nZVI@mesoSiO2的可控合成及应用性能研究

采用改进的两步法在原位基础上合成了以纳米零价铁(nano Zero Valent Iron,nZVI)为核芯的核壳型介孔二氧化硅(nZVI@mesoSiO_2).同时,通过简单地调控铁源用量得到具有单一nZVI核芯和不同壳层厚度的核壳型纳米复合材料.结果发现,铁源用量的增加会导致核芯尺寸减小、壳层厚度增加及颗粒比表面积下降.当铁源用量为2.78 g时,得到的nZVI@mesoSiO_2不仅具有较高的比表面积和单一且均匀的孔径分布,而且对2,4,6-三氯苯酚(2,4,6-Trichlorophenol, 2,4,6-TCP)的去除表现出很高的性能.影响因素实验表明,材料的最佳投加量为1.0 g·L~(-1),体系适宜初始pH为5.0,污染物初始浓度升高会导致去除效果下降,并且反应体系内乙二胺四乙酸(EDTA)的存在可以提高2,4,6-TCP的去除率.材料的重复利用实验结果表明,经过多次循环反应后会导致材料nZVI核芯的失活和孔道的堵塞.本研究不仅为制备可控壳层厚度的核壳型介孔材料提供了理论指导,而且为进一步改性合成对2,4,6-TP具有高选择性的复合材料提供了依据.     

Radical/radical vs radical/molecule reactions in the formation of PCDD/Fs from (chloro)phenols in incinerators

Pathways from chlorinated phenols as precursors to PCDD/Fs are discussed with focus on the effect of (poly)chlorination on thermochemistry and rate in the displacement of chlorine from a chlorophenol molecule by a (chloro)phenoxy radical (reaction (A) as a key example). Through measurements on the respective methylethers (anisoles) the O-H bond of 2,4,6-TCP turns out to be 5 kcal/ mol, and that in PCP 4 kcal/mol, less strong than O-H in phenol itself. On this basis it is concluded that-in contrast with earlier proposals--displacements such as in reaction (A) are at least as slow as reaction (B) of phenoxy radical with chlorobenzene. PhO. + PhCl -->PhOPh + Cl. reaction B Compared with condensation of two (chloro)phenoxy radicals, such radical/molecule reactions are therefore an insignificant pathway to dioxins in incinerators.     

不同基质共代谢降解2,4,6-三硝基苯酚的研究

以葡萄糖、可溶性淀粉、乙酸钠和苯酚作为共基质，通过35℃恒温生化培养箱缺氧驯化污泥，间歇恒温振荡试验研究了在不同共代谢基质条件下，2,4,6-三硝基苯酚（TNP）的缺氧降解性能。结果表明，经过驯化的微生物加入葡萄糖和苯酚作为碳源，在TNP∶苯酚∶葡萄糖为10∶3∶100的比例下，TNP生物降解率可以从不加碳源时的31.2%提高到86.6%；不同共基质条件下TNP的降解均符合一级反应动力学方程，反应速率常数大小依次是K_苯酚＜K_葡萄糖＜K_{葡萄糖+苯酚}，其中葡萄糖和苯酚同时作为共基质时TNP降解速率常数最大为0.019 h^-1。     

DFT M06-2X investigation of alkaline hydrolysis of nitroaromatic compounds

The nitroaromatic compounds 2,4,6-trinitrotoluene (TNT), 2,4-dinitrotoluene (DNT) and 2,4-dinitroanisole (DNAN) are potential environmental contaminants and their transformations under a variety of environmental conditions are consequently of great interest. One possible method to safely degrade these nitrocompounds is alkaline hydrolysis. A mechanism of the initial stages of this reaction was investigated computationally. Simulations of UV-VIS and NMR spectra for this mechanism were also produced. The results obtained were compared to available experimental data on the alkaline hydrolysis of TNT and suggest that the formation of Meisenheimer complexes and an anion of TNT are potential first-step intermediates in the reaction path. As the reaction proceeds, computational results indicate that polynegative complexes dominate the degradation pathway, followed by cycles of carbon chain opening and breaking. A second possible pathway was identified that leads to polymeric products through Janovsky complex formation. Results from this study indicate that the order of increasing resistance to alkaline hydrolysis is TNT, DNT and DNAN.     

Serum concentrations of chlorinated dibenzo-p-dioxins and dibenzofurans among former New Zealand trichlorophenol workers

This study examined serum levels of 2,3,7,8-substituted chlorinated dioxins and furans, and 15 PCBs for 346 New Zealand employees who worked at a site that manufactured 2,4,5-trichlorophenol (TCP) and 2,4,5-trichlorophenoxy acetic acid (2,4,5-T). Participants with potential TCP or 2,4,5-T exposures had mean lipid-adjusted 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) levels of 9.9 ng kg⁻¹ lipid compared to 4.9 ng kg⁻¹ for workers with no exposure at the site. Among exposed workers, we found evidence of differences in 2,3,7,8-TCDD levels by department and duties. Workers involved in an accidental release had the highest mean 2,3,7,8-TCDD levels, 37.9 ng kg⁻¹, followed by workers in the trichlorophenol plant, 23.4 ng kg⁻¹. Workers with potential intermittent exposures to 2,3,7,8-TCDD in construction, maintenance, mechanics, and transport had 2,3,7,8-TCDD levels above New Zealand background levels of 3.9 ng kg⁻¹, indicating workplace exposures. Among participants with work history indicating no 2,3,7,8-TCDD exposures, we observed some individuals with 2,3,7,8-TCDD levels above background levels. However, in most cases, these workers reported workplace exposures not recorded on their work histories or held other jobs with the potential for 2,3,7,8-TCDD exposures outside the plant. All other dioxin, furan, and PCB levels were similar among the exposed and unexposed workers.     

表面活性剂淋洗与投菌法联合修复2,4,6-三氯苯酚污染土壤

为了解决高浓度氯酚土壤污染问题,提出了一种表面活性剂淋洗与投菌法相结合的土壤修复方法。该方法采用表面活性剂淋洗污染土壤,使高浓度氯酚得到大部分去除后再加入微生物降解菌,从而实现低浓度氯酚的持续降解。通过2,4,6-三氯苯酚(2,4,6-TCP)的增溶实验、吸附实验以及表面活性剂的酶抑制实验,对蔗糖酯(SE)、鼠李糖脂(RL)、茶皂素(TS)、脂肪醇聚氧乙烯醚(AEO-9)4种表面活性剂进行了筛选。结果表明,SE增溶、解吸的综合效果较好,且具备良好的生物相容性,适用于淋洗有机污染土壤。淋洗-投菌联合实验表明,以0.5wt%蔗糖酯水溶液作为淋洗剂淋洗土壤并投菌降解,25 d内土壤中的2,4,6-三氯苯酚从190.4降至3.1 mg/kg,去除率达到98.4%。     

3种典型污染物对水生生物的急性毒性效应及其水质基准比较

我国本土水生生物急性毒性数据较少,通过研究Cr(Ⅵ)、2,4,6-三氯酚和硝基苯对蛋白核小球藻(Chlorella pyrenoidosa)、斜生栅藻(Scenedesmus obliqnus)和摇蚊幼虫(Chironomidae larvae)的急性毒性效应,为制定和完善我国水质基准提供本土数据支持.结果表明,Cr(Ⅵ)、2,4,6-三氯酚和硝基苯对蛋白核小球藻的96 h半抑制效应浓度(96 h-EC50)依次为1.34、4.55和86.58 mg·L-1;对斜生栅藻的96 h-EC50依次为19.52、3.71和74.15 mg·L-1;当Cr(Ⅵ)达到1 500 mg·L-1时,摇蚊幼虫48 h死亡率仅为15%,2,4,6-三氯酚和硝基苯对摇蚊幼虫的48 h半致死效应浓度(48 h-LC50)分别为9.29 mg·L-1和98.34 mg·L-1.3种典型污染物的毒性评估结果显示,Cr(Ⅵ)对小球藻为高等毒性、对斜生栅藻为中等毒性,2,4,6-三氯酚对两种微藻均为高等毒性,硝基苯对两种微藻均为中等毒性;3种污染物对摇蚊幼虫的毒性顺序为:2,4,6-三氯酚>硝基苯>Cr(Ⅵ).     

不同电子供体下三氯苯酚的还原脱氯机制研究

研究了葡萄糖、乳酸钠、丙酮酸钠、乙酸钠这4种电子供体条件下,2,4,6-三氯苯酚(2,4,6-trichlorophenol,2,4,6-TCP)的降解效果及其还原脱氯途径.结果表明,与葡萄糖的作用相比,乳酸钠、丙酮酸钠、乙酸钠均可有效提高2,4,6-TCP的脱氯效果,其中乳酸钠能作为一类缓释氢物质持续供给2,4,6-TCP还原脱氯所需电子.外加电子供体可提高微生物体内基质代谢脱氢酶活性,反应240 h后,4种电子供体体系中脱氢酶活性增长依次为21.49%、25.78%、136.85%和139.3%.2,4,6-TCP还原脱氯的主要产物包括2,4-二氯苯酚(2,4-dichlorophenol,2,4-DCP)、4-氯苯酚(4-chlorophenol,4-CP)和苯酚,其中乙酸钠作为电子供体时,4-CP为其主要降解产物,转化率达到22%以上.     

C60丙二酸二(2,4,6-三硝基苯乙基)酯马来酸聚合物铅盐的合成

以TNT和甲醛为原料,首先得到2,4,6-三硝基苯乙醇(TNPE),TNPE和丙二酰氯经酯化反应合成得到丙二酸二(2,4,6-三硝基苯乙基)酯(TNPEM),TNPEM与C60通过Bingel反应制备了C60丙二酸二(2,4,6-三硝基苯乙基)酯(FTNPEM).FTNPEM再与马来酸和硝酸铅通过共聚合成盐反应得到含能的C60丙二酸二(2,4,6-三硝基苯乙基)酯马来酸聚合物铅盐5.采用FT-IR、UV-Vis、GPC、XPS、XRD等表征方法对聚合物及其铅盐的结构进行了分析.利用差热分析法(DTA)和热重分析法(TGA)对聚合物铅盐5的热稳定性及其对RDX的热分解催化作用进行了研究.结果表明,在空气气氛下,聚合物铅盐5初始分解峰值温度为239℃,表明产物热稳定性良好.对RDX热分解催化作用研究结果表明,聚合物铅盐5能加速RDX的分解,并使RDX分解峰温降低6℃.     

A study of 2,4,6-trinitrotoluene inhibition of benzo[a]pyrene uptake and activation in a microbial mutagenicity assay

A number of in vitro and in vivo studies have determined that binary and complex mixtures may interact to produce a toxicity that could not be predicted based on the individual chemicals. The present study was conducted with a binary mixture of model compounds to investigate possible interactions affecting their mutagenicity. The compounds included Benzo[a]pyrene (BAP), a polycyclic aromatic hydrocarbon that is an indirect-acting mutagen of great environmental concern, and 2,4,6-Trinitrotoluene (TNT), a nitro-aromatic compound that is a direct-acting mutagen frequently found as a soil contaminant at munitions sites. This study indicated that a binary mixture of BAP and TNT failed to induce the positive mutagenic response in Salmonella typhimurium strain TA98 characteristic of either compound alone. Spectrofluorometric analysis of BAP, and kinetic analyses of ³HBAP uptake in the presence or absence of TNT using TA98 cells that were treated or untreated with activated rat liver microsomes were performed. In cells preloaded with BAP, cellular BAP fluorescence was rapidly suppressed in the presence of TNT. Mass spectroscopy of BAP and TNT mixtures revealed a number of products, believed to be the result of complexation and nitration, that may account for the antagonistic action of TNT on BAP-induced mutagenicity in TA98 cells. Further, kinetic studies indicated that TNT inhibited the incorporation of BAP into cells.