Abstract
AbstractThe soil water density is defined as the ratio of soil water mass to soil water volume. It is a cornerstone in defining thermodynamic states of either saturated or unsaturated soils for quantifying water storage and movement in the subsurface and for mechanical stability of landscape. So far, it has been widely treated as identical to the free water density, that is, a constant of 0.997 g/cm3, but can be remarkably different from this value as it is subject to a wide range of variation in energy levels. Some experimental and theoretical evidence indicate that it can be as high as 1.680 g/cm3 and as low as 0.752 g/cm3. However, to date, there is no unanimous agreement upon a reliable experimental method to measure the soil water density or a unified theory to explain why and how the soil water density can deviate remarkably from the free water density. Consequently, the understanding of the soil water density is controversial and elusive, or some theories are contradictory to each other. In this review, the authors will (1) conduct critical reviews on the experimental and theoretical methodologies to identify their limitations, flaws, and uncertainties, (2) synthesize some recent findings on intermolecular forces, interfacial interactions, and soil water retention mechanisms to clarify molecular‐scale physicochemical mechanisms governing the soil water density, and (3) propose a unified model to quantify soil water density variation. It is found that capillarity associated with surface tension tends to generate tensile stress in soil water and thereby decreases the soil water density, whereas adsorption stemmed from cation hydration, surface hydration, and interlamellar cation hydration tends to produce compressive stress thus increases the soil water density. Furthermore, the abnormally high water density greater than 1.15 g/cm3 is a result of cation and surface hydration that involves significant water structure change around exchangeable cations and mineral surface hydroxyls. The unified soil water density model, explicitly quantifying adsorptive and capillary water, could potentially reconcile the unresolved controversies. The critical reviews and the unified model also would allow us to further confine the upper and lower bounds of the soil water density. The upper bound is theoretically inferred to be around 1.872 g/cm3, whereas the lower bound is around 0.995 g/cm3; both are higher than that reported in the literature. With the unified model and measured soil water retention curves, it is demonstrated quantitatively that the soil water density significantly impacts the magnitude of various fundamental soil properties such as matric potential, specific surface area, and volumetric water content. The abnormally high soil water density has significant implications to the conventional concepts of matric potential and pore water pressure in soils and other earthen porous materials.
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