Sorption and transport of aqueous FeII in a goethite-coated sand column under anoxic conditions

Experiments were conducted under static batch and dynamic flow conditions to evaluate the sorption of Fe^II onto three goethites (G1, G2 and G3) having different crystal habits, morphologies and surface properties. Results reveal that G1 exhibited the highest Fe^II sorption extent and lowest kinetic rate constant, which may result from higher surface site density, surface roughness and edge surface faces. Surface complexation modeling parameters derived from batch experiments were combined with hydrodynamic parameters to simulate breakthrough curves in goethite-coated sand packed columns. The total sorbed amount of Fe^II at complete breakthrough was in agreement with that expected from the batch experiments, except for G1. Sorption breakthrough predictions that make use of surface complexation parameters accurately predicted Fe^II mobility in G2 and G3 columns, but poorly in G1 column. Experiments at various flow rates in G1 columns represented different amounts of Fe^II sorbed at complete breakthrough, thereby underscoring the impact of kinetic sorption. Moreover, Fe dissolution/re-precipitation or Fe^II-induced transformation of goethite was suspected at the lowest flow rate in the G1 column. The influence of goethite phase specific reactivity on Fe^II sorption under batch versus advective–dispersive flow is herein demonstrated. These findings have strong implications to assess transport of Fe^II and environmental contaminants both in natural and engineered systems.     

Pesticide transport and transformation modeling in soil column and groundwater contamination prediction

Pesticide transport and transformation were modeled in soil column from the soil surface to groundwater zone. A one dimensional dynamic mathematical and computer model is formulated to simulate two types of pesticides namely 2,4-dichlorophenoxy acetic acid and 1,2-dibromo 3-chloro propane in soil column. This model predicts the behavior and persistence of these pesticides in soil column and groundwater. The model is based on mass balance equation, including convective transport, dispersive transport and chemical adsorption in the phases such as solid, liquid and gas. The mathematical solution is obtained by finite difference implicit method. The model was verified with experimental measurements and also with analytical solution. The simulation results are in good agreement with measured values. The major findings of this research are the development of the model which can calculate and predict the concentration of pesticides in soil profiles, as well as groundwater after 4, 12, 31 days of pesticide application under steady state and unsteady water flow condition. With the results of this study, the distribution of various types of pesticides in soil column to groundwater table can be predicted.     

Reactive transport modeling of the interaction between a high-pH plume and a fractured marl: the case of Wellenberg

In the context of the proposed low- and intermediate-level radioactive waste repository at Wellenberg (Switzerland), calculations simulating the interaction between hyperalkaline solutions and a fractured marl, at 25 °C, have been performed. The aim of these calculations is to evaluate the possible effects of mineral dissolution and precipitation on porosity and permeability changes in such a fractured marl, and their impact on repository performance. Solute transport and chemical reaction are considered in both a high-permeability zone (fracture), where advection is important, and the wall rock, where diffusion is the dominant transport mechanism. The mineral reactions are promoted by the interaction between hyperalkaline solutions derived from the degradation of cement (a major component of the engineered barrier system in the repository) and the host rock. Both diffusive/dispersive and advective solute transport are taken into account in the calculations. Mineral reactions are described by kinetic rate laws. The fluid flow system under consideration is a two-dimensional porous medium (marl, 1% porosity), with a high-permeability zone simulating a fracture (10% porosity) crossing the domain. The dimensions of the domain are 6 m per 1 m, and the fracture width is 10 cm. The fluid flow field is updated during the course of the simulations. Permeabilities are updated according to Kozeny's equation. The composition of the solutions entering the domain is derived from modeling studies of the degradation of cement under the conditions at the proposed underground repository at Wellenberg. Two different cases have been considered in the calculations. These 2 cases are representative of 2 different stages in the process of degradation of cement (pH 13.5 and pH 12.5). In both cases, the flow velocity in the fracture diminishes with time, due to a decrease in porosity. This decrease in porosity is caused by the precipitation of calcite (replacement of dolomite by calcite) and other secondary minerals (brucite, sepiolite, analcime, natrolite, tobermorite). However, the decrease in porosity and flow velocity is much more pronounced in the lower pH case. The extent of the zone of mineral alteration along the fracture is also much more limited in the lower pH case. The reduction of porosity in the fractures would be highly beneficial for repository performance, since it would mean that the solutions coming from the repository and potentially carrying radionuclides in solution would have to flow through low-conductive rock before they would be able to get to higher-conductive features. The biggest uncertainty in the reaction rates used in the calculations arises from the surface areas of the primary minerals. Additional calculations making use of smaller surface areas have also been performed. The results show that the smaller surface areas (and therefore smaller reaction rates) result in a smaller reactivity of the system and smaller porosity changes.     

Characterization of solute transport parameters in leach ore: inverse modeling based on column experiments

Heap leaching is essentially a process in which metals are extracted from mine ores with lixiant. For a better understanding and modeling of this process, solute transport parameters are required to characterize the solute transport system of the leach heap. For porous media like leach ores, which contain substantial gravelly particles and have a broad range of particle size distributions, traditional small-scale laboratory experimental apparatus is not appropriate. In this paper, a 2.44 m long, 0.3 m inner diameter column was used for tracer test with boron as the tracer. Tracer tests were conducted for 2 bulk densities (1.92 and 1.62 g/cm³) and 2 irrigation rates (2 and 5 L/ (m²·h⁻¹)). Inverse modeling with two-region transport model using computer code CXTFIT was conducted based on the measured breakthrough curves to estimate the transport parameters. Fitting was focused on three parameters: dispersion coefficient D, partition coefficient β, and mass transfer coefficient ω. The results turned out to fall within reasonable ranges. Sensitivity analysis was conducted for the three parameters and showed that the order of sensitivity is β > ω > D. In addition, scaling of these parameters was discussed and applied to a real scale heap leach to predict the tracer breakthrough.     

砂土与硫酸腐蚀混凝土接触面剪切试验研究

为了研究酸腐蚀作用对桩-土接触面剪切特性的影响,利用大型多功能界面剪切仪,进行了砂土与被硫酸加速腐蚀0、31、93、154 d的混凝土板之间接触面剪切试验,量测了不同腐蚀时间的混凝土与砂土接触面的剪切应力和剪切位移关系。研究结果表明:砂土与硫酸腐蚀混凝土接触面剪切应力与剪切位移符合双曲线模型,接触面剪切破坏符合摩尔-库仑准则。随着腐蚀时间的增加,接触面黏聚力减小,摩擦角、剪切强度以及达到峰值剪切应力所需的剪切位移增大,接触面的破坏趋向于土体自身剪切破坏。取未腐蚀混凝土与砂土接触面达到峰值剪应力时的剪切位移为基准,对该位移对应的不同腐蚀时间下混凝土与砂土接触面的剪切应力进行对比分析,发现腐蚀5个月后的剪切应力要小于未腐蚀时的剪切应力。按双曲线模型对试验测得的接触面剪切应力和剪切位移关系进行了拟合,获得了该模型中的参数,为进一步进行数值模拟提供参考。     

Arsenic release and attenuation in a multilayer aquifer in the Po Plain (northern Italy): Reactive transport modeling

Groundwater As concentrations >WHO limit (10 μg/L) are frequently found in the Po Plain (N. Italy). Although several hypotheses on As mobilization exist (i.e., reductive dissolution driven by peat degradation), the mechanisms of As release and subsequent attenuation acting in the multilayer aquifer in the Po Plain were poorly understood.The present work aims at implementing a reactive transport modeling of the aquifer system in Cremona, affected by As <183 μg/L, in order to quantify and test the feasibility of As release by the reductive dissolution of Fe-oxides driven by the degradation of peat contained in leaky aquitards and As attenuation downstream by the co-precipitation in iron sulfides.The model, based on a partial equilibrium approach, revealed that the observed As, Fe and Mn chemistry could be mostly explained by the simultaneous equilibrium between Fe-oxide and sulfate reduction and FeS precipitation and by the equilibrium of rhodochrosite precipitation/dissolution. Model results, together with litholog analysis, supported the assumption of peat as the likely source of organic matter driving As release. The model fitted to measured data showed that the peak in the organic carbon degradation rate at 20–40 m below surface (average of 0.67 mM/y), corresponding to the shallow peaty aquitard and the upper portion of the underlying semiconfined aquifer, is associated with the peak of net release of As (average of 0.32 μM/y) that is followed just downstream by a net precipitation in iron sulfides at 40–60 m below surface (average of 0.30 μM/y). These results support the assumptions of peaty aquifers as drivers of As release and iron sulfides as As traps. The model also outlined the following aspects that could have a broad applicability in other alluvial As affected aquifers worldwide: (a) shallow peaty aquitards may have a greater role in driving the As release since they likely have young and more reactive organic matter; (b) the occurrence of Fe-oxide reduction and FeS precipitation, that represent the As source and sink, together with sulfate reduction occurring simultaneously close to equilibrium may restrict the As mobility limiting the extent of contamination just downstream the source of organic matter that drives its release.     

Fate and transport of ethanol-blended dissolved BTEX hydrocarbons: a quantitative tracing study of a sand tank experiment

To estimate the behavior of ethanol-blended dissolved BTEX hydrocarbons in groundwater, a quantitative tracing study instead of qualitative analysis was carried out by using a large sand tank, into which 2-L solution including bromide, ethanol and dissolved BTEX was injected under a controlled hydraulic condition. Mean residence time (MRT), pore volume swept by solute (V _p), retardation coefficient (R) and biodegradation rate constant (k) of injected solutes were estimated. Compared with bromide that was used as a conservative tracer, ethanol and BTEX had shorter MRT and smaller V _p with the sequence of EtOH < T < E < m/p-X < o-X < B < Br. Biodegradation was confirmed as evidenced by the consumptions of dissolved oxygen (DO), nitrate and sulfate, and the production of acetate. The sequence of k as EtOH > T > E > m/p-X > o-X > B was just opposite to the sequences of MRT and V _p. The relationship among above sequences implies that MRT and V _p can be used as indicators to assess in situ biodegradability of a solute. Biodegradation of a reactive solute can make its MRT shortened and V _p shrunk. In addition, the sorption of ethanol could be neglected (R = 1.0), whereas BTEX compounds were adsorbed (R = 1.04–1.15). It should be noted that biodegradation of a solute can affect the estimation of its retardation coefficient. To our knowledge, this paper provides an available route to quantitatively estimate biodegradability of a solute in groundwater.     

Estimation of contaminant transport parameters for a tropical sand in a sand tank model

This research describes the goals, design and implementation of a quasi natural gradient, laboratory scale, sand tank (aquifer) model experiment. The model was used to study the transport of an inorganic tracer (Chloride) in groundwater, within a tropical aquifer (porous medium) material. Three-dimensional sand tank (1.8 m × 0.3 m × 0.8 m) experiments were conducted to investigate contaminant transport and natural attenuation within the sand tank. In all, 360 samples were collected during 24 sampling sessions, for the three days of the tracer experiments in the Sand Tank. The Owena sand is a poorly graded sand with 88.1 % sand and 11.9 % gravel. Geotechnical properties including; coefficient of uniformity C_u = 2.53, coefficient of gradation C_z = 0.181, hydraulic conductivity K = 5.76 × 10^?4 m/s, bulk density p = 1.9 Mg/m³, effective porosity n_e = 0.215 and median grain diameter D₅₀ = 0.55 mm, were determined. Other relevant hydraulic and solute transport parameters, such as dispersion coefficients and dispersivities were also established for the tropical soil.     

Adsorption of rare earth elements onto Carrizo sand: Experimental investigations and modeling with surface complexation

Rare earth element (REE) adsorption onto sand from a well characterized aquifer, the Carrizo Sand aquifer of Texas, has been investigated in the laboratory using a batch method. The aim was to improve our understanding of REE adsorption behavior across the REE series and to develop a surface complexation model for the REEs, which can be applied to real aquifer-groundwater systems. Our batch experiments show that REE adsorption onto Carrizo sand increases with increasing atomic number across the REE series. For each REE, adsorption increases with increasing pH, such that when pH >6.0, >98% of each REE is adsorbed onto Carrizo sand for all experimental solutions, including when actual groundwaters from the Carrizo Sand aquifer are used in the experiments. Rare earth element adsorption was not sensitive to ionic strength and total initial REE concentrations in our batch experiments. It is possible that the differences in experimental ionic strength conditions (i.e., 0.002-0.01 M NaCl) chosen were insufficient to affect REE adsorption behavior. However, cation competition (e.g., Ca, Mg, and Zn) did affect REE adsorption onto Carrizo sand, especially for light rare earth elements (LREEs) at low pH. Rare earth element adsorption onto Carrizo sand can be successfully modeled using a generalized two-layer surface complexation model. Our model calculations suggest that REE complexation with strong surface sites of Carrizo sand exceeds the stability of the aqueous complexes LnOH²⁺, LnSO₄⁺, and LnCO₃⁺, but not that of Ln(CO₃)₂^- or LnPO₄^o in Carrizo groundwaters. Thus, at low pH (<7.3), where major inorganic ligands did not effectively compete with surface sites for dissolved REEs, free metal ion (Ln³⁺) adsorption was sufficient to describe REE adsorption behavior. However, at higher pH (>7.3) where solution complexation of the dissolved REEs was strong, REEs were adsorbed not only as free metal ion (Ln³⁺) but also as aqueous complexes (e.g., as Ln(CO₃)₂^- in Carrizo groundwaters). Because heavy rare earth elements (HREEs) were preferentially adsorbed onto Carrizo sand compared to LREEs, original HREE-enriched fractionation patterns in Carrizo groundwaters from the recharge area flattened along the groundwater flow path in the Carrizo Sand aquifer due to adsorption of free- and solution-complexed REEs.     

各向异性砂土K0试验研究

静止土压力系数K0是岩土工程分析计算中的重要力学参数之一。实际工程中墙后填土由于碾压都具有不同程度的各向异性。制备了不同沉积方向的砂土试样,通过三轴排水剪切试验研究了砂土的各向异性。在研制应变路径试验设备的基础上给出了静止土压力系数的测量方法,研究了不同沉积方向对于K0的影响,并将试验测得的静止土压力系数与Jaky公式以及土压力离心模型试验结果进行了对比,离心模型试验结果与材料单元试验结果一致,证明了测量方法的有效性及结果的正确性。研究结果表明,各向异性条件下的K0值比各向同性时明显偏大。     

砂类土力学强度试验研究

通过对砂土的抗剪强度试验结果进行统计,分析了砂土内摩擦角和粘聚力随不同颗粒粒组含量、密实度的变化趋势及规律。试验结果表明,随着砂粒组含量的增大,内摩擦角呈线性增大趋势;当粉粒和粘粒含量增加时,粘聚力亦呈线性增大趋势。同时,试样干密度的增大使内摩擦角和粘聚力呈线性增大。砂土中的粗粒和细粒含量变化存在一个对应的内摩擦角和粘聚力变化的区间。通过回归分析砂土抗剪强度与所含颗粒不同粒径、密实度关系,在特殊条件下,可以有效快速判定砂土剪切指标。     

火山灰增强微生物固化砂土效果的试验研究

为了提升微生物固化砂土的效果,考虑火山灰的多孔结构及活性特征,设计进行了火山灰增强微生物诱导碳酸钙沉淀（MICP）固化砂土试验,综合宏观物理力学试验和微细观检测,系统分析了火山灰对微生物固化砂土的增强效果及增强机制。结果表明：（1）火山灰能够显著提高砂土微生物加固过程中的固菌率和胶结物产量,火山灰掺量在10%左右达到最佳,与常规MICP相比,固菌率提高了118.28%,胶结物生成量提高了29.55%。（2）火山灰的掺入提高了固化体的抗压强度和抵抗变形的能力,不同围压下固化体的抗压强度提升了52.26%～62.96%,破坏时的应变增加了100.00%～112.58%。（3）火山灰掺入后,固化体的孔隙大小及孔隙率明显减小,整体的密实性及抗渗性能进一步提升,孔隙率从20.12%减小为14.17%,渗透系数降低了一个数量级。（4）火山灰对微生物固化砂土的增强机制主要包括3个方面,一方面,火山灰在砂颗粒间起到了良好的充填作用,大幅减少了颗粒间的大孔隙,使得固化体的密实性增强;另一方面,火山灰良好的吸附作用有效提高了试样内细菌的含量,使固化体碳酸钙的产量及分布的均匀性均增加;第3方面,火山灰中的活性物质参与反应生成的胶凝物质与碳酸钙晶体形成复合凝胶体,使得固化体的胶结性能和密实程度进一步增强。     

Experimental study of sand streaks formed in turbulent boundary layers

Fine- to medium-grained sand transported as bedload moves in lanes parallel to the flow that are thought to be preserved as parting lineation. A series of six flume experiments was designed to discover the morphology and spacing of these lanes, here called sand streaks, as functions of local shear velocity, U* (9 × 10^-3 to 4.8 × 10^-2 m s^-1), depth (5 × 10^-2 and 9.5 × 10^-2 m), mean grain diameter (150, 200, 290, 1380 μm), and sediment bedload concentration (0.0–0.39). Low U* flows produce predominantly straight, non-intersecting sand streaks, moderate U* flows produce sub-parallel and en échelon sand streaks, and moderate to high U* flows produce wavy sand streaks and secondary streaks with a spacing an order of magnitude larger. The wavy sand streaks are thought to be composed of sand grains in suspension close to the bed. An upper grain-size limit for the sand streak structure occurs at a grain size between 290 and 1380μm. The spacings of the fine-and medium-grained sand streaks, at low to moderate U* (0.9 × 10^-2 to 3 × 10^-2m s^-1), are similar to those predicted for low-speed fluid streaks, although the fine-grained sand forms more closely-spaced streaks than the medium-grained sand. The spacings of sand streaks formed at moderate to high U* and at bedload concentrations greater than 0.15, are wider than those predicted for the low-speed fluid streaks. The wider spacing is thought to reflect a new type of flow immediately above the moving bed layer in which the formation of low-speed streaks is inhibited. This results from an increase in either grain concentration or grain size. The spacing of parting lineation, also wider than that predicted for low-speed streaks, may reflect this.     

砂砾石与砂接触冲刷试验研究

渗流作用下土层之间的接触面是较易发生渗透破坏的薄弱环节。在开展砂砾石渗透破坏试验研究的基础上,针对砂砾石与砂的接触面渗流及渗透破坏特性,利用大型竖向渗透仪和自主研制的环状径向水平渗透仪,研究了竖向和水平渗流作用下接触面渗流和渗透破坏的影响因素及接触冲刷的发生、发展过程。研究结果表明,典型的砂砾石与砂的接触冲刷破坏过程可分为稳定渗流阶段、过渡阶段和破坏阶段3个阶段,可用2个特征水力坡降进行划分,稳定渗流阶段与过渡阶段的分界点对应的水力坡降称为启动坡降,过渡阶段与破坏阶段的分界点对应的水力坡降称为破坏坡降;砂砾石与砂组合试样的渗透系数随砂砾石密度的增大、颗粒变细而减小,砂砾石与砂接触冲刷的抗渗坡降则随砂砾石密度的增大、颗粒变细而增大,在水平渗流情况下试样的渗透系数较竖向的大,但接触冲刷的抗渗坡降较竖向的小。     

砂土中群锚锚周土体变形特性模型试验研究

群锚是常见的基础形式应用较为广泛,由于群锚之间的相互作用,群锚上拔过程中锚周土体的变形破坏机制比较复杂。采用非接触式数字图像相关方法（DIC）对群锚上拔过程开展模型试验研究,分析了群锚上拔过程中上拔力-位移关系曲线特征和锚周土体变形破坏机制。试验结果表明,密实度和埋深对群锚上拔力-位移关系曲线特征具有显著影响,在相同密实度、相同埋深率下浅埋与深埋群锚与同条件下的单锚具有相似的上拔力-位移关系曲线特征;群锚抗拔承载力具有明显的叠加效应,且砂土密实度、埋深和锚间距等参数因素对群锚效应具有显著影响。通过变形场的研究,得出了砂土密实度、埋深以及锚间距对群锚效应的影响规律。     

钙质砂中毛细水高度与影响因素试验研究

钙质砂是指富含碳酸钙或其他难溶碳酸盐类的海洋成因的特殊介质,具有形状不规则、多孔隙且富含内孔隙等特点;土体因孔隙特性而存在广泛的毛细现象,植物根茎内的导管有如极细的毛细管,能由此吸收土壤里的水分,故钙质砂地层毛细水上升高度研究对岛礁生态研究有重要的意义。采用竖管法研究级配、粒径、干密度、盐度等因素对钙质砂毛细水上升高度的影响,结果显示：细颗粒含量越多、级配越好的连续级配钙质砂试样毛细水上升高度越高;单一粒径钙质砂试样毛细水上升高度随粒径的增大而减小;随着钙质砂干密度增加,粒径小于0.075 mm时毛细水上升高度逐渐减小,而粒径为0.075～0.250 mm时毛细水上升高度逐渐增大;与淡水相比,在低盐度下NaCl溶液对毛细水上升有抑制作用,海水对毛细水上升有促进但效果微弱。钙质砂中毛细水上升高度随时间变化关系符合双对数坐标下的二次多项式关系,其参量与钙质砂的物理性质以及溶液类型相关。     

非饱和黏土质砂的渗气规律试验研究

为了探讨非饱和黏土质砂的渗气规律,对常规三轴仪进行了改造,使其能够进行非饱和土渗气性量测,改进后的渗气装置具有构造简单、制样方便、试样均匀性好、加载系统稳定、可用量测的气压力梯度范围较大、提高了量测精度等优点,并解决了量测空气体积困难的问题和渗气试验气体从刚性壁和试样边缘流出的问题。使用该套仪器研究了不同干密度和不同含水率条件下气体流速与渗透系数随压力梯度变化的规律,分析了气体流速、渗气系数同含水率和干密度之间的依存关系,建立了渗气系数与含水率和干密度之间的函数关系。研究结果表明：试样在所研究的含水率、干密度范围,非饱和黏土质砂中气体流动可用达西定律描述。     

人工胶结砂物理力学特性试验研究

采用二次掺水法制备氧化钙胶结砂样,为加速碳酸化将试样放置在充满干冰的养护箱中养护,养护完成后对不同氧化钙掺入比的试样进行固结排水三轴试验和碳酸钙定量化学试验,分析了氧化钙掺入量对胶结砂物理力学特性的影响,定义了反映胶结物生成量的化学指标 ,利用 修正了摩尔-库仑强度理论。结果表明：二次掺水法可有效控制人工胶结砂的初始含水率,CaCO3胶结物的形成对试样物理力学特性有极大影响。在不同围压下,试样均表现出应力软化。随氧化钙掺入比的增加,试样应力软化现象逐渐增强,并且黏聚力及内摩擦角增量逐渐增大。胶结砂具有压硬性,围压、氧化钙的掺入比对试样剪胀有抑制作用。随着 的增加,试样黏聚力、摩擦角增量均有明显提高,通过试验数据得到了 与试样黏聚力、内摩擦角增量之间的函数关系,进而对摩尔-库仑强度理论进行了修正,修正后的公式能够反映胶结物的形成对胶结砂强度的影响。     

砂土中群桩的压拔加载试验研究

进行砂土的单桩和2×2群桩的压、拔试验,测定桩身轴力、桩顶荷载、位移以及桩端阻力。试验研究结果表明,群桩的抗压群桩效应系数 >1,最优桩间距为4D(D为直径),对应的 约为1.2;桩端阻力群桩效应系数 大于桩侧摩阻力群桩效应系数 ,其最优桩间距为5D,对应的 值约为1.3;桩侧摩阻力群桩效应系数在3D时约为1.2,但随桩间距的增大而减小。与前人理论分析的结果不同,由于砂土的挤密效应,试验测得抗拔群桩效应系数也大于1,最优桩间距在4D～5D之间,系数约为1.2。桩间距为7D时压、拔群桩效应系数均趋近于1,可基本忽略群桩效应。