Clay minerals from the MacAdams Sandstone, Kettleman North Dome, California, have been studied by electron microscopy. The clay minerals fill pore space associated with fractured and brecciated clasts of K-feldspar. Curved packets of muscovite and kaolinite are caused by deformation of detrital muscovite that resulted in opening of fissures subsequently filled with dominant kaolinite and minor intergrown mixed-layer illite/smectite (I/S). Regions of authigenic R1 I/S (rectorite) with characteristic ~20 Å periodicity are intergrown with kaolinite in microfissures within K-feldspar or detrital muscovite. Clusters of small grains of muscovite with nearly ideal composition occur as stacks and intergrown with kaolinite and are tentatively inferred to be authigenic. Contrary to previous reports, no illite was found in these samples.

Electron microprobe analyses previously obtained on Kettleman Dome “illite” and subsequently used as a prime example of analyses of illite rich in excess interlayer water (H2O) and hydronium ion (H3O+) are shown to have been obtained on mixtures, and are not representative of the actual clay mineral compositions. Previous conclusions regarding significant H3O+ and H2O contents of illite are invalid because of inaccuracies inherent in bulk and EMPA analyses of illite, and do not affect arguments regarding the metastability of illite. Hydronium substitution should be favored via the reaction H2O + H+ = H3O+ only in highly acidic fluids. Ordinary illite forming in sedimentary environments with carbonates and iron oxides is unlikely to have significant H3O+ substituted for K+.

In spite of decades of research on the subject, the crystal structure of illite is still poorly understood. The purpose of this study was to address this problem by investigating the nature of the interlayer content in illite IMt-2 from Silver Hill, Montana, using analytical transmission electron microscopy (ATEM), thermogravimetry (TG), and X-ray powder diffraction (XRPD) analyses. The ATEM data, together with literature and TG results, yielded the formula K0.70a0.01(H2O)0.42 (Al1.53Fe2+0.06Fe3+0.19Mg0.28)Σ−2.06(Si3.44Al0.56)O10(OH)2 or, assuming the presence of H3O+, K0.69Na0.01(H3O)+0.28(Al1.47Fe2+0.06Fe3+0.19Mg0.28)Σ−1.99(Si3.40Al0.60)O10(OH)2. The first formula indicates surplus interlayer and octahedral species, whereas the second shows no excess. The XRPD data were refined by Rietveld techniques, down to an Rp factor of 10.48–13.8%. The mineral composition consists largely of illite-2M1, illite-1M, and minor quartz. Although the refinement accuracy is limited by the intrinsic poor quality diffraction of the illites, the partially refined model is consistent with the chemical composition; in particular, attempts to introduce octahedral cations in excess of 2 were fruitless. All the results support the simple structural model, by which the illite structure strictly corresponds to a dioctahedral mica with H3O+ replacing K. As a consequence, the crystalchemical formula of illites should be calculated on the basis of six tetrahedral plus octahedral cations.

Some aspects of the crystal structure of illite are not understood properly yet, in spite of its abundance and significance as a component of soils, sediments, and low-grade metamorphic rocks. The present study aimed to explore the role of hydronium cations in the interlayer space of illite in a theoreticalexperimental approach in order to clarify previous controversial reports. The infrared spectroscopy of this mineral has been studied experimentally and by means of atomistic calculations at the quantum mechanical level. The tetrahedral charge is critical for the stability of the hydronium cations, the presence of which has probably been underestimated in previous studies. In the present study, computational studies have shown that the hydronium cations in aqueous solutions are likely to be intercalated in the interlayer space of illite, exchanging for K cations. During the drying process these cations are stabilized by hydrogen bonds in the interlayer space of illite.

The presence, percentage, origins, and rate of formation of clay minerals have been important components in studies involving the geochemical and structural composition of waste-rock piles. The objective of the present study was to investigate the use of tritium as an indicator of the origin of clay minerals within such piles. Tritium values in pore water, interlayer water, and structural hydroxyl sites of clay minerals were examined to evaluate the origins of clay minerals within waste-rock piles located near Questa, New Mexico. Five clay minerals were identified: kaolinite, chlorite, illite, smectite, and mixedlayer illite-smectite, along with the hydrous sulfate minerals gypsum and jarosite. Analysis of waters derived from clay minerals was achieved by thermal reaction of dry-sieved bulk material obtained from the Questa site. In all Questa samples, the low-temperature water derived from pore-water and interlayer sites, as well as the intermediate-temperature water derived from interlayer cation sites occupied by hydronium and structural hydroxyl ions, show tritium values at or near modern levels for precipitation. Pore water and interlayer water ranged from 5.31 to 12.19 tritium units (TU) and interlayer hydronium and structurally derived water ranged from 3.92 to 7.93 TU. Tritium levels for local precipitation ranged from ~4 to 8 TU. One tritium unit (TU) represents one molecule of 3H1HO in 1018 molecules of 1H1HO. The elevated levels of tritium in structural sites can be accounted for by thermal incorporation of significant amounts of hydronium ions in interlayer cation sites for illite and mixed-layer clays, both common at the Questa site. In low-pH environments, such as those found within Questa waste-rock piles (typically pH ~3), the hydronium ion is an abundant species in the rock-pile pore-water system.

The arguments of Vidal et al. (2010) against the incorporation of H3O+ rather than of H2O in the interlayer position of illite are disputable. Stoichiometric arguments do indeed suggest that the excess water in the Silver Hill illite is in the formof H3O+. No reason exists to assume less water content in the IMt-2 sample than in those determined by Hower and Mowatt (1966) and confirmed by the thermogravimetric analyses of Nieto et al. (2010). The comparison between element contents calculated from end-members and those from the structural formula in figure 1 of Vidal et al. (2010) is not an experimental result, but rather a trivial mathematical artifact. The fact that thermodynamic models, based on the incorporation of interlayer H2O in illite, may provide reasonable estimates neither proves nor disproves the presence of H3O+; this is because thermodynamics is a non-atomistic, macroscopic approach.

The arguments of Nieto et al. (2010) in favor of the incorporation of H3O+ rather than H2O in interlayer positions of illite are disputable. Stoichiometric arguments suggest that the excess water in the Silver Hill illite is in the form of H2O. Moreover, recent thermodynamic models assuming the incorporation of interlayer H2O in illite provide reasonable estimates of temperature and water content using the AEM/TEM analyses of Nieto et al. (2010).

The crystal structure of H3O+-exchanged pharmacosiderite (pharmacosiderite is KFe4(AsO4)3(OH)4·nH2O, sensu stricto) has been determined by single-crystal X-ray diffraction and refined to R1 = 0.0418. H3O+-exchanged pharmacosiderite, (H3O+)Fe4(AsO4)3(OH)4·4.5H2O, is cubic, space group Pm, with a = 7.982(9) Å, V = 508.5(9) Å3 and Z = 1. The structure broadly conforms to that of the general pharmacosiderite structure type, with the hydronium ion generated by partial protonation of a site corresponding to a molecule of water of crystallization and its symmetry-related equivalents. In addition, the structure of a “pharmacosiderite” from Cornwall, United Kingdom, in which no alkali metals could be detected, has been re-evaluated and found to be consistent with that of the H3O+- exchanged structure. Its composition is (H3O+)Fe4(AsO4)3(OH)4·4H2O, with the partially occupied water found for the exchanged structure at (½, ½, ½) being absent in this case.

Hydroniumpharmacosiderite, ideally (H3O)Fe4(AsO4)3(OH)4·4H2O, is a new mineral from Cornwall, UK, probably from the St. Day group of mines. It occurs as a single yellowish green, slightly elongated cube, measuring 0.17 mm ×0.14 mm ×0.14 mm. The mineral is transparent with a vitreous lustre. It is brittle with a cleavage on {001}, has an irregular fracture, a white streak and a Mohs hardness of 2–3 (determined on H3O-exchanged pharmacosiderite). Hydroniumpharmacosiderite has a calculated density of 2.559 g cm–3 for the empirical formula. The empirical formula, based upon 20.5 oxygen atoms, is: [(H3O)0.50K0.48Na0.06]1.04(Fe3.79Al0.22)4.01[(As2.73P0.15)2.88O12](OH)4·4H2.14O. The five strongest lines in the X-ray powder diffraction pattern are [dobs(Å),Iobs,(hkl)]: 8.050,100,(001); 3.265,35,(112); 2.412,30,(113); 2.830,23,(202); 4.628,22,(111). Hydroniumpharmacosiderite is cubic, space group with a = 7.9587(2) Å, V = 504.11(2) Å3 and Z = 1. The crystal structure was solved by direct methods and refined to R1 = 0.0481 for 520 reflections with I > 2σ(I). The structure is consistent with determinations for H3O-exhchanged pharmacosiderite and the general pharmacosiderite structure type.