Silicate-carbonate model

BLAG model (silicate-carbonate model) concerning long-term carbon cycle (Berner et al. 1983) is shown in Fig. 5.3. Basic reactions for BLAG model include reactions between CO2 and Ca- and Mg-minerals (calcite, dolomite, Ca-silicate, Mg-sUicate). 

Giving the changes in seafloor spreading rate and continental area with time, amount of atmospheric CO2 during the last one hundred million years compared with that of present-day atmospheric CO2 was calculated by Berner et al. (1983) (Fig. 5.4) based on silicate-carbonate geochemical cycle model (BLAG model). 

Tetravalent silicon is the only structural feature in all silicon sources in nature, e.g. the silicates and silica even elemental silicon exhibits tetravalency. Tetravalent silicon is considered to be an ana-logon to its group 14 homologue carbon and in fact there are a lot of similarities in the chemistry of both elements. Furthermore, silicon is tetravalent in all industrially used compounds, e.g. silanes, polymers, ceramics, and fumed silica. Also the reactions of subvalent and / or low coordinated silicon compounds normally lead back to tetravalent silicon species. It is therefore not surprising that more than 90% of the relevant literature deals with tetravalent silicon. The following examples illustrate why "ordinary" tetravalent silicon is still an attractive field for research activities Simple and small tetravalent silicon compounds - sometimes very difficult to synthesize - are used by theoreticians and preparative chemists as model compounds for a deeper insight into structural features and the study of the reactivity influenced by different substituents on the silicon center. As an example for industrial applications, the chemical vapor decomposition (CVD) of appropriate silicon precursors to produce thin ceramic coatings on various substrates may be mentioned. 

Fig. 3.12 Model of an agglomerate consisting of many small interstellar dust particles. Each of the rod-shaped particles consists of a silicate nucleus surrounded by yellowish organic material. A further coating consists of ice formed from condensed gases, such as water, ammonia, methanol, carbon dioxide and carbon monoxide. Photograph Gisela Kruger, University of Bremen...

Predictably, alkyltrisilanols react with dialkylzincs to yield larger aggregates, such as 133, which are much more inorganic in nature than those formed by mono- and disilanols (Scheme 84). Often these zinc siloxanes are without direct zinc-carbon bonds and resemble the silicates for which they serve as model compounds.192 The specific structures of these products depend heavily on the substituents of the silanetriols and diorganozincs, as well as the reaction stoichiometries.193... 

CASH CBM CBO CBPC CC CCB CCM CCP CDB CEC CFBC CFC CFR CMM COP CSH CT Calcium aluminosilicate hydrate Coal bed methane Carbon burn-out Chemically-bonded phosphate ceramics Carbonate carbon Coal combustion byproducts Constant capacitance model Coal combustion product Citrate-dithionate-bicarbonate Cation exchange capacity Circulating fluidized bed combustion Chlorofluorocarbon Cumulative fraction Coal mine methane Coefficient of performance Calcium silicate hydrate Collision theory... 

By comparing the actual composition of sea water (sediments + sea -f- air) with a model in which the pertinent components (minerals, volatiles) with which water has come into contact are allowed to reach true equilibrium, Sillen in 1959 epitomized the application of equilibrium models for portraying the prominent features of the chemical composition of this system. His analysis, for example, has indicated that contrary to the traditional view, the pH of the ocean is not buffered primarily by the carbonate system his results suggest that heterogeneous-equilibria of silicate minerals comprise the principal pH buffer systems in oceanic waters. This approach and its expansion have provided a more quantitative basis for Forchbammer s suggestion of 100 years ago that the quantity of the different elements in sea water is not proportional to the quantity of elements which river water pours into the sea but is inversely proportional to the facility with which the elements in sea water are made insoluble by general chemical actions in the sea. 

The spring waters of the Sierra Nevada result from the attack of high C02 soil waters on typical igneous rocks and hence can be regarded as nearly ideal samples of a major water type. Their compositions are consistent with a model in which the primary rock-forming silicates are altered in a closed system to soil minerals plus a solution in steady-state equilibrium with these minerals. Isolation of Sierra waters from the solid alteration products followed by isothermal evaporation in equilibrium with the eartKs atmosphere should produce a highly alkaline Na-HCO.rCOA water a soda lake with calcium carbonate, magnesium hydroxy-silicate, and amorphous silica as precipitates. 

We may now examine specific information from chemical analyses of the Great Lakes (7, 8, 13) to determine to what degree the variations of the proposed model fit the actual data. Rather than consider all of the variables at once, it is simpler to consider smaller portions to get a better idea of what actually is happening. We shall look at calcium carbonate equilibria, dolomite equilibria, phosphate equilibria, and silicate equilibria. 

Using stoichiometric model systems, it can be shown that some naturally occurring redox processes have a pronounced pH-controlling action, even in the presence of substances that act as buffers. High pH values can be reached particularly in systems where higher metal oxides act as oxidizers whereas an acid condition often develops when free oxygen is the oxidizer. However, in most natural systems carbonates and silicates have a more pronounced pH controlling effect than redox processes. 

Reactions between organic matter and iron (III) silicates have not yet been considered in this discussion. In the models above, all iron was assumed to be present originally as FeOOH. However, in actual sediments some probably is present as nontronite, which possibly could react with organic matter, forming carbon dioxide and a hypothetical iron (II) sheet silicate ... 

Figure 10.42. A quantitative box model of the carbonate-silicate geochemical cycle. Reservoir masses are in units of 1018 moles, and fluxes in units of 1018 moles per million years. Comparison with Figure 10.32 gives some idea how flux values and portrayal of the cycle have changed during the last decade and a half. (After Lasaga et aJ., 1985.)...

Figure 10.43. Results of model calculations of the carbonate-silicate geochemical cycle illustrated in Figure 10.42. The corresponding changes in atmospheric CO2 and temperature during the last 100 million years are evident. Notice how organic carbon burial may play a strong role as a negative feedback mechanism for a perturbation in atmospheric CO2 driven by tectonics. (After Lasaga et al., 1985.)...

From a fit of Equation (10) to spatially resolved relaxation curves, images of the parameters A, B, T2, q M2 have been obtained [3- - 32]. Here A/(A + B) can be interpreted as the concentration of cross-links and B/(A + B) as the concentration of dangling chains. In addition to A/(A + B) also q M2 is related to the cross-link density in this model. In practice also T2 has been found to depend on cross-link density and subsequently strain, an effect which has been exploited in calibration of the image in Figure 7.6. Interestingly, carbon-black as an active filler has little effect on the relaxation times, but silicate filler has. Consequently the chemical cross-link density of carbon-black filled elastomers can be determined by NMR. The apparent insensitivity of NMR to the interaction of the network chains with carbon black filler particles is explained with paramagnetic impurities of carbon black, which lead to rapid relaxation of the NMR signal in the vicinity of the filler particles. 

This motivated a number of attempts, starting around 1970 with the models published by Hoyle Wickramasinghe (1969), Wickramasinghe (1970), and Wickramasinghe Nandy (1970) to reproduce the interstellar extinction curve with mixtures of silicate and carbon grains, and, occasionally, additional components. These models provided already successful fits to the observed extinction curve. This established silicate and carbon dust as the primary dust components of interstellar dust. In most of these studies it was assumed that interstellar dust is stardust, i.e. dust born in stellar ejecta. 

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