The apatite-group minerals of the general formula, M10(ZO4)6X2 (M = Ca, Sr, Pb, Na…, Z = P, As, Si, V…, and X = F, OH, Cl…), are remarkably tolerant to structural distortion and chemical substitution, and consequently are extremely diverse in composition (e.g., Kreidler and Hummel 1970; McConnell 1973; Roy et al. 1978; Elliott 1994). Of particular interest is that a number of important geological, environmental/paleoenvironmental, and technological applications of the apatite-group minerals are directly linked to their chemical compositions. It is therefore fundamentally important to understand the substitution mechanisms and other intrinsic and external factors that control the compositional variation in apatites.

The minerals of the apatite group are listed in Table 1⇓, and representative compositions of selected apatite-group minerals are given in Table 2⇓. Also, more than 100 compounds with the apatite structure have been synthesized (Table 3⇓). Phosphate apatites, particularly fluorapatite and hydroxylapatite, are by far the most common in nature and are often synonymous with “apatite(s)”. For example, fluorapatite is a ubiquitous accessory phase in igneous, metamorphic, and sedimentary rocks and a major constituent in phosphorites and certain carbonatites and anorthosites (McConnell 1973; Dymek and Owens 2001). Of particular importance in biological systems, hydroxylapatite and fluorapatite (and their carbonate-bearing varieties) are important mineral components of bones, teeth and fossils (McConnell 1973; Wright et al. 1984; Grandjean-Lecuyer et al. 1993; Elliott 1994; Wilson et al. 1999; Suetsugu et al. 2000; Ivanova et al. 2001).

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 Table 1. 
Summary of the apatite-group minerals



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 Table 2. 
Representative compositions and unit-cell parameters of selected apatite-group minerals.



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 Table 3. 
Formulas of selected synthetic compounds with the apatite structure.



Following Fleischer and Mandarino (1995), Table 1⇑ also includes melanocerite-(Ce), tritomite-(Ce), and tritomite-(Y), the compositions …

Compositions of the Apatite-Group Minerals: Substitution Mechanisms and Controlling Factors

The Layer Silicates

Hydration of the <1 μm size fraction of SWy-1 source clay (low-charge montmorillonite) was studied by modeling of X-ray diffraction (XRD) patterns recorded under controlled relative humidity (RH) conditions on Li-, Na-, K-, Mg-, Ca-, and Sr-saturated specimens. The quantitative description of smectite hydration, based on the relative proportions of different layer types derived from the fitting of experimental XRD patterns, was consistent with previous reports of smectite hydration. However, the coexistence of smectite layer types exhibiting contrasting hydration states was systematically observed, and heterogeneity rather than homogeneity seems to be the rule for smectite hydration. This heterogeneity can be characterized qualitatively using the standard deviation of the departure from rationality of the 00 l reflection series (ξ), which is systematically larger than 0.4 A when the prevailing layer type accounts for ~70% or less of the total layers (~25% of XRD patterns examined). In addition, hydration heterogeneities are not distributed randomly within smectite crystallites, and models describing these complex structures involve two distinct contributions, each containing different layer types that are interstratifed randomly. As a result, the different layer types are partially segregated in the sample. However, these two contributions do not imply the actual presence of two populations of particles in the sample.

XRD profile modeling also has allowed the refinement of structural parameters, such as the location of interlayer species and the layer thickness corresponding to the different layer types, for all interlayer cations and RH values. From the observed dependence of the latter parameter on the cation ionic potential ( v / r; v = cation valency and r = ionic radius) and on RH, the following equations were derived:

\batchmode \documentclass[fleqn,10pt,legalpaper]{article} \usepackage{amssymb} \usepackage{amsfonts} \usepackage{amsmath} \pagestyle{empty} \begin{document} \[Layer\ thickness\ (1W)\ =\ 12.556\ +\ 0.3525\ {\times}\ ({\nu}/\mathit{r}\ {-}\ 0.241)\ {\times}\ ({\nu}\ {\times}\ RH\ {-}\ 0.979)\] \end{document} 

\batchmode \documentclass[fleqn,10pt,legalpaper]{article} \usepackage{amssymb} \usepackage{amsfonts} \usepackage{amsmath} \pagestyle{empty} \begin{document} \[Layer\ thickness\ (2W)\ =\ 15.592\ +\ 0.6472\ {\times}\ ({\nu}/\mathit{r}\ {-}\ 0.839)\ {\times}\ ({\nu}\ {\times}\ RH\ {-}\ 1.412)\] \end{document} 

which allow the quantification of the increase of layer thickness with increasing RH for both 1W (one water) and 2W (two water) layers. In addition, for 2W layers, interlayer H2O molecules are probably distributed as a unique plane on each side of the central interlayer cation. This plane of H2O molecules is located at ~1.20 A from the central interlayer cation along the c* axis.

/pdf/investigation-of-smectite-hydration-properties-by-modeling-4d3mn4ajay.pdf

Investigation of smectite hydration properties by modeling experimental X-ray diffraction patterns: Part I. Montmorillonite hydration properties

https://personalpages.manchester.ac.uk/staff/j.gough/lectures/te/7_8_bone/BONE_ENG/ceramic/ceram1.pdf

Biphasic calcium phosphate nanocomposite porous scaffolds for load-bearing bone tissue engineering.

Adsorption of cobalt from aqueous solutions onto sepiolite

Terra rossa samples were taken from the B horizons of soil profiles and from cracks within limestone in Italy. The average annual temperature (AAT) of the sites ranged from 8.4 to 20.3°C and the average annual precipitation (AAP) from 511 to 3113 mm, with either a 5–6 month water deficit or a large water surplus. Goethite and hematite were identified in all the samples. Under a moist (> 1700 mm AAP) and cool (13°C AAT) climate, a xeric, hematitic pedoenvironment was preserved by the well-litified carbonate rock. Hematite occurred in trace amounts, even with an AAT of 8.4°C and an AAP of 3300 mm, confirming the specific role of the hard limestone on the pedoclimate of terra rossa. The lowest mean crystallite dimension of goethite and hematite was found in the samples from the wettest sites, and in these samples hematite was nearly free of Al substitution. Rubification in terra rossa appeared to be due to the specific pedoenvironment. The hematite cannot be considered a relict phase formed under another climate. Illite and kaolinite were the main clay minerals in samples from xeric sites whereas more weathered clays, such as Al-interlayered vermiculite, occurred in cool, moist sites. We postulate that the processes of rubification and vermiculitization could have taken place at the same time. The effects of layer charge magnitude and location on expansion were represented by an energy change (expansion energy: ΔEr) during the hydration and solvation processes. Plots of basal spacings versus ΔEr show a reasonable relationship; the spacings generally decrease stepwise as the value of ΔEr increases. The basal spacings of K-samples with glycerol solvation, Na-saturated and K-saturated samples at 100% RH are apt to contract stepwise with increasing value of ΔEr. For these samples, the figures showing the relationship between each expanded phase and the charge characteristics are obtained from the isoquants of ΔEr, given the boundary of the expanded phases. A behavior test using these figures may be combined with the Greene-Kelly test to estimate the amount and the location of the layer charge of common smectites.

Effects of Layer Charge, Charge Location, and Energy Change on Expansion Properties of Dioctahedral Smectites

Recent studies on the decomposition of the dolomite group by thermal analysis

Infrared study of sepiolite and paly-gorskite on heating

In order to synthesize well-crystallized magadiite and kenyaite as a single phase in a short reaction time, amorphous silica was hydrothermally reacted with alkaline solutions in the temperature range from 150°C to 200°C. From a suspension containing SiO2 and NaOH with molar ratios of H2O/SiO2=18.5 and NaOH/SiO2=0.23, magadiite was formed after a reaction time of 48 h at 150°C or after 18h at 170°C. The formation of Na-kenyaite, however, required 6h at 200°C. Then, KOH and K2CO3 were used to lower the formation temperature of kenyaite. K-kenyaite was synthesized after 16h at 185°C from a suspension with molar ratios of H2O/SiO2=18.5 and KOH/SiO2=0.23. Furthermore, (Na, K)-kenyaite was formed after 48h at 150°C or after 24h at 170°C from suspensions with molar ratios of H2O/SiO2=18.5, NaOH/SiO2=0.23 and NaOH/K2CO3=0.95-23. Magadiite and kenyaite were formed through a difinite induction period after dissolution of amorphous silica.

Ryohei Otsuka

Papers

Effects of Layer Charge, Charge Location, and Energy Change on Expansion Properties of Dioctahedral Smectites

Recent studies on the decomposition of the dolomite group by thermal analysis

Infrared study of sepiolite and paly-gorskite on heating

Hydrothermal Synthesis of Magadiite and Kenyaite

Thermal expansion of hydroxyapatite-β-tricalcium phosphate ceramics