Theoretical study on the formation mechanism of polychlorinated dibenzothiophenes/thianthrenes from 2-chlorothiophenol molecules

Homogeneous formation of polychlorinated dibenzothiophenes/thianthrenes(PCDT/TAs),sulfurated compounds analogous to polychlorinated dibenzo-p-dioxin/dibenzofurans(PCDD/Fs), has been well-documented to occur via radical–radical coupling reactions from chlorinated thiophenol precursors. However, the current understanding of the formation mechanism of PCDT/TAs is exclusively limited to the inherent point of view that chlorothiophenoxy radicals act as the only required intermediates for PCDT/TAs. This study investigates reaction pathways for the formation of PCDT/TAs involving two new types of radical species, i.e., substituted phenyl radicals and substituted thiophenoxyl diradicals. Taking 2-chlorothiophenol(2-CTP) as a model compound for chlorothiophenols,we found that apart from the mostly discussed chlorothiophenoxy radicals, substituted phenyl radicals and substituted thiophenoxyl diradicals could also be readily formed via the reaction of 2-CTP with H radicals. Furthermore, direct self-and cross-coupling of these radicals can result in the formation of PCDT/TAs, including 1-monochlorothianthrene(1-MCTA), 1,6-dichlorothianthrene(1,6-DCTA), 4,6-dichlorodibenzothiophene(4,6-DCDT)and 1,6-dichlorodibenzothiophene(1,6-DCDT). The pathways proposed in this work are proven to be both thermodynamically and kinetically favorable. Particularly, comparisons were made between the formation mechanisms of sulfurated and oxygenated dioxin systems from an energetic point view, showing that replacing oxygen with sulfur atoms greatly reduces the activation barriers of the rate-controlling steps involved in the PCDT/TA formation processes compared with those involved for PCDD/Fs. The calculated results in this work may improve our understanding of the formation mechanism of PCDT/TAs from chlorothiophenol precursors and should be informative to environmental scientists.     

Decomposition of Al13 promoted by salicylic acid under acidic condition: Mechanism study by differential mass spectrometry method and DFT calculation

Decomposition of the polycation Al₁₃O₄(OH)₂₄(H₂O)₁₂⁷⁺ (Al₁₃) promoted by ligand is a vital subject to advance our understanding of natural and artificial occurrence and evolution of aluminum ions, especially in the case of acidic condition that dissolved Al³⁺ species can be released from the Al-bearing substances. However, the microscopic pathway of synchronous proton-promoted and ligand-promoted decomposition process for Al₁₃ is still in the status of ambiguity. Herein, we applied differential mass spectrometry method and DFT calculation to study the initial detailed process of Al₁₃ decomposition under the presence of proton and salicylic acid (H₂Sal). Mass results showed that the mononuclear Al³⁺-H₂Sal complexes dominated the resulting Al species, whereas the monodentate complex Al₁₃HSal⁶⁺ was not observed in the spectra. The difference of decomposition levels between the ligand/Al ratio 0.2 and 0.5 cases revealed that proton and ligand performed synergistic effect in initial Al₁₃ decomposition process, and the proton transfer determined the ring closure efficiency. The ring closure reaction is the prerequisite for the collapse of Al₁₃ structure and detachment of the mononuclear complex. DFT calculations reveal that hydrogen bond plays an important role in inducing the formation of chelated complex accompanying proton transfer. Attachment of protons at the bridging OH⁻ can elongate and weaken the critical bond between targeted Al³⁺ and µ₄-O^2- resulting from delocalization of electron pairs in the oxygen atom. These results demonstrate the detailed mechanism of Al₁₃ composition promoted by ligand and proton, and provide significant understanding for further application and control of Al₁₃.     

交通事故发生规律与城市道路系统的规划设计研究

笔者分析了城市交通事故发生率与道路等级、道路断面形式、路网密度、交叉口形式、道路车速的关系及交通事故人群的分布规律,认为道路宽而稀、支路缺乏、街道功能不清是我国城市道路网与用地微观布局的基本特点。大量数据分析表明,这种路网体系与我国的城市交通事故率偏高有着密切关系。路网规划是城市路网建设的基本依据,笔者认为,应当将降低城市交通事故率作为路网规划的考虑内容之一,同时指出,应在路网规划中合理选择道路断面形式、交叉口形式,建议适度加密路网、健全支路体系、理清街道功能,并考虑城市道路的车速控制与驾驶心态调整。     

WATERSHED AND INSTREAM IMPACTS ON THE FISH POPULATION IN THE SOUTH FORK OF THE CLEARWATER RIVER,IDAHO1

ABSTRACT: This paper presents the results of a statistical analysis performed for the watershed and stream corridor in the South Fork of the Clearwater River (SFCR) basin, in north central Idaho. The analysis was performed for 61 six‐field hydrological unit codes (HUCs) of the SFCR basin using an extensive record (up to 100 years) for 50 watershed and in‐stream parameters, including hydrologic, flow, fish, anthropogenic, and natural activity data. The objective of this research was twofold: first, the development of quantitative relations that describe the Index of Fish Density (IFD) of particular fish species as a function of watershed and instream parameters; and second, to provide a robust confirmation for the effects of some of these parameters, previously recorded by the fisheries profession, by using well established statistical techniques. The uniqueness of this work is the compilation and statistical analysis of large data sets to quantitatively describe the impacts of watershed and instream parameters on the IFD of all salmonids and specific fish species. Factor analysis was employed to regroup parameters that are highly correlated to each other into a set of single factors and to relate the IFD to these factors. Using factor extraction, 12 factors were developed from the 50 watershed and instream parameters. Multiple regression diagnostic tests indicated that only 7 of the 12 factors are strong predictors offish indicators. The strongest predictors are longitude, latitude, elevation, watershed gradient, and water temperature. The analysis indicated that the present model has reasonable predictive power, considering the uncertainty involved in estimating the interdependence of IFD with watershed parameters.     

不同香蒲种植密度对模拟污水的净化试验研究

在不同种植密度处理下,研究香蒲净化污染水体的去除效果。结果表明：种植密度和处理效果成正比,密度为27株/㎡时,净化效果最好,氨氮、TP、TN的去除率分别为94．81％、77．42％、82．84％。     

饥饿期间增加曝气量好氧颗粒污泥的形成特点

高有机负荷率8.0kgCOD(/m3·d)条件下,通过两种不同的曝气方式研究好氧颗粒污泥的形成特点,即在反应器R1中采用恒定的曝气流量,而在反应器R2中,30min曝气后,进行沉淀和排水,然后采用较大的曝气流量进行曝气。研究发现:(1)外部基质在前30min被快速降解,其溶解性有机碳DOC基本被消耗到最低水平;(2)在中途排水后的饥饿状态下增加曝气量的反应器R2相对于曝气量一直不变且中途未排水的R1而言,颗粒变的大而疏松,即:在R2中颗粒尺寸>0.9mm占有93%,而颗粒密度均<1.016g/mL。(3)反应器R2在饥饿状态下增加曝气量可以使胞外多聚物(EPS)糖类被当作基质被消耗。     

Decomposition of 2,2',4,4',5,5'-hexachlorobiphenyl with iron supported on an activated carbon from an ion-exchange resin

An activated carbon (AC) containing a high concentration (374 mg g⁻¹) of Fe was prepared by carbonization of an ion-exchange resin. To examine its chemical reactivity as a catalyst to decompose 2,2′,4,4′,5,5′-hexachlorobiphenyl (PCB-153), the decomposition parameters of temperature and time were varied under air or N₂. Decomposition at 350 °C was achieved within 15 min under air and 30 min under N₂, and the efficiency of PCB-153 decomposition was 99.7% and 98.0%, respectively. An analysis of inorganic chloride ions revealed that PCB-153 was mineralized effectively during the decomposition. The Brunauer-Emmett-Teller (BET) surface area and pore volume of the AC were measured to assess the adsorption capacity before and after the decomposition. The differences between decomposition under air and N₂ reflected the differences in the BET surface and pore volume measurements. A decomposition pathway was postulated, and the reactive characteristics of chlorine atoms loaded on the benzene rings followed the order of para > meta > ortho, which agrees with the calculated results from a density functional theory study.     

浮油自动回收设备两例

油和水物理性能的差异是设计浮油回收设备的基础。依据两者导电率差异研制出全自动浮油回收机,适用于粘度较低的浮油回收。利用两者粘度的不同,生产出收油效率较高的盘片式自动浮油回收设备,特别适合于粘度较高的浮油回收。     

Refinement of the density-modified displacement method for efficient treatment of tetrachloroethene source zones

A novel method to remediate dense nonaqueous phase liquid (DNAPL) source zones that incorporates in situ density conversion of DNAPL via alcohol partitioning followed by displacement with a low interfacial tension (IFT) surfactant flood has been developed. Previous studies demonstrated the ability of the density-modified displacement (DMD) method to recover chlorobenzene (CB) and trichloroethene (TCE) from heterogeneous porous media without downward migration of the dissolved plume or free product. However, the extent of alcohol (n-butanol) partitioning required for in situ density conversion of high-density NAPLs, such as tetrachloroethene (PCE), could limit the utility of the DMD method. Hence, the objective of this study was to compare the efficacy of two n-butanol delivery approaches: an aqueous solution of 6% (wt) n-butanol and a surfactant-stabilized macroemulsion containing 15% (vol) n-butanol in water, to achieve density reduction of PCE-NAPL in two-dimensional (2-D) aquifer cells. Results of liquid-liquid equilibrium studies indicated that density conversion of PCE relative to water occurred at an n-butanol mole fraction of 0.56, equivalent to approximately 5 ml n-butanol per 1 ml of PCE when in equilibrium with an aqueous solution. In 2-D aquifer cell studies, density conversion of PCE was realized using both n-butanol preflood solutions, with effluent NAPL samples exhibiting density reductions ranging from 0.51 to 0.70 g/ml. Although the overall PCE mass recoveries were similar (91% and 93%) regardless of the n-butanol delivery method, the surfactant-stabilized macroemulsion preflood removed approximately 50% of the PCE mass. In addition, only 1.2 pore volumes of the macroemulsion solution were required to achieve in situ density conversion of PCE, compared to 6.4 pore volumes of the 6% (wt) n-butanol solution. These findings demonstrate that use of the DMD method with a surfactant-stabilized macroemulsion containing n-butanol holds promise as an effective source zone remediation technology, allowing for efficient recovery of PCE-DNAPL while mitigating downward migration of the dissolved plume and free product.     

Examining the colonization process of exotic species varying in competitive abilities using a cellular automaton model

Current threats of invasive species have significant implications for ecological systems. Given their potential impacts, invasive species have been the subject of extensive empirical and theoretical studies. However, these studies have tended to focus on species that produce highly visible ecological and economic impacts. In our study, we take a step back from focusing on these high-impact invasive species, and examine the general colonization (invasion) process of exotic species that have various “competitive abilities” against the native species. Using a two-species cellular automaton model, we demonstrate that: (1) a threshold level of competitive ability is required for the exotic species to successfully establish in a new landscape and (2) an exotic species with superior competitive ability does not necessarily become dominant in a landscape (alternatively, a species that has inferior competitive ability may successfully colonize a new system). Our findings have significant implications for the study of species invasions and also provide clues to how species assemble in ecological communities.