Kaolinite Modeling

FIGURE 14.8 Predicted Cu adsorption as a function of pH on mixtures of kaolinite and HFO. Lines indicate fits using the 1-site HFO model and 1-site kaolinite model (Sveijensky and Sahai 1996) with formation of a monodentate Cu complex on a variable-charge site in the presence of 10"5 M Cu, 0.01 M NaNOj. (Reprinted from Lund, T. et al, Geochem. Trans., 9, 1, 9, 2008.)... 

Typical adsorption isotherms are shown in Figs. 16 and 17. Despite the large experimental scatter, a steep increase in adsorption can be seen at low concentrations, followed by a plateau at concentrations exceeding the CMC. Similar behavior has been observed before with model surfactants [49-54] and has also been predicted by modem theories of adsorption [54]. According to Fig. 16, adsorption increases modestly with salinity provided that the calcium ion concentration remains low. The calcium influence, shown in Fig. 17, cannot be explained by ionic strength effects alone but may be due to calcium-kaolinite interactions. 

In their model they used a kaolinite-like clay for the degraded silicate and allowed Na, Mg, and K to react to form sodic montmorillonite, chlorite, and illite respectively. The balance is essentially complete with only small residuals for H4Si04 and HCOT The newly formed clays would constitute about 7% of the total mass of sediments. 

The micellization and adsorption properties of industrial sulfonate/ ethoxylated nonionic mixtures have been assessed in solution in contact with kaolinite. The related competitive equilibria were computed with a simple model based on the regular solution theory (RST). Starting from this analysis, the advantage of adding a hydrophilic additive or desorbing agent to reduce the overall adsorption is emphasized. 

Calculation examples of mixed surfactant adsorption The solid chosen as the model adsorbent was made up of a natural sand (specific area =380 cm2/g) mixed with 5% clay (Charentes kaolinite with specific area = 26.8 m2/g). This material was taken as a model of clayey sandstone reservoirs. 

Viscosity A 16 ml sample of the suspension removed after remixing was used for torque measurements using a Brookfield viscometer (Model LVTD) with a UL adapter. Initial torque readings were used for estimating viscosity in order to avoid problems arising from any settling of the kaolinite in the viscometer during the measurements. 

To construct an alternative model of Amazon River water, we assume that equilibrium with kaolinite (a clay mineral, Al2Si205 (OH)4) and hematite (ferric oxide, Fe203) controls the aluminum and iron concentrations ... 

By this reaction, we can expect the modeled fluid to be rather acidic, since it is rich in potassium. We could have chosen to fix pH by equilibrium with the siderite, which also occurs in the veins. It is not clear, however, that the siderite was deposited during the same paragenetic stages as the fluorite. It is difficult on chemical grounds, furthermore, to reconcile coexistence of the calcium-rich ore fluid and siderite with the absence of calcite (CaCOs ) in the district. In any event, assuming equilibrium with kaolinite leads to a fluid rich in fluorine and, hence, to an attractive mechanism for forming fluorite ore. 

In a final application of kinetic reaction modeling, we consider how sodium feldspar (albite, NaAlSisOs) might dissolve into a subsurface fluid at 70 °C. We consider a Na-Ca-Cl fluid initially in equilibrium with kaolinite [Al2Si20s (OF )/ ], quartz, muscovite [KAl3Si30io(OH)2, a proxy for illite], and calcite (CaC03), and in contact with a small amount of albite. Feldspar cannot be in equilibrium with quartz and kaolinite, since the minerals will react to form a mica or a mica-like... 

In summary, the model proposed on the basis of acid-base characteristics of kaolinite platelets explains the pH-dependent charge primarily to the protonation of the hydroxyl groups at the basal gibbsite and the edge surface. We will later illustrate how this charge characteristics (surface protonation) influences the reactivity (dissolution characteristics) of kaolinite. 

Study of hydrated kaolinites shows that water molecules adsorbed on a phyllosilicate surface occupy two different structural sites. One type of water, "hole" water, is keyed into the ditrigonal holes of the silicate layer, while the other type of water, "associated" water, is situated between and is hydrogen bonded to the hole water molecules. In contrast, hole water is hydrogen bonded to the silicate layer and is less mobile than associated water. At low temperatures, all water molecules form an ordered structure reminiscent of ice as the temperature increases, the associated water disorders progressively, culminating in a rapid change in heat capacity near 270 K. To the extent that the kao-linite surfaces resemble other silicate surfaces, hydrated kaolinites are useful models for water adsorbed on silicate minerals. 

Subsequent work showed that a modification of the synthesis procedure produced a 10A hydrate which> if dried carefully, would maintain the interlayer water in the absence of excess water (27). This material is optimal for adsorbed water studies for a number of reasons the parent clay is a well-crystallized kaolinite with a negligible layer charge, there are few if any interlayer cations, there is no interference from pore water since the amount is minimal, and the interlayer water molecules lie between uniform layers of known structure. Thus, the hydrate provides a useful model for studying the effects of a silicate surface on interlayer water. 

Characterization of Interlayer Water. X-ray diffraction studies of the 10A hydrate show no hkl reflections indicating a lack of regularity in the stacking of the kaolin layers. In addition to the 10A hydrate, two other less hydrated kaolinites were synthesized. Both have one molecule of water for each formula unit in contrast to the 10A hydrate which has two. These less hydrated clays consequently have smaller d(001) spacings of 8.4 and 8.6 A. The synthesis conditions for these two hydrates are described in (22.). By studying the interlayer water in the 8.4 and 8.6A hydrates, it was possible to formulate a model of the water in the more complicated 10A hydrate. 

To the extent that the surfaces of the kaolinite layers resemble the surfaces of other silicate minerals, the structure of the adsorbed hole and associated water can serve as a useful model. To determine the applicability of our model to a specific mineral, it will be necessary to know in some detail the structure of the external surfaces of that mineral. 

Mingelgrin, U., Saltzman, S., and Yaron, B. A possible model for the surface-induced hydrolysis of organophosphorus pesticides on kaolinite clays. Soil Sol. Soc. Am. J., 41 519-523, 1977. 

Na -loess clay, where batch experiments were analyzed by X-ray diffraction and infrared and far-infrared measurements. The adsorption isotherm (Fig. 8.36) shows that loess clay is selective for cesium cations. The raw material contained a large amount of quartz, and the clay material was a mixture of kaolinite and an interstrati-fied iUite-smectite mineral as a result, equilibrium Cs" adsorption data are not consistent with a single site Langmuir model. Cesium adsorption on this particular soil clay occurs by cation exchange on sites with various cesium affinities. At low concentration, far-infrared spechoscopy shows the presence of very selective adsorption sites that correspond to internal collapsed layers. At high concentration, Cs MAS-NMR shows that cesium essentially is adsorbed to external sites that are not very selective. 

Schofield RK, Samson HR (1954) Flocculation of kaolinite due to the attraction of opposite charged crystal faces. Discuss Faraday Soc 18 135-145 Schofield RK, Samson HR (1953) The defiocculation of kaolinite suspensions and the accompanying change-over from positive to negative chloride adsorption. Clay Miner BuU 2 45-51 Schulten HR (2001) Models of humic structures association of humic acids and organic matter in soils and water. In Qapp CE et al. Humic substances and chemical contaminants. Soil Science Society of America, Madison, Wl, pp 73-88... 

If one considers an imaginary and highly oversimplified model for the sea water system in which the kaolinite-muscovite equilibrium is assumed to take place in a closed system to which strong acid or strong base is added incrementally, a buffer capacity can be computed. The electroneutrality would be... 

We now have seven candidates, and the phase rule allows seven phases to be stable together. We shall state as a working hypothesis that these seven phases—(1) aqueous solution, (2) quartz, (3) kaolinite, (4) hydromica (illite) (5) chlorite, (6) montmorillonite, and (7) phillip-site—are the stable assemblage in the intermediate model, and we shall test this hypothesis against various evidence. Some of these phases may prove unstable and be replaced by some other phase—e.g., phillipsite by another zeolite or a feldspar. Chlorite might also be replaced by some of the magnesium silicates described by Arrhenius (3). 

Most laboratory experiments demonstrating the utility of EO transport of organic compounds were conducted with kaolinite as the model clay-rich soil medium. Shapiro et al. (1989) used EO to transport phenol in kaolinite. Bruell et al. (1992) have shown that TCE can be transported down a slurry column by electroosmotic fluid flow, and more recently, Ho et al. (1995) demonstrated electroosmotic movement of p-nitrophenol in kaolinite. Kaolinite is a pure clay mineral, which has a very low cation exchange capacity and is generally a minor component of the silicate clay mineral fraction present in most natural soils. It is not, therefore, representative of most natural soil types, particularly those which are common in the midwestem United States. The clay content can impact the optimization and effectiveness of electroosmosis in field-scale applications, as has recently been discussed by Chen et al. (1999). 

The objective of this study was to demonstrate the physical transport of TCE by EO through cores of undisturbed soil. While research approaches have been performed on packed columns of pure clay (e.g. kaolinite), few have used native soils, and only in the form of slurries. At this time, no information is available for transport of TCE by EO through intact cores of natural soil. Therefore, the results of EO experiments using undisturbed soil are more applicable to actual site conditions than using single mineral soil. Parameters governing TCE transport in the soil are used in a one dimension advective model to describe TCE transport during the experiment. 

Detailed experimental procedures have been previously reported (Ko, 1998 Ko et al., 1998a,b) therefore, they are only briefly described here. Phenanthrene (Aldrich, 99.5+%), naphthalene (Aldrich, 99+%), SDS (Sigma, 99.5+%), and Tween 80 (Aldrich, no purity reported) were used as received selected physicochemical properties for these compounds are shown in Table 1. Kaolinite, a nonswelling 1 1 layer phyllosilicate clay and common constituent of many subsurface environments, was used as received from Sigma. Solution pH and ionic strength were adjusted as necessary with 0.5 M HC1 and/or 0.5 M NaOH and NaCl, respectively. Aqueous phenanthrene and naphthalene concentrations were quantified by fluorescence (PTI, Inc.) at the excitation/emission wavelengths of 250/364 and 278/322 nm, respectively. A total organic carbon (TOC) analyzer (Shimadzu Model 5050) was used to determine aqueous SDS concentrations and Tween 80 concentrations were determined by UV absorbance at 234 nm. 

Figure 4 shows phenanthrene and naphthalene sorption isotherms to kaolinite covered with varying levels of sorbed surfactant these levels of surfactant coverage correspond to the different regions existing in the surfactant sorption isotherms discussed earlier (Fig. 1). The linearity of each isotherm was evaluated using Freundlich and linear sorption models. It is apparent from Fig. 4 and Table 4 that HOC partitioning to kaolinite with and without adsorbed surfactants results in linear or near-linear isotherms. As the amount of surfactant adsorbed on the kaolinite surface increased, the sorption of phenanthrene and naphthalene to the solid phase also increased. However, upon normalizing by the amount of sorbed surfactant present, the sorbed surfactant partition coefficient (Kss) decreased with increasing sorbed surfactant amounts (Table 4).

Jardine et al. (1985b) employed a two-site nonequilibrium transport model to study Al sorption kinetics on kaolinite. They used the transport model of Selim et al. (1976b) and Cameron and Klute (1977). Based on the above model, Jardine et al. (1985a) concluded that there were at least two mechanisms for Al adsorption on Ca-kaolinite. It appeared that there were equilibrium (type-1) reactions on kaolinite that involved instantaneous Ca-Al exchange and rate-limited reaction sites (type-2) involving Al polymerization on kaolinite. The experimental breakthrough curves (BTC) conformed well to the two-site model. 

The sorption kinetics of 2,4-D on illite, kaolinite, and montmorillonite was modeled by Haque et al. (1968) using... 

Jardine, P. M., Parker, J. C., and Zelazny, L. W. (1985b). Kinetics and mechanisms of aluminum adsorption on kaolinite using a two-site nonequilibrium transport model. Soil Sci. Soc. Am. J. 49, 867-873. 

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