大气环境中OH自由基测定

采用自旋捕集技术和电子自旋共振法结合测定大气环境中ＯＨ自由基，首先用自旋捕集剂将ＯＨ自由基捕集，生成比较稳定的自然旋加合物，，然后带回实验室处理测定，该法为开展大气光化学研究提供了一种采样方便，利于实测的方法，据３个采样点的实测结果表明，相对误差约为３５％，比文献所示结果略大。     

Role of interfacial electron transfer reactions on sulfamethoxazole degradation by reduced nontronite activating H2O2

It has been documented that organic contaminants can be degraded by hydroxyl radicals ( • OH) produced by the activation of H₂ O₂ by Fe(II)-bearing clay. However, the interfacial electron transfer reactions between structural Fe(II) and H 2 O 2 for • OH generation and its effects on contaminant remediation are unclear. In this study, we first investigated the relation between • OH generation sites and sulfamethoxazole (SMX) degradation by activating H₂O₂ using nontronite with different reduction extents. SMX (5.2–16.9 μmol/L) degradation first increased and then decreased with an increase in the reduction extent of nontronite from 22% to 62%, while the • OH production increased continually. Passivization treatment of edge sites and structural variation results revealed that interfacial electron transfer reactions between Fe(II) and H 2 O 2 occur at both the edge and basal plane. The enhancement on basal plane interfacial electron transfer reactions in a high reduction extent rNAu-2 leads to the enhancement on utilization efficiencies of structural Fe(II) and H 2 O 2 for • OH generation.However, the • OH produced at the basal planes is less efficient in oxidizing SMX than that of at edge sites. Oxidation of SMX could be sustainable in the H 2 O 2 /rNAu-2 system through chemically reduction. The results of this study show the importance role of • OH generation sites on antibiotic degradation and provide guidance and potential strategies for antibiotic degradation by Fe(II)-bearing clay minerals in H 2 O 2 -based treatments.     

自由飞行下基于航空器定位误差修正的碰撞风险研究

自由飞行能够提高空域容量从而缓解空域拥挤问题,在保障自由飞行安全性的基础上尽可能减小飞机的安全间距,需要研究自由飞行条件下飞机的安全评估问题。分析了所需CNS性能、防撞系统、风的因素等自由飞行下航空器定位误差的影响因素,考虑到航空器定位误差在短时间内具有累积性,提出采用INS、GPS数据融合算法对定位误差进行周期性修正。给出修正后的航空器定位误差分布在时间上的变化规律,并将其运用到自由飞行下碰撞风险评估中。结果表明,碰撞风险随安全间距增加呈下降趋势,以1.5×10-8次/飞行小时的目标安全水平为例,对航空器定位误差修正的最小安全间距为8 600 m,不对航空器定位误差进行修正的最小安全间距为9 100 m。     

Driver speed selection on high-speed two-lane highways: Comparing speed profiles between uniform and differential speed limits

Objective: Although a considerable amount of prior research has investigated the impacts of speed limits on traffic safety and operations, much of this research, and nearly all of the research related to differential speed limits, has been specific to limited access freeways. The unique safety and operational issues on highways without access control create difficulty relating the conclusions from prior freeway-related speed limit research to 2-lane highways, particularly research on differential limits due to passing limitations and subsequent queuing. Therefore, the objective of this study was to assess differences in driver speed selection with respect to the posted speed limit on rural 2-lane highways, with a particular emphasis on the differences between uniform and differential speed limits.

Methods: Data were collected from nearly 59,000 vehicles across 320 sites in Montana and 4 neighboring states. Differences in mean speeds, 85th percentile speeds, and the standard deviation in speeds for free-flowing vehicles were examined across these sites using ordinary least squares regression models.

Results: Ultimately, the results of the analysis show that the mean speed, 85th percentile speed, and variability in travel speeds for free-flowing vehicles on 2-lane highways are generally lower at locations with uniform 65 mph speed limits, compared to locations with differential limits of 70 mph for cars and 60 mph for trucks.

Conclusions: In addition to posted speed limits, several site characteristics were shown to influence speed selection including shoulder widths, frequency of horizontal curves, percentage of the segment that included no passing zones, and hourly volumes. Differences in vehicle speed characteristics were also observed between states, indicating that speed selection may also be influenced by local factors, such as driver population or enforcement.     

游离亚硝酸抑制硝化杆菌属(Nitrobacter)活性动力学研究

为探究游离亚硝酸（FNA）对亚硝酸盐氧化细菌中硝化杆菌属（Nitrobacter）活性抑制动力学影响,采用序批式活性污泥（SBR）反应器,在通过改变系统进水FNA浓度达到富集Nitrobacter基础上,以富含Nitrobacter污泥为对象（宏基因组物种注释和丰度分析显示上Nitrobacter占细菌总数40.3%）,基于批次试验,考察不同FNA浓度梯度下亚硝酸盐氧化过程比亚硝态氮氧化速率（SNiOR）变化规律,进而拟合FNA抑制Nitrobacter活性抑制动力学模型,并进行统计学分析.结果表明,当FNA≤0.1mg/L时,随着FNA浓度升高,SNiOR迅速升高.当FNA>0.1mg/L时,SNiOR随着FNA浓度升高而降低.尤其当FNA浓度高于0.7mg/L时,SNiOR始终维持在0gN/（gVSS·d）,表明Nitrobacter活性统被完全抑制.统计学分析结果显示相对于Haldane、Aiba、Edwards-1#、Edwards-2#、Luong抑制动力学模型,Han-Levenspiel模型最适合描述FNA对Nitrobacter活性的抑制影响.其统计学常数：残差平方和（RSS）为0.02、可决系数（R²）为0.90、拟合方程的方差检验统计量F值为78.1、可信度P值为3.29×10^-12,其动力学常数值分别为：最大比亚硝态氮氧化速率（r_max）为1.57gN/（gVSS·d）;半饱和常数（K_S）为0.01mg/L;临界抑制常数（S_m）为0.66mg/L.     

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.     

Free ‐ living animals as indicators of environmental pollution by chlorinated hydrocarbons

As some species of game and free‐living animals promptly respond to ecosystem damage by a reaction that is easy to interpret, they are important ecological indicators in assessing the total contamination of the environment. Consumers of the highest order like predators, predatory and fish‐eating birds are among the most important bioindicators of environmental contamination by chlorinated hydrocarbons and PCB.

Data on chlorinated hydrocarbons and PCB levels were collected throughout 1988–1992 and obtained from 16 species of free‐living animals from 9 protected areas of Slovakia. Muscle tissue, liver, kidney and egg samples were examined for HCB, HCH isomers, DDT and its analogues, and PCB.

Levels of organic chlorinated contaminants reveal a decreasing tendency and thus cease to be a toxicologically important risk factor in game, with the exception of predatory birds, as significant values have been recorded in their eggs and reproductive organs.     

超声、过硫酸钾协同去除水中诺氟沙星的效果

过硫酸钾活化可产生强氧化性硫酸根自由基(SO-4·),采用超声/过硫酸钾体系氧化降解诺氟沙星,考察了过硫酸钾浓度、诺氟沙星初始浓度、溶液初始p H值及自由基淬灭剂甲醇、叔丁醇对降解效果的影响.结果表明,超声/过硫酸钾体系能够显著降解和矿化诺氟沙星,与单独过硫酸钾、超声相比,超声/过硫酸钾对诺氟沙星的去除率分别提高了3.2和8.9倍,降解过程符合一级反应动力学.诺氟沙星的去除率随过硫酸钾浓度的增加趋于平缓.p H对诺氟沙星的降解影响较大,这是因为随p H的升高,体系中的氧化性物种由SO-4·转化为以SO-4·/HO·为主.TOC去除和大肠杆菌抗菌实验表明,反应180 min,超声/过硫酸钾能够实现49.12%的诺氟沙星矿化,且对大肠杆菌的抑菌圈直径由45 mm减小到14 mm(滤纸直径),完全去除其抗菌性.结果表明超声/过硫酸钾能够有效用于诺氟沙星废水处理.