Dehydroxylated sericites were stirred in the various salt solutions, or washed several times with various salt solutions using a centrifuge. By these treatments a seriate of the 2M type was easily transformed into an interstratified mineral of the rectorite type when a sericite was treated with sodium salts, and random mixed-layer mineral was formed from 1M sericite. The formation of a rectorite-type mixed-layer mineral from 2M sericite can be explained by the (OH) bond direction after the extraction of the potassium ions.

Blood pressure (BP) is influenced by both genetics and diet. Dietary management of hypertension includes increasing potassium-rich foods while reducing sodium intakes. Dietary sodium and potassium intakes can be measured objectively using urinary sodium and urinary potassium, with lower urinary sodium to potassium ratios associated with lower BP(1). Understanding the interplay between diet and genetics may be useful in treating hypertension and determining which individuals may receive an outsized benefit from lowering their sodium potassium ratio. This study aims to investigate whether identifying genetic risk for hypertension could be utilised to identify individuals who may benefit most from lowering sodium intake and increasing potassium intake. UK Biobank cohort participants (n = 296,475) with data on genotype, BP and spot urinary sodium and potassium data were used. Diet quality was assessed using Oxford WebQ. Biologically directed genetic scores for BP were constructed for pathways related to sodium/potassium biology (pharmagenic enrichment scores [PES]), as well as traditional polygenic risk scores (PRS). A gene-by-environment effect between urinary electrolytes, diet quality and PRS on BP were tested. Genetic risk, diet quality and urinary electrolytes independently correlated with BP. Urinary sodium had larger BP increasing effects amongst individuals who had high genetic risk in sodium/potassium pathways than those with comparatively lower genetic risk. Higher diet quality had a small effect on reducing BP in baseline PRS models, but this did not remain significant in the full model. Polygenic scores for BP personalised to individual sodium/potassium biology (PES) could be used to identify individuals who may receive an outsized benefit from a personalised sodium/potassium dietary intervention. These findings may inform future precision and personalised dietary advice for the management of hypertension.

Mordenite occurs in hydrothermally altered rhyolitic volcanic rocks at the margin of a Late Miocene lake basin on the island of Samos, Greece. The mordenite was identified by its X-ray powder diffraction pattern and appearance in scanning electron micrographs. Electron microprobe analyses show high Si, Ca, and K, low Na, and high balance errors. The b cell dimension is consistent with a high Si/(Al + Si) ratio, and the balance errors are apparently due to Na deficiency. The missing Na was estimated from the amount required to give (Si + Al) = 48 and yielded analyses comparable with X-ray fluorescence analyses of samples predominantly of mordenite. Even after this correction, the mordenite had a low Na:K ratio compared with most analyses reported in the literature. The peculiar chemistry of the mordenite may have resulted from a high-temperature metasomatic origin as a result of basaltic volcanism at the basin margin and characterized by hydrothermal circulation of alkaline lake water rich in K.

The <0.1-μm size fraction of an Ordovician K-bentonite from northern Kentucky was characterized by X-ray powder diffraction (XRD). Using A.I.P.E. A. criteria for interstratification nomenclature and Reynolds’ computer algorithm the dominant clay mineral proved to be an R2 ordered illite/smectite. The best fit of observed and calculated XRD tracings was obtained using 12 > N > 5, where N is the number of layers within a diffracting domain.

Sections of the K-bentonite were prepared by ion-beam milling and examined in an analytical transmission electron microscope (ATEM). One-dimensional lattice images observed parallel to the a-b plane showed subparallel packets, about 50–100 Å thick, each of which consisted of about 10-Â thick unit layers. Somewhat thicker unit layers (as much as 14.5 Å) were also seen. The former are presumed to be illite, whereas the latter may be partially collapsed smectite. Selected-area electron diffraction patterns suggested simultaneous diffraction from several packets, each containing at least five layers. Both h0l and 0kl spacings were usually present, indicating that the stacking of the subparallel packets was random. Quantitative analysis by AEM and electron microprobe show the clay to be low in tetrahedral Al but high in octahedral Mg, the latter presumably contributing largely to the interlayer charge responsible for K fixation. The TEM data are broadly reconcilable with the accepted XRD interpretation of a two-component, mixed-layer clay. Alternatively, the TEM images may be interpreted as a single phase having numerous packet boundaries, the latter being responsible for swelling behavior. These two interpretations will not be fully reconciled until greater analytical precision and resolution permit individual packets to be studied. This work suggests that mineral definitions based purely on XRD interpretations may have to be reconsidered as more electron microscope data become available.

The oxidation of As(III) to As(V) by K-birnessite was examined at different temperatures, pHs, and birnessite/As(III) ratios. Experiments ranged in duration from 5 to 64 hr, and solution and solid products were determined at several intervals. All experiments showed that the reaction produced large amounts of K+ to solution and very little Mn2+. As(V) was released to solution and incorporated into the K-birnessite. The oxidation was initially rapid and then slowed. The oxidation of As(III) was probably facilitated initially by autocatalytic Mn-As(V) reactions occurring mostly in the interlayer, in which large amounts of As(V) and K+ could be easily released to solution. The reaction also slowed when interlayer Mn was exhausted by forming Mn-As(V) complexes. Mn(IV) could only be acquired from the octahedral sheets of the birnessite. The two-stage reaction process proposed here depended on the layered structure of birnessite, the specific surface, and presence of exchangeable cations in K-birnessite.

On the basis of progressive acid dissolution the Thompson-Hower model states that mixed-layer glauconite/smectite and illite/smectite contain potassium in two structural sites: a mica-type K position (site 1) and a position of uncertain structural status more prone to dissolution (site 2). Site 2 was thought not to retain radiogenic argon (40Ar*). Using extensive progressive acid dissolution and K/Ar studies on a sized illite/smectite (I/S), determining the amount of K in site 2 is shown to be somewhat more complicated than previously thought because the dissolution pattern depends on acid normality. More important, site 2 fully retains 40Ar*, and no age correction is thus necessary as is required by the Thompson-Hower model, further affirming the geochronologic value of illite in mixed-layer clay. These data are also relevant to understanding the crystal and particle structure of I/S. Site 2 is probably a partly filled K interlayer that develops as an intermediate kinematic step on the way to being fully filled during the transformation of smectite to illite.

Glauconites in early ankerite concretions, ferroan calcite-cemented sandstones, and uncemented sandstones in the first Wilcox sandstone of the Lockhart Crossing field, Livingston Parish, Louisiana, show a progressive substitution of Fe for octahedral Al with increasing diagenesis. An octahedral Fe content of 0.50 atoms was calculated from glauconite located in early ankeritic concretions. Octahedral Fe averaged 0.60 and 0.90 atoms in later ferroan calcite-cemented sandstone and uncemented sandstone, respectively. Corresponding octahedral Al averages were 1.16, 1.03, and 0.67, respectively. A systematic increase in average interlayer K from 0.49 to 0.54 to 0.61 was also observed, with apparent increases in diagenesis. All element determinations were made with an electron microprobe and recast on an anion equivalent basis to structural formulae based on the O10(OH)2 unit. The clay preserved in the early ankerite concretions was found to be an illite/smectite containing about 20% expandable layers, and the mineral in the glauconite pellets from uncemented areas of the sandstone, an ordered glauconite. “Minus cement” porosities of the sandstone indicate that glauconitization may have taken place at burial depths greater than 0.6 to 1.8 km, but the mechanism for the incorporation of Fe3+ in the glauconite at that depth is not apparent.

The < 1-μm fraction of 17 bentonite samples from Kinnekulle, southwest Sweden, were studied by chemical analysis, X-ray powder diffraction, and cation-exchange capacity. The bentonites are interbedded with undeformed, flat-laying Ordovician and Silurian sediments and were formed by the transformation of volcanic ash (dated at about 450 Ma) into smectite, which later converted to mixed-layer illite/smectite (I/S). The reaction, possibly driven by heat from an overlaying diabase intrusion (about 300 Ma), stopped at different stages of conversion, as evidenced by the I/S which ranges in composition from 60 to 10% smectite layers. A 2-m-thick bed shows zonation, with decreasing smectite proportions towards the upper contact. The zonation is not symmetrical towards the lower contact. In thin beds the illite proportion is higher and the regularity of ordering is inversely proportional to the thickness of the bed. K:Sr and K:Rb ratios follow the illite pattern; the ratios are highest at the contact and in thin beds. The inhibiting effect of Ca and Mg on the smectite-to-illite conversion probably was the cause of less-reacted smectite in the center of the thick bed.

Changes in hydraulic conductivity of smectite-sand mixtures (using four reference smectites) as a function of the concentration (0.01, 0.003, 0.002, 0.001 M Cl- and distilled water) and potassium adsorption ratio (of 2, 4, and 6) of the percolating solution were measured. Swelling and dispersion of the clays were evaluated from the changes in hydraulic conductivity of the mixture and from the clay concentration in the effluent.

The effect of exchangeable potassium percentage (EPP) on the hydraulic conductivity of the smectites depended on the charge density of the clays. The effect of potassium at EPPs <20 on the hydraulic conductivity of smectites having high charge density was negligible. Conversely, the hydraulic conductivity of smectites having low charge density (smectites from Wyoming and Belle Fourche, South Dakota), changed markedly when leached with dilute solutions as the EPP of the clay increased. The dispersive effect of exchangeable potassium on low-charge smectites was similar to that of exchangeable sodium. The low hydration energy of the K+ cations, coupled with the strong electrostatic attraction forces between platelets of smectites with high charge density account for the “inefficiency” of K+ in dispersing these smectites.

The amount of K fixed in K- and Ca-saturated montmorillonite, vermiculite (trioctahedral), rectorite-type and IMII-ordered mica/montmorillonites was measured as a function of time (1–64 days), temperature (25o-300°C), pH (6.0, 9.7, and 10.7), and K-concentration (0.02 and 1.0 M) in solution. The amount of K fixed by the clays generally increased with increasing temperature, pH, and K-concentration and reached saturation in response to each experimental condition in 5 or 6 days. The K-montmorillonite and K-vermiculite fixed considerable amounts of K even at 25°C. Fixed K in montmorillonite increased with an increase of the layer charge which is also influenced significantly by the interlayer cation. In detail, the behavior in K-fixation was specific to each clay.

The type of structural transformation with K-fixation was different for each clay. In montmorillonite, especially, the type of transformation was related to the cationic composition of the system; in K homoionic system, montmorillonite transformed rapidly into illite/montmorillonite with about 40% expandable layers at 300°C and in a mixed cation system with Ca and K, it reacted gradually to random illite/montmorillonites with increasing temperature. These data indicate that the cation-exchange process of a natural pore solution plays an important role in the gradual transformation of detrital montmorillonite to illite.

Chemical analysis by X-ray fluorescence (XRF) and calculated structural formulae of clay-size fractions of smectites from Cretaceous bentonites and illitic clays from Cretaceous, Devonian, and Ordovician bentonites and Jurassic and Permian sandstones indicate the nature and extent of various types of ionic substitution. The determination of tetrahedral (Al, Si) and octahedral (Al, Mg, Fe) composition shows the variable chemistry of these materials. Structural formulae of the illitic clays show that they have tetrahedral charges between 0.4 and 0.8 per half unit cell, and can be divided into phengitic types having octahedral charges of 0.2-0.4 and muscovitic types having octahedral charges <0.2. Evaluation of the formulae in the light of X-ray powder diffraction (XRD) and transmission electron microscopy (TEM) data shows that the occupancy of non-exchangeable interlayer sites (predominantly K) varies from 47% to 90% of that of ideal muscovite. In some minerals as much as 20% of these sites is occupied by ammonium ions (determined independently). The amount of surface silicate charge balanced by non-exchangeable cations versus that balanced by exchangeable cations has been examined in conjunction with TEM data and suggests that in most samples the charges are about equal. The octahedral composition of smectites in Cretaceous bentonites precludes their having served as transformation precursors for most of the Cretaceous illitic bentonites. The results suggest that these illitic clays originated by neoformation.

The characterization of cations associated with clay materials has generally been approached by the sequential use of specific chemical reagents. To avoid the disturbing effect of the chemical reagents on the state and location of compensating cations of clays and to get information in situ, far-infrared spectroscopy was used. The far-infrared vibrational spectra of the potassium cation in muscovite, phlogopite, and biotite were recorded before and after heating at the dehydroxylation temperature. The vibrational frequency of K in micas before dehydroxylation was found to be a function of the di- or trioctahedral character and of the Fe content. After dehydroxylation or deprotonation, shifts of the K absorption band to lower frequencies were observed for the heated muscovite, in which K exchangeability increased, and to higher frequencies for the heated biotite, in which K exchangeability decreased. These results suggest that the vibrational frequency of potassium is characteristic of the state of K in these minerals and of its ability to be exchanged.

Diffusion of K during analytical electron microscopy (AEM) results in anomalously low count rates for this element. As the analysis area and specimen thickness decrease, count rates become disproportionally lower. Adularia and muscovite show different diffusion profiles during AEM; for muscovite a strong dependence of diffusion on crystallographic orientation has been observed. Conditions giving rise to reliable chemical data by AEM are the use of a wide scanning area (>800 × 800 Å) and/or large beam size to reduce the effect of diffusion of alkali elements, a specimen thickness greater than about 1000 Å, constant instrument operating conditions, and the use of a homogeneous, well-characterized standard sample. The optimum thickness range was obtained by determining the element intensity ratio vs. thickness curve for given operating conditions. The standard and unknown should have a similar crystal structure and, especially for strongly anisotropic minerals such as phyllosilicates, a similar crystallographic orientation with respect to the electron beam.

The conversion of Malawi vermiculite into K-vermiculite by treatment with bi-ionic K-Mg solutions of 1 N total ion concentration (KCl and MgCl2 mixed solutions of ionic strength equal to 0.5) was studied by following the 00l X-ray powder diffraction (XRD) reflections. Flakes of Mg-saturated samples were treated at 160°C during 24 hr with bi-ionic solutions, with the K concentration varying from zero to pure 1 N KCl solution. The K-Mg interlayer exchange began at a critical value xK = .0196 (K/Mg = 1/100) of the molar fraction of K in the solution. Above the critical concentration and extending to pure 1 N KCl, the XRD diagrams were characteristic of a 10-Å/14-Å interstratification that had a marked tendency towards regularity. Experiments with KCl and MgCl2 mixed solutions of ionic strength equal to 0.75 and 1.0 showed that the exchange began at the same critical value xK as the experiments with ionic strength equal to 0.5, if the K added was equivalent. X-ray fluorescence analysis further showed that the amount of K adsorbed was proportional to the molar fraction xK and to the proportion of K-saturated layers (10 Å) in the interstratification. To explain the mechanism of this quasi-regular interstratification, a crystallochemical rather than a thermodynamic mechanism is proposed.