Equilibrium-partitioning coefficient water-solid

Since the open water column is nearly pure water (op =1, rs p = 0), for compounds with small to moderate solid-water distribution ratios (Kd < 10 m3kg ), the above equilibrium partition coefficient can be simplified to ... 

The concept of the equilibrium sampler is analogous to that of the octanol-water equilibrium partition coefficient (fQ,w) used since the 1970s to predict the potential for persistent nonpolar contaminants to concentrate in aquatic organisms [71]. The use of equilibrium-t) e passive samplers in the aquatic environment depends on the development of a sampler-water partition coefficient (fCs ) defined as the ratio of sampler to water concentration of the compound of interest at thermod)mamic equilibrium. The other key parameter determining the utility of an equilibrium-type passive sampler is the time taken to reach an approximate equilibrium condition. A range of approaches applied in developing equilibrium-t)q)e passive samplers include polyethylene or silicon sheets of various volume to surface area ratio [72] and solid-phase microextraction techniques [73]. 

In its simplest form a partitioning model evaluates the distribution of a chemical between environmental compartments based on the thermodynamics of the system. The chemical will interact with its environment and tend to reach an equilibrium state among compartments. Hamaker(l) first used such an approach in attempting to calculate the percent of a chemical in the soil air in an air, water, solids soil system. The relationships between compartments were chemical equilibrium constants between the water and soil (soil partition coefficient) and between the water and air (Henry s Law constant). This model, as is true with all models of this type, assumes that all compartments are well mixed, at equilibrium, and are homogeneous. At this level the rates of movement between compartments and degradation rates within compartments are not considered. 

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. 

In nonporous membranes, diffusion occurs as it would in any other nonporous solid. However, the molecular species must first dissolve into the membrane material. This step can oftentimes be slower than the diffusion, such that it is the rate-limiting step in the process. As a result, membranes are not characterized solely in terms of diffusion coefficients, but in terms of how effective they are in promoting or limiting both solubilization and diffusion of certain molecular species or solutes. When the solute dissolves in the membrane material, there is usually a concentration discontinuity at the interface between the membrane and the surrounding medium (see Figure 4.55). The equilibrium ratio of the solute concentration in one medium, c, to the solute concentration in the surrounding medium, C2, is called the partition coefficient, K12, and can be expressed in terms of either side of the membrane. For the water-membrane-water example illustrated in Figure 4.55,... 

Metal concentrations and metal activities in the pore water are dependent upon both the metal concentration in the solid phase and the composition of both the solid and the liquid phase. In matrix extrapolation, and with emphasis on the pore water exposure route, it is therefore of great practical importance to have a quantitative understanding of the distribution of heavy metals over the solid phase and the pore water. A relatively simple approach for calculating the distribution of heavy metals in soils is the equilibrium-partitioning (EP) concept (Shea 1988 van der Kooij et al. 1991). The EP concept assumes that chemical concentrations among environmental compartments are at equilibrium and that the partitioning of metals among environmental compartments can be predicted based on partition coefficients. The partition coefficient, Kp, used to calculate the distribution of heavy metals over solid phase and pore water is defined as... 

For air-water systems, this equation is known as Henry s law. For solids-water systems, the equilibrium constant is known as the partition coefficient (Ky) or distribution constant (KA). Partition coefficients are available for many organic chemicals from laboratory and field measurements. As organic carbon (OC) present in water (dissolved organic carbon, or DOC), sediment, or soil is the main sink for hydrophobic organic contaminants, the partition coefficients for these compounds are often adjusted (normalized) with respect to the organic carbon content of these compartments ... 

Partition coefficients are used to describe the distribution of nonpolar organic compounds between water and organisms. It can be viewed as a partitioning process between the aqueous phase and the bulk organic matter present in biota (Schwarzenbach et al. 1993). The premise behind the use of equilibrium models is that accumulation of compounds is dominated by their relative solubility in water and the solid phases, respectively. Equilibrium models, therefore, rely on the following assumptions (Landrum et al. 1996) ... 

Equilibrium partitioning and mass transfer relationships that control the fate of HOPs in CRM and in different phases in the environment were presented in this chapter. Partitioning relationships were derived from thermodynamic principles for air, liquid, and solid phases, and they were used to determine the driving force for mass transfer. Diffusion coefficients were examined and those in water were much greater than those in air. Mass transfer relationships were developed for both transport within phases, and transport between phases. Several analytical solutions for mass transfer were examined and applied to relevant problems using calculated diffusion coefficients or mass transfer rate constants obtained from the literature. The equations and approaches used in this chapter can be used to evaluate partitioning and transport of HOP in CRM and the environment. 

Solid phase micro-extraction (SPME) allows isolation and concentration of volatile components rapidly and easily without the use of a solvent. These techniques are independent of the form of the matrix liquids, solids and gases can be sampled quite readily. SPME is an equilibrium technique and accurate quantification requires that the extraction conditions be controlled carefully. Each chemical component will behave differently depending on its polarity, volatility, organic/water partition coefficient, volume of the sample and headspace, speed of agitation, pH of the solution and temperature of the sample (Harmon, 2002). The techniques involve the use of an inert fiber coated with an absorbant, which govern its properties. Volatile components are adsorbed onto a suitable SPME fiber (which are usually discriminative for a range of volatile components), desorbed in the injection chamber and separated by a suitable GC column. To use this method effectively, it is important to be familiar with the factors that influence recovery of the volatiles (Reineccius, 2002). 

The application of UNIFAC to the solid-liquid equilibrium of sohds, such as naphthalene and anthracene, in nonaqueous mixed solvents provided quite accurate results [11]. Unfortunately, the accuracy of UNIFAC regarding the solubility of solids in aqueous solutions is low [7-9]. Large deviations from the experimental activity coefficients at infinite dilution and the experimental octanol/water partition coefficients have been reported [8,9] when the classical old version of UNIFAC interaction parameters [4] was used. To improve the prediction of the activity coefficients at infinite dilution and of the octanol/water partition coefficients of environmentally significant substances, special ad hoc sets of parameters were introduced [7-9]. The reason is that the UNIFAC parameters were determined mostly using the equihbrium properties of mixtures composed of low molecular weight molecules. Also, the UNIFAC method cannot be applied to the phase equilibrium in systems containing... 

FIGURE 1-10 Freundlich isotherms having exponents less than, equal to, and greater than one. An exponent of one corresponds to a linear isotherm, in which case the relationship between the aqueous concentration of a chemical and the chemical s concentration on a solid phase at equilibrium with the water can be described by a single partition coefficient. If the exponent is less than one, the ratio of sorbed concentration to aqueous concentration decreases as the chemical concentration in the system increases. Such a decrease would happen, for example, if the solid contained a finite number of sites that became filled (saturated) at higher aqueous chemical concentrations. An exponent greater than one might occur if the sorbed chemical modified the solid phase to favor further sorption. 

The hypothesis has been advanced that changes in relative concentrations of lipid type compounds, when comparing aquatic biota and their habitat, can be explained in large part by an estimate of their tendency to partition into tissues which has been related to octanol/water partition coefficients - K s (, 22). Table Vll presents tabulated data for and water to biota bloaccumu-latlon concentration factors calculated from data in Tables III and IV. Representative data from Table Vll are plotted in Figure 6 in the manner of Mackay (21) and Chlou (22), who have reviewed data on bloaccumulatlon of neutral hydrophobic compounds in aquatic biota. The solid line Is the expected distribution of data based on Chlou s review (22) of predictability for equilibrium situations. Our data is different in an absolute sense than the data used by Mackay and Chlou, because they used concentrations in biota... 

Solid-phase microextraction is controlled by diffusion rates and partition effects. In typical quantitative analyses, for this technique to be reproducible, the extraction process should continue until the partitioning events reach equilibrium and all variables affecting the partitioning must be controlled. For a two-phase system, the extraction is dependent on the analyte s partition coefficient and the volumes of the solid phase and the water. In the headspace technique, equilibrium must be reached between all three phases the water, the vapor, and the solid phase. 

The determination of R (see Eq. 7.25) by a measurement of the partition coefficient k in the laboratory, by some type of sorption experiment for the determination of adsorbed solid-phase concentration versus solution-phase concentration in equilibrium (so-called isopleths or isotherm), however, supplies values of R which are not comparable with the actual in field retardation factors in a mineral liner, because the specific surface susceptible to the pollutant is very different in both cases. Therefore, based on diffusion coefBcients in free aqueous solutions, the effective diffusion coefficients of organic substances for water-saturated mineral liners were estimated by using a tortuosity factor F= 1/3 (Muller et al. 1997a). Table 7.6 shows the results for various soil materials. 

A substance released to the environment can volatilize from water to air, or sublime from solid to vapor phase. It can also be washed out of the air with rainfall that deposits the substance on land or in surface water. Scientists characterize the tendency of a chemical substance to partition between air and water by its vapor pressure and solubility in water, or, in dilute solutions at equilibrium, by the Henry s law coefficient (which can be measured or calculated from the ratio of the vapor pressure to solubility at a specified temperature). The Henry s law coefficient is sometimes referred to as an air-water partition coefficient. 

We will start our discussion by considering a special case, that is, the situation in which the molecules of a pure compound (gas, liquid, or solid) are partitioned so that its concentration reflects equilibrium between the pure material and aqueous solution. In this case, we refer to the equilibrium concentration (or the saturation concentration) in the aqueous phase as the water solubility or the aqueous solubility of the compound. This concentration will be denoted as Qf. This compound property, which has been determined experimentally for many compounds, tells us the maximum concentration of a given chemical that can be dissolved in pure water at a given temperature. In Section 5.2, we will discuss how the aqueous activity coefficient at saturation, y, , is related to aqueous solubility. We will also examine when we can use yf as the activity coefficient of a compound in diluted aqueous solution, y (which represents a more relevant situation in the environment). 

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