Planar detonation structure for chain-branching kinetics with large activation energy and small initiation rate

The structure of the steady planar detonation wave is analyzed for three-step chain-branching kinetics consistent with hydrogen–air chemistry. The initiation and chain-branching steps are described by an Arrhenius rate. Both are thermally neutral, so that heat release is due to termination. The initiation rate is typically very low and very stiff. As a result, a small fraction of the reactant is consumed in the initiation region, which is very long but ends in an exponential chain-branching explosion. Next, the reactant is rapidly converted into chain-branching radicals, within a very thin zone, which ends when the concentration of the chain-branching radical reaches a peak, because of reactant depletion. Finally, the termination step consumes the chain-branching radicals and releases heat within a region thicker than the peak zone, but much thinner than the initiation region. The analysis is based upon two assumptions: that the chain-branching activation energy is high and that initiation is slow. The structure of the initiation and chain-branching zones is different for post-shock states within or outside the explosion region in the chain-branching diagram. In the former situation, chain-branching is already stronger than termination at the von Neumann point, and vice versa. In the no-explosion case, the initiation zone becomes very long, while the little chain-branching specie produced by initiation is directly converted into product by the termination step. Temperature increases slowly until reaching the explosion curve, when chain-branching becomes stronger than termination. The subsequent structure is similar to the explosion case.     

Determination of toxic elements in waters and sediments from River Subin in the Ashanti Region of Ghana

Waters and sediments of Subin River, which flows through the industrial and commercial areas of Kumasi in the Ashanti region of Ghana, were geochemically investigated to ascertain heavy metal pollution levels due to anthropogenic activities. The study shows preoccupying pollution levels that constitute a threat to public and ecological systems. The waters of Subin River are neutral to slightly basic, inferred from pH values of 6.89–7.65). Electric conductivity (EC) of the waters ranges from 822 to 1,821 μs/cm and the range of total dissolved solids (TDS) is from 409 to 913 mg/l. Toxic elements contents of sediments and waters from 10 sites along the river were analysed by instrumental neutron activation analysis (INAA), and Al, As, Cd, Cr, Cu and Zn were determined. The concentrations of Al, As, Cd, Cr, Cu and Zn in the waters range between 4.02–15.18, 0.007–0.16, 0.002–0.05, 0.001–0.019, 1.32–7.04 and 4.28–10.2 mg/l, respectively. The contamination factors (CF) computed for the elements indicate that with the exception of sampling site S10, the sediments are polluted with Cd. Chromium contamination in the sediments is observed at S6 and S7, where the CF values were 1.39 and 1.52, respectively. The pollution load indices (PLI) were low (<1) and ranged from 0.14 to 0.75, suggesting that the overall sediment column of the river is not polluted.     

过硫酸盐氧化修复多环芳烃污染土壤的研究

介绍了过硫酸盐氧化作用的活化方法和机理,在此基础上设置了对比试验,分析了氢氧化钠和硫酸亚铁活化过硫酸钠氧化修复多环芳烃污染土壤的效果,探究了pH、硫酸亚铁与过硫酸钠物质的量之比及反应时间对硫酸亚铁/过硫酸钠体系去除多环芳烃的影响,并分析了反应产物的组分。结果表明:硫酸亚铁比氢氧化钠活化过硫酸钠氧化修复多环芳烃污染土壤的效果好;在pH为酸性或中性、硫酸亚铁与过硫酸钠物质的量之比为1∶2.0、反应时间为5 d时,对多环芳烃的去除效果最佳。在控制反应条件的基础上,过渡金属离子活化过硫酸钠是修复多环芳烃污染土壤的可行方法之一。     

Mutagenicity of polyaromatic hydrocarbons by chemical models for cytochrome P450 in Ames assay

DNA damage is an important step in carcinogenesis. The Ames assay is a short-term screening of carcinogens that induce DNA damage. Most carcinogens require enzymatic activation through oxidation by cytochrome P450 (CYP450) in the presence of S9 mix. A combination of iron (Fe)(III) porphyrin and an oxidant is also able to oxidize compounds as an alternative metabolic pathway to CYP450. Previously it was reported that a chemical model containing a water-soluble 5,10,15,20-tetrakis(1-methylpyridinium4-yl)porphyrinatoiron(III) chloride (4-MPy) and tert-butyl hydroperoxide (t-BuOOH) activated aromatic amines and amides. In this study, a chemical model composed of an Fe porphyrin, water-insoluble 5,10,15,20-tetrakis(pentafluorophenyl)porphyrinatoiron(III) chloride (F₅P) or water-soluble 4-MPy was optimized with an oxidant – t-BuOOH, magnesium monoperoxyphthalate (MPPT), or iodosylbenzene (PhIO). Subsequently the mutagenicity of benzo[a]pyrene (B[a]P) and chrysene in Salmonella typhimurium TA strains was compared. B[a]P was activated by a combination of F₅P or 4-MPy plus MPPT or PhIO in S. typhimurium TA1538. The B[a]P-induced mutagenicity with F₅P plus oxidant was higher than 4-MPy plus oxidant. Mutagenicity of chrysene, a tetracyclic aromatic hydrocarbon, was not detected in the presence of F₅P/PhIO in S. typhimurium TA98, but was activated in the presence of F₅P/MPPT. The F₅P/MPPT activated other polyaromatic hydrocarbons (PAH) in the S. typhimurium TA98 assay including dibenz[a,c]anthracene, dibenz[a,h]anthracene, 3-methylcholanthrene, and benzo[a]anthracene. The results indicated that the F₅P/MPPT was the most efficient model for detecting PAH-induced mutagenicity in the Ames assay.     

铅在棉秆基活性炭上的吸附动力学与热力学

以棉秆与棉秆纤维为原料,利用磷酸活化法制备了低成本的高比表面微孔棉秆基活性炭,通过静态实验研究了活性炭对水溶液中铅的吸附特性,测定了溶液pH值、吸附时间、溶液温度对吸附的影响,探讨了吸附动力学、热力学及吸附机制.根据低温液氮(N2/77K)吸附测定数据,以BET方程、BJH法及H-K法对活性炭孔结构进行了表征,以Boehm滴定、FTIR、零电荷点pHPZC测定及元素分析定量表征活性炭表面含氧官能团.结果表明,以棉秆和棉秆纤维为原料制备的活性炭的比表面积分别为1570和1731m2·g-1,含氧酸官能团含量分别为1.43和0.83mmol·g-1,均高于商业活性炭ST1300.静态吸附实验表明,棉秆基活性炭对铅有较大的吸附容量和吸附效率,最大吸附量超过120mg·g-1,溶液pH对吸附有较大的影响,吸附量随时间增大而增大,在5min内可达饱和吸附量的80%;吸附动力学数据符合假二级方程,Freundlich方程能更好地描述等温吸附行为;热力学研究表明,吸附吉布斯自由能(ΔG0)0,而焓变(ΔH0)0,说明吸附为吸热的自发反应过程,升温有利于吸附,离子交换可能在吸附过程中起了重要作用.     

Rapid and simple spectrophotometric determination of persulfate in water by microwave assisted decolorization of Methylene Blue

A rapid and simple method for determination of persulfate in aqueous solution was developed. The method is based on the rapid reaction of persulfate with Methylene Blue(MB) via domestic microwave activation, which can promote the activation of persulfate and decolorize MB quickly. The depletion of MB at 644 nm(the maximum absorption wavelength of MB) is in proportion to the increasing concentration of persulfate in aqueous solution. Linear calibration curve was obtained in the range 0–1.5 mmol/L, with a limit of detection of 0.0028 mmol/L. The reaction time is rapid(within 60 sec), which is much shorter than that used for conventional methods. Compared with existing analytical methods, it need not any additives, especially colorful Fe2+, and need not any pretreatment for samples, such as p H adjustment.     

Phenol degradation in waters with high iodide level by layered double hydroxide-peroxodisulfate: Pathways and products

Recently, layered double hydroxide-peroxodisulfate (LDH-PDS) as an advanced oxidation system can effectively remove organics by the pathway of free radical. However, little has been known if there is a potential risk regarding the formation of high toxic iodine byproducts through another pathway when LDH-PDS is used in high iodide waters at coastal areas. Therefore, this study investigated phenol degradation pathways and transformation products to evaluate both removal mechanism and potential risk by LDH-PDS in high iodide waters. The results showed that in LDH-PDS system, with the degradation of PDS, phenol degraded till below detection limit in 1 hr in the presence of iodide, while PDS and phenol were hardly degraded in the absence of iodide, indicating iodide accelerated the transformation of PDS and the degradation of phenol. What is more, it reached the highest phenol removal efficiency under the condition of 100 mg/L LDH, 0.1 mmol/L PDS and 1.0 mmol/L iodide. In LDH-PDS system, iodide was rapidly oxidized by the highly active interlayer PDS, resulting in the formation of reactive iodine including hypoiodic acid, iodine and triiodide instead of free radicals, which contributed rapid degradation of phenol. However, unfortunately toxic iodophenols were detected. Specifically, 2-iodophenol and 4-iodophenol were formed firstly, afterwards 2,4-diiodophenol and 2,6-diiodophenol were produced, and finally iodophenols and diiodophenols gradually decreased and 2,4,6-Triiodophenol were produced. These results indicated that LDH-PDS should avoid to use in high iodide waters to prevent toxic iodine byproduct formation although iodide can accelerate phenol degradation.     

石英表面配合物与溶解动力学模型

阐述了石英表面配合物和溶解动力学机理之间的关系，指出了石英的反应性主要受负电性表面物种的控制，从而导致电解质、离子强度、pH等因素对石英溶解的催化效应．溶解达率的提高与反应活化能的降低成活化熵的增大有关。最后，介绍了在过渡态理论和表面反应模型基础上建立的石英溶解速率方程。     

强化土著微生物处理硝基苯和苯胺污染地下水

以硝基苯、苯胺为主要污染物的污染地下水为研究对象,加入激活剂(乳糖、Na2HPO4、乳糖+Na2HPO4、乙醇、牛肉膏、蛋白胨)激活土著微生物,并考察其对土著微生物生长及硝基苯、苯胺降解效果的影响。加入激活剂3d后测各个水样的脱氢酶活性,对培养9d后的水样进行气相色谱/质谱(GC/MS)分析。结果表明,加入乳糖的水样中,其微生物相对增长率达157.2%,硝基苯、苯胺的相对去除率分别为14.90%和0.79%;加入Na2HPO4和乙醇的水样中,其微生物增长和硝基苯、苯胺降解情况均没有明显变化;加入乳糖+Na2HPO4的水样中,微生物相对增长率达180.3%,硝基苯、苯胺的相对去除率分别为24.20%和1.21%;加入牛肉膏的水样中,微生物的相对增长率为830.7%,硝基苯、苯胺的相对去除率分别为99.99%和99.67%;加入蛋白胨的水样中,其微生物相对增长率为686.0%,硝基苯、苯胺的相对去除率分别为99.33%和58.94%。GC/MS分析结果表明,加入激活剂后对氯苯胺、1-甲基-4-硝基苯等其他有机物的降解率均有提高。由此可见,通过激活土著微生物修复有机物污染地下水是可行的。     

化学活化法制取污泥衍生吸附剂的实验研究

用有机污泥按照一定的工艺制作污泥衍生吸附剂。结果表明，氯化锌作为化学活化剂在吸附剂的生成过程中起到了关键作用，热解温度是影响吸附剂性能的最主要因素，750℃是最佳热解温度。