离子化有机污染物在沉积物和水相间的平衡分配计算

本文从热力学平衡原理出发,推导出离子化有机污染物在沉积物／水相间分配系数的理论计算模型,并以苯酚,邻氯酚,２,４－二氯酚、五氯酚和苯胺的吸附实验数据为例,计算了它们在中性分子和带电荷的离子形态下的分配系数Ｋｄ和Ｋｄｉ。以及总体分配系数Ｋｄｏ研究结果表明,离子化有机污染物在沉积物和分配行为不仅与该化学物的ｐＫａ和存在形态有关。而且还取决于环境介质的ｐＨ。     

苯甲酰苯胺类化合物溶解度和分配系数的测定及定量结构—性质相关研究

本文采用摇瓶法测定了１４各甲酰苯胺类化合物的溶解度及正辛醇／水分配系数,二者之间具有较好的相关性,应用线性溶剂化相关方法获得的相关方程,能更好地预测测苯甲酰苯胺类化合物的的水溶解度和正辛醇／水分配系数。     

传递系数法在滑坡稳定性评价中的几个问题探讨

本文运用LASA软件,分析了采用传递系数法计算滑坡稳定系数时,传递系数计算式、条块划分、渗透压力计算对稳定系数的影响。传递系数计算式的分析得出采用迭代法求解是比较合理的方法;通过实例对条块划分导致的影响分析,可知条块划分应当尽量与滑体的实际情况相符合才可以减小计算误差;渗透压力计算分析指出稳定性计算考虑动水压力时,应当根据不同情况选择不同水力坡降计算式。     

稀土元素对于减小电镀废液污染与提高钻头安全使用系数的作用研究

通过在生产电镀金刚石钻头的镀液中添加适当比例的稀土元素，可以促进毒性大，对环境污染严重的重金属离子的沉积，可以减小镀液浓度，控制污染总量，可以有效地提高电镀速度和电流效率，通过稀土元素在电镀钻头，热压钻头胎体中与其它有害物质的相互作用，改善了胎体性能，提高了钻头使用过程中的安全系数。     

Assessing microbial degradation of o-xylene at field-scale from the reduction in mass flow rate combined with compound-specific isotope analyses

In recent years, natural attenuation (NA) has evolved into a possible remediation alternative, especially in the case of BTEX spills. In order to be approved by the regulators, biodegradation needs to be demonstrated which requires efficient site investigation and monitoring tools. Three methods--the Integral Groundwater Investigation method, the compound-specific isotope analysis (CSIA) and a newly developed combination of both--were used in this work to quantify at field scale the biodegradation of o-xylene at a former gasworks site which is heavily contaminated with BTEX and PAHs. First, the Integral Groundwater Investigation method [Schwarz, R., Ptak, T., Holder, T., Teutsch, G., 1998. Groundwater risk assessment at contaminated sites: a new investigation approach. In: Herbert, M. and Kovar, K. (Editors), GQ'98 Groundwater Quality: Remediation and Protection. IAHS Publication 250, pp. 68-71; COH 4 (2000) 170] was applied, which allows the determination of mass flow rates of o-xylene by integral pumping tests. Concentration time series obtained during pumping at two wells were used to calculate inversely contaminant mass flow rates at the two control planes that are defined by the diameter of the maximum isochrone. A reactive transport model was used within a Monte Carlo approach to identify biodegradation as the dominant process for reduction in the contaminant mass flow rate between the two consecutive control planes. Secondly, compound-specific carbon isotope analyses of o-xylene were performed on the basis of point-scale samples from the same two wells. The Rayleigh equation was used to quantify the degree of biodegradation that occurred between the wells. Thirdly, a combination of the Integral Groundwater Investigation method and the compound-specific isotope analysis was developed and applied. It comprises isotope measurements during the integral pumping tests and the evaluation of delta13C time series by an inversion algorithm to obtain spatially integrated mean isotope values at the control planes. It was shown that the Rayleigh equation is applicable to spatially integrated mean isotope values in order to obtain the mean biodegradation between the consecutive control planes. All three approaches yielded consistently a 98-99% degradation of o-xylene.     

Simultaneous estimation of effective and apparent diffusion coefficients in compacted bentonite

Effective diffusion coefficients (D(e)) are usually measured by means of "through-diffusion" experiments in which steady state is reached, and the "time-lag" methods are used to estimate the apparent diffusion coefficient (D(a)). For sorbing radionuclides (as caesium), the time needed to reach steady-state conditions is very large, and the precision in D(a) determinations is not satisfactory. In this paper, a method that allows determining simultaneously effective and apparent diffusion coefficients in compacted bentonite without reaching steady-state conditions is described. Basically, this method consists of an "in-diffusion" experiment in which the concentration profile in the bentonite sample is used to estimate D(a), and the temporal evolution of the solute concentration in the reservoir is used to estimate D(e). This method has several advantages over the typical "through-diffusion" experiments, in particular: (a) experiment duration is significantly shorter, (b) D(a) values are measured with greater precision and (c) it is not necessary to maintain a constant solute concentration in the reservoir. This new method has been used to estimate the effective and apparent diffusion coefficients for caesium in FEBEX bentonite and in order to validate it, the results have been compared with results previously obtained with standard methods. Experimental results have been satisfactorily modelled using a simple model of diffusion in porewater and the measured value of D(e)(Cs) is very similar to D(e)(HTO) in the same bentonite. There is no evidence of "surface diffusion" in FEBEX bentonite for caesium.     

密度泛函方法预测二英类化合物(PCDD/Fs)的正辛醇/水分配系数

在B3LYP/6-31G水平上全优化计算了多氯代二苯并—对-二英和多氯代二苯并呋喃(PCDD/Fs)系列物的分子结构;基于得到的分子结构描述符,依据修正的线性溶解能理论,分别建立了PCDDs和PCDFs的正辛醇/水分配系数的定量结构-性质关系模型(R2分别为0.985和0.966),并用交叉验证法对模型进行了验证(q2分别为0.983和0.936),用t-检验对各变量进行了检验.检验结果表明,模型的预测能力优于AM1法、单苯环氯取代指数法和拓扑量子方法得出的模型.     

一种基于离心机试验辨识惯导平台误差系数的方法

针对离心机试验中惯导平台误差系数辨识问题,提出了一种基于谐波分析辨识误差系数的方法。首先,根据惯性器件误差模型推导了离心机试验下陀螺和加速度计的输出方程,其输出由各阶谐波分量构成。然后通过傅里叶分析得到各项谐波的幅值。最后根据谐波幅值与各项误差系数之间的关系反解得到各项误差系数。仿真结果验证了方法的有效性。     

东平湖CDOM吸收光谱特性及其来源解析

为分析东平湖有色可溶性有机物（CDOM）吸收特性、来源和空间分布的季节变化,分别于2013年8、12月以及2014年3月采集了35个表层水样,分析了各基本水质参数、CDOM吸收系数[a（440）]、比吸收系数[a^*（440）]和相对分子量参数M值的分布规律及CDOM吸收系数与水质参数之间的相关关系.结果表明：东平湖CDOM吸收系数a（440）呈现出枯水期 > 丰水期 > 平水期的规律,空间分布与CDOM比吸收系数[a^*（440）]相似.M值呈现出丰水期 < 平水期 < 枯水期的变化趋势.丰水期CDOM吸收系数与叶绿素a（Chla）具有显著相关关系;丰、平水期两季CDOM吸收系数与DOC存在显著相关关系.丰水期CDOM同时受外源和内源输入的影响,但以内源输入为主,主要来源于浮游植物降解产物;老湖镇湖区外源特征明显.平水期CDOM亦受内源和外源输入的双重影响,但浮游植物的腐烂降解不是CDOM的主要来源;北部湖区以外源输入为主.枯水期CDOM整体表现出较强的自生源特征,但相关分析显示,浮游植物降解并不是CDOM的主要来源,自生源特征可能与挖沙活动导致的悬浮物浓度增高有关;东南湖区因大汶河输入的影响呈现出较强的外源特征.利用东平湖丰、平水期两季CDOM浓度反演DOC浓度具有可行性.     

Heterogeneous uptake of gaseous hydrogen peroxide on mineral dust

The heterogeneous uptake processes of hydrogen peroxide on Arizona test dust and two types of authentic Chinese mineral dusts, i.e., Inner Mongolia desert dust and Xinjiang calciferous dust, were investigated using a Knudsen cell reactor coupled with a quadrupole mass spectrometer. The uptake coefficients were measured as a function of the initial concentration of H_2O_2 from 2.6 × 10~(11) to 1.2 × 10~(12)molecules/cm~3, and the temperature dependence of the uptake coefficients was investigated over a range from 253 to 313 K. The concentration of H_2O_2 showed little effect on the uptake coefficients of these heterogeneous processes. As a function of temperature, the initial uptake coefficients decrease with increasing temperature, whereas the steady state uptake coefficients of Arizona test dust and Inner Mongolia desert dust increase with increasing temperature. Implications for the understanding of the uptake processes onto mineral dust samples were also discussed.