几种天然矿物去除苯酚效果及日光光解效应评价

本文以四种天然矿物为受试矿物,评价了它们去除苯酚的效果,以及日光光解放应及温度,ＰＨ值,矿物浓度,苯酚初始浓度对去除效果的影响。     

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.     

新农药环境化学行为研究（V）─—三氟羧草醚（Acifluorfen）在土壤和水环境中的滞留、转化

从如下几方面研究了三氟羧草醚在土壤－水环境中的化学行为：一是土壤对该药的吸附，结果表明，吸附强度与土壤理化特性密切相关，Ｆｒｅｕｎｄｌｉｃｈ常数ｋ＿ｆ＝０．９４Ｗ＿（ＯＭ）＋０．６５Ｗ＿（ＣＬＡＹ）－９．５９ｐＨ（ｒ￣２＝０．９４）；二是吸附机理研究，发现三氟羧草醚能与碱金属以外的许多金属离子形成配合物，并证实了与Ｃｕ￣（２＋）形成的双核桥联配合物的可能性；三是实验指出它在水中避光有一定的稳定性，不易水解；四是它在＜３５０ｎｍ的光辐照下，易脱羧转化，速度较快，光解产物有较好的稳定性。     

在TiO2催化剂上苯酚光催化氧化反应研究2-多相光催化氧化与直接光解反应的比较

在ＴｉＯ２悬浆体系，中压汞灯作用下，通过苯酚降解过程中总碳浓度变化及二氧化碳生成速度的变化规律，研究了光催化氧化与直接光解反应的不同，并着得比较了当反应条件如催化剂量，气相氧浓度以及光强度变化对两种反应的影响。实验结果证明了两种反应的历程和产物各不相同，多相光催化氧化更有利于有机物分子的降解，而光解作用会引起聚合反应，同时也说明充分利用太阳能不仅是开发光催化水处理技术的重要途径，也是抑制直接光解加     

乙烯菌核利在水溶液中的光解动力学

以高压汞灯和太阳光为光源，研究乙烯菌核利在重蒸水、自来水、湖水及pH缓冲液中的光解动力学。高压汞灯下，乙烯菌核利在重蒸水中的光解半衰期约为28min，而在太阳光下为3．86h。自来水和湖水中溶解性物质对乙烯菌核利在高压汞灯下的光解动力学仅有微弱的淬灭效应，但在太阳光下表现出显著的敏化效应，照光3h的敏化效率分别为138％和126％。2种光源下，pH5．0和pH7．0缓冲液对乙烯菌核利的光解均表现为光淬灭效应，高压汞灯照光60min的淬灭效率分别为69％和57％，太阳光照光7h的淬灭效率分别为77％和33％；pH9．0缓冲液则表现出显著的敏化效应，高压汞灯照光20min的敏化效率为58％，而太阳光照光1h的敏化效率则达到了415％。     

有机磷农药敏化作用的初步研究

本文研究了有机磷农药甲基1605和毒死蜱对~1O_2探针性物质二乙基二硫酸(DES)、萜品烯(α-terp)及ROO和RO探针性物质2.6-二叔醒基-4-甲基苯酚(BHT)和1,2,3,4-四氢萘(tetra)光降解的敏化作用.结果表明基态氧直接参与了DES和α-terp的光解;在甲基1605的作用下,1/K_(exptl)与[α-terp]的关系表明,α-terp的降解不为~1O_2历程;同时BHT和tetra的敏化降解说明ROO的量子产率为~1O_2量子产率的5倍;对氯氰菊酯的光敏降解产物的检测表明,在甲基1605存在下,产物仍然以~3O_2氧化产物为主.     

品红的深度氧化机理研究

选用 2 5 3 7nm的紫外光为激发光源 ,对品红 /过氧化氢体系中的紫外光解离进行了研究 .结果表明 ,该体系中品红的解离近似为表观一级反应 ,解离反应的速率常数为 0 0 386 7s- 1.品红水溶液的脉冲瞬态光谱结果表明 ,品红主要与OH自由基反应而导致脱色 ,其在 5 4 0nm处的脱色与 34 0nm处的瞬态吸收存在很好的相关性 ,品红在5 4 0nm处脱色为一级反应 ,速率常数为 8 1 0× 1 0 5s- 1,34 0nm处新的瞬态物种生成较快而衰减较慢 ,其衰减速率为 5 33× 1 0 3 s- 1.     

Photodegradation of polychlorinated dibenzo-p-dioxins and dibenzofurans in soil with vegetable oil

GOAL, SCOPE AND BACKGROUND: This study was carried out to investigate the effect of olive oil on the photodegradation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in contaminated sawmill soil. Previous studies had shown that the solubility of PCDD/Fs in olive oil is high and a rapid photodegradation of PCDD/Fs takes place in olive oil when irradiated with ultraviolet (blacklight) lamps. The efficiency of this treatment method was evaluated under more practical conditions. These included the use of sunlight irradiation and a lower-grade olive oil, without a preliminary extraction of soil with olive oil. METHODS: A 1-cm layer of contaminated sawmill soil was blended with 20 weight-% of olive oil and exposed to sunlight for four weeks. In another experiment, a new dose of olive oil was added at the middle of the exposure period. The PCDD/F concentrations of the soils were monitored periodically. RESULTS AND DISCUSSION: A reduction in the concentration of 2,3,7,8-chlorinated PCDD/Fs by 59% and in WHO-TEQ in contaminated sawmill soil by 48% was attained after blending the soil with two doses (20 + 20%) of olive oil and exposing the mixture to sunlight for four weeks. Photodegradation with only one dose of olive oil was less efficient. This suggests that periodical additions of olive oil would be needed to maintain a proper degradation rate. After the oil additions, the WHO-TEQ content of the soil declined with first order reaction half-lives of 19.2 to 19.7 d. The overall half-life during the four-week treatment, however, was 30 d. CONCLUSION: A significant reduction in the PCDD/F concentration of aged sawmill soil can be achieved with a relatively simple olive oil-sunlight treatment. RECOMMENDATIONS AND OUTLOOK: Some theoretical and technological questions need to be solved before using the investigated soil decontamination method in larger-scale applications. The functions of vegetable oils in photodegradation processes should be studied in more detail. The amount of oil that is needed for a proper solubilisation and photodegradation of PCDD/Fs should be minimised. Moreover, special care should be taken to prevent mobilisation of PCDD/Fs to the surrounding environment and to avoid leaving bioavailable residuals of PCDD/Fs in soil.     

Photolytic degradation of fluoroquinolone carboxylic acids in aqueous solution

Subsequent to irradiation with a xenon lamp simulating sunlight, fluoroquinolone carboxylic acids in aqueous solution form polar pyridone dicarboxylic and tricarboxylic acids. After liquid/liquid partition with chloroform/water these substances can be isolated by ion exchange chromatography of the aqueous phase. They can be regarded as intermediate compounds on the route to a complete photomineralization. The structural elucidation is performed by such mass spectroscopic methods as MS, GC/MS and HPLC/MS, whereby HPLC/MS shows the highest reliability. Additionally¹H- and¹³C-NMR measurements confirm the structure of the main polar degradation product.     

乙草胺和丁草胺在土壤中的紫外光化学降解

采用实验室模拟实验研究了水分、pH值和表面活性剂对乙草胺和丁草胺在土壤中的紫外光降解行为的影响。结果表明，在湿度80％的土壤中，丁草胺和乙草胺的光解深度及光解速率均大于无水条件。随土壤pH值的增大，丁草胺在土壤中的光降解速率加快和光解深度加深。低浓度的阴 离子表面活性剂十二烷基苯磺酸钠（DDBS）促进丁草胺在土壤中的光解，使丁草胺在土壤中的光解深度增加。高浓度的DDBS对丁草胺在土壤中的光解有阻碍作用。阳离子表面活性剂十六烷基三甲基溴化铵（HDTMA）对丁草胺在土壤中的光解也有阻碍作用。