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.     

负载型颗粒活性炭催化过硫酸钠氧化降解橙黄G

通过在颗粒活性炭(GAC)上负载氧化铁,并以此作为催化剂(Fe/GAC)在常温常压下催化过硫酸钠(PS)产生硫酸根自由基降解偶氮染料橙黄G.研究了体系pH、氧化剂浓度、催化剂浓度对橙黄G去除率的影响,并且对催化剂的重复使用性能进行了测试.结果表明,在Fe/GAC/PS体系中,[OG]0=0.2 mmol/L,[GAC] =1 g/L,[PS]0=2 mmol/L,降解2h后OG去除率为99％,且有较高的矿化率;随着氧化剂浓度和催化剂浓度的增加,OG的去除效率提高;催化剂有较好的重复使用性.利用扫描电镜(SEM)对催化剂进行了表征,可以看出在活性炭上成功负载氧化铁.利用化学分子探针竞争实验鉴定催化反应中的活性物种SO4-·和OH·.     

微等离子弧放电催化水处理技术的研究

采用钛为阳极的微等离子弧放电技术,研究了在模拟废水处理中放电催化效应及其机理,发现该技术对甲基橙有好的放电催化处理效果.甲基橙的脱色程度与峰值电压、脉冲频率、占空比、阳极电极面积等有关.在0.3mol·L-1的H3PO4电解液中,在峰值电压为550V、脉冲频率200Hz,占空比1∶180、阳极电极面积50mm×50mm条件下,20min内600mL、20mg·L-1的甲基橙溶液脱色率达90%.实验结果表明,该放电催化体系具有协同效果好、能效高、反应器设计要求简单等特点,是一种有发展前景的水处理新技术.     

UV-Fenton氧化高浓度木糖生产废水的研究

采用UV-Fenton技术光催化氧化高浓度木糖生产废水,确定最佳操作条件为:pH=2.5,H2O2=46.62g/L,H2O2/Fe2+摩尔配比为50∶1,光照反应60min。此条件下废水COD去除率最高可达91.2%。经正交试验确定影响处理效果各因素的重要性顺序为:pH>H2O2浓度>光照反应时间>H2O2/Fe2+摩尔配比。UV的加入与单独的Fenton体系存在正相关的协同作用。经UV-Fenton处理后的木糖废水,可生化性大大改善,B/C指标从0.21升高到0.49。     

Ce(Ⅲ)对UV-B辐射胁迫下大豆幼苗光化学反应的影响

用水培法研究Ce(Ⅲ)对UV-B辐射胁迫下大豆幼苗光化学反应的影响.结果表明, 20 mg·L^-1 CeCl₃使大豆幼苗净光合速率(Pn)、Hill反应、Mg²⁺-ATPase活性与光合磷酸化活力4项指标较对照提高23.2%～14.3%; 有效抑制UV-B辐射(T₁=0.15 W·m^-2和T₂=0.45 W·m^-2)胁迫下4项指标下降, 4项指标降幅［Ce(Ⅲ)+T₁为36.6%～15.9%,Ce(Ⅲ)+T₂为65.6%～33.2%］小于对应的UV-B辐射组(T₁为50.9%～23.3%,T₂为77.3%～51.4%). 动态变化显示, Ce(Ⅲ)减缓了胁迫期4项指标的下降趋势,促进了恢复期4项指标上升幅度. 说明Ce(Ⅲ)通过减轻UV-B辐射对大豆幼苗光化学反应的伤害, 遏制UV-B辐射胁迫下大豆幼苗Pn下降.     

模拟可见光下土壤表面石油的光化学降解研究

在模拟可见光照射下,分析了土壤中的初始含油量、土壤类型和土壤pH值对石油在土壤表面光降解过程的影响,并利用紫外-可见分光光度法(UV-Vis)、气相色谱-氢火焰离子化检测器(GC-FID)和傅立叶红外光谱(FTIR)等方法对石油在光降解过程中的演变规律进行研究.结果表明,石油在土壤表面上的光化学降解行为符合准一级反应动力学,实验测得石油的光解速率常数为0.002 6～0.017 2 h^-1,半衰期为40～267 h.GC-FID分析结果表明,在光降解50 h后,石油的饱和烃组分中高碳数的烷烃相对含量降低,低碳数的烷烃相对含量提高;芳香烃组分的大部分色谱峰有明显地降低或消失.红外光谱分析发现,光照60 h后土壤萃取液中可能产生了羰基类化合物,说明石油在光降解过程中逐渐发生氧化.     

染料废水电催化氧化及降解动力学研究

以新型钛基二氧化铅电极为阳极、石墨为阴极、活性炭-纳米二氧化钛为催化粒子电极降解染料模拟废水酸性红B溶液,考察了槽电压、pH值、催化剂量等对处理效果的影响。实验结果表明:纳米二氧化钛催化剂的催化效果显著,该反应器能够有效的降解酸性红B,降解机制主要是电致H2O2、.OH对有机物的氧化、降解。同时用一级反应拟合了酸性红B溶液COD去除反应,由实验数据确定了反应动力学方程。     

二氧化碳资源化技术研究进展

过量的二氧化碳(CO2)排放可导致温室效应的不断加剧,因此CO2减排受到越来越多的关注,其中将CO2转化为附加值较高的化工产品,即CO2资源化利用技术不仅可实现CO2减排,同时具有一定的经济效益。CO2资源化利用技术主要包括光化学还原法、电化学还原法和催化转移氢化法等。重点介绍并总结了以上3种方法的特点、优势和不足,指出未来需研究解决的关键问题和研究方向,为实现高效的CO2资源化利用提供借鉴和参考。     

介质阻挡放电联合催化臭氧化降解甲苯

采用介质阻挡放电区后结合MnOx/Al2O3/发泡镍去除甲苯,考察甲苯进气方式、臭氧产生方法及湿度对甲苯与O3同时去除的影响。结果表明,O3是等离子体区后催化降解甲苯的主要物种,介质阻挡放电联合催化臭氧化可实现甲苯及O3的同时高效去除。输入电压为9.0 kV时,甲苯的去除效率达92.8%,在80 min内O3的去除效率维持在99%以上。水蒸气对催化剂催化分解臭氧的活性没有直接的影响,O3浓度较高时湿度对甲苯降解效率的影响很小。GC-MS分析结果表明,甲苯降解的主要气相副产物有烷烃、酸、酮和含苯环有机物,提出了甲苯的降解途径。     

镍基催化剂对污泥微波热解制生物气效能的影响

为实现污水污泥减量化、无害化及资源化的目标,在微波热解污水污泥基础上,进行了镍基催化剂对制取生物气效能影响的研究。采用元素分析对污泥元素进行检测,气/质联用分析(GC-MS)和气相色谱(GC)对热解生物气的组成和含量进行测定。实验结果表明,镍基催化剂的添加对微波热解污水污泥制取生物气有较大促进作用。5%添加量与800℃热解终温条件下具有最佳催化效果:生物气中H2、CO产量最大,H2产量由29 g/kg增加到35.8 g/kg,提升23.4%,CO产量由302.7 g/kg增加到383.3 g/kg,提升26.6%;同时催化剂还能提高热能利用效率,降低热解终温,即5%添加量在700℃热解终温时可达到空白800℃时的产气效果;镍基催化剂主要在500~600℃时发挥催化作用,加快了H2和CO的释放。微波热解污泥制取的生物气具有产量大、富含H2与CO等优点,可推动污水污泥的资源化进程。