Refractory clay, derived from hornblende chlorite schist that was hydrothermally altered along nearly vertical fractures and faults, occurs near Guanajuato, Mexico, a few kilometers south and east of the famous monument, El Cristo Rey. Part of the chlorite is expanding, i.e. probably mixed-layer vermiculitic chlorite or biotite. The most refractory clay is comprised chiefly of kaolinite, with variable amounts of finely crystalline quartz. Huge, thick “gossans” of silica have been deposited as surface-covers over the fractures; such silica gossans are fairly common over Mexican hydrothermal clay deposits and may be used as probable field guides to argillation.

The trend of mineralogical and chemical changes (analyses tabulated in the paper) during argillation of the Guanajuato material is traced in overlapping sequence, as follows:

1. (a) bleaching of green ferro-ferric silicates accompanied by oxidation of part of the iron to “limonite”.

2. (b) leaching of alkali and alkaline earths accompanied by

3. (c) partial desilication of parent silicate minerals yielding kaolinite whose flakes are commonly oriented parallel with the chlorite of the schist, mobile silica, and finely divided quartz intermixed with the kaolinite

4. (d) refinement (“purification”) of the clay by further kaolinization and removal of silica minerals and some iron oxide.

The final clay may run higher in silica than does its parent rock.

This paper documents the first report of flint clay in Mexico, located at Estola, Guerrero, 199 km south of Mexico City, on Mexico Highway 95. It is the first report (known to the writers) of flint clay formed by hydrothermal alteration. It describes the in-situ alteration of a calcareous, silty shale to flint clay (well-ordered kaolinite).

The changes during alteration are mineralogical, chemical, and structural. Calcite, comprising about one-third of the shale, quartz and probably some feldspar comprising a scant third, and a mixture of greenish-yellow (limonitic) clay minerals are dissolved or altered ultimately to white kaolinite (monomineralic). Calcium carbonate, free and combined silica, and iron compounds are dissolved, while simultaneously the alumina is relatively enriched. The fissility, inequigraularity, and cementitous fabric of shale are changed to the massively homogeneous, finegrained, interlocking fabric that is typical of flint clay.

The sequence of changes, which overlap, are; (1) dissolution of carbonate minerals, (2) mobility of iron, replacement of quartz and feldspar by kaolinite; and (3) intensive “digestion” of rock substance to homogeneous, essentially monomineralic, kaolinite flint clay. Alunite, and secondary vein-calcite or gypsum may accompany the flint clay.

This occurrence lends support to the concent that flint clay is formed from presumably only sedimentary parent rock.

Dissimilar fabrics, observed by scan electron micrography (SEM) on freshly broken surfaces of kaolins from weathered, water-laid material vs hydrothermally altered material in Mexico are illustrated, contrasted, and tentatively related to their respective environments of genesis. Coarse, open-textured, well-preserved books and vermiforms of kaolinite characterize the kaolin from water-laid material at Jacal, Mexico. Hydrothermal kaolins tend to have more tightly compacted crystals of either kaolinite flakes (individuals or in packets) or elongates (halloysite morphology) or mixtures of both in the same deposit. Variations in porosity of parent rock whether sedimentary or igneous, and dissimilar permeation by meteoric water and by vapor and liquids of hydrothermal fluids are deemed to be significant in the processes producing distinctive fabrics. The question is raised as to the fundamental distinction between kaolinite and halloysite and their nomenclature.

A deposit of kaolin clay, the site of the General Zaragosa Mine, located about 50 km northwest of San Luis Potosi, S. L. P., Mexico, has produced more than 250,000 tons of refractory clay by room and pillar mining methods during the last 32 years. The clay was formed by hydrothermal argillation of part of a fault block of rhyolite flow-breccia and probably welded tuff, presumably lower Tertiary in age. A silica-rich gossan now exposed at the surface caps the clay deposit.

Samples collected sequentially from the fresh rock to the most highly altered kaolin and studied by optical, X-ray, DTA, and chemical methods, show progressively:

1. Bleaching of the breccia matrix accompanied by mobilization of much of the iron, which was concentrated locally as spots of reddish oxide in the least altered areas.

2. Mobilization, and removal of considerable alkali and alkaline earth metals, in excess of that required to form montmorillonite; mobilization of silica, which was redeposited as fine anhedral quartz crystals disseminated within the montmorillonite and associated kaolinite-halloysite, or developed tripolitic, argillized rock peripheral to the clay ore body.

3. Further desilication of the silica and clay yielding relatively pure, but poorly ordered, kaolinite-halloysite as the most intense end product of argillation. Much silica removed during intense argillation was reprecipitated as tripolitic clay, as minor cristobalite in microscopic globules and massive aggregates characteristic of colloform opal, and in vastly larger amounts as opal and chalcedony replacing the rock overlying the clay (forming a silica gossan).

4. Minor amounts of alunite are present at two places in the deposit, which are interpreted tentatively as being the most probable loci of rising solutions.

Previously reported deposits of kaolin of hydrothermal origin in Mexico have been described from igneous parent rocks dominantly extrusive in occurrence. Recently observed evidence from other localities confirms an intrusive mode of occurrence, however, for hydrothermally kaolinized agglomerate and tuff within limestone host rock. Three such occurrences have been recognized near Jasso-Calera, north of Mexico City, and near Coacoyula, Guerrero, and Sombrerete, Zacatecas.

The contacts of these clay deposits with limestone show regularly a concentration of iron-rich minerals such as red to brown oxides and/or nontronite, but less commonly an irregular development of grossularite, and bands or pockets of endellite. Silica gossans indicate that hypogene altering solutions were active into the current geomorphic cycle. Kaolinite at the center of the clay body and endellite at the border zones are interpreted as originating, respectively, from in situ alteration of solid rock and deposition from ambient solutions.

Sequential alteration of volcanic rock of rhyolitic composition to a precursor of endellite, and thence to tubular endellite, may be observed at a hot spring about 27 km north of Ciudad Hidalgo, Michoacan, Mexico. Ojo Caliente de Laguna Larga (or Verde) yields H2S-SO2-containing water, temperature about 45°C pH 3·5–3·7, from multiple orifices in vesicular and slabby rock with which the water reacts.

First-stage alteration of the rock consisted of permeation and dissolution, accompanied by deposition of clay substance in vesicle walls. The clay substance, although “amorphous” to X-rays, yields a weak DTA of endellite, and kaolinite. It is interpreted as a precursor of endellite. Further reaction included continued filling of vesicles and spreading argillation which coalesced between vesicles and other rock pores. Ultimately, the rock was completely “digested” to well-defined endellites.

Strong desilication and depotassication of the rock is indicated by the dissolved substances in the spring water: Si 59·1 (equivalent to 127 SiO2) ug/ml: Al, 1·63; Fe, 0·65: Mg, 0·21: Ca, 178: Na, 0·73: K, 13·7. Despite high K+, predominantly high H+ and Al3+ induce formation of endellite. The clay-water system accords well with stability diagrams.

Allophane-endellite in Indiana and endellite at Stanford, Kentucky, are formed from cold, strongly acid, meteoric-water solutions high in Si and Al relative to kaolinite dissolved in water. Factors of genesis common to both hot- and cold-water endellite are cited, suggesting that they are premissively critical, but not necessarily restrictive, to the origin of endellite.

This paper describes in detail phosphate minerals occurring in refractory clays of Missouri and their effect on the refractory degree of the clays. The minerals identified include carbonate-fluorapatite (francolite), crandallite, goyazite, wavellite, variscite and strengite. It is emphasized that these phosphates occur only in local isolated concentrations, and not generally in Missouri refractory clays.

The Missouri fireclay region comprises 2 districts, northern and southern, separated by the Missouri River. In this region, clay constitutes a major part of the Lower Pennsylvanian Cheltenham Formation. The original Cheltenham mud was an argillic residue derived from leaching and dissolution of pre-Pennsylvanian carbonates. The mud accumulated on a karstic erosion surface truncating the pre-Cheltenham rocks. Fireclays of the northern district consist mainly of poorly ordered kaolinite, with variable but minor amounts of illite, chlorite and fine-grained detrital quartz. Clays of the southern district were subjected to extreme leaching that produced well-ordered kaolinite flint clays. Local desilication formed pockets of diaspore, or more commonly, kaolinite, with oolite-like nubs or burls of diaspore (“burley” clay).

The phosphate-bearing materials have been studied by X-ray diffraction (XRD), scanning electron microscopy-energy dispersive spectral analysis (SEM-EDS) and chemical analysis. Calcian goyazite was identified in a sample of diaspore, and francolite in a sample of flint clay. A veinlet of wavellite occurs in flint clay at one locality, and a veinlet of variscite-strengite at another locality.

The Missouri flint-clay-hosted francolite could not have formed in the same manner as marine francolite. The evidence suggests that the Cheltenham francolite precipitated from ion complexes in pore water, nearly simultaneously with crystallization of kaolinite flint clay from an alumina-silica gel. Calcian goyazite is an early diagenetic addition to its diaspore host. The wavellite and variscite-strengite veinlets are secondary, precipitated from ion complexes in ground water percolating along cracks in the flint clay. The flint clay host of the variscite-strengite veinlet contains strontian crandallite. All of the phosphates contain significant amounts of strontium. The source of P, Ca and Sr was the marine carbonates. Dissolution of these carbonates produced the argillic residue that became the primordial Cheltenham paludal mud, which ultimately altered to fireclay.

Preliminary firing tests show that the presence of phosphates lowers fusion temperature. However, it is not clear whether poor refractoriness is due to the presence of phosphates, per se, or to Ca, Sr and other alkaline elements present in the phosphates.

Hill (Twin Research and Human Genetics, Vol. 21, 2018, 84–88) presented a critique of our recently published paper in Cell Reports entitled ‘Large-Scale Cognitive GWAS Meta-Analysis Reveals Tissue-Specific Neural Expression and Potential Nootropic Drug Targets’ (Lam et al., Cell Reports, Vol. 21, 2017, 2597–2613). Specifically, Hill offered several interrelated comments suggesting potential problems with our use of a new analytic method called Multi-Trait Analysis of GWAS (MTAG) (Turley et al., Nature Genetics, Vol. 50, 2018, 229–237). In this brief article, we respond to each of these concerns. Using empirical data, we conclude that our MTAG results do not suffer from ‘inflation in the FDR [false discovery rate]’, as suggested by Hill (Twin Research and Human Genetics, Vol. 21, 2018, 84–88), and are not ‘more relevant to the genetic contributions to education than they are to the genetic contributions to intelligence’.

In the northern Owens Valley, the Owens River has cut and preserved three terraces uplifted above its modern floodplain. We have analyzed soils and used other relative-dating techniques in order to differentiate the terrace surfaces, to correlate from the terraces to moraines of the eastern Sierra Nevada, and to test the effects of relief and climatic differences on relative-dating results. Most of the relative-dating techniques attempted were successful in differentiating the terraces of the Owens River sequence. In addition, weathering rinds, soil descriptions, and an early Holocene 14 C date for the youngest terrace support correlation of the three terrace levels with the three post-Sherwin-age glacial stages (Tioga, Tahoe, and pre-Tahoe) found in nearby canyons of the Sierra Nevada. Other relative-dating techniques that are commonly employed, however, suggest distinct differences between the terrace and moraine sequences. These differences probably reflect the difference in relief, such that slow erosion of the moraine crests may have retarded soil development relative to the flat terrace surfaces and altered surface-weathering processes. Use of relative-dating analyses to correlate between dissimilar geomorphic systems requires caution but use of a broad range of techniques and absolute-age calibration may make correlation possible.

A microchannel plate was used as an ion sensitive detector in a commercial helium ion microscope (HIM) for dark-field transmission imaging of nanomaterials, i.e. scanning transmission ion microscopy (STIM). In contrast to previous transmission HIM approaches that used secondary electron conversion holders, our new approach detects forward-scattered helium ions on a dedicated annular shaped ion sensitive detector. Minimum collection angles between 125 mrad and 325 mrad were obtained by varying the distance of the sample from the microchannel plate detector during imaging. Monte Carlo simulations were used to predict detector angular ranges at which dark-field images with atomic number contrast could be obtained. We demonstrate atomic number contrast imaging via scanning transmission ion imaging of silica-coated gold nanoparticles and magnetite nanoparticles. Although the resolution of STIM is known to be degraded by beam broadening in the substrate, we imaged magnetite nanoparticles with high contrast on a relatively thick silicon nitride substrate. We expect this new approach to annular dark-field STIM will open avenues for more quantitative ion imaging techniques and advance fundamental understanding of underlying ion scattering mechanisms leading to image formation.