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Kaolin ores are usually contaminated by some Fe-bearing minerals, the strong colors of which degrade the quality of the final product. A spectroscopic technique is sought to quantify the content of hematite and goethite, the main contaminant minerals in the kaolin from Capim River in Brazil, was the focus of this study. The total Fe content obtained through X-ray fluorescence showed a poor correlation with the brightness of kaolin, due to the inability to differentiate between the Fe contained in the (oxyhydr)oxides and the Fe present in the crystalline structure of kaolinite, especially when the Fe-bearing minerals occur in small quantities. Here, a new generic technique to quantify Fe (oxyhydr)oxides in kaolin, based on the Kubelka-Munk theory, is presented. A new interpretation of the theory was made that enables its use without the need to measure thin layers of material. The results with synthetic goethite and hematite were very positive (R2pred ≈ 0.99) and experiments with contaminants from the mine are already underway.
To date, ~1% of all bacteria that occur in environmental ecosystems such as soil, sedimentary rocks, and groundwater have been described. Comprehensive explanation of ecological interactions on a microscale level is thus almost impossible. The Dynamic Cultivation System (DCS) was developed in order to detect more microbial taxa than with common cultivation approaches, as well as previously undescribed bacterial species. The DCS is a quick and easy in situ method for the cultivation of numerous bacterial taxa in support of the description of microbial colonized ecosystems. To investigate the bacterial populations within a clay-maturation process after mining the raw material, the DCS was used to increase the microbial biomass for further molecular analysis. Two different methods were applied to extract the bacteria from the DCS and these were compared in terms of efficiency at detection of large numbers of different taxa and in terms of applicability to the detection of previously undescribed species in raw clays. A collection of different undescribed species was detected with sequencing. While direct picking of bacterial colonies leads to the detection of different genera, species mainly of the genus Arthobacter were proved in the phosphate-buffered saline-suspended biomass. Thus, a combination of the approaches mentioned above is recommended to increase the number of detectable species. The DCS will help to describe better the microbial content of ecosystems, especially soils that contain charged particles.
Gray-black kaolinitic claystones of industrial value are abundant in Upper Carboniferous–Lower Permian coal-bearing strata of the Datong Coalfield of northern China. The main types are tonsteins and cryptocrystalline kaolinitic claystones, distinguished by the thinness and greater crystallinity of kaolinite in the former and by the presence of detrital illite and authigenic pyrite in the latter. In order to determine the formation history of these two types of kaolinitic claystone, the petrological, mineralogical, and geochemical characteristics of borehole samples from the Upper Carboniferous Taiyuan Formation which comprises siliciclastics and coal seams deposited in a coastal environment, were analyzed. In addition to kaolinite, the claystones contain subordinate illite, quartz, pyrite, anatase, feldspar, siderite, and calcite. The tonsteins and cryptocrystalline kaolinitic claystones have different sources, as shown by petrographic data, elemental ratios, and chondrite-normalized rare earth element (REE) patterns. The volcanic origin of the tonsteins is revealed by an abundance of volcanic quartz and vitric fragments as well as Al2O3/TiO2, Zr/Hf, and Nb/Ta ratios consistent with a felsic igneous source. Their REE fraction was derived from feldspars or micas of the parent rocks, and the fraction decreased with alteration of these minerals to kaolinite. The sedimentary origin of the cryptocrystalline kaolinitic claystones is revealed by an abundance of detrital quartz and illite grains derived from either granite or sedimentary upper crust, and by the total REE contents (ΣREE) and (La/Yb)N values which are consistent with granitic material. Their depositional environment was in a transitional (coastal) setting (as shown by intermediate Sr/Ba ratios) hosting an open acidic hydrologic system (as shown by high chemical index of alteration (CIA) values indicative of intensive chemical weathering) that was suboxic to anoxic (as shown by high U/Th ratios and trace-metal enrichment factors). The present chemistry of these claystones was thus controlled by a combination of parent rock type and diagenetic alteration.
The chapter on fundamental rights in the Constitution of India, under article 12, identifies the “state” as the actor against whom fundamental rights can be enforced. Decades-long jurisprudence invoking article 12 has established the vertical enforcement of fundamental rights against state actors. However, a constitutional bench judgment in Kaushal Kishor (2023) alters this position, wherein the Supreme Court of India expanded the scope of fundamental rights against both state and non-state actors. This article analyzes the dictum in Kishor to argue that even when fundamental rights have been sporadically enforced against non-state actors, it has been by obligating the state to mitigate fundamental rights transgressions by non-state actors (doctrine of indirect horizontal application). The article raises constitutional concerns about the Court's reasoning in Kishor, positing that it ignores the constitutional mandate of article 12, disregards the judicial precedents supporting the vertical application of fundamental rights, and grants an unbounded sanction to enforce fundamental rights against virtually “anyone.”
The dissolution of brucke, Mg(OH)2, on the (001) surface was investigated using in situ atomic force microscopy in solutions at near-neutral pH. Dissolution proceeded by the formation of crystallographically oriented triangular etch pits with monolayer step and expansion of the pits. The sides of the triangle are parallel to the [100], [110] and [010] directions of the brucite structure, and the orientation of lines from the center of the triangle to the three apices are along the [210], $[\bar 110]$ and $[\bar 1\bar 20]$ directions. This orientation may produce pit edges where OH groups coordinate to two Mg2+. Although triangular etch pits with monolayer depth formed mostly at random on the (001) surface, concentric pits penetrating several layers were also observed. Etch pits with spiral steps were rarely observed. Coalescence of the pits resulted in stranded terraces that diminished in size rapidly and formed a rounded irregular form. The step-retreat velocity around the triangular pit is 0.015–0.04 nm/s at pH 5–8. The retreat velocity around the stranded terraces was about three times more rapid than that around the triangular etch pits.
Certain characters and their roles in the European conquest of America are well known: Christopher Columbus, Hernando Cortés, Francisco Pizarro, Gonzalo Jiménez de Quesada, and a few others. Likewise, scholarly interest in the conquest has focused on the centers of great political, economic, and cultural entities such as the Aztec Empire in Mesoamerica and the Inca Empire in the Central Andes.
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.
Several procedures for hydrothermal synthesis of saponite can be found in the literature. They differ in terms of the preparation conditions of the precursor and of the synthesis temperature. The objective of the present study was to investigate how these two parameters influence the structure of the final synthesis product. The precursor was prepared from Mg(NO3)2, Al(NO3)3, and Na4SiO4 in three different ways: as a gel, a dried gel, and a calcined gel. The influence of the synthesis temperature on the structure of saponite was investigated in the range 90–200°C. The results showed that the use of a calcined precursor yielded a single mineral phase, saponite, with up to 90% aluminum in tetrahedral configuration. In comparison, the use of a gel precursor resulted in a product with only 60% aluminum in the tetrahedral configuration. The synthesis temperature had no significant effect on the saponite structure. The reported synthesis method showed the possibility of obtaining saponite with superior characteristics, in terms of crystallinity, surface acidity, and thermal stability compared to the natural mineral, even at 90°C, and thus with greater potential for industrial application.
Floating, mixed-valent Fe films have been observed worldwide in wetlands, ferrous iron-rich seeps, and in seasonally reduced soils, but are usually misidentified as oil or biofilms. There has been little characterization or explanation of their formation. Along the Oregon coast such films were found on ephemeral pools where Fe(II)-rich groundwater (∼100 µM Fe) has been discharged at the base of Pleistocene sand dunes. Fe(II) oxidized to Fe(III) at the air-water interface to form ∼100–300 nm thick films. Analyses indicated that the films contained both Fe(III) and Fe(II) in a ratio of 3:1; Si was the other main cation; OH was the main anion and some C was also identified. The film morphology was flat under optical and electron microscopy with some attached floccules having a string-like morphology. Energy-filtered electron diffraction patterns showed three diffraction rings at 4.5, 2.6 and 1.4 Å in some places and two rings (2.6 and 1.4 Å) in others. Upon further oxidation the films became 2-line ferrihydrite. We are proposing the name ‘schwimmeisen’ for the floating, mixed-valent Fe film.
The Pleistocene Olorgesailie Formation in the southern Kenya Rift has yielded a remarkable assemblage of Acheulean artifacts and vertebrate fossils, including hominin specimen KNM-OG 45500. Members 1 and 7 both contain clay-rich deposits that have been pedogenically modified into paleosols (UM1p and UM7p, respectively). This study provides the first detailed mineralogical and geochemical analyses of the clays of this important Pleistocene basin. The smectitic clays, which show abundant evidence for pedogenesis, were apparently originally deposited under lacustrine conditions. They have an average structural formula of (Ca0.01Na0.32K0.26)(Si3.76Al0.24)(Al0.86Ti0.04Fe0.68Mg0.42)O10(OH)2. The high layer charge clays indicate diagenetic alteration of detrital clay derived from the volcanic drainage basin, probably involving alkaline waters of variable salinity. Despite overall lower salinity compared to other Plio–Pleistocene basins of the region (e.g. Olduvai Gorge), the basin still shows evidence for authigenic clay mineral precipitation. Clay chemistry and bulk geochemical indicators of pedogenesis imply that UM1p clays more closely reflect depositional paleo-waters, whereas UM7p clays have been more pedogenically altered due to subaerial exposure. UM1p smectites show some Mg enrichment near the western Lava Hump locality, consistent with discharge of Mg-bearing paleo-waters from a volcanic aquifer into a siliceous and alkaline (though not highly saline) paleo-lake. UM7p smectites were deposited in a more saline paleo-lake, but have lost substantial amounts of Mg due to post-depositional weathering. Locally abundant artifacts and vertebrate fossils found in these deposits accumulated at times following deposition of the lacustrine clay, probably concurrent with pedogenesis. The limnological conditions associated with initial clay deposition, therefore, preceded hominin occupation of the exposed surfaces.
This article critiques the decision of the Court of Appeal in Re SA (Declaration of Non-Recognition of Marriage) [2023] EWCA Civ 1003. In Re SA the Court of Appeal held that: (1) by operation of section 16 of the Matrimonial Causes Act 1973, a voidable marriage is not void at its inception and is therefore not caught by section 58(5)(a) of the Family Law Act 1986, and (2) the effect of section 16 of the 1973 Act is that a voidable marriage starts off fully valid but only on making a decree absolute of nullity becomes invalid. This article contends that the approach adopted by the Court of Appeal in SA is conceptually challenging, based on a misreading of the statutory language, and is directly contrary to long-established and powerful authorities.
Natural soils change by long-term pedogenetic mechanisms, but tillage effects can also strongly affect the evolution of soils, mainly their physicochemical properties. The present paper describes the impact of fertilizers and amendments on soil mineralogy in experimental plots, without plant interaction.
The soils of the 42 plots experiment at the INRA experimental station in Versailles (France) have been managed with fertilizers without plant growth since 1929. Strong changes in pH were observed and cation exchange capacities doubled between low and high pH (from 3.6 to 8.2). Strong acidification caused more evolution in the clay particle distribution without selective action on the clay composition.
While the clay content varied only slightly, the organic matter content changed considerably, decreasing with non-organic treatment and increasing in the plot with manure treatment. The major clay minerals in the experimental plots are two disordered illite-smectite mixed-layer minerals, with minor amounts of illite/mica and kaolinite. Most treatments effected only minor changes in clay mineralogy. However the illite (non-expandable mineral) content increased in plots with K addition either as KCl treatment or in manure amendments by increasing the illite content and the illite (non-expandable layer) content of the I-S minerals. Manure changed the I-S mineral to a greater extent.
In the search for rare earth and other critical elements in coal measures, the coals are emphasized with lesser consideration for the accompanying rocks. In this investigation, the focus is on a lanthanide-rich, 315–317 Ma (after Machlus et al., Chemical Geology, 539, art. no. 119485, 2020) volcanic ash-fall trachyandesite to trachyte tonstein which occurs in association with the Middle Pennsylvanian Duckmantian-age Fire Clay coal in eastern Kentucky. The tonstein was deposited largely during peat accumulation, although it is known to occur at the base of the coal or within the underclay. The mineralogy is dominated by kaolinite with illite and quartz as minor to major minerals. A number of accessory minerals, as detected by X-ray diffraction + Siroquant XRD software and scanning and transmission electron microscopy (S/TEM), include REE-bearing phosphates (apatite, crandallite, florencite, monazite), and Y-bearing zircon. The highest rare earth element + Y concentrations occur in the weathered tonsteins, probably due to the concentration of these minerals after weathering of kaolinite from the rock.