Sorption of 3,4-dichloroaniline on four contrasting Greek agricultural soils and the effect of liming

Sorption of 3,4-dichloroaniline (3,4-DCA) on four typical Greek agricultural soils, with distinct texture, organic matter content and cation exchange capacities, was compared by using sorption isotherms and the parameters calculated from the fitted Freundlich equations. The sorption process of 3,4-DCA to the soil was completed within 48–72 h. The 3,4-DCA sorption on all soils was well described by the Freundlich equation and all sorption isotherms were of the L-type. The sandy clay loam soil with the highest organic matter content and a slightly acidic pH was the most sorptive, whereas the two other soil types, a high organic matter and neutral pH clay and a low organic matter and acidic loam, had an intermediate sorption capacity. A typical calcareous soil with low organic matter had the lowest sorption capacity which was only slightly higher than that of river sand. The 3,4-DCA sorption correlated best to soil organic matter content and not to clay content or cation exchange capacity, indicating the primary role of organic matter. The distribution coefficient (K _d) decreased with increasing initial 3,4-DCA concentration and the reduction was most pronounced with the highly sorptive sandy clay loam soil, suggesting that the available sorption sites of the soils are not unlimited. Liming of the two acidic soils (the sandy clay loam and the loam) raised their pH (from 6.2 and 5.3, respectively) to 7.8 and reduced their sorption capacity by about 50 %, indicating that soil pH may be the second in importance factor (after organic matter) determining 3,4-DCA sorption.     

Long-range atmospheric transport of three toxaphene congeners across Europe. Modeling by chained single-box FATEMOD program

Background, aims, and scope  Since toxaphene (polychlorocamphene, polychloropinene, or strobane) mixtures were applied for massive insecticide use in the 1960s to replace the use of DDT, some of their congeners have been found at high latitudes far away from the usage areas. Especially polychlorinated bornanes have demonstrated dominating congeners transported by air up to the Arctic areas. Environmental fate modeling has been applied to monitor this phenomenon using parallel zones of atmosphere around the globe as interconnected environments. These zones, shown in many meteorological maps, however, may not be the best way to configure atmospheric transport in air trajectories. The latter could also be covered by connecting a chain of simple model boxes. We aim to study this alternative approach by modeling the trajectory chain using catchment boxes of our FATEMOD model. Polychlorobornanes analyzed in biota of the Barents Sea offered one case to study this modeling alternative, while toxaphene has been and partly still is used massively at southern East Europe and around rivers flowing to the Aral Sea. Materials and methods  Pure model substances of three polychlorobornanes (toxaphene congeners P26, P50, and P62) were synthesized, their environmentally important thermal properties measured by differential scanning calorimetry, as evaluated from literature data, and their temperature dependences estimated by the QSPR programs VPLEST, WATSOLU, and TDLKOW. The evaluated property parameters were used to model their atmospheric long-range transport from toxaphene heavy usage areas in Ukraine and Aral/SyrDarja/AmuDarja region areas, through East Europe and Northern Norway (Finnmarken) to the Barents Sea. The time period used for the emission model was June 1997. Usual weather conditions in June were applied in the model, which was constructed by chaining FATEMOD model boxes of the catchment’s areas along assumed maximal air flow trajectories. Analysis of the three chlorobornanes in toxaphene mixtures function as a basis for the estimates of emission levels caused by its usage. High estimate (A) was taken from contents in a Western product chlorocamphene and low estimate (B) from mean contents in Russian polychloroterpene products to achieve modeled water concentrations. Bioaccumulation to analyzed lipid of aquatic biota at the target region was estimated by using statistical calculation for persistent organic pollutants in literature. Results  The results from model runs A and B (high and low emission estimate) for levels in sea biota were compared to analysis results of samples taken in August 1997 at Barents Sea. The model results (ng g⁻¹ lw): 4–95 in lipid of planktovores and 7–150 in lipid of piscivores, were in fair agreement with the analysis results from August 1997: 21–31 in Themisto libellula (chatka), 26–42 in Boreocadus saida (Polar cod), and 5–27 in Gadus morhua (cod) liver. Discussion  The modeling results indicate that the application of chained simple multimedia catchment boxes on predicted trajectory is a useful method for estimation of volatile airborne persistent chemical exposures to biota in remote areas. For hazard assessment of these pollutants, their properties, especially temperature dependences, must be estimated by a reasonable accuracy. That can be achieved by using measurements in laboratory with pure model compounds and estimation of properties by thermodynamic QSPR methods. The property parameters can be validated by comparing their values at an environmental temperature range with measured or QSPR-estimated values derived by independent methods. The chained box method used for long-range air transport modeling can be more suitable than global parallel zones modeling used earlier, provided that the main airflow trajectories and properties of transported pollutants are predictable enough. Conclusions  Long-range air transport modeling of persistent, especially photo-resistant organic compounds using a chain of joint simple boxes of catchment’s environments is a feasible method to predict concentrations of pollutants at the target area. This is justified from model results compared with analytical measurements in Barents Sea biota in August 1997: three of six modeled values were high and the other three low compared to the analysis results. The order of magnitude level was similar in both modeled (planktovore and piscivore) and observed (chatka and polar cod) values of lipid samples. The obtained results were too limited to firm validation but are sufficient to justify feasibility of the method, which prompts one to perform more studies on this modeling system. Recommendations and perspectives  For assessment of the risk of environmental damages, chemical fate determination is an essential tool for chemical control, e.g., for EU following the REACH rules. The present conclusion of applicability of the chained single-box multimedia modeling can be validated by further studies using analyses of emissions and target biota in various other cases. To achieve useful results, fate models built with databases having automatic steps for most calculations and outputs accessible to all chemical control professionals are essential. Our FATEMOD program catchments at environments and compound properties listed in the database represent a feasible tool for local, regional, and, according our present test results, for global exposure predictions. As an extended use of model, emission estimates can be achieved by reversed modeling from analysis results of samples corresponding to the target area. This article is dedicated to the memory of Professor Alexander B Terentiev (who passed away in November 2006), our true friend. With his Institute of Organo-Element Compounds, Russian Academy of Science, Moscow, he was an important main organizer of the six joint Finnish–Russian seminars (every third year since 1989) on the field (‘Chemistry and Ecology of Organo-Element Compounds’). He prompted us especially to search properties and environmental fates for various polyhalogen compounds. We remember him for his friendly character and great sense of humor.     

海岛非点源污染负荷估算方法研究

基于流域单元思想,提出一种非点源污染负荷估算方法：借助GIS提取模拟河网,识别流域边界,并划分汇水区和子流域,为流域非点源污染的估算提供基础的数据平台.在此基础上,与土地利用专题图叠加,计算各子流域内不同土地利用类型的面积,构建非点源负荷系统,利用各污染排放系数和入海系数,结合多年的降雨量,并引入坡度因子作为限制条件,估算污染负荷总量.结果显示,南长山岛非点源全氮、全磷年负荷量分别为11539kg和2025kg.氮污染中,各污染源强的贡献率依次为居民生活> 大气沉降> 土地利用> 畜禽养殖;磷污染中,各污染源强的贡献率依次为居民生活> 土地利用> 大气沉降> 畜禽养殖.基于此,探讨海岛地区非点源污染排放特征及对水环境质量影响,可为海岛地区污染物总量调控和环境健康发展提供一种技术方法.     

祁连山区亚高山灌丛土壤含水量的空间分布与月份变化规律

为了探究祁连山区不同灌丛类型的土壤水分时空变异规律,论文以祁连山排露沟小流域的箭叶锦鸡儿（Caragana jubata）、吉拉柳（Salix gilashanica）、金露梅（Potentilla fruticosa）、鲜黄小檗（Berberis diaphana）、甘青锦鸡儿（Caragana tangutica）5种灌丛为对象,建立固定样地,进行了一个生长季的分层（0~10、10~20、20~30、30~40、40~60 cm）土壤含水量监测。结果表明：1）在各灌丛类型样地之间,土壤含水量差异很大,由大到小依次为：箭叶锦鸡儿>吉拉柳>金露梅>鲜黄小檗>甘青锦鸡儿。2）在小流域内空间尺度上,地形（海拔、坡向）、气象（降水、温度）、植被、土壤等作为主要因素共同影响着土壤含水量的差异,导致土壤含水量的空间分布具有随海拔（降水）升高而增大、随地形遮荫作用增强而增大（阴坡高于阳坡）的变化规律。3）不同灌丛类型样地土壤含水量在生长季内各月的变异程度均为弱变异或中等变异,相同土层含水量变异系数大小顺序基本为：鲜黄小檗>箭叶锦鸡儿>吉拉柳>金露梅>甘青锦鸡儿。     

Multiphase redistribution differences of polycyclic aromatic hydrocarbons (PAHs) between two successive sediment suspensions

Successive sediment suspensions often happen in estuary, yet little research has probed into the difference in the release behaviors of organic compounds among different suspensions. This study took polycyclic aromatic hydrocarbons (PAHs) as typical organic contaminants and investigated the release behaviors between two successive suspensions with a particle entrainment simulator (PES). Results showed that successive sediment suspensions lowered the concentration of dissolved PAHs in the overlying water via facilitating the re-adsorption of dissolved PAHs onto the suspended particles. Fast-release and slow-release periods of PAHs were successively observed in the both suspensions. The concentration changes of dissolved PAHs in the second suspension were generally similar with but hysteretic to those in the first suspension. More vigorous desorption and re-absorption of PAHs were induced in the second suspension. Successive sediment suspensions obviously decreased the concentrations of mineral composition and organic matters in the overlying water, which significantly affects multiphase distribution of PAHs.     

Regression models for octanol‐water partition coefficients,and for bioconcentration in fish

Octanol‐water partition coefficients (P) of a number of organochlorine insecticides (OCs) are presented. The merits of log‐log regressions between experimental ? values and calculated estimates of P, solute activity coefficients in water, solute molecular surface area data, and reversed‐phase liquid‐chromatographic net retention data, are critically evaluated for several classes of pollutants: polycyclic aromatic hydrocarbons (PAHs), chlorinated benzenes, chlorinated biphenyls and OCs. Special attention is paid to the predictive accuracy of such semi‐empirical regressions in connection with possible effects of solute molecular shape and polarity.

Finally, bioconcentration and ‐accumulation of hydrophobic pollutants in fish are briefly discussed.     

基于TLSER和QSPR关系预测PAHs和PCBs的LDPE膜-空气分配系数

有机污染物在被动采样材料与环境介质之间的平衡分配系数(K_P),是测定环境中有机污染物浓度的重要参数,但K_P值大部分都需要经过繁琐的实验测定获取,无法逐个测定数量繁多的污染物,因此需开发一种预测K_P值的方法。为此,搜集整理了一些多环芳香烃(PAHs)和多氯联苯(PCBs)的低密度聚乙烯(LDPE)-空气分配系数(K_PA)的实测值,基于理论线性溶解能(TLSER)和定量结构性质关系(QSPR),利用逐步多元线性回归(MLR)分别构建了预测K_PA值的模型。模型的决定系数R2adj分别为0.927和0.956,交叉验证系数Q2LOO分别为0.915和0.946,外部系数Q2ext分别为0.913和0.960。结果表明,2种模型具有良好的拟合优度、稳健性和预测能力,并解释了模型的机理。所构建的2种模型均可用来预测应用域内有机污染物的LDPE膜-空气分配系数。     

Volatilization characteristics of organic solutes in stirred solution

The effects of turbulence intensity (velocity gradient, G (s⁻¹)), Henry's law constant (H), and molecular weight (M) on the volatilization rates of organic compounds are examined using changes in the mass transfer coefficients (K_OL (cm/min)) under specific liquid-mixing intensities. The selected compounds were divided into three groups according to their H values (mole in gas/mole in liquid, dimensionless), which ranged from 10² to 10⁻⁵. The relationship of the K_OL relative to G, H and M was obtained via multiple regression. The obtained values of these parameters indicate that the primary factor affecting the K_OL values of the high H compounds is their M values. The effects of the H values on the K_OL values of the high H compounds can be neglected. On the other hand, the H value is the major factor determining the K_OL values of the low H compounds. The changes in the K_OL values of the different H compounds exhibit different profiles as the liquid-mixing intensity increases. The M and H values of middle H compounds possibly affect their K_OL values. The effects of the liquid-mixing intensity on the K_OL values of the organic compounds increase with increasing H values. The variation in the K_OL values might be a result of the concentration of the organic compounds at the interface between the liquid and gas films. The empirical relationship between K_OL and some selected parameters, G, H and M, is examined in this study. The obtained results can help to estimate volatilization loss of organic solutes in wastewater treatment facilities.     

多环芳烃在岩溶地下河表层沉积物-水相的分配

利用实测老龙洞地下河水中和沉积物中多环芳烃(polycyclic aromatic hydrocarbons,PAHs)的实际浓度,获取了溶解相-沉积物中PAHs的分配系数Kp值.研究了老龙洞地下河PAHs在水相和沉积物中的质量浓度变化及其在水相和沉积物间的分配.研究结果表明水相和沉积物中PAHs质量浓度分别为81.5~8 089 ng·L-1,平均值(1 439±2 248)ng·L-1和58.2~1 051 ng·g-1,平均值(367.9±342.6)ng·g-1;PAHs组成均以2~3环为主,但沉积物中明显富集高环PAHs.沉积物-水相Kp值分布在55.74~46 067 L·kg-1范围内,随PAHs环数的增加而增大.沉积物-水相中实测的有机碳分配系数(lg Koc)大部分高于预测值上限,PAHs强烈吸附在沉积物上.lg Koc与正辛醇-水分配系数(lg Kow)呈较好的线性自由能关系(R2=0.75),但其斜率小于1,推测地下河沉积物对PAHs化合物的吸收能力较差.     

安全投入模型的研究

从安全投入产出分析的角度为安全投入决策提出一个新视角,相比于直接用生产函数等数学方法得到安全投入与安全产出的关系,通过软件分析得出各个要素与安全产出的关系,再进行拟合,最后得到安全产出回归方程,这样得到的分析结果更准确和可信。通过实例可以证明如果要确定安全投入要素之间的分配比例可以采用生产函数分析方法,如要预测安全产出可以采用根据散点图做出的回归方程。另外,在分析安全投入要素相对重要度时,因为各个投入要素的数量级和单位的不同,回归方程系数应选择标准化回归系数;要预测安全投入产生的安全产出则应采用非标准化回归系数。