Photochemical behaviour of musk tibetene

BACKGROUND: Synthetic musk compounds are widely used as additives in personal care and household products. The photochemical degradation of musk tibetene in aqueous solutions or in acetonitrile/water mixtures under different conditions was studied in order to assess its environmental fate. METHODS: Musk tibetene dissolved (or suspended) in water and/or acetonitrile/water mixtures was irradiated at different times by UV-light and by solar light. The irradiation mixtures were analyzed by NMR and TLC. The photoproducts formed were identified by GC-MS and NMR data. RESULTS: The experimental results indicated that musk tibetene was photodegradable in water or acetonitrile/water mixtures with half-life reaction times close to 20 minutes. The irradiation mixtures were separated by chromatographic techniques yielding three photoproducts (3,3,5,6,7-pentamethyl-4-nitro-3H-indole, 3,3,5,6,7-pentamethyl-4-nitro-1H-indoline and 3,3,5,6,7-pentamethyl-4-nitro-3H-indolinone) identified by means of spectroscopic analysis. DISCUSSION: The numerical modelling of the photodegradation concentration-time profiles gave (8.13 +/- 0.15) x 10(-2) and (1.34 +/- 0.04) x 10(-2) mol/E for the overall primary quantum yield of direct photolysis for musk tibetene and the major intermediate (3,3,5,6,7-pentamethyl-4-nitro-3H-indolinone), respectively, in the wavelength range 305-366 nm. The half-life times of photodegradation of the both substances varied from 1-1.5 hours at 20 degrees N during the summer season to 6-10 hours for highest latitudes in winter. CONCLUSIONS: Under solar light, musk tibetene was photolabile in acetonitrile and acetonitrile/water 1/1, while it was slowly degraded when suspended in water. In all media, musk tibetene was photodegraded into three photoproducts. By using a kinetic model, the overall primary quantum yields of direct photolysis of musk tibetene and its main photoproduct, in the wavelength range 305-366 nm, were estimated, indicating that the photodegradation rate for musk tibetene is faster than the photolysis rate of the major by-product. RECOMMENDATIONS AND PERSPECTIVES: The results indicate that, in order to assess the environmental impact of musk tibetene on the aquatic ecosystem, great attention should be focused on the major photoproduct which is proved to be more persistent than the parent compound under light irradiation. The predicted half-life times of direct photolysis for both substances ranged from 1-1.5 hours at 20 degrees N during the summer season to about 6-10 hours for highest latitudes in winter, indicating that, from a photochemical point of view, the environmental persistence of these substances increases by increasing the latitudes and during the cold seasons, making more realistic an intake of these xenobiotic molecules into the food chain of aquatic living organisms. Tanabe reports in his Editorial (Tanabe 2005) that "It is necessary to have knowledge of the global picture of synthetic musk pathways. So, it is conceivable that now is the time to study the transport, persistency, distribution, bioaccumulation and toxic potential of this new environmental menace on a global scale, especially in developing countries". Therefore, the future environmental analysis and investigations on the eco-toxicity of nitro musk compounds should take into account not only the presence of the parent compounds but also their photochemical intermediates or end-by-products.     

PCBs污染土壤的CaO诱导低温热处理脱氯研究

研究了低温热处理脱氯技术对废弃电容器封存点附近污染土壤中多氯联苯脱氯的效果,考察反应温度、反应时间及CaO添加比例对PCBs去除率、脱氯率的影响以及反应前后土壤中污染物的组分变化.实验土样中PCBs浓度为107.7 mg/g,属于罕见高浓度PCBs污染土壤.当反应温度为400℃、停留时间4h、CaO添加比例为10%,PCBs的去除率为87.7%,脱氯率为85.3%.土壤样品中五氯联苯和四氯联苯反应后含量降低或未检出,部分反应后样品检出一氯联苯和联苯,说明在CaO诱导PCBs低温热处理脱氯反应中存在逐步脱氯/加氢反应途径.     

零价铁耦合芬顿氧化法处理TNT红水

采用零价铁耦合芬顿氧化法处理TNT红水,研究了初始pH、零价铁投加量、过氧化氢（H2O2）投加量及温度对红水中总有机碳（TOC）去除效果的影响,同时进行了TOC去除过程中反应动力学的探讨。结果表明,零价铁耦合芬顿氧化体系可有效降解TNT红水中的2,4-二硝基甲苯-3-磺酸钠和2,4-二硝基甲苯-5-磺酸钠。在初始pH为2,温度为20 ℃的条件下,加入1.5 g·L-1零价铁反应1 h后,再加入100 mL·L-1H2O2反应4 h,红水中二硝基甲苯磺酸盐浓度从500 mg·L-1降至0 mg·L-1,去除率为100%,TOC浓度从150 mg·L-1降至30 mg·L-1,去除率达到80%。反应中TOC的降解过程遵循拟二级反应动力学方程。零价铁耦合芬顿氧化法可以作为TNT红水的有效处理途径。     

O3氧化结合化学吸收同时脱硫脱硝的动力学及热力学研究

构建了O3氧化多种污染物的反应机制,并对O3氧化SOx、NOx过程进行动力学模拟,然后利用热力学原理计算出Ca(OH)2和CaCO3湿法烟气同时脱硫脱硝吸收反应达到平衡时SOx和NOx的分压力.结果表明,Ca(OH)2作吸收剂湿法烟气同时脱硫脱硝比CaCO3作吸收剂效果好,而且两者几乎100％地去除烟气中的SOx和NO...     

基于静电纺丝膜的Fenton法降解双氯芬酸钠

通过浸渍法将铁盐负载于静电纺丝纤维膜制备了类Fenton催化剂,并通过扫描电子显微镜（SEM）对静电纺丝膜进行了表征,研究了该催化剂降解双氯芬酸钠的特性及其重复利用率。结果表明,静电纺丝纤维膜反应前后膜结构良好,反应过程中铁离子几乎无溶出;膜对双氯芬酸钠有一定的吸附能力,去除率约为6.96%。当双氯芬酸钠初始浓度为20 mg·L-1,按0.310 g·（100 mL）-1比例加入催化剂时,H2O2最佳用量为340 mg·L-1。溶液的初始pH值对实验结果影响较大,酸性条件更利于双氯芬酸钠的降解,最佳pH值为3.14,但该催化剂所适用的pH值范围较之传统Fenton法有明显拓展。所制备的催化剂重复利用率高,循环使用4次后,催化活性无明显改变,4 h的去除率依然高达95%以上。反应中双氯芬酸钠主要生成乙酸等小分子化合物,最终可氧化为CO2和H2O。     

2013年北京市臭氧时空分布及预报

根据2013年1-12月北京市O3小时浓度监测数据,探讨了北京市O3的时空分布特征,并建立了O3回归统计模型。结果显示:2013年北京市O3 8 h全年平均为84.75 μg/m3,O3超标日主要集中在5-9月份;O3日变化呈现单峰型分布,一般在15:00、16:00左右达到峰值,且存在明显的周末效应,空间分布上,中心城区O3浓度相对较低,生态植被优良的北部、西部山区站点浓度较高;建立的O3回归统计模型对北京市2013年O3 8 h临近预报的级别准确率在75%以上,能较好地反映O3浓度变化趋势。     

污泥在CO2气氛下热解CO与CH4的生成特性

利用热重-红外(TG-FTIR)联用技术研究了典型市政污水污泥在CO2和N2气氛下的热解特性。基于TG-FTIR分析结果,采用等温模式配合法研究了CO2气氛下污泥固定床热解过程中CO和CH4的生成特性,建立了CO和CH4的生成动力学机理模型,并同传统N2气氛下污泥热解情况进行了对比,理论模型利用实际实验数据进行了验证分析。结果表明,在实验温度范围内2种气氛下CO与CH4的生成情况有着比较明显的差异,CO2气氛下CH4释放浓度在峰值和总量上都要低于N2气氛,CH4释放峰值来得更早,释放时间更为集中,释放过程也结束得更快。相反,CO的释放浓度峰值,总量以及持续时间在CO2气氛下都要远远高于N2气氛,随着温度的升高,差距越来越大,CO2的存在大大促进了CO的生成。经实验验证,理论推导所得的模型公式对于热解产物生成有着良好的预测结果。     

Fenton法处理垃圾渗滤液的参数优化及反应动力学模型

采用Fenton法处理垃圾渗滤液,研究反应时间、初始浓度、pH、Fenton试剂用量对垃圾渗滤液TOC去除率的影响。研究结果表明,最优反应条件是反应时间30 min,初始pH为3.0,初始[H2O2]0=7 310 mg/L,最佳[H2O2]/[Fe2+]摩尔比为5,反应温度为室温,此时渗滤液的TOC去除率达到70.3%。渗滤液矿化过程符合一级反应动力学,并建立了符合该渗滤液的反应动力学模型。     

壳体缓释技术对带壳装药慢速烤燃反应烈度的缓解作用研究

为了研究2种典型壳体缓释技术对弹药慢速烤燃响应烈度的缓解作用,基于试验条件分别建立无缓释设计、侧壁加工应力槽和端盖加工泄压孔的带壳PBX装药慢速烤燃仿真模型,提出使用热分解反应动力学模型和燃烧反应模型模拟计算不同约束条件下带壳PBX装药从开始加热发生热分解反应到点火燃烧以及炸药与壳体耦合作用的烤燃过程的计算方法。研究结果表明：通过侧壁加工应力槽以及端盖加工泄压孔的缓释结构设计,可以有效地降低壳体破裂时炸药内部的压力及反应度,以达到缓解反应烈度的目的。     

煤矿照度对人反应时间和可靠度的影响研究

煤矿综采工作面狭窄,工作环境昏暗,照明环境普遍不好,是近年来井下事故多发的重要因素之一。针对目前煤矿综采工作面存在的照度问题,通过控制光照时间和操作难度,利用舒尔特表测算反应时间和操作可靠度,使用SPSS20. 0和Excel进行数据处理,设计试验组和对照组来进行对比试验。结果表明,1)从反应时间来看,0～25 min,试验组平均反应时间的变化趋势与对照组相反,被试者的注意力先下降后上升; 25～55 min,被试者逐渐适应低照度环境,反应时间也在逐渐缩短;被试者在低照度条件下操作55 min后,反应时间随光照时间增加而大幅度增加,超过劳动时间临界值后,视觉疲劳度迅速增加,反应急速减慢,从而可能导致安全事故的发生,影响生产效率,此时应合理安排工人休息。2)从操作难度来看,在简单及正常操作难度时,试验组和对照组操作可靠度变化比较接近,表明低照度条件对一般操作的可靠度影响不明显;在极难操作难度时,低照度条件对可靠度影响明显,在井下生产过程中,低照度环境下应尽量避免安排复杂的机械化操作。3)反应时间与光照时间呈二次函数关系,通过建立回归方程量化了两者的关系,为以后合理安排煤矿工人劳动休息时间提供了理论依据。