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An understanding of the reaction mechanism of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) formation is crucial for any attempt to prevent PCDD/Fs formation. Among the polychlorophenols, 2,4,5-trichlorophenol (2,4,5-TCP) has the minimum number of CI atoms needed to form 2,3,7,8-tetrachlorinated dibenzo-p-dioxin (2,3,7,8-TeCDD), which is the most toxic among all 210 PCDD/F isomers. Experiments on the formation of PCDD/Fs from the 2,4,5-TCP precursor have been hindered by the strong toxicity of 2,3,7,8-TeCDD. In this work, we carried out molecular orbital theory calculations for the homogeneous gas-phase formation of PCDD/Fs from the 2,4,5-TCP precursor. Several energetically favorable formation pathways were revealed for the first time. The rate constants of crucial elementary steps were deduced over a wide temperature range of 600-1200 K, using canonical variational transition state theory with small curvature tunneling contribution. The rate temperature formulas were fitted. This study shows that the formation of polychlorinated dibenzo-p-dioxins (PCDDs) from the 2,4,5-TCP precursor is preferred over the formation of polychlorinated dibenzofurans (PCDFs). The chlorine substitution pattern has a significant effect on the dimerization of chlorophenoxy radicals.

The chlorophenoxy radical (CPR) is a key intermediate species in the formation of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). In municipal waste incinerators, the reactions of chlorophenols with OH radicals play the most central role in the formation of chlorophenoxy radicals. In this paper, molecular orbital theory calculations have been performed to investigate the formation of chlorophenoxy radicals from the complete series reactions of 19 chlorophenol congeners with OH radicals. The single-point energy calculation was carried out at the MPWB1K/6-311+G(3df,2p) level on the basis of the MPWB1K/6-31+G(d,p) optimized geometries. The kinetic modeling of the PCDD/PCDF (PCDD/F for short) formation demands the knowledge of the rate parameters for the formation of chlorophenoxy radicals from chlorophenols. So, the kinetic properties of the reactions of chlorophenols with OH radicals were deduced over a wide temperature range of 600-1200 K using canonical variational transition-state theory (CVT) with small curvature tunneling contribution (SCT). This study shows that the chlorine substitution at the ortho position in chlorophenol not only has a significant effect on the structures of chlorophenols, prereactive intermediates, the transition states, and chlorophenoxy radicals, but also plays a decisive role in determining the rate parameters.

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The United States Geological Survey (USGS) reports that U.S. water withdrawals have been steady since 1980, but the population and economy have grown since then. This implies that other factors have contributed to offsetting decreases in water withdrawals. Using water withdrawal data from USGS and economic data from Bureau of Economic Analysis (BEA), direct and total water withdrawals were estimated for 134 industrial summary sectors in the 1997 U.S. economic input-output (EIO) table and 136 industrial sectors in the 2002 EIO table. Using structural decomposition analysis (SDA), the change in water withdrawals for the economy from 1997 to 2002 was allocated to changes in population, GDP per capita, water use intensity, production structure, and consumption patterns. The changes in population, GDP per capita, and water use intensity led to increased water withdrawals, while the changes in production structure and consumption patterns decreased water withdrawals from 1997 to 2002. Consumption patterns change was the largest net contributor to the change in water withdrawals. The model was used to predict aggregate changes in total water withdrawals from 2002 to 2010 due to known changes in population and GDP per capita; a more complete model assessment must await release of updated data on USGS water withdrawals and EIO data.

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Abstract-A low radar cross section (RCS) microstrip antenna is proposed and investigated in this letter. This design is based on implementation of frequency selective surfaces (FSSs) and microstrip resonators. By using the FSS ground instead of the solid metal ground, out-of-band RCS reduction can be realized. Moreover, in-band RCS reduction can be obtained by loading microstrip resonators. Significant RCS reduction has been accomplished in the frequency ranges of 3-10GHz. Compared with the reference antenna, the simulation results show that RCS reduction of the proposed antenna in and out of the operation band is as much as 13dB and 17dB, respectively. Measured results satisfactorily agree with the simulated ones. Radiation performance of the proposed antenna is preserved compared with the reference antenna.Index Terms-Microstrip resonator, frequency selective surface, microstrip patch antenna, radar cross section reduction.