单甲脒水中溶解度及正辛醇／水分配系数的测定

有毒有机化合物在水中的溶解度(WS)及正辛醇/水分配系数(K_(ow)),是描述其在环境中行为的两个重要物理化学参数。本文用溶解度平衡曲线法和振荡法,测得单甲脒在水中的溶解度为21.8±1.3mg/1(25℃),其在正辛醇/水中的分配系数lgK_(ow)为2.92±0.06。     

Selective removal of organochlorine pesticides (OCPs) from aqueous solution by triolein-embedded composite adsorbent

A novel composite adsorbent (CA-T) was used for the selective removal of organochlorine pesticides (OCPs) from aqueous solution. The adsorbent was composed of the supporting activated carbon and the surrounding triolein-embedded cellulose acetate membrane. Scanning electron microscopy (SEM), N₂ adsorption isotherms and fluorescence methods were used to characterize the physicochemical properties of CA-T. Triolein was perfectly embedded in the cellulose acetate membrane and deposited on the surface of activated carbon. The adsorbent was stable in water and no triolein leakage was detected during the test periods. Some organochlorine pesticides (OCPs), such as dieldrin, endrin, aldrin, and heptachlor epoxide, were used as model contaminants and removed by CA-T in laboratory batch experiments. The adsorption isotherm followed the Freundlich equation and the kinetic data fitted well to the pseudo-second-order reaction model. Results also indicated that CA-T appeared to be a promising adsorbent with good selectivity and satisfactory removal rate for lipophilic OCPs from aqueous solutions when present in trace amounts. The adsorption rate and removal efficiency for lipophilic OCPs were positively related to their octanol-water partition coefficients (log K _ow). Lower residual concentrations of OCPs were achieved when compared to granular activated carbon (GAC).     

农药微生物降解性与农药疏水性参数间的相关性

在纯培养条件下，产碱菌属广说性降解菌ＹＦ１１对对硫磷，甲基对硫磷，杀螟松，氰戊菊酯，溴氰菊酯，甲氰菊酯，氯氰菊酯，三氟氯氰菊酯，氯菊酯的降解速率的差异主要是由各杀虫剂的疏水性参数的不同引起的，两之间存在较好的相关性：ｌｏｇＫ＝２．２１－０．２６ｌｏｇＫｏｗ，ｒ＝０．９７３９。     

一种区域环境风险评价方法——信息扩散法

针对区域环境风险多源、多途径和多敏感目标的特点,基于网格法提出一种区域环境风险评价的信息扩散法.该方法基于模糊集理论,可对单个环境风险源的风险值进行有效扩散.通过信息扩散获得的区域环境风险值可在一定的区域环境风险分级标准下进行聚类分析,并得到环境风险分区图.选取广州市南沙区黄阁镇和南沙镇为案例应用该方法进行区域环境风险评估.结果表明,利用该方法可为政府部门优化产业布局、制订风险预防措施和应急管理措施等提供科学依据.     

12种有机物在鲤鱼体内富集与释放行为的研究

本实验对第二松花江江水和鱼体中多次检出的12种化合物在鲤鱼(Cyprinus carpio L.)体内累积与释放行为进行了研究。提出了一个描述有机物在鱼体内富集行为的模式。给出了几种化合物生物富集因子(BCF)以及该因子与辛醇-水分配系数(K_(ow))之间的关系。研究结果表明,这些有机污染物在鱼体内的富集行为互不影响。含硝基化合物富集倍率低且易于释放,有机物是以一级动力学方式在鱼体内累积和释放。     

海水条件下Cd-CaCO3共沉淀过程的动力学表达:方解石

采用稳定加液系统对海水中方解石(CaCO3)沉淀形成时镉元素(Cd)的共沉淀现象进行了实验模拟,并对Cd-Ca-CO3共沉淀过程中Cd的分异行为进行了定量评估。实验结果显示:Cd在共沉淀过程中发生了明显的分异,基于方解石沉淀和海水溶液各自Cd/Ca比值计算得出的分异系数分别为33.0～61.8(5℃)、31.8～55.0(15℃)和17.4～31.8(25℃)。在各个温度下,DCd值都随着方解石沉淀速率的增加而有规律的下降。进一步分析表明温度和碳酸根浓度是影响Cd分异行为的根本因素。这一实验结果对于Cd/Ca古海洋指标的应用具有重要的参考价值。     

Model-based experimental design for assessing effects of mixtures of chemicals

We exposed flour beetles (Tribolium castaneum) to a mixture of four poly aromatic hydrocarbons (PAHs). The experimental setup was chosen such that the emphasis was on assessing partial effects. We interpreted the effects of the mixture by a process-based model, with a threshold concentration for effects on survival. The behavior of the threshold concentration was one of the key features of this research. We showed that the threshold concentration is shared by toxicants with the same mode of action, which gives a mechanistic explanation for the observation that toxic effects in mixtures may occur in concentration ranges where the individual components do not show effects. Our approach gives reliable predictions of partial effects on survival and allows for a reduction of experimental effort in assessing effects of mixtures, extrapolations to other mixtures, other points in time, or in a wider perspective to other organisms.     

基于TLSER关系预测POPs在PUF与空气中的分配系数

为开发一种简洁高效预测K_PA值的方法,本文收集了包含多氯联苯（PCBs）、苯类（Benzenes）、多环芳香烃（PAHs）和杀虫剂（Pesticides）等,共95种污染物在聚氨酯泡沫塑料（PUF）与空气中分配系数（K_PA）的实验值,基于理论线性溶解能关系（TLSER）,运用逐步多元线性回归（MLR）构建了预测K_PA值的模型.结果表明,模型的决定系数R_adj²为0.901,外部验证系数Q_ext²为0.748.TLSER模型有较好的拟合度、稳健性和预测能力,可以预测应用域内POPs在PUF和空气之间的分配系数.     

Partition Constants and Adsorption/Desorption Hysteresis for Volatile Organic Compounds on Soil from a Louisiana Superfund Site

The adsorption of four volatile organic compounds (1,4-dichloro-benzene, 1,2-dichloroethane, 1,2,2-trichloroethane and 1,1,2,2,-tetrachloroethane) on three soil types from a Superfund site (Petroprocessors Inc) in Baton Rouge, LA was studied with the purpose of obtaining an overall correlation for inclusion in a groundwater transport model being developed for site remediation. The soil-water partition constant, K_d was determined using a standard ASTM procedure (E–1195–87). Using the data for different soil types (fraction organic carbon between 0.11% and 1.13%) and different mineral surface areas (7 to 45 m²/g), the organic carbon contribution (K_oc) and the mineral matter contribution (K_min) to the partition constant were determined. The soils obtained were either from the Pleistocene period or recent shallow deposits at the site. Both log K_oc and log K_min were linearly correlated to log K_ow, the octanol-water partition constant. This data provided the basis for obtaining a general correlation for K_d on different soil types at the site. The predicted values were in agreement with that for a composite soil from the same site. The desorption of compounds from the high clay soil after the 24 hour adsorption period was observed to show a biphasic behavior, namely, an easily desorbed fraction and a desorption resistant fraction. The easily desorbed fraction was found to be satisfactorily predicted using the conventional K_d as obtained from the adsorption experiment. The slowly desorbing fraction had a time constant of several weeks. The concentration in the desorption resistant compartment was found to be dependant on the initial amount of contaminant available for adsorption. The aqueous phase concentration in equilibrium with the desorption resistant fraction was found to be 8 g/L for dichlorobenzene and 12 g/L for dichloroethane.     

硅酸盐熔/流共存体系中元素分配系数研究的几个问题

随着实验地球化学的快速发展,元素在熔/流体系中的分配行为引起研究者的广泛关注。自二十世纪70年代以来,研究者对元素在硅酸盐熔/流体系中的分配行为进行了大量研究,并取得了一些重要成果。本文对近30年来国内外在该领域的研究现状进行了归纳、总结,探讨了固相组成、金属元素本身的物理化学性质、流体组分中阴、阳离子对硅酸盐熔/流体系中元素分配行为的影响,并指出了当前研究中存在的主要问题,希望对今后的实验研究起到一定的借鉴作用。