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.     

静电场和聚乙二醇等处理对大豆种子抗吸胀冷害的促进作用的比较

用正、负高压静电场（HVEF），聚乙二醇（PEG），氯化钙（CaCl2）和二甲基亚矾（DMSO）等方法预处理大豆种子，比较种子抗低温吸胀冷害的能力结果表明：负高压静电场处理能促进膜相转变或损伤修复，并能在低温吸胀时减少无机离子，有机大分子物质的外渗；还能提高种子内自由基清除酶系的活性，促进糖原和贮存蛋白的代谢及生长调节物质的水平比较几种处理方法的效果表明：高压静电场处理主要提高自由基清除酶系和基础代谢酶的活性，而对吸胀时的膜损伤修复的促进效果较小；聚乙二醇和氯化钙则在促进种子吸胀时的睦相转变和膜损伤修复方面有显著作用所有的处理方法均在不同程度上抑制羟自由基（HO）的产生，从而减轻膜脂质过氧化的伤害.     

铬、镉、铅胁迫对青菜叶片几种生理生化指标的影响

研究了溶液培养条件下铬、镉、铅胁迫对青菜叶片细胞膜透性、叶绿素含量和游离脯氨酸含量等的影响，结果表明：随着Ｃｒ＾６＋，Ｃｄ＾２＋，Ｐｂ＾２＋处理时间的延长和处理浓度的增加，青菜叶片细胞膜透性显著增大，叶绿素ａ／ｂ值逐渐降低，游离脯氨酸含量明显增加，其中游离脯氨酸含量增加的时间比细胞膜透性增大明显超前，而叶绿素ａ／ｂ植降低的时间在这３种重金属中未见明显的规律性。     

Ca5（AsO4）3OH的溶解度与稳定性研究

通过在不同pH值,温度等条件下Ca5（AsO4）3OH的溶解,确定其稳定存在的pH值范围,得出它的溶度积和生成的自由能（ΔG0f）。结果表明,Ca5（AsO4）3OH在水中的溶解度和稳定范围与pH和温度有关,在酸性条件下（初始pH=2）它的溶解度较大,而且在水中的溶解度随着温度的升高而降低。利用PHREEQC程序计算确定Ca5（AsO4）3OH的溶度积为10-40.86,生成自由能ΔG0f为-5 063.53 kJ/mol。利用JADE5软件计算得到其晶格参数a=b=9.696,c=6.967和晶胞体积为567.304 3。     

重庆市无公害蔬菜基地环境和产品质量评价标准初探

通过对重庆市环境污染情况的调查分析 ,结合现行的国家相关环境质量标准和食品卫生标准 ,提出了适合重庆市无公害蔬菜基地建设的环境质量和产品质量评价标准体系 ,为建立规范化、标准化绿色蔬菜基地打下了基础     

N,N-二乙基对苯二胺分光光度法测定饮用水中的游离余氯

文中采用N,N-二乙基对苯二胺分光光度法测定饮用水中的游离余氯,实验结果表明,该方法可以准确测定水中的游离余氯且有好的线性,相关系数大于99%。方法检测限为0.01 mg/L,相对标准偏差为2.47～9.08%,回收率在92.5～105%之间,检测方法符合《生活饮用水卫生标准》(GB 5749-2006)的要求。     

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.