不流动水与非平衡吸附作用对溶质运移影响的数值模型-MIENESOR

不流动水与非平衡吸附作用对溶质在孔隙介质中的运移有很大影响,“两点-两区”模型是目前研究不流动水与非平衡吸附作用的较为完善和实用的模型。在溶质运移的“两点-两区”模型的基础上,同时考虑了土壤对溶质的平衡和非平衡吸附作用,开发了MIENESOR数值模型,并给出了基于有限差和有限元法联合的数值解,编制了相应的计算机程序。对MIENESOR数值模型的案例验算表明：该模型能很好地揭示溶质在包气带和含水层中运移的规律,所开发的计算机程序稳定性较强,可用于实际。     

Three-Dimensional Numerical Method of Moments for Linear Equilibrium-Adsorbing Solute Transport in Physically and Chemically Nonstationary Formations

A Lagrangian perturbation method is applied to develop a method of moments for reactive solute flux through a three-dimensional, nonstationary flow field. The flow nonstationarity may stem from medium nonstationarity, finite domain boundaries, and/or fluid pumping and injecting. The reactive solute flux is described as a space–time process where time refers to the solute flux breakthrough in a control plane at some distance downstream of the solute source and space refers to the transverse displacement distribution at the control plane. The analytically derived moments equations for solute transport in a nonstationary flow field are too complicated to solve analytically; therefore, a numerical finite difference method is implemented to obtain the solutions. This approach combines the stochastic model with the flexibility of the numerical method to boundary and initial conditions. The approach provides a tool to apply stochastic theory to reactive solute transport in complex subsurface environments. Several case studies have been conducted to investigate the influence of the physical and chemical heterogeneity of a medium on the reactive solute flux prediction in nonstationary flow field. It is found that both physical and chemical heterogeneity significantly affect solute transport behavior in a nonstationary flow field. The developed method is also applied to an environmental project for predicting solute flux in the saturated zone below the Yucca Mountain Project area, demonstrating the applicability of the method in practical environmental projects.     

Crossover from Nonlinearity Controlled to Heterogeneity Controlled Mixing in Two-Phase Porous Media Flows

We use high resolution Monte Carlo simulations to study the dispersive mixing in two-phase, immiscible, porous media flow that results from the interaction of the nonlinearities in the flow equations with geologic heterogeneity. Our numerical experiments show that distinct dispersive regimes occur depending on the relative strength of nonlinearity and heterogeneity. In particular, for a given degree of multiscale heterogeneity, controlled by the Hurst exponent which characterizes the underlying stochastic model for the heterogeneity, linear and nonlinear flows are essentially identical in their degree of dispersion, if the heterogeneity is strong enough. As the heterogeneity weakens, the dispersion rates cross over from those of linear heterogeneous flows to those typical of nonlinear homogeneous flows.     

用镭同位素评价海水滞留时间及海底地下水排泄

海底地下水排泄(submarine groundwater discharge, SGD)难以直接测量, 镭同位素和氡-222等天然示踪剂使得间接评价SGD通量成为可能.为了评价五缘湾的水体滞留时间和SGD通量, 实测了湾内海水、湾外海水和地下水中224Ra和226Ra的活度, 利用224Ra和226Ra半衰期的差异, 采用224Ra与226Ra的活度比值计算湾内水团的年龄和平均滞留时间, 利用224Ra和226Ra的质量平衡模型计算SGD通量.五缘湾13个站位的水团年龄在0.6~2.4 d之间, 湾顶水团年龄相对较大, 平均海水滞留时间1.4 d.地下水输入五缘湾的224Ra和226Ra通量分别为5.17×106 Bq/d和5.28×106 Bq/d, 将该通量用地下水端元的活度转换成为SGD通量分别是0.21 m3/m2/d(224Ra平衡模型)和0.23 m3/m2/d(226Ra平衡模型), 两种模型的结果较接近, 其平均值0.22 m3/m2/d可作为五缘湾的海底地下水排泄通量.      

野外非饱和土壤水流运动速度的空间变异性及其对溶质运移的影响

根据野外非饱和溶质运移试验资料,分析了港质运移速度的空间变异性,求得了呈对数正态分布的流速分布函数,并依此推导出有效弥散系数α=0.068t.根据流速的随机分布特征,分别用带有随机参数的对流模型、对流一弥散模型和传统的对流-弥散模型,求得了区域平均浓度分布及其方差.计算结果与实测结果拟合良好.通过分析得到,浓度方差与浓度梯度成正比,与孔隙弥散系数成反比,方差最大值分布在浓度锋面附近.     

铀在北山花岗岩中的吸附迁移影响因素研究

运用水文地球化学模拟软件PHREEQC-Ⅱ,对铀元素进入中国高放废物处置预选场研究区地下水后的状况进行了模拟和预测。模拟得到核素铀进入研究区地下水后的元素浓度分布和迁移情况及外界因素变化引起地下水中铀迁移的行为,同时采用批式法测定不同条件下铀在甘肃北山花岗岩中的分配系数,研究了岩石粒径、溶液初始浓度、水相pH和温度对分配系数的影响,实验结果表明花岗岩对铀的吸附能力较弱,其中溶液初始浓度、粒径、温度影响较小,pH值对岩石的吸附性能有较大影响,在接近中性条件下影响达到最大,这与采用模拟软件模拟结果基本吻合。通过模拟和实验对比,能更好地研究在北山预选区处置条件下地下水-废物-岩石的相互作用过程中核素的迁移行为,从而为处置库系统安全评价提供有关依据。     

粘土矿物的掺杂对沉积物吸持Cu、Zn能力的影响

通过考察粘土矿物及掺杂粘土矿物前后沉积物的吸附/解吸特性,分析了伊利石与蒙脱石对重金属污染沉积物中Cu与Zn稳定固定化的可行性。结果表明：伊利石与蒙脱石的掺杂均降低了沉积物吸持Cu的能力（最大下降量分别为5.4%和3.8%）,伊利石的掺杂同样降低了沉积物吸持Zn的能力（最大下降量为4.4%）,但蒙脱石掺杂后沉积物吸持Zn的能力明显增强,最高增加5.7%。因此,蒙脱石具有固定污染沉积物中Zn的能力,但不能提高污染沉积物中Cu的稳定性。     

A Numerical Simulation of Residual Circulation in Tampa Bay. Part II: Lagrangian Residence Time

Lagrangian retention and flushing are examined by advecting neutrally buoyant point particles within a circulation field generated by a numerical ocean model of Tampa Bay. Large temporal variations in Lagrangian residence time are found under realistic changes in boundary conditions. Two 90-day time periods are examined. The first (P1) is characterized by low freshwater inflow and weak baroclinic circulation. The second (P2) has high freshwater inflow and strong baroclinic circulation. At the beginning of both time periods, 686,400 particles are released uniformly throughout the bay. Issues relating to particle distribution and flushing are examined at three different spatial scales: (1) at the scale of the entire bay, (2) the four major regions within the bay, and (3) at the scale of individual model grid cells. Two simple theoretical models for the particle number over time, N(t), are fit to the particle counts from the ocean model. The theoretical models are shown to represent N(t) reasonably well when considering the entire bay, allowing for straightforward calculation of baywide residence times: 156 days for P1 and 36 days for P2. However, the accuracy of these simple models decreases with decreasing spatial scale. This is likely due to the fact that particles may exit, reenter, or redistribute from one region to another in any sequence. The smaller the domain under consideration, the more this exchange process dominates. Therefore, definitions of residence time need to be modified for “non-local” situations. After choosing a reasonable definition, and removal of the tidal and synoptic signals, the residence times at each grid cell in P1 is found to vary spatially from a few days to 90 days, the limit of the calculation, with an average residence time of 53 days. For P2, the overall spatial pattern is more homogeneous, and the residence times have an average value of 26 days.     

非均质性对非饱和-饱和系统 水流时空变化的作用

通过模拟均质和非均质两种情形下非饱和-饱和系统中压力水头的时空变化,研究非饱和-饱和系统对水流波动的 阻尼作用和系统非均质性对水流波动的作用。结果显示,两种情形下非饱和-饱和系统对水流波动均有阻尼作用,随深度 增加,压力水头波动减弱,方差、自协方差和功率谱减小;压力水头在早期因初始条件做非平稳波动,而后随时间增长演 变为平稳波动;系统的非均质性加剧了压力水头的波动,是波动的主要来源,使得压力水头方差、自协方差和功率谱增 大;非均质性减小压力水头波动的短期相关性。     

井内混合效应与尺度效应对注入井附近溶质径向弥散过程的影响

径向弥散是指溶质在径向流场下的迁移规律,被广泛用于描述含水层修复领域中污染物的迁移过程.然而,在现有描述径向弥散的模型中,往往忽略了井内混合效应对溶质径向弥散的影响.建立新的注入井附近溶质径向运移动力学模型,同时考虑井内混合效应与弥散度的尺度效应.采用Laplace变换推导该模型的半解析解,利用Stehfest数值逆变换获取溶质在实数空间的解.通过与不考虑混合效应的模型对比研究混合效应对溶质径向弥散的影响,并利用室内渗流槽中的溶质径向弥散实验数据验证模型的合理性与适用性.结果表明:混合效应和尺度效应对注水井附近溶质径向弥散有显著影响.具体地讲,井内的混合效应越显著,在井壁处及含水层中的穿透曲线越低,溶质浓度达到峰值所需时间越长,与不考虑混合效应模型的差异越明显;随尺度效应的增强,溶质提前穿透且扩散范围变大,溶质浓度达到峰值所需时间越长;与前人的模型相比,本研究模型能更好地模拟注水井附近的溶质径向弥散问题.      

野外非饱和土壤中溶质运移的试验研究

通过在野外3×6m2面积上均匀入渗条件下非饱和土壤溶质运移试验,同时对8个点定时取样,得到170cm深度内土壤溶液浓度和含水量剖面分布.据此研究了小区域范围内土壤水分和溶质的运移特征,讨论了土壤水分和盐分分布的空间变异性和统计特征.研究结果表明,在本试验条件下,土壤溶液浓度剖面的空间变异性远大于土壤水分剖面.单一测点的取样结果不能代表区域的溶质运移特征.区域上溶质浓度的平均结果能反映溶质运移的基本规律.由于土壤结构等因素的影响,不动水体含量占土壤含水量的24%～39%.     

坡度作用下土壤水分时空异质性研究

国内外对于坡度作用下土壤水分空间异质性尚无定论,且国内时间异质性研究尚很缺乏,以野外水文山实验流域为研究对象,选取偏干和偏湿年份分析了土壤水分的时空异质性。空间异质性的研究表明,土壤水分的主要趋势是60cm大于30cm,但在有的时间段30cm含水量也会超过60cm;总体而言从坡顶到坡脚土壤含水量依次增加,但是在某种特殊情况下也会发生变化。即土壤水分在空间上的分布结构在时间上具有一定的稳定性,并且降水量越多坡度的作用表现得越明显。时间异质性的分析表明,土壤水分的时间变异表现出明显的季节性差异,并且坡面不同位置的变异性不同,偏干年份的年内变化类似于正弦曲线。     

Sorption of metals on humic acid

The sorption on humic acid (HA) of metals from an aqueous solution containing Hg(II). Fe(III), Pb, Cu, Al, Ni, Cr(III), Cd, Zn, Co and Mn, was investigated with special emphasis on effects of pH, metal concentration and HA concentration. The sorption efficiency tended to increase with rise in pH, decrease in metal concentration and increase in HA concentration of the equilibrating solution. At pH 2.4. the order of sorption was: Hg? Fe? Pb? CuAl ? Ni ? CrZnCdCoMn. At pH 3.7. the order was: Hg and Fe were always most readily removed, while Co and Mn were sorbed least readily. There were indications of competition for active sites (CO₂H and phenolic OH groups) on the HA between the different metals. We were unable to find correlations between the affinities of the eleven metals to sorb on HA and their atomic weights, atomic numbers, valencies, and crystal and hydrated ionic radii. The sorption of the eleven metals on the HA could be described by the equation $\text{Y =}\text{100}\text{[1 + exp ? (A + BX)]}$, where Y = % metal removed by HA; X = mgHA; and A and B are empirical constants.     

黄土对含油废水的吸附作用研究

通过静态吸附实验,研究了兰州地区黄土对含油废水中石油类污染物的吸附作用,并对温度、pH、土壤粒径、有机质含量和含盐量等影响吸附作用的因素进行了分析。实验结果表明:该类型黄土对可溶性石油饱和溶液的吸附等温线符合Langmuir吸附模式,其吸附能力随温度、pH的升高而降低;吸附量随土壤粒径的减小呈增大趋势;吸附量与土壤有机质含量、含盐量呈线性关系,随着有机质含量、含盐量的增高吸附量增大。     

Effect of Microbial Siderophore DFOB on Pb, Zn, and Cd Sorption Onto Zeolite

Recent studies suggest that siderophores form stable complexes with divalent metals and affect their mobility. In this work, effects of trihydroxamate microbial siderophores and desferrioxamine-B (DFOB) on Pb(II), Zn(II), and Cd(II) sorption by two kinds of synthesized zeolites (13X and Na?CY) as a function of pH were investigated. Results showed that 13X zeolite has a higher sorption affinity for studied metals than Na?CY. DFOB strongly affected metal sorption on both zeolites. Under slightly acidic to neutral condition, DFOB increased the metal sorption on zeolites due to the sorption of positively charged heavy metal?CDFOB complexes. Whereas by increasing pH (>7), the mobilizing effect of DFOB was observed for Pb, Zn, and Cd. DFOB drastically decreased (80?%) Zn sorption in alkaline condition. As a result, siderophores can weaken the treatment efficiency of zeolites and increase the bioavailability of metals in soils. Surface complexation modeling revealed that the effects of DFOB on metal sorption by 13X and Na?CY zeolites can be explained by the differences in their surface charge. In general, the result shows the influence of DFOB on metal sorption by zeolites over the pH range 4?C9 and decreasing in the sequence Zn?>?Pb?>?Cd.     

Effect of Multipoint Heterogeneity on Nonlinear Transformations for Geological Modeling： Porosity-Permeability Relations Revisited

An analysis of statistical expected values for transformations is performed in this study to quantify the effect of heterogeneity on spatial geological modeling and evaluations. Algebraic transformations are frequently applied to data from logging to allow for the modeling of geological properties. Transformations may be powers, products, and exponential operations which are commonly used in well-known relations (e.g., porosity-permeability transforms). The results of this study show that correct computations must account for residual transformation terms which arise due to lack of independence among heterogeneous geological properties. In the case of an exponential porosity-permeability transform, the values may be positive. This proves that a simple exponential model back-transformed from linear regression underestimates permeability. In the case of transformations involving two or more properties, residual terms may represent the contribution of heterogeneous components which occur when properties vary together, regardless of a pair-wise linear independence. A consequence of power- and product-transform models is that regression equationswithin those transformations need corrections via residual cumulants. A generalization of this result isthat transformations of multivariate spatial attributes require multiple-point random variable relations. This analysis provides practical solutions leading to a methodology for nonlinear modeling using correct back transformations in geology.     

Sorption of lanthanides on smectite and kaolinite

Experiments were carried out to investigate the sorption of the complete lanthanide series (Ln or rare earth elements, REE) on a kaolinite and an a Na-montmorillonite at 22°C over a wide range of pH (3-9). Experiments were conducted at two ionic strengths, 0.025 and 0.5 M, using two different background electrolytes (NaNO₃ or NaClO₄) under atmospheric conditions or N₂ flow (glove box). The REE sorption does not depend on the background electrolyte or the presence of dissolved CO₂, but is controlled by the nature of the clay minerals, the pH and the ionic strength. At 0.5 M, both clay minerals exhibit the same pH dependence for the Ln sorption edge, with a large increase in the sorption coefficient (K_D) above pH 5.5. At 0.025 M, the measured K_D is influenced by the Cation Exchange Capacity (CEC) of the minerals. Two different behaviours are observed for smectite: between pH 3 and 6, the K_D is weakly pH-dependent, while above pH 6, there is a slight decrease in log K_D. This can be explained by a particular arrangement of the particles. For kaolinite, the sorption coefficient exhibits a linear increase with increasing pH over the studied pH range. A fractionation is observed that due to the selective sorption between the HREEs and the LREEs at high ionic strength, the heavy REE is being more sorbed than the light REE. These results can be interpreted in terms of the surface chemistry of clay minerals, where two types of surface charge are able to coexist: the permanent structural charge and the variable pH-dependent charge. The fractionation due to sorption observed at high ionic strength can be interpreted either because of a competition with sodium or because of the formation of inner-sphere complexes. Both processes could favour the sorption of HREEs according to the lanthanide contraction.     

舟山地区静压管桩时间效应初步研究

通过复压及静载试验,对舟山地区软土地基静压管桩的时间效应进行了初步研究,指出压桩力在不同性质土层中变化特点,压桩力与休止时间,以及恢复系数与桩侧软弱土性质的关系.