Distribution coefficients surfaces

For a radionuclide to be an effective oceanic tracer, various criteria that link the tracer to a specihc process or element must be met. Foremost, the environmental behavior of the tracer must closely match that of the target constituent. Particle affinity, or the scavenging capability of a radionuclide to an organic or inorganic surface site i.e. distribution coefficient, Kf, is one such vital characteristic. The half-life of a tracer is another characteristic that must also coincide well with the timescale of interest. This section provides a brief review of the role of various surface sites in relation to chemical scavenging and tracer applications. 

Physical characteristics Molecular weight Vapour density Specific gravity Melting point Boiling point Solubility/miscibility with water Viscosity Particle size size distribution Eoaming/emulsification characteristics Critical temperature/pressure Expansion coefficient Surface tension Joule-Thompson effect Caking properties... 

Although, for most moderators, the surface of a stationary phase in LC can be considered stable at moderator concentrations above about 5%v/v, the results from the same experiments as those carried out by Purnell and his group could still be considered invalid and, at best, would not lead to unambiguous conclusions. Katz et al. [9] avoided this problem by examining liquid/liquid distribution systems using water as one phase and a series of immiscible solvent mixtures as the other and by measuring absolute distribution coefficients as opposed to retention volumes. 

For chromatography purposes the product of the distribution coefficient and the volume of stationary phase, or stationary phase surface area, gives the corrected retention volume,/, e.,... 

For a building with sharp corners, Cp is almost independent of the wind speed (i.e., Reynolds number) because the flow separation points normally occur at the sharp edges. This may not be the case for round buildings, w here the position of the separation point can be affected by the wind speed. For the most common case of the building with a rectangular shape, Cp values are normally between 0.6 and 0.8 for the upwind wall, and for the leeward wall 0,6 < C, < —0.4. Figure 7.99 and Table 7.32 show an example of the distribution of surface pressure coefficient values on the typical industrial building envelope. 

Table I summarizes some typical distribution coefficients. Sediments become enriched in plutonium with respect to water, usually with a factor of vlO5. Also living organisms enrich plutonium from natural waters, but usually less than sediments a factor of 103 - 101 is common. This indicates that the Kd-value for sediment (and soil) is probably governed by surface sorption phenomena. From the simplest organisms (plankton and plants) to man there is clear evidence of metabolic discrimination against transfer of plutonium. In general, the higher the species is on the trophic level, the smaller is the Kd-value. One may deduce from the Table that the concentration of plutonium accumulated in man in equilibrium with the environment, will not exceed the concentration of plutonium in the ground water, independent of the mode of ingestion.

This equation has been used for estimating migration velocities of radionuclides (e.g. 66). Here Pr is the density of the rock (kg/m3), p the density of water, e the fissure porosity, af the specific surface of fissures in the bedrock (m2/m3) and ap the specific surface of particles used in the Kd determinations (m2/m3). The distribution coefficient Kd represents ar. equilibrium value for the particular rock under the pertinent conditions. 

Baskaran and Santschi (1993) examined " Th from six shallow Texas estuaries. They found dissolved residence times ranged from 0.08 to 4.9 days and the total residence time ranged from 0.9 and 7.8 days. They found the Th dissolved and total water column residence times were much shorter in the summer. This was attributed to the more energetic particle resuspension rates during the summer sampling. They also observed an inverse relation between distribution coefficients and particle concentrations, implying that kinetic factors control Th distribution. Baskaran et al. (1993) and Baskaran and Santschi (2002) showed that the residence time of colloidal and particulate " Th residence time in the coastal waters are considerably lower (1.4 days) than those in the surface waters in the shelf and open ocean (9.1 days) of the Western Arctic Ocean (Baskaran et al. 2003). Based on the mass concentrations of colloidal and particulate matter, it was concluded that only a small portion of the colloidal " Th actively participates in Arctic Th cycling (Baskaran et al. 2003). 

This equation is widely used to describe adsorption in soil and near-surface aquatic environments. Another widely used linear coefficient is the organic-carbon partition coefficient Koc, which is equal to the distribution coefficient divided by the percentage of organic carbon present in the system as proposed by Flamaker and Thompson.131... 

In this chapter, we consider several simple models of ion sorption and exchange that can be applied within the context of a geochemical model. These models include distribution coefficients, Freundlich and Langmuir isotherms, and ion exchange theory. In the following chapter (Chapter 10), we consider surface com-plexation theory, which is more complicated but in some ways more robust than the models presented here. 

To compare the approaches, we repeat the simulation using the reaction K( method (Section 9.1) instead of surface complexation theory. By Equation 21.6, the distribution coefficient K d corresponding to a retardation factor of two has a value of 2.4 x 10-4 mol g 1. Saving this value in dataset Pb Kd.dat , we enter the XlT commands (corn d)... 

The first of these environmentally-important parameters can be expressed as a partition coefficient. In aqueous solution many, but not all pesticide compounds exhibit strong affinity for soil organic matter or concentrate in the lipid phase of soil organisms. Some, notably the cationic group, also exhibit marked affinity for clay or other mineral surfaces. An overall partition (or distribution) coefficient (kD) can be defined ... 

Organic compounds released into the vadose zone exist in four closely interrelated forms free-phase NAPL, attenuated to surface of soil grains, dissolved in water retained on and between the soil particles, and present as a gaseous phase. The mass distribution of each of these phases is controlled by such factors as concentration gradients, distribution coefficients, and Henry s law constants. 

The distribution coefficients are independent of the concentration of suspended solids in water, which can vary over a wide range they thus give a better picture than the fraction of metal ions in solution. Such distribution coefficients can be predicted on the basis of the equilibrium constants defining the complexation of metals by surfaces and their complexation by solutes (Table 11.1). 

Distribution coefficients based on adsorption equilibria are independent of the total concentrations of metal ions and suspended solids, as long as the metal concentrations are small compared with the concentration of surface groups. Examples of the Kd obtained from calculations for model surfaces are presented in Fig. 11.1. A strong pH dependence of these Kd values is observed. The pH range of natural lake and river waters (7 - 8.5) is in a favorable range for the adsorption of metal ions on hydrous oxides. 

Table 11.1 Determination of the Distribution Coefficient Kd from Surface Complex Formation (From Schindler, 1984 and Sigg, 1987)...

Comparing Field Data with Laboratory Experiments. Can the distribution of metal ions between particulate and dissolved phases be explained in terms of simple interactions with surfaces on the basis of the obtained surface parameters Can the differences in distribution (as reflected by the distribution coefficients) be explained by different binding properties of the particles ... 

The semi-empirical descriptions of adsorbate/solid interactions are based on net changes in system composition and, unlike surface complexation models, do not explicitly identify the details of such interactions. Included in this group are distribution coefficients (Kp) and apparent adsorbate/proton exchange stoichiometries. Distribution coefficients are derived from the simple association reaction... 

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