Subsurface Liquid Phase

Within the subsurface zone, two hquid phase regions can be defined. One region, containing water near the solid surfaces, is considered the most important surface reaction zone. This near solid phase water, which is affected by the sohd phase properties, controls the diffusion of the mobile fraction of the solute adsorbed on the solid phase. The second region constimtes the free water zone, which governs liquid and chemical flow in the porous medium. 

The composition and reactivity of the liquid phase (known as the soil solution) is defined by the quality of the incoming water and affected by fluxes of matter and energy originating from the vicinity of the solid phase, microbiological activity, and the gas phase. To understand the properties of the subsurface hquid phase, it is first necessary to consider the structure of the water molecule. 

10% of the molecules to change from tetrahedral environments to two hydrogen-bonded configuration. 

The subsurface liquid phase generally is an open system and its composition is a result of dynamic transformation of dissolved constituents in various chemical species over a range of reaction time scales. At any particular time the liquid phase is an electrolyte solution, potentially containing a broad spectrum of inorganic and organic ions and nonionized molecules. The presently accepted description of the energy characteristics of the liquid phase is based on the concept of matrix and osmotic potentials. The matrix potential is due to the attraction of water to the solid matrix, while the osmotic potential is due to the presence of solute in the subsurface water. 

---

A system is homogeneous when the intensive properties are not a function of position, while a system is heterogeneous when the composition of a given mixture varies as a function of position. For example, the subsurface liquid phase usually comprises an aqueous solution incorporating a number of solutes in contaminated subsurface environments, nonaqueous phase liquids also may be present. The air phase of the subsurface includes gases with various partial pressures, and the solid phases comprise a mixture of minerals and organic compounds. 

Reversible and irreversible retention of contaminants on the subsurface solid phase is a major process in determining pollutant concentrations and controlling their redistribution from the land surface to groundwater. After being retained in the solid, contaminants may be released into the subsurface liquid phase, displaced as water-immiscible liquids, or transported into the subsurface gaseous phase or from the near surface into the atmosphere. The form and the rate of release are governed by the properties of both contaminant and solid phase, as well as by the subsurface environmental conditions. We consider here contaminants adsorbed on the solid phase. 

One way that contaminants are retained in the subsurface is in the form of a dissolved fraction in the subsurface aqueous solution. As described in Chapter 1, the subsurface aqueous phase includes retained water, near the solid surface, and free water. If the retained water has an apparently static character, the subsurface free water is in a continuous feedback system with any incoming source of water. The amount and composition of incoming water are controlled by natural or human-induced factors. Contaminants may reach the subsurface liquid phase directly from a polluted gaseous phase, from point and nonpoint contamination sources on the land surface, from already polluted groundwater, or from the release of toxic compounds adsorbed on suspended particles. Moreover, disposal of an aqueous liquid that contains an amount of contaminant greater than its solubility in water may lead to the formation of a type of emulsion containing very small droplets. Under such conditions, one must deal with apparent solubility, which is greater than handbook contaminant solubility values. 

Phosphorus in the subsurface originates from a natural parent material or anthropogenic application on land surface (e.g., fertilizers, pesticides, surfactant products, sludge, and effluents). This element may be found in inorganic or organic forms, which are in a dynamic equihbrium with dissolved P in the subsurface liquid phase. 

Multiphase extraction uses a vacuum system to remove various combinations of contaminated groundwater, separate-phase petroleum product, and vapors from the subsurface. The system lowers the water table around the well, exposing more of the formation. Contaminants in the newly exposed vadose zone are then accessible to vapor extraction. Once above ground, the extracted vapors or liquid-phase organics and groundwater are separated and treated. 

Panday, S., Forsyth, R A., Falta, R. W., Wu, Y., and Huyakorn, P. S., 1995, Considerations for Robust Compositional Simulations of Subsurface Nonaqueous Phase Liquid Contamination and Remediation Water Resources Research, Vol. 31, No. 5, pp. 1273-1289. 

Injection of steam or heated air into the subsurface provides large amounts of thermal energy, which speeds the mobilization of adsorbed organic contaminants and results in their removal as either a vapor or liquid phase. Elevated temperature increases the vapor pressure of the chemicals involved and promotes transfer of constituents across the air-water interface, which results in the increased removal of contaminants in high-humidity or nearly saturated soil systems. Additionally, the presence of high-temperature water sometimes results in oxidation or hydration of organic contaminants. 

The composition of the subsurface gas phase may change as a result of gas dissolution into the liquid phase. The solubility of gases in water depends on the type of gas, temperature, salt concentration, and the partial pressure of the gases in the atmosphere. The most soluble gases are those that become ionized in water (CO, NHj, H S), while and are much less soluble (Table 1.2). 

Dissolution and precipitation in the subsurface are controlled by the properties of the solid phases, by the chemistry of infiltrating water, by the presence of a gas phase, and by environmental conditions (e.g., temperature, pressure, microbiological activity). Rainwater, for example, may affect mineral dissolution paths differently than groundwater, due to different solution chemistry. When water comes in contact with a solid surface, a simultaneous process of weathering and dissolution may occur under favorable conditions. Dissolution of a mineral continues until equilibrium concentrations are reached in the solution (between solid and liquid phases) or until all the minerals are consumed. 

Contaminants may reach the subsurface in a gaseous phase, dissolved in water, as an immiscible hquid, or as suspended particles. Contaminant partitioning in the subsurface is controlled by the physicochemical properties and the porosity of the earth materials, the composition of the subsurface water, as well as the properties of the contaminants themselves. While the physicochemical and mineralogical characteristics of the subsurface sohd phase define the retention capacity of contaminants, the porosity and aggregation stams determine the potential volume of liquid and air that are accessible for contaminant redistribution among the subsurface phases. Enviromnental factors, such as temperature and water content in the subsurface prior to contamination, also affect the pollution pattern. 

Contaminants may be adsorbed on the solid phase or on suspended particles in the liquid phase. Environmental factors, such as temperature, pH, and water content in the subsurface prior to contamination, also affect the nature of contaminant adsorption. Other physical processes of retention include precipitation, deposition, and trapping. Under natural conditions, pollutants often consist of more than a single contaminant, comprising a mixture of organic and inorganic toxic compounds. Each of these compounds can react differently with the existing minerals and chemicals in the subsurface. 

Volatilization (also referred to as vaporization or evaporation) is the conversion of a chemical from the sohd or hquid phase to a gas or vapor phase. The partitioning of a volatile compound in the subsurface environment comprises two distinct patterns volatilization of contaminant molecules (from the liquid, sohd, or adsorbed phase) and dispersion of the resulting vapors in the subsurface gas phase or the overlying atmosphere by diffusive and turbulent mixing. Even though the two processes are fundamentally different and controlled by different chemical and environmental factors, they are not wholly independent under natural conditions only by integrating their effects can volatilization be characterized. 

Gas-liquid relationships, in the geochemical sense, should be considered liquid-solid-gas interactions in the subsurface. The subsurface gas phase is composed of a mixture of gases with various properties, usually found in the free pore spaces of the solid phase. Processes involved in the gas-liquid and gas-solid interface interactions are controlled by factors such as vapor pressure-volatilization, adsorption, solubility, pressure, and temperature. The solubility of a pure gas in a closed system containing water reaches an equilibrium concentration at a constant pressure and temperature. A gas-liquid equilibrium may be described by a partition coefficient, relative volatilization and Henry s law. 

Volatilization of contaminants from subsurface aqueous solutions into the subsurface gas phase or the (above ground) atmosphere is controlled by the vapor pressnre. Componnds with high vapor pressure tend to accnmnlate in the gas phase, which may be considered a kind of componnd solnbility in the atmosphere. Partitioning between the liquid and the gas phases is described by Henry s law and is expressed as... 

Nonadsorptive retention of contaminants may occur when chemicals reach the subsurface as a separate liquid phase or are adsorbed on suspended particles or orgaiuc residues. Contaminated suspended particles originating from sludge disposal or polluted runoff, for example, can represent a substantial hazard to the subsurface environment. 

After reaching the subsurface, contaminants are partitioned among the solid, liquid, and gaseous phases. A fraction of the contaminated gaseous phase is transported into the atmosphere, while the remaining part may be adsorbed on the subsurface solid phase or dissolved into the subsurface water. Contaminants dissolved in the subsurface aqueous phase or retained on the subsurface solid phase are subjected, over the course of time, to chemical, biochemical, and surface-induced degradation, which also lead to formation of metabolites. 

As a first approximation, we consider the main subsurface transformation processes to comprise reactions leading to chemical transformation or degradation and metabolite formation in the liquid phase or the solid-liquid interface and reactions resulting in complexation of chemicals, which in turn lead to a change in their physicochemical properties. 

In the subsurface the density of a gas increases with depth, despite increasing temperature, because of the pressure-induced compression. When a fluid s critical temperature (Tc) and pressure (pc) are exceeded there are no longer separate gas and liquid phases only a single supercritical fluid can exist. For methane Tc = -82.6 °C and pc = 4.6 MPa, whereas for carbon dioxide the corresponding values are -31.0°C and 7.4MPa (a typical phase diagram is shown in Fig. 4.28). A supercritical fluid has a much higher density than a gas and many of its properties are intermediate between those of a gas and a liquid. Consequently, supercritical methane and carbon dioxide are potentially excellent solvents for oil. 

The liquid and gas bubbles underneath the propellant surface are treated together and referred to as the subsurface two-phase region. The physiochemical processes in this region are extremely complicated, involving an array of intricacies such as thermal decomposition, evaporation, bubble formation, gas-phase reactions in bubbles, interfacial transport of mass and... 

---