Infrared (Visible-Near Infrared-Shortwave Infrared (VNIR-SWIR)) spectroscopy is a cost-effective technique for mineral identification in the field. Modern hand-held spectrometers are equipped with on-board spectral libraries that enable rapid, qualitative analysis of most minerals and facilitate recognition of key alteration minerals for exploration. Spectral libraries can be general or customized for specific mineral deposit environments. To this end, careful collection of spectra in a controlled environment on pure specimens of key minerals was completed using the National Mineral Reference Collection (NMC) of the Geological Survey of Canada. The spectra collected from specimens in the ‘Kodama Clay Collection’ were processed using spectral plotting software and each new example was validated before being added to a group of spectra considered for incorporation into the on-board library of the handheld ASD-TerraSpec Halo near-infrared (NIR) mineral identification instrument. Spectra from an additional suite of mineral samples of the NMC containing REE, U, Th, and/or Nb are being prepared for a new, publicly available spectral library. These minerals commonly occur in carbonatite or alkali intrusive deposits, and as such will assist in the exploration for critical metals.

The swelling property of smectite is dominated by the hydration of exchangeable cations in the interlayer spacing (‘interlayer hydration’). By investigating systematically the swelling behavior of various exchangeable cations with different valences and ionic radii, the interlayer hydration of smectite was explored. The swelling behavior of Li+-, K+-, Rb+-, Cs+-, Mg2+-, Sr2+-, Ba2+-, and La3+- montmorillonites in undersaturated conditions was measured precisely over the range 50–150°C by in situ X-ray diffraction (XRD) analyses. The systematic swelling behavior of ten homocationic montmorillonites, the aforementioned eight homoionic montmorillonites, plus Na+ and Ca2+ from a previous study, and the cation hydration energies were analysed by studying the changes occurring in the basal spacing and the 001 peak width. With decreasing cation hydration energy, swelling curves (i.e. plots of basal spacing vs. relative humidity (RH)) change from continuous (Mg2+, La3+, and Ca2+) to stepwise (Sr2+, Li+, Ba2+, and Na+) to one-layer only (K+, Rb+, and Cs+). For the first two groups, the RH at the midpoint between the one- and two-layer hydration states increased as the cation hydration energy decreased. Under low RH, with increasing temperature, the basal spacings of Mg-, La-, Ca-, Sr-, Li-, and Ba-montmorillonites decreased continuously to the zero-layer hydration state, whereas Na-, K-, Rb-, and Cs-montmorillonites swelled from the zero-layer hydration state even at the lowest temperature (50°C). A decrease in the basal spacing at the same RH but at different temperatures suggests the existence of metastable states or that the layer-stacking structure changes with temperature. The systematics of the swelling behavior of various homocationic montmorillonites as functions of RH and temperature (<150°C) at 1 atmare reported here.

We report on how the effects of mechanical compaction and clay mineral diagenesis have affected the alignment of phyllosilicates in a suite of Miocene-Pliocene mudstones buried to sub-seabed depths of between 1.8 and 5.8 km in the deep-water Gulf of Mexico. Mechanical compaction has reduced the porosity of the samples to 15% at 5 km, with modal pore sizes between 10 and 20 nm. High-resolution X-ray texture goniometry data show that the intense mechanical compaction has not resulted in a strongly aligned phyllosilicate fabric. The muds were apparently deposited with a weak or isotropic phyllosilicate fabric which was not substantially realigned by mechanical compaction. Unusually, X-ray diffraction of <0.2 µm separates shows that: (1) there is no illitization trend between 90 and 120°C; and (2) discrete smectite persists to ∼120°C, coexisting with R1 I-S or R0 I-S with 30–40% expandable layers. Between 120 and 130°C, discrete smectite disappears and the expandability of I-S decreases to ∼25–30%. We propose a two-stage diagenetic process involving (1) the alteration of volcanic glass to smectite and (2) the illitization of smectite and I-S; the alteration of glass results in smectite without a preferred orientation and retards the illitization reaction. We suggest that the lack of a strongly aligned phyllosilicate fabric reflects the apparently limited extent of illitization, and thus recrystallization, to which these mudstones have been subjected.

A number of organobentonites were synthesized by exchanging the metal ions in bentonite with the cationic surfactant, cetyltrimethylammonium bromide. Samples of natural bentonite and organobentonites were analyzed for their organic carbon contents, examined by X-ray diffraction (XRD) for interlayer spacings, and viewed using a scanning electron microscope (SEM) for surface morphology. The sorption isotherm of benzene vapor from ambient air (relative humidity (RH) = 45 ± 5%) on natural bentonite was nonlinear; however, the isotherms of benzene from ambient air onto organobentonites were virtually linear over a large range of relative vapor concentrations. The sorption capacities of air-dried organobentonites were far greater than that of the natural bentonite. For air-dried organobentonites, the sorption coefficients correlated positively with the sample organic carbon contents and negatively with the sample BET-N2 surface areas. The heats of benzene vapor sorption onto air-dried organobentonites were less exothermic than the heat of benzene-vapor condensation. These findings suggest that benzene vapor sorption by air-dried organobentonites occurs essentially by vapor partition into the sample organic-matter fractions. This offers a potential application of organobentonites for the removal of organic vapors from flue gases and for assessing the efficiency of vapor removal.

Adsorption of uranyl (UO22+) ions to mineral surfaces is a potentially effective method for removing this hazardous metal from water, but other toxic trace metal ions (Xn+: Rb+, Sr2+, Cr3+, Mn2+, Ni2+, Zn2+, Cd2+) in uraniferous wastewaters compete with UO22+ for adsorption sites and thus may diminish the capacity of adsorbents to sequester UO22+. A better understanding of competitive adsorption among these metal ions and the development of better adsorbents are, therefore, of critical importance. The purpose of the present study was to synthesize and characterize magnetic adsorbents, consisting of MFe2O4 (M = Mn, Fe, Zn, Co, or Ni) nanoparticles synthesized on montmorillonite (Mnt) edge sites, and to investigate their use as adsorbents for UO22+, including competitive adsorption with trace metal ions. Selective adsorption was studied using Langmuir, Freundlich, and Dubinin-Radushkevich isotherms, and the results showed that Xn+ ions were adsorbed primarily on MFe2O4-montmorillonite surfaces, and the UO22+ ions were adsorbed on the interfaces between montmorillonite edge surfaces and MFe2O4 nanoparticles. Using the Freundlich model, the interface adsorption capacity of UO22+ reached 25.1 mg·g–1 in mixed solution. Further, the UO22+ and Cr3+ ions had a redox reaction on the interfaces with synergistic adsorption. Herein, the adsorption capacity of Cr3+ was 60.2 mg·g–1 using the Freundlich isotherm. The results demonstrated that the MFe2O4-montmorillonite with highly selective adsorption of UO22+ ions is applicable to UO22+ treatment in the presence of toxic trace metal ions.

Graphical abstract

In Iran, the writing of history has consistently been intertwined with political decisions, and official historiography written after the Islamic Revolution is no exception. The majority of books and articles on Pahlavi I have inherited this historiographic tradition, and are thus highly politicized, particularly around the topic of the role of the clergy during this era. Official narratives of this period are based on two representations: portraying intellectuals and Britain as the sole forces involved in bringing Reza Shah to power and consolidating his rule, while concealing the role of the clergy, or depicting this social group as the sole opposition to his government. This article aims to assess this binary narrative and answer the following question: What role did the clergy play in establishing and consolidating Reza Shah's reign? Research findings indicate that neither of these claims are accurate, as the clergy played a key role in the transfer of power from the Qajar to Pahlavi dynasties by supporting Reza Khan during his ministry, participating in the coup on February 22, 1921 (3 Esfand 1299), and supporting him in the Constituent Assembly. Further, the majority of clergy not only did not play the role of opposition, but indeed actively participated in the governmental institutions of the era. This research utilizes a historical-documentary approach to examine the subject.

Boron and lithium were analyzed in three nanometer-sized (<20, 20-50 and 50-100 nm) separates of two Santonian (85.8-83.5 Ma) bentonite samples collected closely in the Campos Basin along the southeastern Atlantic coast (Brazil). The B and Li data give various trends that suggest varied crystallization conditions for separates that consist of overwhelming smectite with less than 9% illitic layers. The δ11B of the few illitic tetrahedral sites from one of the samples remains quite constant, while its contents are strictly correlated with those of K, which suggests that illitization proceeded by interaction with pore fluids of the host sediments that supplied the K. In the second sample, the δ11B of the illite layers from the two coarser fractions is indicative of an early volcanic origin, while the smaller size fraction also interacted with sedimentary fluids. Favored by octahedral substitutions of the smectite layers, the δ7Li is more strictly regulated by a volcanic link. In turn, the information of the B and Li isotopic compositions and contents from studied mixed-layers suggests a various origin for the few illite layers of the smectite-rich I-S that contain more B than the smectite layers that host more Li. The difference appears to be sample-site and crystal-size dependent, fueled by pore fluids of the hosting turbidites.

The Brunauer-Emmett-Teller (BET) theory models the effective specific surface area and water content of solids as a function of the relative vapor pressure of water. A modified form of the BET equation has been used successfully to model water activity in concentrated electrolyte solutions as a function of electrolyte concentration. This modified form, referred to here as the Stokes-Robinson BET model, is based on the electrolyte molality rather than on the mass of solute sorbed. The present study evaluates the Stokes-Robinson form of the BET equation to model water-sorption data on two smectites with different layer charges. One smectite was saturated with Na+ and another with Na+, Ca2+, or Mg2+. These results are compared to the Stokes-Robinson BET results of aqueous electrolyte solutions. Given published data on cation exchange capacities and water-vapor sorption isotherms for various clays, the molality of the aqueous phase in contact with the clay surface is calculated and related to water activity. The Stokes-Robinson BET model was found to describe accurately the water activity as a function of cation molality below water activities of 0.5 for the smectites. Good relative agreement was obtained between the number of water binding sites predicted by the model and the experimental data reported in the literature for other smectites. Water molecules were found to have a significantly greater affinity for montmorillonite than electrolyte solutions with the same cation molality as the montmorillonite interlayer. This modified BET approach simplifies water-activity modeling in highly saline environments because the same equation can be used for both the liquid- and mineral-surface phases.

Accidents are a prevalent feature of working in the maritime industry. While studies have shown to what extent accidents and fatalities have occurred, the current research has generally been limited to commercial shipping. There is nearly no academic research focusing on the safety issues in the superyacht industry. This paper analyses the importance of promoting safety culture in the superyacht industry, the role of maritime legislation in maintaining safety and the role of Port State Control in ensuring all legislation is implemented. It aims to provide a critical examination of safety culture in the superyacht industry and evaluate the appropriateness for further measures to ensure safe working practices. It found out that while some superyachts do maintain an effective safety system, there remains almost 50% of the investigated fleet that do not promote the desired safety culture. It becomes evident that complacency and poor education contribute to the reduced and limited safety culture. The lack of education and awareness is demonstrated when the study shows individuals believing they maintain good safety practices but still admitting to taking various life-threatening risks.

The As sorption capacity of a natural Mn and Fe mineral-containing sample from the Iron Quadrangle province, Brazil, was investigated. A detailed mineralogical identification was obtained by combining X-ray diffraction analyses (with Rietveld refinement), X-ray fluorescence spectroscopy, optical microscopy, and scanning electron microscopy coupled with X-ray energy dispersive spectrometry-EDS. The oxidation state of the adsorbed As species was determined by X-ray absorption near edge structure spectroscopy. The results demonstrate that the presence of naturally occurring Mn oxides promotes the effective oxidation of As (III) to As(V). Also, the Mn minerals show a significant uptake of both the trivalent and pentavalent As species. This study demonstrates that the combined influences of As(III) depletion by oxidation and adsorption on a natural oxide sample consisting of Mn minerals and Fe oxides may effectively contribute to the reduction the As concentration in waters.

Phyllosilicate mineralogy is key to understanding hydrothermal processes within accepted epithermal deposit models but little information has been published about the mineral chemistry of epithermal deposits. X-ray diffraction, optical and electronic microscopy (scanning and transmitted), electron microprobe, and Fourier transform infrared spectroscopy were used in this work to study phyllosilicates in the Palai-Islica Au-Cu epithermal, volcanic-hosted deposit, in order to link phyllosilicate mineralogy and mineral chemistry to ore genesis. Different phyllosilicate assemblages are characteristic of two types of mineralization, and related hydrothermal alteration. Chlorite and mica appear in polymetallic quartz veins with sulfides, and in the related chloritic and sericitic hydrothermal alteration. These minerals have notable textural and chemical differences (i.e. Fe/(Fe+Mg), Si and Al in chlorite and illitic and phengitic components in mica) amongst veins and altered rocks, revealing different genetic conditions. These chemical features also distinguish propylitic and regional, non ore-related, low-temperature alteration. Hot hydrothermal fluids of near-neutral pH are responsible for vein mineralization and alteration. Illite, interstratified illite-smectite, kaolinite, and pyrophyllite are characteristic, with a distribution pattern by zones, of the intermediate argillic and advanced argillic alteration around areas of silicification. In the latter, native gold appears associated with interstratified illite-smectite, suggesting a relatively low-temperature formation. Hot, low-pH fluids are responsible for this mineralization and alteration assemblage. The present study contributes to epithermal models showing the co-existence of two different alteration styles in the same hydrothermal system.

One day in 2018, I arrived at Playwrights Horizons in New York City excited to see a new play by Lindsey Ferrentino called This Flat Earth. I did not know much about the story aside from the fact that it had teenage actors playing teenager characters, but I quickly realized that it was about two teens trying to make sense of a recent mass shooting event as their school. The most striking part of this experience was watching Ella Kennedy Davis playing a thirteen-year-old white girl named Julie who takes out her anger, grief, and confusion about this senseless violence on those around her. Davis spent much of the play on the emotional limits of anguish, screaming, crying, and shaking to the point where she continued to do so throughout the curtain call. Both my discomfort with the actor's obvious distress, and my genuine dislike for the whiny, sad, one-dimensional role—whose main characteristic is her ignorance of previous school shootings—were enough to distract me from the play itself. But what created this distancing effect? I first thought of Bert O. States's phenomenological observation that children onstage often break our illusion of the theatrical world, but I noted that my phenomenological response was distinctly different from what I feel when I see children acting onstage. Instead of wondering if the actor understood the play she was in, I instead feared she understood all too well.

The Carrera de Indias, considered as a set of circuits connecting Hispanic America to world markets, does not appear as a “monopoly” reserved solely for the Spanish merchants of Cadiz, but rather as a complex commercial system, structured into three autonomous segments, each of them dominated by a mercantile corporation, more or less formalized. In the central part, which linked the two shores of the Atlantic, the merchants registered in the Consulado of the Indies of Cadiz (cargadores) obviously dominated the market. However, these were in turn dominated by the merchants from the consulates of Mexico and Lima in the inland trade (comercio de tierra adentro), which linked the great American ports and fairs with the markets of the interior of the continent, and by the foreign merchants of Cadiz, structured into “nations,” in the exchanges that linked the Andalusian port with the rest of Europe and the world. Thus, the beneficiaries of the Spanish colonial trade in the second half of the eighteenth century were neither only cargadores, nor foreign “smugglers” enjoying the weakness of the Spanish empire as the historiography of the Carrera de Indias has traditionally postulated, but those three groups of traders.

After highlighting this singular structure of colonial trade in the Spanish Atlantic, we will consider the different institutional and relational factors that could explain it. Obviously, it is because the different groups of actors involved in these exchanges had a specific social, relational, cultural, and institutional capital that they had a comparative advantage over their rivals in certain segments of the Carrera de Indias circuits, and that they were able to obtain the dominant position that we observe.

The interaction of cytochromes (heme proteins) with mineral surfaces is important from an environmental perspective (e.g. heavy metal remediation and reductive dehalogenation reactions), for designing biosensors and bioanalytical systems, and for emerging photovoltaic applications. In addition, the cytochrome studied here shares properties with some cytochromes from Fe-reducing bacteria and its general behavior sheds light on how other cytochromes might behave during Fe(III) reduction. The objectives of this study were to characterize the direct electrochemistry and sorption mechanism of horse heart ferricytochrome c (a mitochondrial cytochrome referred to as Hcc) on hematite surfaces as a function of pH, time of sorption and ionic strength. Hcc sorption on hematite mainly occurs between pH 8 and 10, the pH range in which hematite surfaces and Hcc are oppositely charged. Calculated net attractive forces correspond closely with the pH range of peak sorption, suggesting that sorption is mainly electrostatically controlled. Hcc sorption with ionic strength is consistent with this conclusion. The pH-dependent conformation of Hcc sorbed on hematite appears to be different from that in solution as indicated by UV-visible spectroscopy and its more negative reduction potential compared to native Hcc. Sorption kinetics were rapid and pH-independent across the pH range 3–10 with slow conformational changes occurring at >60 h. Our results suggest that the electrostatic attraction of the cytochrome towards the surface orient the cytochrome for favorable electron transfer between the heme group of the cytochrome and hematite.

Nontronite is a significant component of commercially important nickel laterite ores. Its behavior during high-pressure acid leaching of such ores may have an impact upon the efficiency of the process. The present study was conducted in order to further investigate the response of this material during high-pressure acid leaching. In situ synchrotron powder X-ray diffraction data were collected from a number of nontronite samples during hydration and leaching reactions at ambient and elevated temperatures. The present study followed previous high-pressure acid-leaching studies of nontronite where unexpected contraction and expansion behavior of the clay was observed by means of in situ X-ray diffraction. In the earlier studies the data sets only extended to ~20 Å so that when the nontronite expanded to greater than 19.5 Å (hydrated) the main 001 peak was only partially visible in the observed d-spacing range. The aim of the current work was to collect similar in situ diffraction data over a greater d-spacing range to observe more fully the movement of the main 001 reflection in order to better understand the changes taking place. This work was undertaken at the powder diffraction beamline of the Australian Synchrotron which was configured such that an upper d-spacing limit of ~34.5 Å could be achieved. Suggestions arising out of the previous work were confirmed along with additional information from testing of samples from the Source Clays Repository of The ClayMinerals Society. These results also show contradictory behavior of clays with the layer charge distributed over tetrahedral and octahedral sheets.

A diapiric intrusion of clays in the Carlentini Formation (Tortonian) was discovered in a quarry at S. Demetrio High (Hyblean Plateau, Sicily, Italy). Seven clay samples were analyzed by different analytical methods, including X-ray powder diffraction (XRD) and Fourier-transform infrared (FTIR) spectroscopy, to determine the composition and mechanism of formation (sedimentary vs. hydrothermal) of these clays. Ferric saponite, carbonates (calcite and traces of ankerite), quartz, pyrite, and zeolites (phillipsite and harmotome) were detected using XRD and FTIR. This mineral assemblage, dominated by Fe-rich saponite, and the abundance of light rare-earth elements (LREE), Eu, fluid-mobile elements (FME > 10 × primordial mantle: Li, Be, B, As, Sb, Pb, U, Ba, Sr, Cs), and other incompatible elements (Zr = 169 ppm, Nb = 46 ppm, Th = 11 ppm, on average) imply that S. Demetrio clays precipitated from a mixture of hot Si-rich hydrothermal fluids (350–400°C) and cold seawater. The evidence is in accord with the affinity of clays for hydrothermally modified mafic and ultramafic rocks, forming the Hyblean lower crust, based on multi-element comparisons, and on the occurrence of trace amounts of chrysotile 2Mc1 and sepiolite. The association of long-chain aliphatic-aromatic hydrocarbons (intensity ratios I2927/I2957 > 0.5) with hydrothermal clays, the lack of fossils, and the similarity of the IR absorption bands with those of organic compounds detected previously in some metasomatized Hyblean gabbroic xenoliths suggest a possible abiogenic origin of hydrocarbons via a Fischer-Tropsch-type reaction. The S. Demetrio clay diapir was emplaced at shallow crustal levels in the Late Miocene as a consequence of the interaction, at a greater depth, of an uprising basalt magma and the products of an early, serpentinite-hosted hydrothermal system.

A new method has been developed for quantifying smectite abundance by sorbing polyvinylpyrrolidone (PVP) on smectite particles dispersed in aqueous solution. The sorption density of PVP-55K on a wide range of smectites, illites and kaolinites is ∼0.99 mg/m2, which corresponds to ∼0.72 g of PVP-55K per gram of montmorillonite. Polyvinylpyrrolidone sorption on smectites is independent of layer charge and solution pH. PVP sorption on SiO2, Fe2O3 and ZnO normalized to the BET surface area is similar to the sorption densities on smectites. γ-Al2O3, amorphous Al(OH)3 and gibbsite have no PVP sorption over a wide range of pH, and sorption of PVP by organics is minimal. The insensitivity of PVP sorption densities to mineral layer charge, solution pH and mineral surface charge indicates that PVP sorption is not localized at charged sites, but is controlled by more broadly distributed sorption mechanisms such as Van der Waals’ interactions and/or hydrogen bonding. Smectites have very large surface areas when dispersed as single unit-cell-thick particles (∼725 m2/g) and usually dominate the total surface areas of natural samples in which smectites are present. In this case, smectite abundance is directly proportional to PVP sorption. In some cases, however, the accurate quantification of smectite abundance by PVP sorption may require minor corrections for PVP uptake by other phases, principally illite and kaolinite. Quantitative XRD can be combined with PVP uptake measurements to uniquely determine the smectite concentration in such samples.