticals studied, demeclocycline, sulfamerazine, erythromycin and tylosin were not detected in the wastewater treatment plant influent. Other target pharmaceuticals detected in wastewater were also found in the corresponding sludge phase. The removal efficiencies of chlortetracycline, tetracycline, sulfamerazine, acetaminophen and caffeine were >99%, while doxycycline, oxytetracycline, sulfadiazine and lincomycin exhibited relatively lower removal efficiencies (e.g., <50%). For sulfamethoxazole, the removal efficiency was approximately 90%. Carbamazepine manifested a net increase of mass, i.e. 41% more than the input from the influent. Based on the mass balance analysis, biotransformation is believed to be the predominant process responsible for the removal of pharmaceuticals (22% to 99%), whereas contribution of sorption to sludge was relatively insignificant (7%) for the investigated pharmaceuticals. 相似文献
In regions with high livestock densities, the usage of antibiotics and metals for veterinary purposes or as growth promoters poses a risk in manured soils. We investigated to which degree the concentrations and depth distributions of Cu, Zn, Cr and As could be used as a tracer to discover contaminations with sulfonamides, tetracyclines and fluoroquinolones. Besides, we estimated the potential vertical translocation of antibiotics and compared the results to measured data. In the peri-urban region of Beijing, China, soil was sampled from agricultural fields and a dry riverbed contaminated by organic waste disposal. The antibiotic concentrations reached 110 μg kg?1 sulfamethazine, 111 μg kg?1 chlortetracycline and 62 μg kg?1 enrofloxacin in the topsoil of agricultural fields. Intriguingly, total concentrations of Cu, Zn, Cr and As were smaller than 65, 130, 36 and 10 mg kg?1 in surface soil, respectively, therewith fulfilling Chinese quality standards. Correlations between sulfamethazine concentrations and Cu or Zn suggest that in regions with high manure applications, one might use the frequently existing monitoring data for metals to identify potential pollution hotspots for antibiotics in topsoils. In the subsoils, we found sulfamethazine down to ≥2 m depth on agricultural sites and down to ≥4 m depth in the riverbed. As no translocation of metals was observed, subsoil antibiotic contamination could not be predicted from metal data. Nevertheless, sulfonamide stocks in the subsoil could be estimated with an accuracy of 35–200 % from fertilisation data and potential leaching rates. While this may not be sufficient for precise prediction of antibiotic exposure, it may very well be useful for the pre-identification of risk hotspots for subsequent in-depth assessment studies. 相似文献
This work explored the influences of the drying and calcination temperatures on a Ce-Cu-Al trimetallic composite catalyst for the simultaneous removal of H2S and PH3. The effects of both temperatures on the structural features and activity were examined. The density functional theory method was used to calculate adsorption energies and further analyze their adsorption behavior on different slabs. Experiments revealed suitable drying and calcination temperatures to be 60 and 500°C, respectively. The capacity reached 323.8 and 288.1 mg/g. Adjusting drying temperature to 60°C is more inclined to form larger and structured grains of CuO. Rising calcinating temperature to 500°C could increase the grain size and redox capacity of CuO to promote performance. Higher temperatures would destroy the surface structure and lead to a crystal phase transformation, which was that the CuO and Al2O3 were gradually recombined into CuAl2O4 with a spinel structure. The exposed crystal planes of surficial CuO and CuAl2O4 were determined according to characterization results. Calculation results showed that, compared with CuO (111), H2S and PH3 have weaker adsorption strength on CuAl2O4 (100) which is not conducive to their adsorption and removal. 相似文献
正Anthropogenic emissions impact significantly the atmospheric environment which human being relies on,e.g.,global warming,stratospheric ozone depletion,photochemical smog,acid rain,haze and so on.Although clean air actions have been legislated by many nations to mitigate pollutants’emission with the aim of protecting the atmospheric environment, 相似文献