Selenite Crystals Research Articles

Gypsum Crystals Formed by the Anhydrite–Gypsum Transformation at Low Temperatures: Implications for the Formation of the Geode of Pulpí

Determining the mechanisms of the formation of giant crystals is a challenging subject. Gypsum, calcium sulfate dihydrate (CaSO4·2H2O), is known to form crystals larger than one meter in several locations worldwide. These selenite crystals grow at different temperatures, either in sedimentary or hydrothermal systems. The famous selenite crystals of the geode of Pulpí (Almería, Spain) are known to have grown at a temperature T = 20 ± 5 °C and have been proposed to form in a subaqueous environment by a self-feeding mechanism triggered by anhydrite dissolution and the ripening of microcrystalline gypsum, enhanced by oscillations in temperature. This paper reports the monitored crystallization of gypsum crystals, from anhydrite powder dissolution, inside airtight evaporation-free reactors under oscillating low temperatures (15 °C < T < 25 °C). These crystals are clearly smaller than the ones in the Pulpí mine but exhibit similar habits (i.e., single blocky crystals and twins following the 100 twinning law). The growth rate of gypsum single crystals has been measured to be between 3.8 and 35.3 µm/day. Noteworthy, we document the occurrence of the 100 contact twinning law of gypsum, which is the most widespread twinning law in natural environments but never univocally reported in laboratory experiments. The selection of the 100 contact twinning law has been correlated to the low supersaturation values obtained in the experiment, where the concentration in these long-duration experiments can be safely assumed to be the equilibrium concentration, i.e., 0.3 (at 25 °C) ≤ SI ≤ 0.4 (at 15 °C). We discuss the relevance of our experiment for forming the gypsum crystals of Pulpí in the framework of the geological history of Pulpí mineralization. These laboratory model experiments contribute to a deeper understanding of mineral nucleation and growth processes in natural environments.

Godel, Escherian Staircase and Possibility of Quantum Wormhole With Liquid Crystalline Phase of Iced-Water - Part II: Experiment Description

The present article was partly inspired by G. Pollack’s book, and also Dadoloff, Saxena & Jensen (2010). As a senior physicist colleague and our friend, Robert N. Boyd, wrote in a journal (JCFA, Vol. 1, No. 2, 2022), for example, things and Beings can travel between Universes, intentionally or unintentionally [4]. In this short remark, we revisit and offer short remark to Neil Boyd’s ideas and trying to connect them with geometry of musical chords as presented by D. Tymoczko and others, then to Escherian staircase and then to Jacob’s ladder which seems to pointto possibility to interpret Jacob’s vision as described in the ancient book of Genesis as interdimensional staircase, e.g. an interdimensional bridge between heaven and earth (cf. classic book: Hofstadter, Godel, Escher, Bach). Jacob’s vision of angels going down to earth from that staircase has been depicted for instance in William Blake art etc. In our communication with others via physics literature and discussions etc, we came to several conclusions as follows: Firstly, possibility of wormhole effect to mirror particle universe, which sometimes it is termed non-orientable wormhole. While such mirror particles effect have been more than 50 years predicted with the so-called parity violation (cf. Lee & Yang, 1950s), and that is called symmetry breaking. Secondly, a series of extended experiments on laser irradiated cold water may suggest possible transition from a phase of water to be at least partially fourth phase of water, which may be composed of crystalline water (see e.g. Gerald Pollack, and also Harold Aspden on liquid crystalline). If we can imagine laser cooling effect can be done in protracted time, then we can achieve a physical representation of Aspden‘s liquid crystalline. Therefore, in this article we outline a series of simple experiments of laser irradiated iced-water along with beryl and selenite crystals in order to see possibility of such a quantum tunneling via quantum liquid crystalline Universe hypothesis, which may likely be modeled with iced-water. It is interesting to remark here that certain experiments by Stockholm University scientists have shown that X-ray triggered water can exhibit properties just like liquid crystal (cf. PRL, 2020). That is why we consider it possible that there can be quantum phase transition where liquid water (comprised of iced cubes and water) can exhibit effects such as tunneling in quantum liquid crystalline Universe. Last but not least, we admit that what we outlined here is just aninitial phase; and if you wish, perhaps we can call such experiments as “wormhole-at-lab” experiments (abbreviated: WHALE).

Messinian resedimented gypsum (branching-like facies) from the Catanzaro Basin (Calabria, Southern Italy): petrographic and geochemical evidence for paleoenvironmental reconstruction

A multidisciplinary approach allowed to investigate the formation and evolution of gypsum blocks within the Riato Conglomerate outcropping in the Catanzaro Basin (Calabria, Southern Italy). Macroscopically, the gypsum blocks seem to belong to the branching facies (primary facies) known in literature, however microscopic observations reveal a detrital origin (secondary facies). Indeed, the gypsum blocks show an alternation of laminae made of selenite clasts (100 to 500μm) and of fine matrix engulfing relicts of selenite crystals (

A Rare-Earth Selenite with Unexpectedly Well-Balanced Ultraviolet Nonlinear Optical Functionality, Sc(HSeO3 )3.

Establishing high performance ultraviolet (UV) nonlinear optical (NLO) selenite crystals with well-balanced properties is very challenging attributable to their strong absorption for UV light. Here a rare-earth selenite, Sc(HSeO3 )3 , with excellent UV NLO propertiesis introduced. Sc(HSeO3 )3 crystallizing in the polar NCS space group, Cc, features a 3D archetiture built up by interconnected ScO6 octahedra and HSeO3 groups. The crystal exhibits remarkably well-balanced UV-NLO functionality, namely, the shortest absorption edge (214nm) among NLO-active selenites, wide bandgap (5.28eV), large phase-matchable SHG response (5 × KDP), and sufficiently large birefringence (cal. 0.105 @1064nm). Detailed DFT calculations have been performed to elucidate the structure-property relationships. This work provides a new example of discovering novel UV NLO selenite materials.

Mechanisms shaping the gypsum stromatolite-like structures in the Salar de Llamara (Atacama Desert, Chile)

The explanation of the origin of microbialites and specifically stromatolitic structures is a problem of high relevance for decoding past sedimentary environments and deciphering the biogenicity of the oldest plausible remnants of life. We have investigated the morphogenesis of gypsum stromatolite-like structures currently growing in shallow ponds (puquíos) in the Salar de Llamara (Atacama Desert, Northern Chile). The crystal size, aspect ratio, and orientation distributions of gypsum crystals within the structures have been quantified and show indications for episodic nucleation and competitive growth of millimetric to centimetric selenite crystals into a radial, branched, and loosely cemented aggregate. The morphogenetical process is explained by the existence of a stable vertical salinity gradient in the ponds. Due to the non-linear dependency of gypsum solubility as a function of sodium chloride concentration, the salinity gradient produces undersaturated solutions, which dissolve gypsum crystals. This dissolution happens at a certain depth, narrowing the lower part of the structures, and producing their stromatolite-like morphology. We have tested this novel mechanism experimentally, simulating the effective dissolution of gypsum crystals in stratified ponds, thus providing a purely abiotic mechanism for these stromatolite-like structures.

James E. Talmage and the Selenite Crystals

James E. Talmage and the Selenite Crystals

Origin and palaeodepositional environment of evaporites in the Bala sub-basin, Central Anatolia, Türkiye

ABSTRACT Bala is located in Central Anatolia and is a sub-basin of the Tuzgölü basin, which consists of many basins formed in response to the closure of the Neotethys ocean. The evaporites in Bala sub-basin formed under the influence of regional uplifting during the Middle Eocene period with gradual shallowing in response to the structural compressional regime. The Bala sub-basin comprises four units from bottom to top: the Lower Unit (BU1) consisting of mudstone, claystone with limestone layers; the Evaporites (BU2) containing dominant gypsum with anhydrite; mixed siliciclastic-carbonate-evaporitic deposits (BU3); and the Upper Unit (BU4) containing conglomerate-sandstone-claystone and siltstones. The evaporitic unit, which are the main subject of study consists of primary selenitic gypsum, anhydrite, locally celestite crystals and secondary gypsum formed due to the anhydritization of primary gypsum and then hydration of these anhydrites. The results obtained from mineralogical-petrographic, geochemical and isotopic (δ18O and δ34S) investigations indicate that these evaporites were deposited in shallow marine to sabkha environments dominated by arid conditions. The presence of primary selenite crystals, the anhydrite with nodular, chicken-wire, and mosaic structures support precipitation occurred in a partially saline shallow water. The excessive thickness of the evaporitic accumulation, chaotic masses including gypsum breccia, salt diapirs and dome structures are attributed to tectonic processes acting during the formation of the Central Anatolian basins.

The Absolute Age and Origin of the Giant Gypsum Geode of Pulpí (Almería, SE Spain)

Subaqueous gypsum (CaSO4·2H2O) crystals are relatively common in epithermal systems where sulfide ore deposits are present. The Giant Geode of Pulpí (Almería, SE Spain) hosts some of the largest (up to 2 m in length) subaqueous gypsum crystals discovered to date. Here, we present the first U-series ages of its crystals and reconstruct the oxygen and hydrogen isotopic composition (δ18O and δ2H) of the Pulpí paleo-aquifer from which the crystals formed by using stable isotopes of gypsum hydration water. We successfully dated the onset of gypsum precipitation in the Geode at 164 ± 15 ka. However, the extremely low U concentration (11 ppb) and relatively high detrital Th content (230Th/232Th 3.2) hinder accurate dating other gypsum samples. The δ18O and δD values of the paleo-aquifer during the growth of the crystals aligned with the local meteoric water line, suggesting that the sulfate-enriched mother solution consisted of meteoric water that recharged the aquifer during that period. The mean isotopic composition of the Pulpí paleo-aquifer (δ18O = −6.5 ± 0.1‰ and δ2H = −42.3 ± 0.5‰) during the formation of the crystals was similar to the current groundwater in this area (δ18O = −6.1 ± 0.8‰, δ2H = −42 ± 6‰). The isotopic differences observed in samples collected from distinct locations and in individual crystals were probably related to changes in the isotopic composition of the aquifer, as a consequence of varying climate that impacted on the isotopic composition of rainwater during thousands of years in this region. Our results indicated that subaqueous selenite crystals may be useful for paleo-hydrological reconstructions. However, improving the current analytical techniques for dating gypsum with low U concentrations will be essential to obtain accurate and reliable records from Quaternary gypsum cave crystals in the future.

A Messinian Gypsum Deposit in the Ionian Forearc Basin (Benestare, Calabria, Southern Italy): Origin and Paleoenvironmental Indications

This study reports the first accurate record of the Messinian Resedimented Gypsum in the forearc and back-arc basins connected to the Calabrian-Peloritan orogen. A multidisciplinary approach has been used to investigate a gypsum deposit located in the Benestare’s area (Calabria, Southern Italy). Such deposit is made of bedded gypsrudites displaying clastic selenite with chaotical textures. On the top, the gypsrudites are interspersed with gypsum lenses belonging to the branching-like facies. Despite these two facies seem different macroscopically, they show petrographic features, fluid inclusions, organic matter and Strontium isotopic values very similar to each other. On the other hand, both facies show fractured and folded crystals. Crystals are only locally corroded and preserve primary structure relict as well as allochthonous (organic debris) and autochthonous putative microbial remains. All crystals are rich in fluid inclusions but these are visibly affected by stretching and leaking (re-equilibration processes) suggesting a moderate plastic deformation during re-sedimentation and subsequent burial. Minimal transport of the deposit is testified by subangular shapes of the gypsum crystals. The gypsrudite and branching-like facies reveal an 87Sr/86Sr average value of 0.709045 and 0.709082, respectively. These values suggest a strong connection with the global Ocean and reduced freshwater input. The Benestare’s deposit originated from the partial to complete dismantling of selenite crystals related to the first stage (5.97–5.60 Ma) of the Messinian Salinity Crisis through gravitational collapse due to local controlling factors.

Two-dimensional bimetallic CoFe selenite via metal-ion assisted self-assembly for enhanced oxygen evolution reaction

A 2D CoFe selenite crystals was used as an efficient OER catalyst, which was obtained in a high yield via a simple metal-ion self-assembly strategy under hydrothermal condition.

The origin of large gypsum crystals in the Geode of Pulpí (Almería, Spain)

Abstract The Geode of Pulpí (Almería, Spain) is an ∼11 m3 ovoid cavity, the walls of which are covered with meter-sized idiomorphic and highly transparent gypsum (CaSO4●2H2O) crystals. We performed a thorough study based on field work, and petrographic and geochemical data collection, which aimed to reconstruct the geological history leading to the formation of this geode. The geode is hosted in mineralized Triassic carbonate rocks with a discontinuous mineral sequence from iron-carbonates and barite to celestine and finally gypsum (microcrystalline and selenite). Data from fluid inclusions show that barite precipitated above 100 °C, celestine at ∼70 °C, and gypsum below 25 °C. All δ34S sulfate phases fall between Triassic and Tertiary evaporite values. Barite and gypsum, either microcrystalline or large selenite crystals, show variable δ34S and δ18O compositions, whereas celestine and centimetric selenite gypsum have homogeneous values. We propose that the growth of the large selenite crystals in the Geode of Pulpí was the result of a self-feeding mechanism consisting of isovolumetric anhydrite replacement by gypsum at a temperature of 20 ± 5 °C, episodically contributed by a ripening process enhanced by temperature oscillations due to climatic change.

Messinian twinned selenite from the Catanzaro Trough, Calabria, Southern Italy: field, petrographic and fluid inclusion perspectives

Field, petrographic and fluid inclusions (FIs) studies are used to investigate the formation of Miocene twinned selenite crystals from the Catanzaro Trough (Calabria, Southern Italy). The selenite was formed during the Messinian salinity crisis (MSC) (~ 6 Ma) and is classified into three facies: giant selenite, banded selenite and massive curvilinear selenite. Petrographic studies revealed the presence of alternating growth intervals (i.e. cloudy and clear intervals) in the selenite crystals that are occasionally separated by transition zones (intermediate interval). The giant selenite facies has cloudy intervals rich in primary FIs and organic matter; transition zones with lower abundances of FIs and organic matter have been observed, while clear zones are devoid of FIs. The banded selenite facies has cloudy and clear zones and relatively low abundances of organic matter. The massive selenite facies has cloudy zones with abundant primary FIs and organic matter and clear zones with low abundances of FIs and organic matter. These transition zones may have formed in response to daily or seasonal climate change oscillations, which in turn triggered alternations in selenite growth rates, in tandem with variations in biological activity and salinities. Microthermometric analyses have highlighted a salinity range between 0.18 and 11.34 eq. wt% NaCl. This indicates that the selenite precipitated from brines with a significant proportion of nonmarine waters. This study helps to place the Calabrian selenite into the interpretive framework of the MSC. The results of this study will contribute to a better understanding of the sedimentary processes active during the Messinian evolution of the northeastern sector of the Catanzaro Trough.

Naica’s Giant Crystals: Deterioration Scenarios

The Cave of Giant Crystals of Naica (Chihuahua, Mexico) is a world geological treasure worth to be preserved. These crystals of up to 12 m in length are made of selenite, the macrocrystalline variety of gypsum (CaSO4·2H2O). They have grown for thousands of years until the cave was dried, which allowed the cave and the crystals to be accessible, but exposed their surfaces in contact with air. Gypsum crystals are fragile because of their trend to dehydrate, the possible replacement to CaCO3 upon reactions with atmospheric CO2 as well as their intrinsic mechanical properties. Several laboratory experiments, designed to study the deterioration of selenite crystals under different artificial atmospheric conditions, are presented. Four atmospheric compositions rich in CO2, CH4, NOx, and air were tested for 1 year at temperatures of 25 and 60 °C and in either liquid or gaseous environments. The surface evolution was monitored by optical microscopy, infrared spectrometry, and grazing incidence X-ray diffraction w...

The Caves of Naica: a decade of research

The caves of the Naica Mine have been the subject of study by scientists from up to seven counties over the past decade. Up to fifty research works have published to date, most relating to the origin of the giant selenite crystals of the Cueva de los Cristales. Nevertheless, a great deal of knowledge has been generated about other relevant aspects of the Naica system. This paper puts together the vast information available about the Naica caves, from the discovery of the Cueva de los Cristales in 2000 to the more recent investigations addressing mineralogy, microclimatology and the use of gypsum speleothems as a palaeo-environmental proxy. Special attention has been paid to novel research lines that have started to use the speleothems of Naica as a study case, particularly in fields such as Astrobiology and Planetary geology. Moreover, the conservation challenges which these caves will face in the near future as consequence of the end of mining activities have also been addressed in this article.

Unraveling the Sulfate Sources of (Giant) Gypsum Crystals Using Gypsum Isotope Fractionation Factors

We combine newly determined isotope fractionation factors of gypsum precipitated in the laboratory with the isotopic compositions of natural anhydrite and gypsum to unravel the sulfate sources of the giant selenite crystals in the Naica mine (Chihuahua, Mexico). Gypsum was precipitated in the laboratory from CaSO4-NaCl-H2O solutions across a broad temperature range to establish the isotopic fractionation behavior of the sulfate molecule between the solid and dissolved phase. Oxygen isotopes show a significant fractionation dependence on temperature, with the solid phase more depleted in light isotopes with decreasing temperature. Sulfur isotopes display only a weak but similar dependence on temperature. At high salinity (4.5 M NaCl) no temperature dependence was found for the isotope composition. Based on this fractionation behavior, we attempt to elucidate the origin of the sulfate source(s) responsible for the formation of the (giant) gypsum crystals in the Naica mine. Detailed analysis of the isotopic composition of anhydrite, gypsum, and water samples strongly suggests that different types of anhydrite (of hypogenic and sedimentary origin) were dissolved to form these unique gypsum formations. The homogeneous isotopic composition of most gypsum crystals analyzed reveals an effective hydrodynamic mixing and a slow kinetics of precipitation fed by solutions of calcium sulfate from different anhydrite sources.

Sedimentologic to metamorphic processes recorded in the high-pressure/low-temperature Mesozoic Rosetta Marble of Anatolia

Anatolia’s high-pressure metamorphic belts are characterized in part by a Neotethyan stratigraphic succession that includes a mid-Cretaceous hemi-pelagic marble sequence. This unit contains, towards its stratigraphic top, dm-to-m-long radiating calcitic rods forming rosette-like textures. Here, we refer to these features as “Rosetta Marble”. The remarkable textural similarity of non-metamorphic selenite crystals and radiating calcite rods in the Rosetta Marble strongly suggests that these textures represent pseudomorphs after selenites. Metamorphosed hemi-pelagic limestones, dominated by Rosetta selenite pseudomorphs, are alternating with siliceous meta-sediments containing relictic radiolaria tests. This stratigraphic pattern is indicative of transient phases characterized by evaporites precipitated from basinal brines alternating with non-evaporative hemi-pelagic deposition from normal-marine seawater. The regional distribution of Rosetta Marble exposures over 600 km is indicative of basin-scale evaporitic intervals. High-pressure, low-temperature metamorphism of these rocks is witnessed by Sr-rich (up to 3500 ppm), fibrous calcite pseudomorphs after aragonite and isolated aragonite inclusions in quartz. Peak metamorphic conditions of 1.2 GPa and 300–350 °C are attested by high-Si white mica thermobarometry. The Rosetta Marble case example examines the potential to unravel the complete history from deposition to diagenesis and metamorphism of meta-sedimentary rocks.

Origin of surface impurities on the Cave of Swords selenite crystals at Naica

The Cave of Swords was discovered in 1910 at Naica mine, Chihuahua, Mexico. Its name refers to the look of the 1-2 m long crystals the cave had when it was discovered. Currently the crystals are 0.1-0.3 m long. The crystals surface is opaque and ocher. For over 100 years these crystals continue to amaze and give us clues about their formation. This work is part of a research aimed at the conservation of the Naica Giant Crystals. Thirteen samples from the Cave of Swords were analyzed by Scanning Electron Microscopy with Energy Dispersive Spectroscopy (SEM-EDS), Confocal Laser Microscopy with Differential Interference Contrast (LCM-DIM) and Transmission Electron Microscopy (TEM). X-Ray Fluorescence (μ-XRF) together with X-ray Absorption Near Edge Structure (μ-XANES) and X-ray Photoelectron Spectroscopy (XPS) were employed for elemental analysis. For phase analysis, X-ray diffraction (XRD) in both symmetric and grazing incidence geometries (GI-XRD) and Micro electron diffraction at TEM were used. Impurities on crystals surfaces show a heterogeneous distribution of the present elements. The thickness of impurities ranges from 120 nm to 150 μm. The phases identified were (see figure) gypsum (1, 2, 3, 6, 9, 10, 13), hematite (4, 7, 8), sphalerite (14), chalcopyrite (11), cuprite (15), galena (5), alabandite (12), halite, fluorite and amorphous Pb and Mn oxy-hydroxides. Al, C, Ca, Cl, Cu, F, Fe, Mg, Mn, Na, O, Pb, S, Si and Zn elements were identified. A model for the origin of impurities follows: Selenite stopped growing when the solution became sub-saturated. Then, hematite was deposited as the main phase, which was dissolved or suspended in the solution. Hematite matrix served for the adsorption of other crystalline and amorphous phases. We concluded that humans have not produced the impurities, which are witnesses of the gypsum crystals formation. Acknowledgment: Stanford Synchrotron Radiation Lightsource, Harvard Museum of Natural History and CONACYT CB-183706.

Did Late Miocene (Messinian) gypsum precipitate from evaporated marine brines? Insights from the Piedmont Basin (Italy)

During the first stage of the Late Miocene Messinian salinity crisis (5.97–5.60 Ma), deposition of sulfates (the Primary Lower Gypsum) occurred in shallow silled peripheral subbasins of the Mediterranean undergoing restricted water exchange with the Atlantic Ocean. Fluid inclusions in Messinian selenite crystals from the Piedmont Basin (northwest Italy) have surprisingly low salinities (average of 1.6 wt% NaCl equivalent), suggesting that parent waters were depleted in Na + and Cl – compared to modern seawater. Modern gypsum from a Mediterranean salt work, in contrast, contains fluid inclusions with elevated salinities that match the normal evaporation trend expected for seawater. The salinity data indicate that the Messinian sulfate deposits from the Piedmont Basin formed from hybrid parent waters: seawater mixed with Ca 2+ and SO 4 2– enriched freshwaters that dissolved coeval marginal marine gypsum. Such mixed parent waters and complex recycling processes should be taken into account when explaining the genesis of other Messinian gypsum deposits across the Mediterranean Basin.

Microstructure and geochemistry studies on Messinian gypsum deposits from the Northern Coast of Egypt

Messinian gypsum deposits from Dir El-Baraqan area, Northern Coast of Egypt, were investigated by stable sulfur isotope method, X-ray diffraction, infrared spectroscopy, optical microscopy, and scanning electron microscopy to differentiate features formed under substantial microbial influences as indicator of paleoenvironments. Petrographically, gypsum deposits were classified into three types: biolaminated gypsum, disordered selenite, and swallow-tail selenitic crystals. Biolaminated gypsum is characterized by regular alternating dark and light laminae, which were formed due to the seasonal environmental changes in Dir El-Baraqan area. Stable sulfur isotope data show that the gypsum deposits are characterized by δ34S values ranging from +18.1 to +28.1 ‰. In swallow-tail gypsum, the δ34S values are characterized by a narrow range (from +20.0 to +20.2 ‰) which is considered as the primary phase. In biolaminated gypsum, the δ34S values ranged from +22.8 to +28.1 ‰ which is considered as the secondary phase. However, the white laminae are characterized by δ34S values ranging from +22.8 to +24.1 ‰, while dark laminae are characterized by δ34S values ranging from +27.2 to +28.1 ‰. The high δ34S values of dark laminae revealed the increasing activity of sulfate-reducing bacteria.

Preliminary U/Th dating and the evolution of gypsum crystals in Naica caves (Mexico)

The origin and the evolution of giant selenite crystals in Naica caves, together withthe understanding of their growthmechanisms, is one of the aims of the international multidisciplinary research, called the “Naica Project”. In this context, the exact timing of when the gypsum nucleation started and whether its growthhas been constant over time, have been investigated. The preliminary data obtained withthe U–Th disequilibrium method show significant differences in ages for gypsum (between 191 ± 13 kyr for one of the Ojo de la Reina cave crystals and 57 ± 1.7 kyr for the base of Espadas cave’s spar) and have produced a coarse chronological interval of growth. The crystal depositional rates vary from 0.56 to 1.22 mm/kyr, in excellent agreement withthe laboratory tests for gypsum deposition under present conditions performed in the deepest part of the mine. These results are also consistent witha multistage precipitation started at different times in the Naica caves (first in caves at the upper level, where gypsum was subsequently dissolved, and only later in the deeper part of the aquifer under stable conditions) and allow us to improve the knowledge on the speleogenetic evolution of these caves.