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.     

用环己烷氧化副产物制备浮选剂

在固体酸催化剂作用下,用环己烷氧化制备环己酮的副产物——酸性油和轻质油进行酯化反应,制备了羧酸混合酯,酯化反应的最佳工艺条件：n（C4-C5醇）：n（有机羧酸）=1．2：1,催化剂质量分数为1．5％,反应温度为110-160℃,反应时间为5h。经应用评价结果表明,该羧酸混合酯是一种性能优异的选煤浮选剂。     

A novel, simple and sensitive resonance scattering spectral method for the determination of chlorite in water by means of rhodamine B

A new resonance scattering method was proposed for the determination of chlorite, basing on the resonance scattering effect of rhodamine dye. In HCl-sodium acetate buffer solution, chlorite oxidizes 1- into 12 and the reaction of 12 and excess 1- results in If. It is respectively combined with rhodaminc dyes, including rhodamine B （RhB）, butyl rhodamine B （b-RhB）, rhodamine G （RhG） and rhodamine S （RhS）, to form association complex particles, which exhibit stronger resonance scattering （RS） effect at 400 nm. The chlorite concentration of ClO2 in the range of 0.00726-0.218 μg/ml, 0.0102-0.292 μg/ml, 0.00726-0.145 μg/ml and 0.0290- 0.174 μg/ml is respectively linear to the RS intensity of association complex particle systems at 400 nm for the RhB, b-RhB, RhG and RhS. The detection limits of the four systems were respectively 0.00436, 0.00652, 0.00580 and 0.01450μg/ml ClO2^-. In the four systems, the RhB system possesses good stability and high sensitivity. It has been applied to the analysis of chlorite in wastewater with satisfactory results.     

基于模糊推理的FRAM事故定量分析方法研究

为有效克服FRAM事故分析中无法进行定量分析的缺陷,提出结合模糊推理技术的Fuzzy FRAM模型。此改进模型基于FRAM识别系统运行状态;依据功能输出要素的时间/精度属性利用Matlab构建2阶模糊推理系统量化功能输出质量;根据通用性能条件(CPC)及功能输入耦合端口构建功能评价体系,针对评价体系中存在的不确定性信息融合及建模问题,采用模糊证据推理技术,通过模糊信度结构建立、数据处理、信息融合测度后获得功能的风险指数;以既有铁路危险品运输事故为例,验证方法的可行性。结果表明:Fuzzy FRAM模型的评估结果较为精确,是FRAM分析方法的有效补充。     

Fe^3＋掺杂TiO2/凹凸棒复合材料的光催化性能

采用酸催化的溶胶-凝胶法制备了一系列Fe^3＋掺杂TiO2/凹凸棒（Fe^3＋-TiO2/ATP）复合光催化剂材料。在可见光条件下,以亚甲基蓝（MB）溶液的光催化降解反应,评价了样品的光催化性能,研究了TiO2负载量、Fe^3＋掺杂量和焙烧温度对复合材料光催化性能的影响。在单因素实验的基础上,采用正交实验设计（L25（53））优化了催化剂的制备条件。光催化实验结果表明,MB在复合材料上的光催化降解反应遵循Langmuir-Hinshelwood（L-H）动力学模型。正交实验结果表明,当TiO2负载量为15%、Fe^3＋掺杂量为0.5%和焙烧温度为550℃时,得到的复合材料对MB的光催化降解效率最佳,测得表观反应速率常数kapp为6.09×10^-3min^-1,反应4 h后MB的降解率（Dt）可达75.88%,相同实验条件下与P25（1.51×10^-3min^-1）相比较,反应速率提高了4.03倍,降解率提高了45.05%。另外,复合材料的沉降性能优于P25,易于分离,是一类有应用前景的复合光催化剂。敏世雄王芳魏立强王永生冯雷佟永纯韩玉琦     

Role of black carbon in the distribution of polychlorinated dibenzo-p-dioxins/dibenzofurans in aged field-contaminated soils

Floodplain soils containing elevated levels of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) were collected from several locations along the Tittabawassee River (Michigan, USA). The PCDD/F profiles of these soils exhibited distinct congener patterns consistent with byproducts from either chloralkali manufacturing or chlorophenols productions. Black carbon (BC) particles were isolated for the first time from floodplain soil impacted by PCDD/Fs. Petrographic analysis showed that BC particles, including coal, oxidized coal, metallurgical coke, depositional carbon, coal tar/pitch, cenosphere, and charcoal, comprised approximately 30% by volume of the organic fraction with size range of 250 μm-2000 μm from a typical floodplain soil. The BC particles with anthropogenic origin such as pitch and coke associated with the chloralkali production process served as both the source and subsequent transporter for the highly hydrophobic PCDD/Fs. These anthropogenic BC particles were enriched with high levels of PCDFs, containing approximately 1000-fold the concentration found in the bulk soil. The strong association of PCDD/Fs with anthropogenic BC directly impacts the physicochemical and biological availability thus the risk associated with these hydrophobic organochlorines in soils and sediments.     

饱和土半空间中地下圆形衬砌洞室对平面SV波的散射

在Biot饱和多孔介质动力学理论的基础上,利用Fourier-Bessel级数展开法,通过对含有衬砌洞室的局部场地进行波场分析,得到饱和土半空间中圆柱形衬砌洞室对平面SV波的散射问题的解析解。经验证,本文得到的解可以退化为半空间单相介质的情况。通过与已有的单相弹性介质半空间中圆柱形衬砌洞室对平面SV波散射问题的解析解的对比,验证了此解的正确性。在解析解的基础上,数值计算给出洞口动应力集中放大系数,分析了入射频率和孔洞埋深对柱面上的应力集中因子的影响。     

The structure of the fire fighting foam surfactant Forafac®1157 and its biological and photolytic transformation products

For several decades, perfluorooctane sulfonate (PFOS) has widely been used as a fluorinated surfactant in aqueous film forming foams used as hydrocarbon fuel fire extinguishers. Due to concerns regarding its environmental persistence and toxicological effects, PFOS has recently been replaced by novel fluorinated surfactants such as Forafac®1157, developed by the DuPont company. The major component of Forafac®1157 is a 6:2 fluorotelomer sulfonamide alkylbetaine (6:2 FTAB), and a link between the trade name and the exact chemical structure is presented here to the scientific community for the first time. In the present work, the structure of the 6:2 FTAB was elucidated by ¹H, ¹³C and ¹⁹F nuclear magnetic resonance spectroscopy and high-resolution mass spectrometry. Moreover, its major metabolites from blue mussel (Mytilus edulis) and turbot (Scophthalmus maximus) and its photolytic transformation products were identified. Contrary to what has earlier been observed for PFOS, the 6:2 FTAB was extensively metabolized by blue mussel and turbot exposed to Forafac®1157. The major metabolite was a deacetylated betaine species, from which mono- and di-demethylated metabolites also were formed. Another abundant metabolite was the 6:2 fluorotelomer sulfonamide. In another experiment, Forafac®1157 was subjected to UV-light induced photolysis. The experimental conditions aimed to simulate Arctic conditions and the deacetylated species was again the primary transformation product of 6:2 FTAB. A 6:2 fluorotelomer sulfonamide was also formed along with a non-identified transformation product. The environmental presence of most of the metabolites and transformation products was qualitatively demonstrated by analysis of soil samples taken in close proximity to an airport fire training facility.     

氮掺杂TiO2可见光光催化剂的制备及性能

以尿素和钛酸丁酯为原料,通过溶胶-凝胶法低温下制备了高可见光催化活性的氮掺杂TiO2(NDT)光催化剂,采用XRD、TEM、BET和UV-Vis DRS等测试手段对其进行了表征,并在自制光催化反应器中降解甲基橙评价了样品的光催化活性。结果表明,当氮与钛的摩尔比为0.5∶1时,350℃焙烧的样品(NDT350)具有最佳的可见光光谱吸收和光催化活性,该催化剂为锐钛矿晶相,平均粒径为21 nm,比表面积为89.13 m2/g。可见光辐照下,NDT350降解甲基橙的表观反应速率常数为1.381×10-2min-1,是商业P25催化剂的16.85倍。NDT350优良的可见光催化活性与其大的比表面积和强烈的可见光光谱吸收有关。