Random fluctuations of turbulence bring random fluctuations of the refractive index, making the atmosphere a random fluctuation medium that destroys the coherence of light-waves. Research in atmospheric turbulence is ...Random fluctuations of turbulence bring random fluctuations of the refractive index, making the atmosphere a random fluctuation medium that destroys the coherence of light-waves. Research in atmospheric turbulence is actually the investigation of the atmospheric refractive index. The atmospheric structure constant of refractive index, C n 2 , is an important parameter denoting atmospheric turbulence. In this paper, C n 2 is measured during the day and at night and in all four seasons using a high sensitivity micro-thermal meter QHTP-2. The vertical profile of C n 2 in Hefei (0-30 km) is investigated by the analysis of experimental data. The average profile of C n 2 in Hefei exhibits conspicuous day and night differences with increased altitude. The distribution of log(C n 2 ) is nearly normal and has conspicuous seasonal differences.展开更多
In this article, the NO3 radical-initiated atmospheric oxidation degradation of DDT was theoretically investigated using molecular orbital theory calculations. All the calculations of intermediates, transition states ...In this article, the NO3 radical-initiated atmospheric oxidation degradation of DDT was theoretically investigated using molecular orbital theory calculations. All the calculations of intermediates, transition states and products were performed at the MPWB1K/6-311+G(3df,2p)//MPWB1K/6- 31+G(d,p) level of theory. Several energetically favorable reaction pathways were revealed. The formation mechanisms of secondary pollutants were presented and discussed. The rate constants were deduced over the temperature range of 273-333 K using canonical variational transition-state (CVT) theory with the small curvature tunneling (SCT) method. Our study shows that H abstraction from the alkyl group and NO3 addition to the Ca atom of the benzene ring are the dominant reaction pathways. The rate-temperature formula of the overall rate constants is k(T)(DDT+NO3) = (7.21 ~ 10-15)exp(-153.81/T) cm3/(mol.sec) over the possible atmospheric temperature range of 273-333 K. The atmospheric lifetime of DDT determined by NO3 radical is about 52.5 days, which indicates that it can be degraded in the gas phase within several months.展开更多
The ozonolysis of 2,3,7,8-tetra-chlorodibenzo-p-dioxin (2,3,7,8-TCDD) is an efficient degradation way in the atmosphere. The ozonolysis process and possible reactions path of Criegee Intermediates with NO and H2O ar...The ozonolysis of 2,3,7,8-tetra-chlorodibenzo-p-dioxin (2,3,7,8-TCDD) is an efficient degradation way in the atmosphere. The ozonolysis process and possible reactions path of Criegee Intermediates with NO and H2O are introduced in detail at the method of MPWB1K/6-31+G(d,p)//MPWB1K/6- 311+G(3df,2p) level. In ozonolysis, H2O is an important source of OH radical formation and initiated the subsequent degradation reaction. The Rice-Ramsperger-Kassel-Marcus (RRKM) theory was applied to calculate rate constants with the temperature ranging from 200 to 600 K. The rate constant of reaction between 2,3,7,8-TCDD and 03 is 4.80 × 10^-20 cm3/(mole.sec) at 298 K and 760 Tort. The atmospheric lifetime of the reaction species was estimated according to rate constants, which is helpful for the atmospheric model study on the degradation and risk assessment of dioxin.展开更多
基金supported by the National High Technology Research and Development Program of China (GrantNo. 2011AA8061007)
文摘Random fluctuations of turbulence bring random fluctuations of the refractive index, making the atmosphere a random fluctuation medium that destroys the coherence of light-waves. Research in atmospheric turbulence is actually the investigation of the atmospheric refractive index. The atmospheric structure constant of refractive index, C n 2 , is an important parameter denoting atmospheric turbulence. In this paper, C n 2 is measured during the day and at night and in all four seasons using a high sensitivity micro-thermal meter QHTP-2. The vertical profile of C n 2 in Hefei (0-30 km) is investigated by the analysis of experimental data. The average profile of C n 2 in Hefei exhibits conspicuous day and night differences with increased altitude. The distribution of log(C n 2 ) is nearly normal and has conspicuous seasonal differences.
基金supported by the National Natural Science Foundation of China(No.21337001,21377073)the Independent Innovation Foundation of Shandong University(IIFSDU)(No.2012JC030)
文摘In this article, the NO3 radical-initiated atmospheric oxidation degradation of DDT was theoretically investigated using molecular orbital theory calculations. All the calculations of intermediates, transition states and products were performed at the MPWB1K/6-311+G(3df,2p)//MPWB1K/6- 31+G(d,p) level of theory. Several energetically favorable reaction pathways were revealed. The formation mechanisms of secondary pollutants were presented and discussed. The rate constants were deduced over the temperature range of 273-333 K using canonical variational transition-state (CVT) theory with the small curvature tunneling (SCT) method. Our study shows that H abstraction from the alkyl group and NO3 addition to the Ca atom of the benzene ring are the dominant reaction pathways. The rate-temperature formula of the overall rate constants is k(T)(DDT+NO3) = (7.21 ~ 10-15)exp(-153.81/T) cm3/(mol.sec) over the possible atmospheric temperature range of 273-333 K. The atmospheric lifetime of DDT determined by NO3 radical is about 52.5 days, which indicates that it can be degraded in the gas phase within several months.
基金supported by National Natural Science Foundation of China(No.21277082,21177076,71201093)the Promotive Research Fund for Excellent Young and Middle-aged Scientists of Shandong Province(No.BS2012HZ009,BS2012SF012)+2 种基金the Hi-Tech Research and Development Program(863)of China(No.2012AA06A301)the New Century Excellent Talents in University(NCET-13-0349)the Open Project from special fund of State Key Joint Laboratory of Environment Simulation and Pollution Control(No.13K05ESPCP)
文摘The ozonolysis of 2,3,7,8-tetra-chlorodibenzo-p-dioxin (2,3,7,8-TCDD) is an efficient degradation way in the atmosphere. The ozonolysis process and possible reactions path of Criegee Intermediates with NO and H2O are introduced in detail at the method of MPWB1K/6-31+G(d,p)//MPWB1K/6- 311+G(3df,2p) level. In ozonolysis, H2O is an important source of OH radical formation and initiated the subsequent degradation reaction. The Rice-Ramsperger-Kassel-Marcus (RRKM) theory was applied to calculate rate constants with the temperature ranging from 200 to 600 K. The rate constant of reaction between 2,3,7,8-TCDD and 03 is 4.80 × 10^-20 cm3/(mole.sec) at 298 K and 760 Tort. The atmospheric lifetime of the reaction species was estimated according to rate constants, which is helpful for the atmospheric model study on the degradation and risk assessment of dioxin.