Silicic volcanism on Mars evidenced by tridymite in high-SiO2 sedimentary rock at Gale crater.

Tridymite, a low-pressure, high-temperature (>870 °C) SiO2 polymorph, was detected in a drill sample of laminated mudstone (Buckskin) at Marias Pass in Gale crater, Mars, by the Chemistry and Mineralogy X-ray diffraction instrument onboard the Mars Science Laboratory rover Curiosity The tridymitic mudstone has ∼40 wt.% crystalline and ∼60 wt.% X-ray amorphous material and a bulk composition with ∼74 wt.% SiO2 (Alpha Particle X-Ray Spectrometer analysis). Plagioclase (∼17 wt.% of bulk sample), tridymite (∼14 wt.%), sanidine (∼3 wt.%), cation-deficient magnetite (∼3 wt.%), cristobalite (∼2 wt.%), and anhydrite (∼1 wt.%) are the mudstone crystalline minerals. Amorphous material is silica-rich (∼39 wt.% opal-A and/or high-SiO2 glass and opal-CT), volatile-bearing (16 wt.% mixed cation sulfates, phosphates, and chlorides-perchlorates-chlorates), and has minor TiO2 and Fe2O3T oxides (∼5 wt.%). Rietveld refinement yielded a monoclinic structural model for a well-crystalline tridymite, consistent with high formation temperatures. Terrestrial tridymite is commonly associated with silicic volcanism, and detritus from such volcanism in a "Lake Gale" catchment environment can account for Buckskin's tridymite, cristobalite, feldspar, and any residual high-SiO2 glass. These cogenetic detrital phases are possibly sourced from the Gale crater wall/rim/central peak. Opaline silica could form during diagenesis from high-SiO2 glass, as amorphous precipitated silica, or as a residue of acidic leaching in the sediment source region or at Marias Pass. The amorphous mixed-cation salts and oxides and possibly the crystalline magnetite (otherwise detrital) are primary precipitates and/or their diagenesis products derived from multiple infiltrations of aqueous solutions having variable compositions, temperatures, and acidities. Anhydrite is post lithification fracture/vein fill.

The origin and implications of clay minerals from Yellowknife Bay, Gale crater, Mars.

The Mars Science Laboratory (MSL) rover Curiosity has documented a section of fluvio-lacustrine strata at Yellowknife Bay (YKB), an embayment on the floor of Gale crater, approximately 500 m east of the Bradbury landing site. X-ray diffraction (XRD) data and evolved gas analysis (EGA) data from the CheMin and SAM instruments show that two powdered mudstone samples (named John Klein and Cumberland) drilled from the Sheepbed member of this succession contain up to ~20 wt% clay minerals. A trioctahedral smectite, likely a ferrian saponite, is the only clay mineral phase detected in these samples. Smectites of the two samples exhibit different 001 spacing under the low partial pressures of H2O inside the CheMin instrument (relative humidity <1%). Smectite interlayers in John Klein collapsed sometime between clay mineral formation and the time of analysis to a basal spacing of 10 Å, but largely remain open in the Cumberland sample with a basal spacing of ~13.2 Å. Partial intercalation of Cumberland smectites by metal-hydroxyl groups, a common process in certain pedogenic and lacustrine settings on Earth, is our favored explanation for these differences. The relatively low abundances of olivine and enriched levels of magnetite in the Sheepbed mudstone, when compared with regional basalt compositions derived from orbital data, suggest that clay minerals formed with magnetite in situ via aqueous alteration of olivine. Mass-balance calculations are permissive of such a reaction. Moreover, the Sheepbed mudstone mineral assemblage is consistent with minimal inputs of detrital clay minerals from the crater walls and rim. Early diagenetic fabrics suggest clay mineral formation prior to lithification. Thermodynamic modeling indicates that the production of authigenic magnetite and saponite at surficial temperatures requires a moderate supply of oxidants, allowing circum-neutral pH. The kinetics of olivine alteration suggest the presence of fluids for thousands to hundreds of thousands of years. Mineralogical evidence of the persistence of benign aqueous conditions at YKB for extended periods indicates a potentially habitable environment where life could establish itself. Mediated oxidation of Fe2+ in olivine to Fe3+ in magnetite, and perhaps in smectites provided a potential energy source for organisms.

Crystallography Open Database (COD): an open-access collection of crystal structures and platform for world-wide collaboration.

Using an open-access distribution model, the Crystallography Open Database (COD, http://www.crystallography.net) collects all known 'small molecule / small to medium sized unit cell' crystal structures and makes them available freely on the Internet. As of today, the COD has aggregated ~150,000 structures, offering basic search capabilities and the possibility to download the whole database, or parts thereof using a variety of standard open communication protocols. A newly developed website provides capabilities for all registered users to deposit published and so far unpublished structures as personal communications or pre-publication depositions. Such a setup enables extension of the COD database by many users simultaneously. This increases the possibilities for growth of the COD database, and is the first step towards establishing a world wide Internet-based collaborative platform dedicated to the collection and curation of structural knowledge.

Discovery of the recoverable high-pressure iron oxide Fe4O5.

Phases of the iron-oxygen binary system are significant to most scientific disciplines, directly affecting planetary evolution, life, and technology. Iron oxides have unique electronic properties and strongly interact with the environment, particularly through redox reactions. The iron-oxygen phase diagram therefore has been among the most thoroughly investigated, yet it still holds striking findings. Here, we report the discovery of an iron oxide with formula Fe(4)O(5), synthesized at high pressure and temperature. The previously undescribed phase, stable from 5 to at least 30 GPa, is recoverable to ambient conditions. First-principles calculations confirm that the iron oxide here described is energetically more stable than FeO + Fe(3)O(4) at pressure greater than 10 GPa. The calculated lattice constants, equation of states, and atomic coordinates are in excellent agreement with experimental data, confirming the synthesis of Fe(4)O(5). Given the conditions of stability and its composition, Fe(4)O(5) is a plausible accessory mineral of the Earth's upper mantle. The phase has strong ferrimagnetic character comparable to magnetite. The ability to synthesize the material at accessible conditions and recover it at ambient conditions, along with its physical properties, suggests a potential interest in Fe(4)O(5) for technological applications.

Calcioferrite with composition (Ca3.94Sr0.06)Mg1.01(Fe2.93Al1.07)(PO4)6(OH)4·12H2O.

Calcioferrite, ideally Ca4MgFe(3+) 4(PO4)6(OH)4·12H2O (tetra-calcium magnesium tetrairon(III) hexakis-phosphate tetra-hydroxide dodeca-hydrate), is a member of the calcioferrite group of hydrated calcium phosphate minerals with the general formula Ca4 AB 4(PO4)6(OH)4·12H2O, where A = Mg, Fe(2+), Mn(2+) and B = Al, Fe(3+). Calcioferrite and the other three known members of the group, montgomeryite (A = Mg, B = Al), kingsmountite (A = Fe(2+), B = Al), and zodacite (A = Mn(2+), B = Fe(3+)), usually occur as very small crystals, making their structure refinements by conventional single-crystal X-ray diffraction challenging. This study presents the first structure determination of calcioferrite with composition (Ca3.94Sr0.06)Mg1.01(Fe2.93Al1.07)(PO4)6(OH)4·12H2O based on single-crystal X-ray diffraction data collected from a natural sample from the Moculta quarry in Angaston, Australia. Calcioferrite is isostructural with montgomeryite, the only member of the group with a reported structure. The calcioferrite structure is characterized by (Fe/Al)O6 octa-hedra (site symmetries 2 and -1) sharing corners (OH) to form chains running parallel to [101]. These chains are linked together by PO4 tetra-hedra (site symmetries 2 and 1), forming [(Fe/Al)3(PO4)3(OH)2] layers stacking along [010], which are connected by (Ca/Sr)(2+) cations (site symmetry 2) and Mg(2+) cations (site symmetry 2; half-occupation). Hydrogen-bonding inter-actions involving the water mol-ecules (one of which is equally disordered over two positions) and OH function are also present between these layers. The relatively weaker bonds between the layers account for the cleavage of the mineral parallel to (010).

Dehydration kinetics of nanoconfined water in beryl probed by high temperature single crystal synchrotron X-ray diffraction.

Understanding changes in material properties through external stimuli plays a key role in validating the expected performance of materials and engineering material properties in a controlled manner. Here, we introduce a fundamental protocol to deduce dehydration reactions kinetics of water confined in nanopore channels, with the cyclosilicate beryl as the scaffold of interest, using time-resolved synchrotron X-ray diffraction (SXRD), in the temperature interval of 298-1038 K. The temperature-dependent intensity ( I ) of the strongest reflection (112) was used as the crystallite variable. An estimation of an isobaric thermal crystallite coefficient, k , analogous with the isobaric thermal expansion coefficient, established the rate of relative crystallization as a function of temperature, ∂ I ∂ T . A plot of lnk and 1 T gives rise to two kinetic steps, indicating a slow dehydration stage up to ~ 700 K and a fast dehydration stage up to the investigated temperature 1038 K. The crystal structure of beryl determined up to 1038 K, in temperature increment as small as 10 K, indicates the presence of channel ions Na and Fe and a gradual decrease of water upon heating.

Molecular assembly indices of mineral heteropolyanions: some abiotic molecules are as complex as large biomolecules.

Molecular assembly indices, which measure the number of unique sequential steps theoretically required to construct a three-dimensional molecule from its constituent atomic bonds, have been proposed as potential biosignatures. A central hypothesis of assembly theory is that any molecule with an assembly index ≥15 found in significant local concentrations represents an unambiguous sign of life. We show that abiotic molecule-like heteropolyanions, which assemble in aqueous solution as precursors to some mineral crystals, range in molecular assembly indices from 2 for H2CO3 or Si(OH)4 groups to as large as 21 for the most complex known molecule-like subunits in the rare minerals ewingite and ilmajokite. Therefore, values of molecular assembly indices ≥15 do not represent unambiguous biosignatures.

Schaurteite, Ca(3)Ge(SO(4))(2)(OH)(6)·3H(2)O.

This report presents the first crystal structure determination of the mineral schaurteite, ideally Ca(3)Ge(SO(4))(2)(OH)(6)·3H(2)O, tricalcium germanium bis-(sulfate) hexa-hydroxide trihydrate. This single-crystal X-ray diffraction study investigated a natural sample from the type locality at Tsumeb, Namibia. Schaurteite is a member of the fleischerite group of minerals, which also includes fleischerite, despujolsite, and mallestigite. The structure of schaurteite consists of slabs of Ca(O,OH,H(2)O)(8) polyhedra (site symmetry mm2) inter-leaved with a mixed layer of Ge(OH)(6) octa-hedra (-3m.) and SO(4) tetra-hedra (3m.). There are two H atoms in the asymmetric unit, both located by full-matrix refinement, and both forming O-H⋯O hydrogen bonds.

Penikisite, BaMg(2)Al(2)(PO(4))(3)(OH)(3), isostructural with bjarebyite.

The bjarebyite group of minerals, characterized by the general formula BaX(2)Y(2)(PO(4))(3)(OH)(3), with X = Mg, Fe(2+) or Mn(2+), and Y = Al or Fe(3+), includes five members: bjarebyite BaMn(2+) (2)Al(2)(PO(4))(3)(OH)(3), johntomaite BaFe(2+) (2)Fe(3+) (2)(PO(4))(3)(OH)(3), kulanite BaFe(2+) (2)Al(2)(PO(4))(3)(OH)(3), penikisite BaMg(2)Al(2)(PO(4))(3)(OH)(3), and perloffite BaMn(2+) (2)Fe(3+) (2)(PO(4))(3)(OH)(3). Thus far, the crystal structures of all minerals in the group, but penikisite, have been determined. The present study reports the first structure determination of penikisite (barium dimagnesium dialuminium triphosphate trihydroxide) using single-crystal X-ray diffraction data of a crystal from the type locality, Mayo Mining District, Yukon Territory, Canada. Penikisite is isotypic with other members of the bjarebyite group with space group P2(1)/m, rather than triclinic (P1 or P-1), as previously suggested. Its structure consists of edge-shared [AlO(3)(OH)(3)] octa-hedral dimers linking via corners to form chains along [010]. These chains are decorated with PO(4) tetra-hedra (one of which has site symmetry m) and connected along [100] via edge-shared [MgO(5)(OH)] octa-hedral dimers and eleven-coordinated Ba(2+) ions (site symmetry m), forming a complex three-dimensional network. O-H⋯O hydrogen bonding provides additional linkage between chains. Microprobe analysis of the crystal used for data collection indicated that Mn substitutes for Mg at the 1.5% (apfu) level.

Redetermination of katayamalite, KLi3Ca7Ti2(SiO3)12(OH)2.

The crystal structure of katayamalite, ideally KLi3Ca7Ti2(SiO3)12(OH)2 (potassium trilithium hepta-calcium dititanium dodeca-silicate di-hydroxide), was previously reported in triclinic symmetry (C-1), with isotropic displacement parameters for all atoms and without the H-atom position [Kato & Murakami (1985 ▶). Mineral. J. 12, 206-217]. The present study redetermines the katayamalite structure with monoclinic symmetry (space group C2/c) based on single-crystal X-ray diffraction data from a sample from the type locality, Iwagi Island, Ehime Prefecture, Japan, with anisotropic displacement parameters for all non-H atoms, and with the H atoms located by difference Fourier analysis. The structure of katayamalite contains a set of six-membered silicate rings inter-connected by sheets of Ca atoms on one side and by an ordered mixture of Li, Ti and K atoms on the other side, forming layers which are stacked normal to (001). From the eight different metal sites, three are located on special positions, viz. one K and one Li atom on twofold rotation axes and one Ca atom on an inversion center. The Raman spectrum of kataymalite shows a band at 3678 cm(-1), similar to that observed for hydroxyl-amphiboles, indicating no or very weak hydrogen bonding.

Agardite-(Y), Cu(2+) 6Y(AsO4)3(OH)6·3H2O.

Agardite-(Y), with a refined formula of Cu(2+) 5.70(Y0.69Ca0.31)[(As0.83P0.17)O4]3(OH)6·3H2O [ideally Cu(2+) 6Y(AsO4)3(OH)6·3H2O, hexa-copper(II) yttrium tris-(arsenate) hexa-hydroxide trihydrate], belongs to the mixite mineral group which is characterized by the general formula Cu(2+) 6 A(TO4)3(OH)6·3H2O, where nine-coordinated cations in the A-site include rare earth elements along with Al, Ca, Pb, or Bi, and the T-site contains P or As. This study presents the first structure determination of agardite-(Y). It is based on the single-crystal X-ray diffraction of a natural sample from Jote West mine, Pampa Larga Mining District, Copiapo, Chile. The general structural feature of agardite-(Y) is characterized by infinite chains of edge-sharing CuO5 square pyramids (site symmetry 1) extending down the c axis, connected in the ab plane by edge-sharing YO9 polyhedra (site symmetry -6..) and corner-sharing AsO4 tetra-hedra (site symmetry m..). Hy-droxyl groups occupy each corner of the CuO5-square pyramids not shared by a neighboring As or Y atom. Each YO9 polyhedron is surrounded by three tubular channels. The walls of the channels, parallel to the c axis, are six-membered hexa-gonal rings comprised of CuO5 and AsO4 polyhedra in a 2:1 ratio, and contain free mol-ecules of lattice water.

Lanthanite-(Nd), Nd2(CO3)3·8H2O.

Lanthanite-(Nd), ideally Nd2(CO3)3·8H2O [dineodymium(III) tricarbonate octa-hydrate], is a member of the lanthanite mineral group characterized by the general formula REE2(CO3)3·8H2O, where REE is a 10-coordinated rare earth element. Based on single-crystal X-ray diffraction of a natural sample from Mitsukoshi, Hizen-cho, Karatsu City, Saga Prefecture, Japan, this study presents the first structure determination of lanthanite-(Nd). Its structure is very similar to that of other members of the lanthanite group. It is composed of infinite sheets made up of corner- and edge-sharing of two NdO10-polyhedra (both with site symmetry ..2) and two carbonate triangles (site symmetries ..2 and 1) parallel to the ab plane, and stacked perpendicular to c. These layers are linked to one another only through hydrogen bonding involving the water mol-ecules.

Pirquitasite, Ag(2)ZnSnS(4).

Pirquitasite, ideally Ag(2)ZnSnS(4) (disilver zinc tin tetra-sulfide), exhibits tetra-gonal symmetry and is a member of the stannite group that has the general formula A(2)BCX(4), with A = Ag, Cu; B = Zn, Cd, Fe, Cu, Hg; C = Sn, Ge, Sb, As; and X = S, Se. In this study, single-crystal X-ray diffraction data are used to determine the structure of pirquitasite from a twinned crystal from the type locality, the Pirquitas deposit, Jujuy Province, Argentina, with anisotropic displacement parameters for all atoms, and a measured composition of (Ag(1.87)Cu(0.13))(Zn(0.61)Fe(0.36)Cd(0.03))SnS(4). One Ag atom is located on Wyckoff site Wyckoff 2a (symmetry -4..), the other Ag atom is statistically disordered with minor amounts of Cu and is located on 2c (-4..), the (Zn, Fe, Cd) site on 2d (-4..), Sn on 2b (-4..), and S on general site 8g. This is the first determination of the crystal structure of pirquitasite, and our data indicate that the space group of pirquitasite is I-4, rather than I-42m as previously suggested. The structure was refined under consideration of twinning by inversion [twin ratio of the components 0.91 (6):0.09 (6)].

Predicting new mineral occurrences and planetary analog environments via mineral association analysis.

The locations of minerals and mineral-forming environments, despite being of great scientific importance and economic interest, are often difficult to predict due to the complex nature of natural systems. In this work, we embrace the complexity and inherent "messiness" of our planet's intertwined geological, chemical, and biological systems by employing machine learning to characterize patterns embedded in the multidimensionality of mineral occurrence and associations. These patterns are a product of, and therefore offer insight into, the Earth's dynamic evolutionary history. Mineral association analysis quantifies high-dimensional multicorrelations in mineral localities across the globe, enabling the identification of previously unknown mineral occurrences, as well as mineral assemblages and their associated paragenetic modes. In this study, we have predicted (i) the previously unknown mineral inventory of the Mars analogue site, Tecopa Basin, (ii) new locations of uranium minerals, particularly those important to understanding the oxidation-hydration history of uraninite, (iii) new deposits of critical minerals, specifically rare earth element (REE)- and Li-bearing phases, and (iv) changes in mineralization and mineral associations through deep time, including a discussion of possible biases in mineralogical data and sampling; furthermore, we have (v) tested and confirmed several of these mineral occurrence predictions in nature, thereby providing ground truth of the predictive method. Mineral association analysis is a predictive method that will enhance our understanding of mineralization and mineralizing environments on Earth, across our solar system, and through deep time.

Redetermination of kovdorskite, Mg(2)PO(4)(OH)·3H(2)O.

The crystal structure of kovdorskite, ideally Mg(2)PO(4)(OH)·3H(2)O (dimagnesium phosphate hydroxide trihydrate), was reported previously with isotropic displacement paramaters only and without H-atom positions [Ovchinnikov et al. (1980 ▶). Dokl. Akad. Nauk SSSR.255, 351-354]. In this study, the kovdorskite structure is redetermined based on single-crystal X-ray diffraction data from a sample from the type locality, the Kovdor massif, Kola Peninsula, Russia, with anisotropic displacement parameters for all non-H atoms, with all H-atom located and with higher precision. Moreover, inconsistencies of the previously published structural data with respect to reported and calculated X-ray powder patterns are also discussed. The structure of kovdorskite contains a set of four edge-sharing MgO(6) octa-hedra inter-connected by PO(4) tetra-hedra and O-H⋯O hydrogen bonds, forming columns and channels parallel to [001]. The hydrogen-bonding system in kovdorskite is formed through the water mol-ecules, with the OH(-) ions contributing little, if any, to the system, as indicated by the long H⋯A distances (>2.50 Å) to the nearest O atoms. The hydrogen-bond lengths determined from the structure refinement agree well with Raman spectroscopic data.

Redetermination of junitoite, CaZn(2)Si(2)O(7)·H(2)O.

The crystal structure of the mineral junitoite, ideally CaZn(2)Si(2)O(7)·H(2)O (calcium dizinc disilicate monohydrate), was first determined by Hamilton & Finney [Mineral. Mag. (1985), 49, 91-95] based on the space group Ama2, yielding a reliability factor R of 0.10, with isotropic displacement parameters for all non-H atoms. The present study reports a structure redetermination of junitoite using single-crystal X-ray diffraction data from a natural sample, demonstrating that the space group of this mineral is actually Aea2, which can be attained simply by shifting the origin. Topologically, the structure models in the space groups Aea2 and Ama2 are analogous, consisting of chains of corner-sharing ZnO(4) tetra-hedra parallel to the b axis, cross-linked by Si(2)O(7) tetra-hedral dimers (the site symmetry of the bridging O atom is ..2) along a and c, forming a three-dimensional framework. The Ca(2+) cations (site symmetry ..2) are situated in cavities of the framework and are bonded to five O atoms and one H(2)O mol-ecule (site symmetry ..2) in a distorted octa-hedral coordination environment. However, some bond lengths, especially for the SiO(4) tetra-hedron, are noticeably different between the two structure models. Hydrogen bonding in junitoite is found between the water mol-ecule and a framework O atom.

Redetermination of clinobaryl-ite, BaBe(2)Si(2)O(7).

Clinobaryl-ite, ideally BaBe(2)Si(2)O(7) (chemical name barium diberyllium disilicate), is a sorosilicate mineral and dimorphic with baryl-ite. It belongs to a group of compounds characterized by the general formula BaM(2+) (2)Si(2)O(7), with M(2+) = Be, Mg, Fe, Mn, Zn, Co, or Cu, among which the Be-, Fe-, and Cu-members have been found in nature. The crystal structure of clinobaryl-ite has been re-examined in this study based on single-crystal X-ray diffraction data collected from a natural sample from the type locality (Khibiny Massif, Kola Peninsula, Russia). The structure of clinobaryl-ite can be considered as a framework of BeO(4) and SiO(4) tetra-hedra, with one of the O atoms coordinated to two Be and one Si, one coordinated to two Si, and two O atoms coordinated to one Si and one Be atom. The BeO(4) tetra-hedra share corners, forming chains parallel to the c axis, which are inter-linked by the Si(2)O(7) units oriented parallel to the a axis. The Ba(2+) cations (site symmetry m..) are in the framework channels and are coordinated by eleven O atoms in form of an irregular polyhedron. The Si-O(br) (bridging O atom, at site symmetry m..) bond length, the Si-O(nbr) (non-bridging O atoms) bond lengths, and the Si-O-Si angle within the Si(2)O(7) unit are in marked contrast to the corresponding values determined in the previous study [Krivovichev et al. (2004 ▶). N. Jb. Miner. Mh. pp. 373-384].

Lotharmeyerite, Ca(Zn,Mn)(2)(AsO(4))(2)(H(2)O,OH)(2).

Lotharmeyerite, calcium bis-(zinc/manganese) bis-(arsenate) bis-(hydroxide/hydrate), Ca(Zn,Mn(3+))(2)(AsO(4))(2)(H(2)O,OH)(2), is a member of the natrochalcite group of minerals, which are characterized by the general formula AM(2)(XO(4))(2)(H(2)O,OH)(2), where A may be occupied by Pb(2+), Ca(2+), Na(+), and Bi(3+), M by Fe(3+), Mn(3+), Cu(2+), Zn(2+), Co(2+), Ni(2+), Al(3+), and Mg(2+), and X by P(V), As(V), V(V), and S(VI). The minerals in the group display either monoclinic or triclinic symmetry, depending on the ordering of chemical components in the M site. Based on single-crystal X-ray diffraction data of a sample from the type locality, Mapimi, Durango, Mexico, this study presents the first structure determination of lotharmeyerite. Lotharmeyerite is isostructural with natrochalcite and tsumcorite. The structure is composed of rutile-type chains of edge-shared MO(6) octa-hedra (site symmetry [Formula: see text]) extending along [010], which are inter-connected by XO(4) tetra-hedra (site symmetry 2) and hydrogen bonds to form [M(2)(XO(4))(2)(OH,H(2)O)(2)] sheets parallel to (001). These sheets are linked by the larger A cations (site symmetry 2/m), as well as by hydrogen bonds. Bond-valence sums for the M cation, calculated with the parameters for Mn(3+) and Mn(2+) are 2.72 and 2.94 v.u., respectively, consistent with the occupation of the M site by Mn(3+). Two distinct hydrogen bonds are present, one with O⋯O = 2.610 (4) Šand the other O⋯O = 2.595 (3) Å. One of the H-atom positions is disordered over two sites with 50% occupancy, in agreement with observations for other natrochalcite-type minerals, such as natrochalcite and tsumcorite.

Pyrosmalite-(Fe), Fe(8)Si(6)O(15)(OH,Cl)(10).

Pyrosmalite-(Fe), ideally Fe(II) (8)Si(6)O(15)(OH,Cl)(10) [refined composition in this study: Fe(8)Si(6)O(15)(OH(0.814)Cl(0.186))(10)·0.45H(2)O, octa-iron(II) hexa-silicate deca-(chloride/hydroxide) 0.45-hydrate], is a phyllosilicate mineral and a member of the pyrosmalite series (Fe,Mn)(8)Si(6)O(15)(OH,Cl)(10), which includes pyrosmalite-(Mn), as well as friedelite and mcgillite, two polytypes of pyrosmalite-(Mn). This study presents the first structure determination of pyrosmalite-(Fe) based on single-crystal X-ray diffraction data from a natural sample from Burguillos del Cerro, Badajos, Spain. Pyrosmalite-(Fe) is isotypic with pyrosmalite-(Mn) and its structure is characterized by a stacking of brucite-type layers of FeO(6)-octa-hedra alternating with sheets of SiO(4) tetra-hedra along [001]. These sheets consist of 12-, six- and four-membered rings of tetra-hedra in a 1:2:3 ratio. In contrast to previous studies on pyrosmalite-(Mn), which all assumed that Cl and one of the four OH-groups occupy the same site, our data on pyrosmalite-(Fe) revealed a split-site structure model with Cl and OH occupying distinct sites. Furthermore, our study appears to suggest the presence of disordered structural water in pyrosmalite-(Fe), consistent with infrared spectroscopic data measured from the same sample. Weak hydrogen bonding between the ordered OH-groups that are part of the brucite-type layers and the terminal silicate O atoms is present.

High-pressure synthetic (Na(0.97)Mg(0.03))(Mg(0.43)Fe(0.17)Si(0.40))Si(2)O(6), with six-coordinated silicon, isostructural with P2/n omphacite.

The title compound, (sodium magnesium) [magnesium iron(III) silicon] disilicate, (Na(0.97)Mg(0.03))(Mg(0.43)Fe(0.17) (3+)Si(0.40))Si(2)O(6), is isotypic with ordered P2/n omphacite. Its structure is characterized by single chains of corner-sharing SiO(4) tetra-hedra, extending along the c axis, which are crosslinked by bands of edge-sharing octa-hedra (site symmetry 2), statistically occupied by (Mg(2+) + Fe(3+) + Si(4+)). Between the bands built up of the octahedra are two non-equivalent highly distorted six-coordinated sites (site symmetry 2), statistically occupied by (Na + Mg). In contrast to omphacites, the great differences in size and charge between Mg(2+) and Si(4+) result in complete, rather than partial, ordering of Mg and Si into two distinct octa-hedral sites, whereas Fe(3+) is disordered between the two sites. The octa-hedron filled by (Mg + Fe) is larger and markedly more distorted than that occupied by (Si + Fe). The average (Mg + Fe)-O and ((VI)Si + Fe)-O bond lengths are 2.075 and 1.850 Å, respectively.