硝基苯在河流—地下水系统中的行为特征与模拟研究
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摘要
河流与地下水存在着密切的水力联系，在河流补给地下水过程中，一旦被污染往往在较短时间内极易导致事发下游河流大面积污染，进而导致地下水污染，而在地下水中最难治理和危害最大的是有机污染，因此河流有机污染对地下水的影响已经成为一个世界性的水环境热点问题。对有机污染物在河流-地下水系统中的行为特征进行研究具有十分重要的理论和实际意义。本研究以国家自然科学基金：“河流污染对地下水的影响和模拟研究（40872163）”项目及国家水重大专项“渭河关中段地下水对河流生态基流的保障研究（2008ZX07012-002-003-003）”为依托，选择具有代表性的“三致”有机化合物硝基苯为特征污染物，以环境化学理论和多孔介质流体动力学为指导，采用室内批量试验与数值模拟相结合的方法，开展硝基苯在渭河及其沿岸地下水中的对流迁移、水动力弥散、吸附阻滞、生物化学转化、模拟预测及修复技术的系统研究，揭示其行为特征，为深入研究硝基苯在河流-地下水系统中的污染机理和修复技术提供参考依据。取得以下成果：
迁移试验表明，硝基苯受对流弥散、吸附和生物降解等作用，各观测点的浓度随时空推移逐渐变小，直至低于检出限。通过渗流槽示踪试验，获得了硝基苯在渗流槽中的水动力弥散系数（0.37cm2/min）和平均孔隙流速（0.026cm/min）等基本水文地质参数。
等温非平衡吸附试验结果表明，渭河关中段上、中、下游三个代表断面的沉积物在2～3小时内对硝基苯能快速达到最大吸附量，且最大吸附量与沉积物中所含有机碳（f oc）正相关，在10～13小时内可达到表观平衡。等温平衡吸附试验结果表明，由Linear和Langmuir方程组成的双模式吸附模型可较好地描述硝基苯的等温平衡吸附规律，并可反映出吸附的主导控制性作用，即对于f oc含量低的沉积物，Langmuir吸附作用强，主要影响因素是与孔内充填或毛细凝结作用；对于f oc含量高的沉积物，Linear吸附作用强，主要影响因素是固相有机质的吸收作用。根据污染物在地下水中运移的数学模型，建立了以Linear和Langmuir组成的双模式吸附特性的阻滞系数（R）表达式，揭示了溶质液相浓度与阻滞系数之间的相关性。试验结果得出渭河原砂的最大吸附容量S0（2.02mg/km）、吸附系数Kd(3.23L/kg)和吸附表面亲合性常数b(2.54L/mg)等吸附特征参数。
硝基苯的生物降解过程满足Monod方程。在渭河上、中、下游三个代表性断面水体中，当硝基苯浓度接近1.5mg/L时，微生物最大比生长速率（q max）达最大；浓度大于1.5mg/L时，因体系微生物生长受到抑制，降解效果增加不明显，甚至还有下降趋势，在河水-沉积物共存条件下，当硝基苯为0.5mg/L时，三个断面中微生物最大比生长速率q max（平均0.40／h左右）均大于河水相同条件的对应值（平均0.29／h左右），此时硝基苯已未检出，说明河水-沉积物共存体系降解能力提高。
基于室内试验所获得的基本水文地质参数，构建了硝基苯在地下水中迁移转化规律的数学模型，用以对模拟渗流槽中硝基苯的迁移转化规律进行数值模拟，其模拟值与实测值相近，效果较为满意。对所得参数做一些相关修正后，将该模型用于研究区地下水中硝基苯污染的模拟预测，其预测结果可为河流硝基苯污染突发事件的控制提供参考。
针对进入含水层介质中的硝基苯有限、浓度一般较低的特性，尝试采用KMnO_4-O_3、KMnO_4-H_2O_2、KMnO_4-超声波三种方法分别进行修复研究，其修复效率可分别达到95%、90%、93.5%以上，三种反应体系均符合一级反应动力学规律。
Rivers and groundwater are closely hydraulic connection. In the process of river rechargegroundwater. The river once contaminated, often in a relatively short time easily lead to thedownstream of large area pollution, resulting in groundwater contamination，However, theorganic contamination in groundwater is the most difficult to control and most harmful.Therefore, the impact of river organic pollution of groundwater has become a global hotissues of the water environment. The behavioral characteristics of organic pollutants in theriver-groundwater system have important theoretical and practical significance. In this study,the National Natural Science Foundation:" the project of river pollution impact ongroundwater and simulation studies (40,872,163), and the major projects of the NationalWater Weihe Guan middle of groundwater to the river ecosystem base flow protection(2008ZX07012-002-003-003)" as the basis, and select representative organic compounds"three to" nitrobenzene as characterized pollutants, and the theory of environmentalchemistry as a guide, using a combination of indoor batch experiment and numericalsimulation methods, carried out the system study of nitrobenzene on migration convection,hydrodynamic dispersion, adsorption and block, biochemical conversion, analog forecastand repair in the Weihe River and its coastal groundwater, and reveal the behavioralcharacteristics, provides the reference for the deep research nitrobenzene's pollutionmechanism and the repair technology in rivers-groundwater system. Makes the followingprogress:
The hydrodynamic force dispersion coefficient (0.38cm2/min) and other basic hydrologygeology parameter were obtained by the tracing experiment in seepage trough. The migrationlaw show that By convective diffusion, adsorption and biodegradation, the role ofnitrobenzene concentration of the observation points over time and space became smaller andsmaller, until below the detection limit.
Isothermal non-equilibrium adsorption results showed that sediments quickly reach themaximum adsorption capacity to nitrobenzene within2to3hours in Wei-he Guan middle ofthe upper, middle and lower reaches of the three represents section, and the maximumadsorption capacity and organic carbon contained in the sediments (f oc) positive correlation,and apparent equilibrium can be achieved within10to13hours. isothermal equilibriumadsorption test result indicated the double model type adsorption model which is composedof Linear and the Langmuir equation may describe the nitrobenzene isothermal equilibriumadsorption rule well, and may reflect the dominant and controlling role of adsorption,forsediments with low organic carbon content, the Langmuir adsorption is strong. the mainfactor is the role of hole filling or capillary condensation. For sediments with high organiccarbon content,linear adsorption is strong, the main factor is the absorption of the solid-phaseorganic matter. The combination of solute migration model in the aquifer, defines theexpression of the block coefficient（R） of the dual-mode adsorption isotherm model, andreveal a correlation between the solute liquid concentration and block coefficient.
The nitrobenzene biodegradable process meet Monod equation. In Wei-he Guan middle ofthe upper, middle and lower reaches of the three represents section. when the nitrobenzene concentration near1.5mg/L, the microbial maximum specific growth rate reached themaximum after8days, this time the nitrobenzene biodegradation rate approximately is60%.When the nitrobenzene concentrations greater than1.5mg/L, microbial growth isinhibited, the degeneration effect increases not obviously, even also has the decliningtrend.Under river water-deposit coexistent condition，When nitrobenzene is0.5mg/L,maximum specific growth rate up to the maximum in three-section microorganisms (averageof about0.40/h),and are greater than the river(average of about0.29/h), thereforeexplained that river water-deposit coexistence system degeneration ability increases.
Based on laboratory test results, and established a mathematical model of migration andconversion of nitrobenzene in underground water, and solute transport processes andadsorption, biodegradation can be mathematically simulated using the Matlab programmingto calculate a one-dimensional on the groundwater flow field in seepage trough, as a result,consistent with the experimental observations better,and the model was used to simulationand prediction of the nitrobenzene concentration in the groundwater of the study area, andalso achieved good results.
In view of the nitrobenzene enters in the water-bearing stratum medium to be limited,the low concentration characteristic, the attempt use the three methods of KMnO_4-O_3,KMnO_4-H_2O_2, and KMnO_4-ultrasonic wave to conduct the repair research separatelygenerally, their repair efficiency can reach more than95%,90%,93.5%,and three reactionsystem are in line with the first-order reaction kinetics.
迁移试验表明，硝基苯受对流弥散、吸附和生物降解等作用，各观测点的浓度随时空推移逐渐变小，直至低于检出限。通过渗流槽示踪试验，获得了硝基苯在渗流槽中的水动力弥散系数（0.37cm2/min）和平均孔隙流速（0.026cm/min）等基本水文地质参数。
等温非平衡吸附试验结果表明，渭河关中段上、中、下游三个代表断面的沉积物在2～3小时内对硝基苯能快速达到最大吸附量，且最大吸附量与沉积物中所含有机碳（f oc）正相关，在10～13小时内可达到表观平衡。等温平衡吸附试验结果表明，由Linear和Langmuir方程组成的双模式吸附模型可较好地描述硝基苯的等温平衡吸附规律，并可反映出吸附的主导控制性作用，即对于f oc含量低的沉积物，Langmuir吸附作用强，主要影响因素是与孔内充填或毛细凝结作用；对于f oc含量高的沉积物，Linear吸附作用强，主要影响因素是固相有机质的吸收作用。根据污染物在地下水中运移的数学模型，建立了以Linear和Langmuir组成的双模式吸附特性的阻滞系数（R）表达式，揭示了溶质液相浓度与阻滞系数之间的相关性。试验结果得出渭河原砂的最大吸附容量S0（2.02mg/km）、吸附系数Kd(3.23L/kg)和吸附表面亲合性常数b(2.54L/mg)等吸附特征参数。
硝基苯的生物降解过程满足Monod方程。在渭河上、中、下游三个代表性断面水体中，当硝基苯浓度接近1.5mg/L时，微生物最大比生长速率（q max）达最大；浓度大于1.5mg/L时，因体系微生物生长受到抑制，降解效果增加不明显，甚至还有下降趋势，在河水-沉积物共存条件下，当硝基苯为0.5mg/L时，三个断面中微生物最大比生长速率q max（平均0.40／h左右）均大于河水相同条件的对应值（平均0.29／h左右），此时硝基苯已未检出，说明河水-沉积物共存体系降解能力提高。
基于室内试验所获得的基本水文地质参数，构建了硝基苯在地下水中迁移转化规律的数学模型，用以对模拟渗流槽中硝基苯的迁移转化规律进行数值模拟，其模拟值与实测值相近，效果较为满意。对所得参数做一些相关修正后，将该模型用于研究区地下水中硝基苯污染的模拟预测，其预测结果可为河流硝基苯污染突发事件的控制提供参考。
针对进入含水层介质中的硝基苯有限、浓度一般较低的特性，尝试采用KMnO_4-O_3、KMnO_4-H_2O_2、KMnO_4-超声波三种方法分别进行修复研究，其修复效率可分别达到95%、90%、93.5%以上，三种反应体系均符合一级反应动力学规律。
Rivers and groundwater are closely hydraulic connection. In the process of river rechargegroundwater. The river once contaminated, often in a relatively short time easily lead to thedownstream of large area pollution, resulting in groundwater contamination，However, theorganic contamination in groundwater is the most difficult to control and most harmful.Therefore, the impact of river organic pollution of groundwater has become a global hotissues of the water environment. The behavioral characteristics of organic pollutants in theriver-groundwater system have important theoretical and practical significance. In this study,the National Natural Science Foundation:" the project of river pollution impact ongroundwater and simulation studies (40,872,163), and the major projects of the NationalWater Weihe Guan middle of groundwater to the river ecosystem base flow protection(2008ZX07012-002-003-003)" as the basis, and select representative organic compounds"three to" nitrobenzene as characterized pollutants, and the theory of environmentalchemistry as a guide, using a combination of indoor batch experiment and numericalsimulation methods, carried out the system study of nitrobenzene on migration convection,hydrodynamic dispersion, adsorption and block, biochemical conversion, analog forecastand repair in the Weihe River and its coastal groundwater, and reveal the behavioralcharacteristics, provides the reference for the deep research nitrobenzene's pollutionmechanism and the repair technology in rivers-groundwater system. Makes the followingprogress:
The hydrodynamic force dispersion coefficient (0.38cm2/min) and other basic hydrologygeology parameter were obtained by the tracing experiment in seepage trough. The migrationlaw show that By convective diffusion, adsorption and biodegradation, the role ofnitrobenzene concentration of the observation points over time and space became smaller andsmaller, until below the detection limit.
Isothermal non-equilibrium adsorption results showed that sediments quickly reach themaximum adsorption capacity to nitrobenzene within2to3hours in Wei-he Guan middle ofthe upper, middle and lower reaches of the three represents section, and the maximumadsorption capacity and organic carbon contained in the sediments (f oc) positive correlation,and apparent equilibrium can be achieved within10to13hours. isothermal equilibriumadsorption test result indicated the double model type adsorption model which is composedof Linear and the Langmuir equation may describe the nitrobenzene isothermal equilibriumadsorption rule well, and may reflect the dominant and controlling role of adsorption,forsediments with low organic carbon content, the Langmuir adsorption is strong. the mainfactor is the role of hole filling or capillary condensation. For sediments with high organiccarbon content,linear adsorption is strong, the main factor is the absorption of the solid-phaseorganic matter. The combination of solute migration model in the aquifer, defines theexpression of the block coefficient（R） of the dual-mode adsorption isotherm model, andreveal a correlation between the solute liquid concentration and block coefficient.
The nitrobenzene biodegradable process meet Monod equation. In Wei-he Guan middle ofthe upper, middle and lower reaches of the three represents section. when the nitrobenzene concentration near1.5mg/L, the microbial maximum specific growth rate reached themaximum after8days, this time the nitrobenzene biodegradation rate approximately is60%.When the nitrobenzene concentrations greater than1.5mg/L, microbial growth isinhibited, the degeneration effect increases not obviously, even also has the decliningtrend.Under river water-deposit coexistent condition，When nitrobenzene is0.5mg/L,maximum specific growth rate up to the maximum in three-section microorganisms (averageof about0.40/h),and are greater than the river(average of about0.29/h), thereforeexplained that river water-deposit coexistence system degeneration ability increases.
Based on laboratory test results, and established a mathematical model of migration andconversion of nitrobenzene in underground water, and solute transport processes andadsorption, biodegradation can be mathematically simulated using the Matlab programmingto calculate a one-dimensional on the groundwater flow field in seepage trough, as a result,consistent with the experimental observations better,and the model was used to simulationand prediction of the nitrobenzene concentration in the groundwater of the study area, andalso achieved good results.
In view of the nitrobenzene enters in the water-bearing stratum medium to be limited,the low concentration characteristic, the attempt use the three methods of KMnO_4-O_3,KMnO_4-H_2O_2, and KMnO_4-ultrasonic wave to conduct the repair research separatelygenerally, their repair efficiency can reach more than95%,90%,93.5%,and three reactionsystem are in line with the first-order reaction kinetics.
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