Modelling the migration of contaminants through variably saturated dual-porosity, dual-permeability chalk

In the Hesbaye region in Belgium, tracer tests performed in variably saturated fissured chalk rocks presented very contrasting results in terms of transit times, according to artificially controlled water recharge conditions prevailing during the experiments. Under intense recharge conditions, tracers migrated across the partially or fully saturated fissure network, at high velocity in accordance with the high hydraulic conductivity and low effective porosity (fracture porosity). At the same time, a portion of the tracer was temporarily retarded in the almost immobile water located in the matrix. Under natural infiltration conditions, the fissure network remained inactive. Tracers migrated downward through the matrix, at low velocity in relation with the low hydraulic conductivity and the large porosity of the matrix. Based on these observations, Brouyère et al. (2004a) [Brouyère, S., Dassargues, A., Hallet, V., 2004a. Migration of contaminants through the unsaturated zone overlying the Hesbaye chalky aquifer in Belgium: a field investigation, J. Contam. Hydrol., 72 (1-4), 135-164, doi: 10.1016/j.conhyd.2003.10.009] proposed a conceptual model in order to explain the migration of solutes in variably saturated, dual-porosity, dual-permeability chalk. Here, mathematical and numerical modelling of tracer and contaminant migration in variably saturated fissured chalk is presented, considering the aforementioned conceptual model. A new mathematical formulation is proposed to represent the unsaturated properties of the fissured chalk in a more dynamic and appropriate way. At the same time, the rock water content is partitioned between mobile and immobile water phases, as a function of the water saturation of the chalk rock. The groundwater flow and contaminant transport in the variably saturated chalk is solved using the control volume finite element method. Modelling the field tracer experiments performed in the variably saturated chalk shows the adequacy and usefulness of the new conceptual, mathematical and numerical model.     

Dip-angle influence on areal DNAPL recovery by co-solvent flooding with and without pre-flooding

A two-dimensional (2D) laboratory model was used to study effects of gravity on areal recovery of a representative dense non-aqueous phase liquid (DNAPL) contaminant by an alcohol pre-flood and co-solvent flood in dipping aquifers. Recent studies have demonstrated that injection of alcohol and co-solvent solutions can be used to reduce in-situ the density of DNAPL globules and displace the contaminant from the source zone. However, contact with aqueous alcohol reduces interfacial tension and causes DNAPL swelling, thus facilitating risk of uncontrolled downward DNAPL migration. The 2D laboratory model was operated with constant background gradient flow and a DNAPL spill was simulated using tetrachloroethene (PCE). The spill was dispersed to a trapped, immobile PCE saturation by a water flood. Areal PCE recovery was studied using a double-triangle well pattern to simulate a remediation scheme consisting of an alcohol pre-flood using aqueous isobutanol ( approximately 10% vol.) followed by a co-solvent flood using a solution of ethylene glycol (65%) and 1-propanol (35%). Experiments were conducted with the 2D model oriented in the horizontal plane and compared to experiments at the 15 degrees and 30 degrees dip-angle orientations. Injection was applied either in the downward or upward direction of flow. Experimental results were compared to theoretical predictions for flood front stability and used to evaluate effects of gravity on areal PCE recovery. Sensitivity experiments were performed to evaluate effects of the alcohol pre-flood on PCE areal recovery. For experiments conducted with the alcohol pre-flood and the 2D model oriented in the horizontal plane, results indicate that 89-93% of source zone PCE was recovered. With injection oriented downward, results indicate that areal PCE recovery was 70-77% for a 15 degrees dip angle and 57-59% for a 30 degrees dip angle. With injection oriented upward, results indicate that areal PCE recovery was 57-60% at the 30 degrees dip angle, which was similar to PCE recovery for injection in the downward flow direction. Lower areal PCE recovery at greater dip angles in either direction of flow was attributed to DNAPL swelling and migration, flood front instabilities and bypassing of the displaced fluid past the extraction wells during the alcohol pre-flood. Additional results demonstrate that the use of an alcohol pre-flood can be beneficial in improving DNAPL recovery in the horizontal orientation, but pre-flooding may reduce areal recovery efficiency in dip-angle orientations. This study also demonstrates the use of theoretical perturbation (fingering) analysis in predicting NAPL recovery efficiency for flooding processes in remediating aquifers with dip angles.     

应急救援物资车辆运输线路的选择

为了给紧急救援物资支持保障中心的物资调度人员提供科学的车辆路线调度决策方法,提高应急救援工作的响应能力,基于应急条件下物资运输调度的时效性、安全性和经济性特征,运用旅行商理论,对上述3个决策属性分量进行了数学描述,构造了它们的目标函数,并进行了无量纲和权重聚合处理,继而按照多属性决策理论建立了用来评价备选线路决策效用函数的数学模型.利用期望效用属性合并所搜集的信息,将多属性决策问题转化成单属性决策问题,确立了选择具有最高期望效用方案的方法,最后进行了实例分析.结果表明,应急救援条件下的运输调度与正常环境下的企业运输调度决策目标之间存在明显的差异,前者虽然本质上属于图论中最短路线问题的范畴,但由于多个决策目标的存在,不能直接运用最短路线模型和Dijkstra算法求解.运用多属性决策理论建立的评价备选线路决策效用函数,是有关人员进行车辆路线安排的有效方法,但其相对优越性尚需做进一步的研究和探讨.     

面向突发事件智能建筑管理系统的集成结构

为了实现面向突发事件的智能建筑管理系统(IBMS),提出了智能建筑突发事件的抽象模型、基本运算操作及优先权分配机制,并根据突发事件监控和管理的目标,提出了IBMS的"分布式虚拟应急中心"集成结构.     

示踪技术用于气体泄漏扩散模拟的多元线性回归分析

采用江苏工业学院油气储运安全综合实验模型平台,利用示踪技术(以CO2为示踪剂),模拟了有害气体瞬时泄漏扩散的整个过程.并结合多元线性回归分析的基本方法,定量分析了气体泄漏扩散过程,建立了多元线性回归模型,初步确定了泄漏气体浓度与相关物理量的变化关系,在此基础上得到了2个定量评价指标:确定性系数R=0.991,相关系数r=0.995.研究表明,在实验室建立的试验模型能较好地反映现实情况,模型仿真度较高,数据拟合效果较好.研究可为评价模型的相似性提供理论参考,对有害气体泄漏扩散事故应急救援、实施有效的现场控制,具有一定的科学参考价值.     

基于微生物相互作用机理的完全耦合活性污泥模型研究

根据微生物生长机理,推导出微生物的耦合作用机理并在该机理的基础上改进了ASM3 Bio-P模型.假设活性污泥系统中有机物氧化过程、生物硝化过程、生物反硝化过程、生物除磷过程可同时存在,在ASM3 Bio-P模型上添加相关的开关函数,推导出完全耦合活性污泥模型(FCASM).基于计算机程序进行数值模拟,并将FCASM模拟结果与实测值以及ASM3 Bio-P模型模拟值进行对比.结果表明,完全耦合活性污泥模型对氨氮模拟的稳态出水值为1.90 g·m-3,ASM3 Bio-P模型模拟的氨氮稳态出水值为0 g·m-3,而实测的氨氮稳态出水值为1.50 g·m-3,完全耦合活性污泥模型的结果更接近真实值.     

pp´DDT and pp´DDE Accumulation in a Food Chain of Lake Maggiore (Northern Italy): Testing Steady-State Condition

- DOI: http://dx.doi.org/10.1065/espr2006.01.010 Background, Aims and Scope Although pp'DDT usage was strongly limited or banned in most parts of the world during the last three or four decades, the parent compound, its homologues and their metabolites still occur at levels which might pose a risk for many ecosystem components. A case of DDT pollution of industrial origin was discovered in 1996 in Lake Maggiore, the second largest (212 km2) and deepest (370 m) lake in Italy, causing concern for wildlife and human health. The extensive monitoring of many biotic and abiotic compartments which followed from 1998 in order to assess the pollution level and its trend in time, provided a great availability of data referring to DDT contamination of the different fish species of the lake. In this study, the recent contamination levels in selected fish species were compared to those measured in 1998 to evaluate the temporal pollution trend of the lake and its natural recovery, given that no remediation measures were carried out on the contaminated soils and sediments in this time span. Moreover, a modelling approach to test the equilibrium condition between water and pelagic fish species was used. Analytical results of pp'DDT and pp'DDE concentrations in lake water were used as input data in the bioenergetic model by Connolly & Pedersen (1988) to calculate concentrations in two fish species and to compare the predicted and the measured contamination. Methods Sampling and analytical determination of DDT homologues in lake water: Five water sampling campaigns were carried out from May 2002 to February 2004 in three sampling sites of Lake Maggiore. Suspended and dissolved pollutants were determined separately. Quantitative DDT homologue analyses were performed by HRGC coupled with ECD detection by the external standard method. Single water extracts were put together in correspondence with the stratification zones of the water column inferred on the basis of the temperature profile to improve analytical sensitivity. Selection of fish data: Concentrations of DDT and DDE in fishes were selected from recent literature (CIPAIS 2003, 2004). Bioaccumulation model: The bioenergetic model proposed by Connolly & Pedersen (1988) was used to assess the bioaccumulation of pp'DDT and pp'DDE of Alosa fallax (landlocked shad) and Coregonus spp. (whitefish), selected among the different species as representative of a secondary consumer level. Results and Discussion The average concentrations of pp'DDT and pp'DDE in water to be used as input data in the bioenergetic model were obtained considering all the concentrations measured at the three sampling stations in the epylimnion where the fish species considered in this study spend most of their life. The resulting values were 0.05 and 0.16 ng/L for pp'DDT and pp'DDE, respectively. Average measured pp'DDT and pp'DDE concentrations in landlocked shad were 0.81 +/- 0.39 and 1.69 +/- 0.71 mg/kg lipids, respectively, and were 0.29 +/- 0.12 and 1.06 +/- 0.41 mg/kg lipids for the whitefish. Calculated and measured values turned out to be in quite good agreement for pp'DDT, while measured pp'DDE concentrations were higher than expected on the basis of the bioenergetic model in both species. Probably metabolic transformations of pp'DDT accumulated in fish tissues in the past are responsible for the observed differences between calculated and expected pp'DDE concentrations in fish. Conclusions Pelagic fishes of Lake Maggiore seem to maintain the DDT accumulated during their life time and the most efficient mechanism responsible for the fish population recoveries is probably their generation changes; for this reason, equilibrium models cannot be used until negligible pp'DDT concentrations are reached in fish tissues. Recommendations and Outlook The limit proposed for pp'DDT in water by the EU Directive 2000/60, which will come in force in 2008, is 0.2 ng/L, four times higher than the average concentration measured in Lake Maggiore waters. Nevertheless, concentrations measured in Lake Maggiore fish were very close and sometimes exceeded the Maximum residue limits (MRLs) settled by the Italian legislation for foods (0.1 mg/kg w.w. for fish containing 5–20% lipid). It seems, therefore, that the 'environmental quality standard' of 0.2 ng/L cannot guarantee the suitability of fish for human consumption.     

Environmental Persistence of Chemicals

- DOI: http://dx.doi.org/10.1065/espr2006.01.008 Background The hazard criterion of persistence as it applies to chemicals in the environment is reviewed and discussed. This quantity can not be measured directly in the environment, thus it must be estimated using models that synthesise information on chemical half-lives and partitioning properties, the nature of the environment and how the chemical is released into the environment. Main Features It is suggested that the preferred criterion is the average residence time of the chemical in the environment, i.e. conceptually the sum of the life-times of all molecules (attributable only to losses by degrading reactions) divided by the number of molecules. If all chemical fate processes are first order, this persistence is independent of the quantity of chemical introduced and whether introduction is steady- or unsteady-state in nature. It is shown that in a multimedia environment persistence is affected not only by degradation kinetics, but also by mode-of-entry and partitioning. For screening level purposes a Level II equilibrium model may be adequate but a Level III model is generally preferable for estimating the average persistence. If a distribution of persistences is required a dynamic Level IV model must be used. Discussion The implications for regulating chemicals on the basis of persistence are discussed. Conclusion It is concluded that the preferred strategy is to use Level II, III, and IV models and that the use of only degradation kinetics or media-specific half-lives can be misleading and uneconomical.     

Modeling thermal analysis for predicting thermal hazards relevant to transportation safety and runaway reaction for 2,2′-azobis(isobutyronitrile)

The pure decomposition behavior of 2,2′-azobis (isobutyronitrile) (AIBN) and its physical phase transformation were examined and discussed. The thermal decomposition of this self-reactive azo compound was explored using differential scanning calorimetry (DSC) to elucidate the stages in the progress of this chemical reaction. DSC was used to predict the kinetic and process safety parameters, such as self-accelerating decomposition temperature (SADT), time to maximum reaction rate under adiabatic conditions (TMR_ad), and apparent activation energy (E_a), under isothermal and adiabatic conditions with thermal analysis models. Moreover, vent sizing package 2 (VSP2) was applied to examine the runaway reaction combined with simulation and experiments for thermal hazard assessment of AIBN. A thorough understanding of this reaction process can identify AIBN as a hazardous and vulnerable chemical during upset situations. The sublimation and melting of AIBN near its apparent onset decomposition temperature contributed to the initial steps of the reaction and explained the exothermic attributes of the peaks observed in the calorimetric investigation.     

基于改进灰色模型的管壁蜡沉积厚度预测研究

为对含蜡原油管道中的蜡沉积厚度进行准确预测,在函数cot(x2)变换的基础上,结合平移变换思想,利用cot(x2+c)变换建立新的改进GM(1,1)模型。以现场管道结蜡数据和室内环道结蜡数据为例,对比改进GM(1,1)模型、基于函数cot(x2)变换建立的GM(1,1)模型及传统GM(1,1)模型之间的预测精度,并分析平移量c对改进GM(1,1)模型预测精度的影响。结果表明:改进GM(1,1)模型的预测精度最高,其次是基于函数cot(x2)变换建立的GM(1,1)模型,而传统GM(1,1)模型的预测精度最低;随着平移量的增大,改进GM(1,1)模型的平均相对预测误差呈现出先减小后增大的趋势,因此合理的平移量有助于模型精度的提高。应用改进GM(1,1)模型来预测管道蜡沉积厚度是可行的,该方法可为含蜡原油管道蜡沉积厚度的准确预测提供参考和借鉴。