Thermodynamic properties of solutions in metastable systems under negative or positive pressures

Metastable systems are created when the interface between the atmosphere (in which P_atm = 1 bar) and water forms a spherical meniscus either concave toward the air (water filling capillaries, wherein P_water < P_atm) or convex toward the air (fog water droplet, wherein P_water > P_atm). Soil water, undergoing negative pressure (“capillary potential”) remains bound to the solid matrix (instead of flowing downward) by the capillary meniscus, concave toward the undersaturated dry atmosphere. The positive counterpart of tensile water in soils is the pressurized water contained in fine droplets suspended in oversaturated humid air, as in clouds. All these systems are anisobaric domains the phases of which have different pressures. Geochemical consequences of such characteristics are assessed here by calculating the consequences of the positive or negative water potential on the equilibrium constants of reactions taking place in stretched or pressurized aqueous solutions. Thermodynamic properties of aqueous species are obtained by using the TH model, used explicitly for positive pressures but extrapolated to negative ones for soil solutions. It appears that soil water dissolves gases, offering an alternative explanation of the observed enrichment of atmospheric noble gases in groundwater and of carbonic gas in the unsaturated zone below the root zone. Water droplets obviously show the opposite behavior, that is, a decreasing dissolutive capability with decreasing droplet size (water pressure increases), inducing some climatic consequences. An application of this approach to the solid-solution equilibria is performed by comparing experimental solubility of amorphous silica in unsaturated media on the one hand, to theoretical calculations taking account of the negative water pressure on the other hand. This comparison outlines the potential complexity of anisobaric situations in nature and the necessity to develop a suitable approach for solid pressure.     

Numerical modelling of groundwater vulnerability: the example Namibia

The UNSAT-H, HELP3 and MACRO4.3 computer codes, which have been developed for simulating the water balance of the unsaturated zone of soils and unconsolidated sediments, are also capable simulating water flow in low-porosity media such as fractured rock. The codes can be used to model the ability of rocks and overlying soils in the vadose zone to protect the groundwater in the uppermost aquifer. The net infiltration rates simulated by the different codes are compared against recharge determined by the chloride-balance method in Namibia. The dual-permeability code MACRO4.3 was found to produce more realistic estimates of net infiltration than the UNSAT-H and HELP3 codes, which are based on a single-permeability or effective-continuum method. The net infiltration rate together with the water storage in the unsaturated zone and the groundwater depth are used to calculate the residence time of pore water in the unsaturated zone. This parameter determines the intrinsic vulnerability of the aquifer.     

Processes controlling acid attenuation in the unsaturated zone of a Triassic sandstone aquifer (U.K.), in the absence of carbonate minerals

Continuous core samples were taken through the unsaturated zone at three sites on the outcrop of Permo-Triassic sandstone in the British West Midlands. Sample sites were chosen for lack of recent, direct anthropogenic disturbance, and for differing vegetation: heathland, birch woodland and conifer forest. Interstitial water was extracted and analyzed for 32 major and trace elements. Solid phases were analyzed for exchangeable cations and mineralogy. The rate of recharge calculated using a Cl mass balance method was three times greater below heathland than below afforested sites owing to higher evapotranspiration rates in the woodlands.Carbonate minerals were absent from the unsaturated zone at each site. Soil solutions were acidic and soils at the woodland sites were more acidic (pH 4.0) than those at the heathland site (pH 4.5). Acidic interstitial water solutions were found to up to 5.0 m depth in the unsaturated zone and are partially neutralized by two aluminosilicate mineral reactions in the unsaturated zone: cation exchange and K-feldspar dissolution. The rate at which these acid neutralizing reactions act to neutralize acidity is revealed by the rate of depletion of base cations from the unsaturated zone in recharge solutions; K⁺ (dissolution), Ca⁺² + Mg⁺² (cation exchange). The total base cation depletion rate was greatest below heathland; this can be attributed mainly to the greater rate of SO₄ assimilation by the woodland biome.     

非饱和土抗剪强度及土压力统一解

基于统一强度理论和非饱和土双应力状态变量抗剪强度,合理考虑中间主应力效应,建立了非饱和土双应力状态变量抗剪强度统一解,并与文献试验结果进行比较,验证了公式的正确性;进而考虑基质吸力的不同分布,得到非饱和土主动土压力和被动土压力统一解,克服了朗肯土压力的不足,并得出中间主应力和基质吸力对土压力的影响特性。研究结果表明,主动土压力随着统一强度理论参数和基质吸力的增大而不断减小,被动土压力则相反;当基质吸力沿深度线性减小时,主动土压力和被动土压力都不像基质吸力沿深度为常数时变化得那么快。该结果为非饱和土抗剪强度和土压力分析提供了理论依据,对工程设计有一定的参考价值。     

Recharge in northern clime calcareous sandy soils: soil water chemical and carbon-14 evolution

Chemical analyses were performed on soil water extracted from two cores taken from a sandy calcareous soil near Delhi, Ontario. Calcite saturation is attained within the unsaturated zone over short distances and short periods of time, whereas dolomite undersaturation persists to the groundwater table. The progressive dissolution of dolomite by soil water, within the unsaturated zone, after calcite saturation is reached results in calcite supersaturation.Deposition of iron and manganese oxyhydroxide phases occurs at the carbonate leached/unleached zone boundary. This is a result of soil water neutralization due to carbonate dissolution during infiltration but may also reflect the increased rate of oxidation of dissolved ferrous and manganous ions at higher pH's. The role of bacteria in this process has not been investigated.The depth of the carbonate leached/unleached zone boundary in a calcareous soil has important implications for ¹⁴C groundwater dating. The depth of this interface at the study site (?2 m) does not appear to limit ¹⁴C diffusion from the root zone to the depth at which carbonate dissolution occurs. Thus, soil water achieves open system isotopic equilibrium with the soil CO₂ gas phase. It is calculated that in soils with similar physical properties to the study soil but with depths of leaching of 5 m or more, complete ¹⁴C isotopic equilibration of soil water with soil gas would not occur. Soil water, under these conditions would recharge to the groundwater exhibiting some degree of closed system ¹⁴C isotopic evolution.     

Eclogites and water pressure

Available data on the stability of amphibolites and the basalt-eclogite transition allow an estimate of the stability field of eclogites in wet systems. It appears that if water and load pressures are comparable, eclogites cannot be stable in the crust; the formation of eclogites in the crust requires moderate total pressures and low water pressures. If the reactions forming eclogites occur in essentially dry rocks, their formation may reflect kinetic as well as equilibrium factors.     

Vapor-phase interactions and diffusion of organic solvents in the unsaturated zone

This article presents an analysis of the interactions and static movement of 37 organic solvents as vapors through the unsaturated soil zone. The physicochemical interactions of the organic vapors with unsaturated soil materials were emphasized with focus on diffusive, and adsorptive interactions. Fick's Law and porous media diffusion coefficients for most of the solvent vapors were either compiled or estimated; coefficients were not available for some of the fluorinated solvents. The adsorption of some of the solvent vapors by silica was concluded to be due to hydrogen bond formation with surface silanol groups. Heats of adsorption data for different adsorbents were also compiled. There were very few data on the adsorption of these solvent vapors by soils, but it appears that the magnitude of adsorption of nonpolar solvents is reduced as the relative humidity of the vapor-solid system is increased. Consequently, the interaction of the vapors may then separated into two processes; (1) gas-water partitioning described by Henry's Law constants, and (2) solid-water adsorption coefficients which may be estimated from liquid-solid partition coefficients (K _d values).     

A theory of loosening earth pressure above a shallow tunnel in unsaturated ground

A theory is proposed to evaluate the loosening earth pressure (vertical earth pressure after excavation) acting on a shallow tunnel in unsaturated ground with an arbitrary groundwater level. The theory is developed based on the limit equilibrium theory, combining soil–water characteristic curves, Mohr–Coulomb failure criteria, and effective stress for unsaturated soils. The proposed theory is applied to predict the vertical distribution of loosening earth pressure in unsaturated ground, which shows a significant difference from that in saturated ground. In unsaturated ground, suction contributes to the increase in effective loosening earth pressure and shear resistance. The remarkable effects of groundwater depth, soil type, and scale of overburden height and trapdoor width on loosening earth pressure are also revealed. Based on the soil–water characteristic curve, the degree of saturation decreases, which causes wet density to decrease and the total and effective loosening earth pressures to have contrary tendencies. Moreover, effective loosening earth pressures vary with soil type as the degree of saturation varies. The total loosening earth pressures are, however, very similar regardless of soil type, because wet density and shear resistance have similar tendencies. The proposed theory provides a valid model for loosening earth pressure in unsaturated ground that will be useful for shallow tunnel excavations.     

Limitations of suction‐controlled triaxial tests in the characterization of unsaturated soils

Behavior of unsaturated soils is influenced by many factors, and the influences of these factors are usually coupled together. Suction‐controlled triaxial (SCTX) tests are considered to allow researchers to investigate influences of individual variables on unsaturated soils under specified stress path with controls of stresses, pore water, and air pressures. In the past 50 years, SCTX testing method has been established as a standard approach to characterize constitutive behavior of unsaturated soils. Most important concepts for modern unsaturated soil mechanics were developed upon results from the SCTX tests. Among these, one of the most important contributions in the constitutive modeling of elasto‐plastic behavior for unsaturated soils is the Barcelona basic model (BBM) proposed by Alonso et al. in 1990. The BBM successfully explained many features of unsaturated soils and received extensive acceptance. However, the SCTX tests are designed based upon the divide‐and‐conquer approach in which an implicit assumption is used: soil behavior is stress‐path independent. However, it is well‐established that unsaturated soil behavior is elasto‐plastic and stress‐path dependent. It is found that the SCTX tests in fact cannot control the stress path of an unsaturated soil during loading. This incapability, in combination with complicated loading/collapse behavior of unsaturated soils, makes the SCTX tests for characterizing unsaturated soil questionable. This paper discusses the limitations of the SCTX tests in the characterization of unsaturated soils. A possible solution to the problem was proposed based on a newly developed modified state surface approach. The discussions are limited for isotropic conditions. Copyright © 2015 John Wiley & Sons, Ltd.     

A simple analytical solution to one‐dimensional consolidation for unsaturated soils

This paper presents a simple analytical solution to Fredlund and Hasan's one‐dimensional (1‐D) consolidation theory for unsaturated soils. The coefficients of permeability and volume change for unsaturated soils are assumed to remain constant throughout the consolidation process. The mathematical expression of the present solution is much simpler compared with the previous available solutions in the literature. Two new variables are introduced to transform the two coupled governing equations of pore‐water and pore‐air pressures into an equivalent set of partial differential equations, which are easily solved with standard mathematical formulas. It is shown that the present analytical solution can be degenerated into that of Terzaghi consolidation for fully saturated condition. The analytical solutions to 1‐D consolidation of an unsaturated soil subjected to instantaneous loading, ramp loading, and exponential loading, for different drainage conditions and initial pore pressure conditions, are summarized in tables for ease of use by practical engineers. In the case studies, the analytical results show good agreement with the available analytical solution in the literature. The consolidation behaviors of unsaturated soils are investigated. The average degree of consolidation at different loading patterns and drainage conditions is presented. The pore‐water pressure isochrones for two different drainage conditions and three initial pore pressure distributions are presented and discussed. Copyright © 2013 John Wiley & Sons, Ltd.     

基质吸力对非饱和土抗剪强度的影响

在自然界和工程实践中遇到的土大多数是非饱和土,研究吸力对非饱和土抗剪强度的作用,对于工程实践具有重要的意义。通过压力板仪和直剪仪组合试验,探讨了击实土抗剪强度和基质吸力的关系。试验结果表明：凝聚力在饱和度为40%-60%时最大,而内摩擦角则随饱和度增加而有所减少。进一步对比土-水特征曲线与抗剪强度的关系,并整合前人研究成果,指出了非饱和土中吸力对其抗剪强度影响的规律。对于无黏性土,在边界效应区不产生假凝聚力,且内摩擦角不变;在过渡区与非饱和残余区,假凝聚力和基质吸力的关系存在峰值且变化较大,内摩擦角则随吸力增加而增加。对于黏性土,残余体积含水率所对应的最小吸力可能是影响抗剪强度的界限值,小于此吸力值,φb可近似为常数。但在非饱和残余区,凝聚力将随土状态路径的不同而变化。对于重塑土,凝聚力降低;而对于原状土,则凝聚力可能不变或增加。     

Semi-analytical solution to one-dimensional consolidation for viscoelastic unsaturated soils

This paper presents a semi-analytical solution to one-dimensional consolidation of viscoelastic unsaturated soils with a finite thickness under oedometric conditions and subjected to a sudden loading. The solution is obtained by using Lee’s correspondence principle based on the semi-analytical solution to one-dimensional consolidation of elastic unsaturated soils. The boundary contains the top surface permeable to water and air and the bottom impermeable to water and air. A typical example is given to show the evolution of excess pore-air and pore-water pressures as well as the total degree of consolidation of the soil layer with time for different ratios of air–water permeability coefficient, elastic modulus and viscoelastic coefficient. The one-dimensional consolidation behavior of viscoelastic unsaturated soil is discussed according to the semi-analytical solution. These results contribute to a better understanding of the consolidation behavior of viscoelastic unsaturated soils.     

非饱和土中水流入渗和气体排出过程的求解

采用孔隙介质力学分析方法,把土体骨架、孔隙水和孔隙气分别作为独立的研究对象,结合孔隙水和孔隙气在气液交界面上满足的力学条件建立耦合方程,求解非饱和土中孔隙水的入渗和孔隙气体的排出过程。对标准砂进行的一维有压水流入渗试验和计算表明,孔隙气的排出过程影响孔隙水的渗流运动。数值计算与试验结果拟合较好。     

高吸力下黏性土的抗剪强度和体变特性

非饱和土中土-水之间的相互作用可区分为毛细作用和吸附作用,已有的非饱和土力学特性的研究大都局限于较低吸力、毛细作用占优范围。实践中由于环境的变化,地表土体常经历干湿循环及处在低含水率、高吸力状态,此时吸附作用占优。针对高岭土-河砂配制的非膨胀性黏性土,采用饱和盐溶液蒸汽平衡法,从脱湿和吸湿两种吸力路径下对土体施加高吸力。测试了高吸力下土体的强度和变形特性,试验中选用了0（接近无侧限）、25、50、100 kPa共4组小围压。试验结果表明,高吸力下土体表现为应变软化型破坏和剪胀性。随着围压的施加,土体从沿纵向开裂的张裂破坏过渡为剪切破坏。验证了修正后的Bishop非饱和土强度公式不适用于描述高吸力时峰值抗剪强度的变化,得到了高吸力下峰值抗剪强度可用相对于净应力的临界状态强度和剪胀作用来表示。分析发现,高吸力时土体的抗剪强度和比表面积直接相关,吸力对土体抗剪强度的作用取决于土体集聚体组构的形成和发展程度及其导致的剪胀作用。     

非均质包气带三氮累积转化模拟砂箱试验

为研究包气带非均质结构对氮素迁移转化的影响,采用室内砂箱实验模拟了1.72 mm/h降雨强度下NH₄-N污染非均质包气带的过程。通过观测出水及土壤溶液中NH₄-N、NO₂-N和NO₃-N质量浓度变化,分析探讨了NH₄-N在含有两个亚粘土透镜体的非均质包气带介质中的迁移转化和累积时空分布特征。结果表明：经过89 d物理吸附和微生物作用,出水NH₄-N首先迅速增加然后逐渐减小,而出水NO₃-N含量持续增加,其间NO₂-N出现累积峰,系统最终达到平衡稳定状态;土壤溶液中NH₄-N在两亚粘土透镜体上表面累积较多,NO₃-N和NO₂-N在上透镜体中的累积含量大于下透镜体;而砂槽上部土壤中出现明显的NO₃-N累积,NH₄-N和NO₂-N则在下部土壤和亚粘土透镜体中累积较多。包气带介质质地、粗 细交互结构及降雨淋溶、水分运移对“三氮”的迁移转化和富集有重要影响。     

吸力、含水率和干密度对重塑非饱和土抗剪强度影响研究

进行了一系列控制吸力、含水率和干密度的直剪试验,研究了重塑非饱和土的抗剪强度特性。试验结果表明,在试验研究的吸力范围内,非饱和土的黏聚力随吸力线性增加,而内摩擦角随吸力的变化则很小。对于控制含水率的试验,非饱和土的黏聚力和内摩擦角均随含水率增加而线性减小,且黏聚力减小的幅度更明显。干密度对非饱和土的内摩擦角几乎没有影响,黏聚力随干密度呈指数增加。对控制吸力和含水率的试验结果进行了比较,提出的考虑含水率影响的抗剪强度公式可供实际工程参考。     

包气带中温度变化对水分分布影响的实验研究

笔者在高180cm、宽50cm的砂槽中,做了温度对水分运移影响的模拟试验。试验结果表明,在包气带一定深度以下,孔隙相对封闭,孔隙内液态水与气态水处于动态平衡,相对湿度接近或达到饱和状态。在此条件下,砂柱内温度场的任何微小变化都会导致孔隙系统内的水分发生蒸发或凝结。当包气带内温度场发生变化时,气态水在温度梯度作用下,向最低温度界面运移,蒸发或是凝结取决于最低温度界面的性质。在不发生聚集的开放性界面上出现蒸散,消耗包气带内水分。在聚集性封闭界面上则出现凝结,使包气带内水分增加。在温度场控制下,包气带中气态水凝结或蒸发是水分运移的另一重要形式,它在一定程度上决定着水分的分布状态,尤其在温差巨大的地区,这种作用显得十分重要。     

Contaminant migration at two low-level radioactive waste sites in arid western United States – A review

 Contamination of the unsaturated zone and ground water at the Beatty, Nevada and Richland, Washington low-level radioactive waste sites shows that pathways exist for rapid lateral and vertical migration of contaminants through unconsolidated clastic sediments that comprise the 100 m-thick unsaturated zones of those arid disposal sites. Disposal of liquid wastes at the Beatty site until 1975 may have contributed to rapid migration of contaminants, but negligible amounts of liquid wastes reportedly were disposed at the Richland LLRW site and similar problems of contaminant migration exist. Pathways for vertical migration in the unsaturated zone include fractures and, at Richland, clastic dikes; lateral migration pathways likely are facies-controlled. Disturbance of the disposal sites contributed to increased infiltration of the unlined waste trenches after closure; simulations that used Beatty sample data show dramatic increases in recharge with disturbances necessary to develop the site. Because neither an arid climate nor presence of a thick unsaturated zone offer effective barriers to ground-water contamination, reliance on those factors at proposed sites such as Ward Valley, California and elsewhere is unwarranted. Received: 4 February 1998 · Accepted: 4 May 1998     

Strength reduction FEM in stability analysis of soil slopes subjected to transient unsaturated seepage

The instability of soil slopes induced by the fluctuation of water level or rainfall has received much attention in the literature recently and the failure mechanism is closely related to the change of matric suction of unsaturated soils. Such a change is basically induced by unsaturated transient seepage. The traditional approach for estimating the stability of slopes subjected to unsaturated transient seepage is based on the limit equilibrium method (LEM). The limit equilibrium approach is limited by assumptions about analysis method and failure mechanism. In order to overcome those limitations, a finite element method with shear strength reduction technique (SSRFEM) has been successfully applied to the slope stability analysis in absence of seepage. The main objective of this paper is to extend the use of the strength reduction FEM to include the effects of unsaturated transient seepage and some primary numerical results concerning the stability of an earth dam under rapid drawdown are presented. Emphasis has been given to comparison of the safety factors obtained by LEM and SSRFEM. Topics for the further research in this area are also suggested.     

Temperature effects on the hydraulic behaviour of an unsaturated clay

The influence of temperature on the hydraulic properties of unsaturated clays is of major concern in the design of engineered barriers in underground repositories for high-level radioactive waste disposal. This paper presents an experimental study centred on the investigation of the influence of temperature on soil hydraulic properties related to water retention and permeability. Laboratory tests were conducted on artificially prepared unsaturated fabrics obtained from a natural kaolinitic-illitic clay. Special attention is given to the testing procedures involving controlled suction and temperature oedometer cells and the application of the vapour equilibrium technique at high temperatures. Retention curves at different temperatures show that total suction tends to reduce with increasing temperatures at constant water content. Temperature influence on water permeability is more relevant at low matric suctions corresponding to bulk water preponderance (inter-aggregate zone). Below a degree of saturation of 75% no clear effect is detected. Experimental data show that temperature dependence on permeability at constant degree of saturation and constant void ratio is smaller than what could be expected from the thermal change in water viscosity. This behaviour suggests that phenomena such as porosity redistribution and thermo-chemical interactions, which alter clay fabric and pore fluid, can be relevant.