Calcium release during dissolution

Figure 4. Calcium released to the aqueous solution during the dissolution of powders from three rock types. fA , Eleana shale (UE-17e) (0), quartz monzonite (V15e-7) (9), umtanum basalt (DC 3-3600).

During the lifetime of a root, considerable depletion of the available mineral nutrients (MN) in the rhizosphere is to be expected. This, in turn, will affect the equilibrium between available and unavailable forms of MN. For example, dissolution of insoluble calcium or iron phosphates may occur, clay-fixed ammonium or potassium may be released, and nonlabile forms of P associated with clay and sesquioxide surfaces may enter soil solution (10). Any or all of these conversions to available forms will act to buffer the soil solution concentrations and reduce the intensity of the depletion curves around the root. However, because they occur relatively slowly (e.g., over hours, days, or weeks), they cannot be accounted for in the buffer capacity term and have to be included as separate source (dCldl) terms in Eq. (8). Such source terms are likely to be highly soil specific and difficult to measure (11). Many rhizosphere modelers have chosen to ignore them altogether, either by dealing with soils in which they are of limited importance or by growing plants for relatively short periods of time, where their contribution is small. Where such terms have been included, it is common to find first-order kinetic equations being used to describe the rate of interconversion (12). 

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. 

For minerals that dissolve incongmently, the determination of reaction rate depends upon which component released to solution is used in Equation (5). Due to preferential release of cations such as calcium and magnesium during inosUicate dissolution, for example, dissolution rates for these phases are usually calculated from observed silicon release (Brantley and Chen, 1995). Here, we report silicate dissolution rates based upon silicon release, but we normalize by the stoichiometry of the mineral and report as mol mineral per unit surface area per unit time. It is important to note that dissolution rates reported on this basis depend upon both the formula unit and the monitored solute. 

It has been demonstrated that the release of citric acid from PHEMA hydrogels hinders the formation of calcium phosphates, especially hydroxyapatites. Because of this inhibitory effect, the calcium phosphate phases formed during in vitro calcification were mainly present as non-apatite phases, possibly MCPM and DCPD. The porous morphology of the outer surface of the spherical calcium phosphate deposits could be due to the dissolution of precipitates in the presence of citric acid. The results obtained after subcutaneous implantation ofPHEMA and PHEMA containing citric acid in rats confirmed the resistance of PHEMA-citric acid to calcification. The calcium phosphate deposits which formed in vivo consisted mainly of Ca2+ and OH deficient hydroxyapatites. However, it is not yet known whether or not the differences between the calcium phosphate phases found in vivo and in vitro arise from the presence of proteins/peptides in the in vivo calcifying medium. 

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