Kinetics sediment

Electro-Kinetic Effects. The appHcation of d-c potential in filtration or sedimentation is known to have a beneficial effect on the separation. Although this has been known and studied since the beginning of the nineteenth century, practical appHcation and development have only accelerated since the late 1980s commercial appHcation is likely. 

The annual cycle depicted in Figure 3 could, therefore, be due to a redox cycle whose kinetics are controlled by pH, decay processes in the sediment, and temperature. 

Diffusion as referred to here is molecular diffusion in interstitial water. During early diagenesis the chemical transformation in a sediment depends on the reactivity and concentration of the components taking part in the reaction. Chemical transformations deplete the original concentration of these compounds, thereby setting up a gradient in the interstitial water. This gradient drives molecular diffusion. Diffusional transport and the kinetics of the transformation reactions determine the net effectiveness of the chemical reaction. 

The failure to identify the necessary authigenic silicate phases in sufficient quantities in marine sediments has led oceanographers to consider different approaches. The current models for seawater composition emphasize the dominant role played by the balance between the various inputs and outputs from the ocean. Mass balance calculations have become more important than solubility relationships in explaining oceanic chemistry. The difference between the equilibrium and mass balance points of view is not just a matter of mathematical and chemical formalism. In the equilibrium case, one would expect a very constant composition of the ocean and its sediments over geological time. In the other case, historical variations in the rates of input and removal should be reflected by changes in ocean composition and may be preserved in the sedimentary record. Models that emphasize the role of kinetic and material balance considerations are called kinetic models of seawater. This reasoning was pulled together by Broecker (1971) in a paper called "A kinetic model for the chemical composition of sea water."... 

Emerson, S. and Widmer, G. (1978). Early diagenesis in anaerobic lake sediments II. Equilibrium and kinetic factors controlling the formation of iron phosphate. Geochim. Cosmochim. Acta 42,1307-1316. 

N02 did not accumulate in lake sediments under conditions where nitrate rapidly disappeared. The low levels of both nitrite and nitrosatable amines in natural waters, along with expected third order kinetics fc make extensive nitrosamine formation unlikely. The prospect has been discussed by Dressel. ... 

The various physical methods in use at present involve measurements, respectively, of osmotic pressure, light scattering, sedimentation equilibrium, sedimentation velocity in conjunction with diffusion, or solution viscosity. All except the last mentioned are absolute methods. Each requires extrapolation to infinite dilution for rigorous fulfillment of the requirements of theory. These various physical methods depend basically on evaluation of the thermodynamic properties of the solution (i.e., the change in free energy due to the presence of polymer molecules) or of the kinetic behavior (i.e., frictional coefficient or viscosity increment), or of a combination of the two. Polymer solutions usually exhibit deviations from their limiting infinite dilution behavior at remarkably low concentrations. Hence one is obliged not only to conduct the experiments at low concentrations but also to extrapolate to infinite dilution from measurements made at the lowest experimentally feasible concentrations. 

Rates of hydrolysis may be influenced by the presence of dissolved organic carbon, or organic components of soil and sediment. The magnitude of the effect is determined by the structure of the compound and by the kinetics of its association with these components. For example, whereas the neutral hydrolysis of chlorpyrifos was unaffected by sorption to sediments, the rate of alkaline hydrolysis was considerably slower (Macalady and Wolf 1985) humic acid also reduced the rate of alkaline hydrolysis of 1-octyl 2,4-dichlo-rophenoxyacetate (Perdue and Wolfe 1982). Conversely, sediment sorption had no effect on the neutral hydrolysis of 4-chlorostilbene oxide, although the rate below pH 5 where acid hydrolysis dominates was reduced (Metwally and Wolfe 1990). 

Peijnenburg WJGM, KGM de Beer, HA den Hollander, MHL Stegeman, H Verboom (1993) Kinetics, products, mechanisms and QSARs for the hydrolytic transformation of aromatic nitriles in anaerobic sediment slurries. Environ Toxicol Chem 12 1149-1161. 

Although the results of experiments on the dechlorination of pentachlorophenol (Bryant et al. 1991) enabled elucidation of the pathways to be elucidated, this study also revealed one of the limitations in the use of such procedures. Detailed interpretation of the kinetics of pentachlorophenol degradation using dichlorophenol-adapted cultures was equivocal due to carryover of phenol from the sediment slurries. 

In a practical sense, stability of a dispersion ofttimes is accompanied by a retarded separation of the phases. Unfortunately, a quantitative definition cannot be based on this rate of separation because of the overwhelming influence of density, viscosity, and thermal effects. In short, a kinetic criterion, such as sedimentation rate, is not as likely to portray stability as one based on thermodynamic considerations. In this latter category are sediment volumes, turbidity, consistency, and electrical behavior. 

Moore WS, Demaster DJ, Smoak JM, McKee BA, Swarzenski PW (1996) Radionuclide tracers of sediment-water interactions on the Amazon shelf. Cont Shelf Res 16 645-665 Moran SB, Moore RM (1989) The distribution of colloidal aluminum and organic carbon in coastal and open ocean waters offNova Scotia. Geochim Cosmochim Acta 53 2519-2527 Nozaki Y (1991) The systematics and kinetics of U/Th decay series nuchdes in ocean water. Rev Aquatic Sci 4 75-105... 

Winters and Lee134 describe a physically based model for adsorption kinetics for hydrophobic organic chemicals to and from suspended sediment and soil particles. The model requires determination of a single effective dififusivity parameter, which is predictable from compound solution diffusivity, the octanol-water partition coefficient, and the adsorbent organic content, density, and porosity. 

Baughman GL, Weber E (1994) Transformation of dyes and related compounds in anoxic sediment Kinetics and products. J Environ Sci Technol 28 267-276... 

The kinetics of dissolution of pure CaC03 and soil CaC03, as indicated by the volume of C02 released and Ca dissolved during extraction, are presented in Fig. 4.3. It shows that dissolution of both pure and soil CaC03 by the NaOAc-HOAc solutions at various pHs reached a plateau after two hours. This indicates that a certain acid dose reacts completely with the proper content of soil carbonate within two hours. Tessier et al. (1979) reported that after five hours of leaching sediments, there was no increase in the calcium concentration, thus indicating that it is unnecessary to allow 16 hours for extraction of the CARB fraction, as was originally done in this sequentially selective dissolution procedure. 

Another HPLC method was described in a series of experiments analyzing the kinetics and mechanisms of [14C] niclosamide degradation in sediment and water systems [71]. 

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