烃的含氧衍生物自燃点的QSPR预测研究

应用定量构效关系（QSPR）方法对烃的含氧衍生物的自燃点（AIT）及其与分子结构间的内在定量关系进行了研究。选取国际电工委员会（IEC）数据库中的76种烃的含氧衍生物作为样本集,选择65 种作为训练集用于建立预测模型,11 种作为测试集。采用遗传算法（GA）对变量进行筛选,结合线性和非线性方法分别建立多元线性回归( MLR) 模型和支持向量机( SVM) 模型,理论预测得到了11种烃的含氧衍生物的自燃点,最后对所构建模型的性能及应用域进行了评价。结果表明,经GA筛选得出MATS2e、nCOH、Dv、BEHv2、nCHR、GATS1v、IDE、Du等8种特征分子描述符,GA-MLR和GA-SVM模型的理论预测值与实验值均较为相符且后者更优,两个预测模型均比较稳定,且具备较强的预测能力和泛化推广性能。     

Construction of response surfaces based on progressive-lattice-sampling experimental designs with application to uncertainty propagation

Response surface functions are often used as simple and inexpensive replacements for computationally expensive computer models that simulate the behavior of a complex system over some parameter space. Here we examine several data fitting and interpolation techniques (finite-element interpolation, kriging, and polynomial regression) that can be used to construct a sequence of progressively upgraded response surface approximations based on Progressive Lattice Sampling (PLS) incremental experimental designs. PLS is a paradigm for structured sampling of a hypercube parameter space by placing and incrementally adding samples at each level of the design in a manner intended to efficiently leverage the samples at all previous levels. When combined with compatible interpolation methods, PLS can be used to construct efficiently upgradable response surface approximations. Upon upgrading, convergence heuristics are gained that can be used to estimate the magnitude of the approximation error entailed in the response surface. The three interpolation methods tried here are examined for fitting and convergence behavior in several test problems.     

节理剪切应力–位移本构模型及剪胀现象分析

 在法向与切向荷载的共同作用下,节理剪切应力–位移曲线宏观表现为峰前呈剪切硬化、峰后呈剪切软化现象：当微凸体爬坡效应占主导地位时,宏观表现为剪切硬化;当微凸体在剪切过程中磨损累积到一定程度时,宏观表现为剪切软化。剪胀硬化、磨损软化共同控制节理的剪切力学行为。在详细分析已有的剪切应力–位移本构模型的局限性的基础上,提出硬化–软化全剪切本构模型,采用单个函数反映节理剪切位移曲线的变化特征,其优点为：(1) 避免分段讨论剪切位移曲线特征、分段求取拟合参数的麻烦;(2) 在整个讨论区域内存在一个峰值且峰值处斜率为0;(3) 当剪切位移足够大时,强度趋于残余值,体现出节理面材料的力学特征。对不同类型的剪切位移曲线进行分析,该模型均表现出较强的适应性。同时分析现有的剪胀模型,其主要缺陷是不能反映初始剪缩现象与体现真正的剪胀起始点。在分析典型剪胀曲线基本特征的基础上,采用分段函数考虑剪胀特征,能较好地拟合剪胀曲线。     

PAH degradation by UV/H2O2 in perfluorinated surfactant solutions.

Polycyclic aromatic hydrocarbons (PAHs) solubilized in perfluorinated surfactant (PFS) solutions were degraded by direct photolysis and UV/H2O2 process. The subsequent recovery and reuse of these surfactant solutions were also demonstrated. Phenanthrene and pyrene were selected as representative PAHs and an anionic PFS: ammonium perfluorooctanoate (APFO) was used. In our experiments, micellar APFO solutions retarded the phenanthrene photolysis and enhanced the pyrene photolysis. The results indicate that the photochemical reactivity of compound in micelles is strongly dependent on specific properties of the solubilizate, possibly due to the different excited state behaviors of compound. UV/H2O2 process exhibits a greatly enhanced rate of PAH photolysis in both water and APFO compared to direct photolysis. indicating that hydroxyl radicals may be generated or penetrated at the sites of PAHs solubilized in the micelles. Additionally. a smaller rate enhancement by UV/H2O2 in micelles than in water suggests that micelles provide some degree of protection from hydroxyl radical attack. The possibility of recovery and reuse of PFS has been demonstrated by measuring the solubilizing capacity of APFO after direct photolysis and UV/H2O2 process. Overall, this study demonstrates UV/H2O2 process can be an effective treatment method for not only PAH degradation but also surfactant recovery and reuse.     

Sources of polycyclic aromatic hydrocarbons (PAHs) in street dust in a tropical Asian mega-city, Bangkok, Thailand

We collected samples of roadside air, automobile exhaust soot, tires, asphalt, and used engine oil in a tropical Asian mega-city, Bangkok, Thailand, and analyzed them for polycyclic aromatic hydrocarbons (PAHs) and hopanes. The concentrations and compositions of PAHs and hopanes were utilized to identify the sources of PAHs in street dust, in which high concentrations of PAHs were reported in our previous study. Weight-based concentrations of total PAHs had the following order: gasoline-powered vehicle soot (2600+/-2900 microg/g; n=4)>diesel-powered vehicle soot (115+/-245 microg/g; n=7) approximately roadside aerosols (101+/-35 microg/g; n=5) approximately used engine oil (97+/-65 microg/g; n=4) approximately tire wear particles (82+/-41 microg/g; n=5)>asphalt (2.3+/-1.6 microg/g; n=3)>street dust (1.1+/-0.8 microg/g; n=10). In cluster analysis, all the source materials fell into different clusters from that in which street dust fell, indicating that multiple source materials contribute to PAHs in the street dust. Multiple regression analysis of PAH profiles and diagnostics of hopane compositions identified tire debris as the major contributor of PAHs to street dust, followed by diesel vehicle exhaust.     

The role of UV-B on the degradation of PCDD/Fs and PAHs sorbed on surfaces of spruce (Picea abies (L.) Karst.) needles

Photodegradation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polycyclic aromatic hydrocarbons (PAHs) sorbed on surfaces of spruce (Picea abies (L.) Karst.) needles was investigated. The role of sunlight and, in particular, the role of short wavelength UV-B radiation were studied in a sun simulator under controlled environmental conditions. The photodegradation of PCDD/Fs and PAHs follows first-order kinetics. Simulated sunlight containing UV-B induced two phases of photodegradation kinetics for PCDD/Fs, whereas no distinct phases of the kinetics were observed for PAHs. UV-B radiation plays a much more important role on the photodegradation for PCDD/Fs than that for PAHs. Direct photolysis dominates the photodegradation of PCDD/Fs and PAHs.     

Carbaryl, propham and chlorpropham: A comparison of the rates of hydrolysis and photolysis with the rate of biolysis

Alkaline hydrolysis half-lives, based on second-order alkaline hydrolysis rate constants, for carbaryl, propham (IPC), and chlorpropham (CIPC) at pH 9 (27°C) are 0.15 > 1 × 10⁴, and > 1 × 10⁴ days, respectively. The direct photolysis half-life for carbaryl in sunlight is 6.6 days in distilled water. Calculated minimum half-lives for the direct photolysis of IPC and CIPC in a clear water body near the surface are 254 and 121 days, respectively. Half-lives, based on second-order fungal rate constants, for the IPC and CIPC are calculated under given conditions. Kinetic data on hydrolysis, photolysis, and biolysis are employed as a basis for comparison of the relative importance of these three degradation processes.     

最优组合预测模型在高填方体沉降中的应用研究

针对Logistic和Gompertz路堤沉降预测模型对于高填方土体后期沉降量预测精度较差的问题,该文基于Logistic和Gompertz预测模型的共性和个性,在充分考虑二者各自优势和特定局限性的基础上,对二者进行了最优化组合。以组合模型的最小对数误差平方和为目标函数求解最优加权系数,进而推导出最优加权几何平均组合预测模型,以提高高填方土体沉降预测精度的置信度。通过各预测模型对实际高填方土体工程的实测沉降数据进行拟合分析,验证最优组合预测模型在高填方土体沉降预测中的可行性。结果表明：最优组合预测模型的精度及可靠性均优于任一单一模型,适应性更强,尤其当监测时间超过曲线拐点后,几乎接近实测值。组合预测模型能够适用于多个模型优化组合,可涵盖各单一模型的优劣势,只要在权重比不出现负值的情况下,可大幅度的提高沉降预测精度。因而此组合预测模型可作为高填方土体后期沉降预测的一种有效方法。     

偏最小二乘回归在GPS高程拟合中的应用

偏最小二乘回归是一种多元统计数据分析方法,它能有效克服自变量间的多重相关性问题。本文简述了偏最小二乘回归的原理、如何确定最佳成分数以及模型辅助分析。通过GPS高程拟合实例证实,偏最小二乘回归受自变量相关性影响小,拟合效果较好,计算结果稳定。     

城市公园声景长时感知模型研究—以加拿大温哥华市3个城市公园为例

为探究循环神经网络(RNN)对长时间模拟城市公园声景感知响度(PLS)和感知协调度(PHS)的适用性,采用具有时序记忆和延迟功能的Elman神经网络和NARX神经网络分别进行验证.将城市公园声景和光景客观指标作为输入层,PLS和PHS作为输出层进行神经网络训练和模拟.研究结果显示:1)PLS和PHS同时与等效A声级(L...     

Biological half-lives of eight polycyclic aromatic hydrocarbons (PAHs) in rainbow trout (Salmo gairdneri)

Adult rainbow trout were exposed to a single oral dose containing a mixture of eight PAHs, and fish were sampled at intervals between 5–48 days after exposure. Regression analyses on whole fish indicate levels declined significantly in four of the compounds monitored. Their biological half-lives were estimated as 9 days for phenanthrene, 7 days for fluorene and anthracene and 6 days for fluoranthene. No reliable estimates could be derived for benzo[a]pyrene, benz[a]anthracene, chrysene or pyrene because of low or nondetectable concentrations at the first sample interval although it could be suggested that their half-lives would be less than several days. The data also suggested that these PAHs are poorly absorbed by trout.