Incorporation mechanism of Fe and Al into bridgmanite in a subducting mid-ocean ridge basalt and its crystal chemistry

The compositional difference between subducting slabs and their surrounding lower-mantle can yield the difference in incorporation mechanism of Fe and Al into bridgmanite between both regions, which should cause heterogeneity in physical properties and rheology of the lower mantle. However, the precise cation-distribution has not been examined in bridgmanites with Fe- and Al-contents expected in a mid-ocean ridge basalt component of subducting slabs. Here we report on Mg0.662Fe0.338Si0.662Al0.338O3 bridgmanite single-crystal characterized by a combination of single-crystal X-ray diffraction, synchrotron 57Fe-Mössbauer spectroscopy and electron probe microanalysis. We find that the charge-coupled substitution AMg2+ + BSi4+ ↔ AFe3+(high-spin) + BAl3+ is predominant in the incorporation of Fe and Al into the practically eightfold-coordinated A-site and the sixfold-coordinated B-site in bridgmanite structure. The incorporation of both cations via this substitution enhances the structural distortion due to the tilting of BO6 octahedra, yielding the unusual expansion of mean <A–O> bond-length due to flexibility of A–O bonds for the structural distortion, in contrast to mean <B–O> bond-length depending reasonably on the ionic radius effect. Moreover, we imply the phase-transition behavior and the elasticity of bridgmanite in slabs subducting into deeper parts of the lower mantle, in terms of the relative compressibility of AO12 (practically AO8) and BO6 polyhedra.

Coupled Substitutions in Natural MnO(OH) Polymorphs: Infrared Spectroscopic Investigation

Solid solutions involving natural Mn3+O(OH) polymorphs, groutite, manganite, and feitknechtite are characterized and discussed based on original and literature data on the chemical composition, powder and single-crystal X-ray diffraction, and middle-range IR absorption spectra of these minerals. It is shown that manganite forms two kinds of solid-solution series, in which intermediate members have the general formulae (i) (Mn4+, Mn3+)O(OH,O), with pyrolusite as the Mn4+O2 end-member, and (ii) (Mn3+, M2+)O(OH, H2O), where M = Mn or Zn. In Zn-substituted manganite from Kapova Cave, South Urals, Russia, the Zn2+:Mn3+ ratio reaches 1:1 (the substitution of Mn3+ with Zn2+ is accompanied by the coupled substitution of OH− with H2O). Groutite forms solid-solution series with ramsdellite Mn4+O2. In addition, the incorporation of OH− anions in the 1 × 2 tunnels of ramsdellite is possible. Feitknechtite is considered to be isostructural with (or structurally related to) the compounds (M2+, Mn3+)(OH, O)2 (M = Mn, Zn) with a pyrochroite-related layered structure.

Influence of Pr3+ and CO32− Ions Coupled Substitution on Structural, Optical and Antibacterial Properties of Fluorapatite Nanopowders Obtained by Precipitation

Coupled substitution of fluorapatite (FAP) crystal lattice plays an important role in the engineering of optically active nanomaterials. Uniform fluorapatite nanopowders doped with praseodymium (Pr3+) and carbonate (CO32−) ions have been successfully synthesized by precipitation method under room temperature (25 °C). The structural, morphological, chemical and optical properties of monophase material were characterized by X-ray diffraction (XRD), Fourier Transform Infrared and Far Infrared Spectroscopy (FTIR and FIR, respectively), Scanning Electron Microscopy with Energy Dispersive Spectroscopy (SEM/EDS), Transmission Electron Microscopy (TEM) and Photoluminescence Spectroscopy (PL). Coupled substitution of FAP crystal lattice with Pr3+ and CO32− reduces the crystallite size with a constant c/a ratio of 1.72. FTIR study showed that synthesized nanopowders were AB-type CO32− substitution, and FIR study revealed new Pr–O vibrations. TEM analysis was found that synthesized nanopowders were composed of irregular spheres in the nanometer range. The fluorescence of FAP nanoparticles was in the violet-blue region of the visible part of the spectrum. When Pr3+ was doped in a lattice, the violet-blue emission becomes sharper due to reabsorption. MCR–ALS analyses of fluorescence spectra indicated the shift of the maximum to the blue color with the increase in the concentration of Pr3+ ions. Additionally, luminescent nanopowders demonstrated significant antibacterial activity against Escherichia coli. As the obtained nanoparticles showed a good absorption of ultraviolet A light and reabsorption of blue-green luminescence, they are suitable for further development of optically active nanomaterials for light filtering. Optically active PrCFAP nanopowders with antibacterial properties may be promising additives for the development of multifunctional cosmetic and health care products.

Modulated Structures, Microstructures and Subsolidus Phase Relations of Labradorite Feldspars

The coupled substitution between Na+Si and Ca+Al, in the plagioclase solid solution, results in a continuous variation in the Al/Si ratio of the composition, which is the reason for the complicated ordering patterns in the intermediate plagioclase feldspars such as labradorite. Both fast-cooled and slow-cooled labradorite feldspars display the incommensurately modulated structures. The ordering pattern in the incommensurately modulated structures of e-plagioclase (characterized by the satellite diffraction peak called e-reflections) is the most complicated and intriguing. The modulated structure has a super-space group symmetry of X(αβγ)0, with a special centering condition of (½ ½ ½ 0), (0 0 ½ ½), (½ ½ 0 ½), and the q-vector has components (i.e., δh, δk, δl) along all three axes in reciprocal space. Displacive modulation, occupational modulation, and density modulation are observed in slowly cooled labradorite feldspars. No density modulation was observed in fast cooled (volcanic) labradorite feldspars. The amplitudes of the modulation waves are new parameters for quantifying the ordering state of labradorite. Iridescent labradorite feldspars display exsolution lamellae with an average periodicity ranging from ~150 nm to ~350 nm. Compositional difference between the lamellae is about 12 mole % in anorthite components. Areas or zones with red (or yellow) iridescent color (i.e., long lamellae periodicity) always contain more Ca (~1 to 3 mole %) than the areas with blue (or green) iridescent color within the same labradorite crystal. We proposed that the solvus for Bøggild intergrowth has a loop-like shape, ranging from ~An44 to ~An63. The Ca-rich side / zone has higher exsolution temperature than the Na-rich side / zone. The shapes of satellite peaks, the distances between e-reflections (modulation periods), and even the intensity of e-reflections may also be used to evaluate the ordering state or cooling rate of the plagioclase feldspar. Both modulated structure and the exsolution lamellae can be used as proxies for quantifying cooling rate of a labradorite and it’s host rock.

The Crystal Chemistry of Francolite in Akashat Phosphorites (Middle Paleocene), Iraqi Western Desert: الكيمياء البلورية لمعدن الفرانكولايت في فوسفورايت عكاشات (الباليوسين الأوسط)، الصحراء الغربية العراقية

The geochemical study of concentrated phosphatic grains show two main groups of elements, the first one represents (CaO, P2O5, F, CO3, SO3, Na, Sr and Cl) which are considered in determining the chemical formula of francolite, and are positively correlated with some trace elements (e.g. U, Y, REE, Cr, Mn and V). The second group of elements represents the clay minerals (palygorskite, sepiolite and montmorillonite). These minerals found in phosphatic grains in fractures and between coated layers by organic activity. This study suggests that the couple substitution of anions and cations for calcium, phosphorous and fluorine in francolite don't take place as coupled substitution but as open substitution of many anions and cations depending on the conformity in the coordination numbers of any site. In the same time, it is a compound substitution because of sharing many ions in the process. The decreasing in moles/formula of Na, S and Cl in the chemical formula of francolite indicates the slightly increasing in salinity and alkalinity of seawater. Sr reflects the effect of chemical composition of interstitial water on the francolite formation. CO3 mole/formula shows the role of the diagenesis process on the growth of francolite. The low Mg mole/formula reflects the consumption of magnesium in dolomite and clay minerals which enable the growth of phosphatic grains.

Trace elements in sulfides from the Maozu Pb-Zn deposit, Yunnan Province, China: Implications for trace-element incorporation mechanisms and ore genesis

The Sichuan-Yunnan-Guizhou Pb-Zn metallogenic province (SYGMP) is an important region for Pb-Zn resources in China. However, considerable controversy remains as to whether the Pb-Zn deposits are Mississippi Valley Type (MVT). The Maozu deposit, a typical example of the carbonate-hosted Pb-Zn deposits in the SYGMP, occurs in the late Ediacaran Dengying Formation and its ore bodies are divided into three types: lower layer (LL), vein layer (VL), and upper layer (UL) ore bodies based on their spatial relationship. In this study, laser ablation–inductively coupled plasma–mass spectrometry (LA-ICP-MS) was used to systematically analyze the trace-element compositions of sphalerite and galena in these three ore bodies. The results show that sphalerite is characterized by Cd and Ge enrichment; Fe, Mn, and Co depletion; and local In and Sn enrichment. Most of these elements likely appear as solid solutions in sphalerite and show a wide compositional variation, which is probably related to the medium- and low-temperature mixing of the ore-forming fluids. The local enrichment of In and Sn is likely attributed to the long-distance migration of ore-forming fluids through In-Sn-bearing volcaniclastic rocks. In vs. Sn and (Cu + Sb) vs. (Ag + Ge) show strong correlations and similar element distribution in the mapped images, indicating that these elements may be incorporated into sphalerite via a coupled substitution for Zn as 2In3+ + Sn4+ + 2☐ ↔ 5Zn2+ (☐ = vacancies) and 4(Cu+ + Sb3+) + (Ge4+ + 2Ag+) + 2☐ ↔ 13Zn2+. Galena is enriched in Ag and Sb with minor Cd and Se and depleted in Bi, and most of the elements may occur as solid solutions. Ag vs. Sb in galena displays a strong positive correlation, implying the coupled substitution of Ag+ + Sb3+ ↔ 2Pb2+. Notably, the majority of the trace-element concentrations gradually decrease in the order LL → UL except Fe, Co, Cu, and Ge, while Fe, In, and Sn in sphalerite and Ag and Sb in galena have the highest concentration in the VL, indicating that the VL is a secondary migration channel for the ore-forming fluids. Furthermore, the trace-element compositions of the sulfides in the Maozu Pb-Zn deposit are consistent with the typical MVT deposit (hosted in the carbonate sequence) but are markedly different from sedimentary exhalative (SEDEX), volcanogenic massive sulfide (VMS) and skarn-type deposits. Based on these results, as well as the geological and geochemical characteristics of the deposit, the Maozu Pb-Zn deposit is an MVT deposit.

Indium and Antimony Distribution in a Sphalerite from the “Burgstaetter Gangzug” of the Upper Harz Mountains Pb-Zn Mineralization

The sphalerite from the Burgstaetter Gangzug, a vein system of the Upper Harz Mountain nearby the town of Clausthal-Zellerfeld, exhibits a very interesting and partly complementary incorporation pattern of Cu, In and Sb, which has not yet been reported for natural sphalerite. A sphalerite specimen was characterized with electron probe micro-analysis (EPMA) and atom probe tomography (APT). Based on the EPMA results and a multilinear regression, a relation expressed as Cu = 0.98In + 1.81Sb + 0.03 can be calculated to describe the correlation between the elements. This indicates, that the incorporation mechanisms of In and Sb in the structure differ substantially. Indium is incorporated with the ratio Cu:In = 1:1 like in roquesite (CuInS2), supporting the coupled substitution mechanism 2Zn2+ → Cu+ + In3+. In contrast, Sb is incorporated with a ratio of Cu:Sb = 1.81:1. APT, which has a much higher spatial resolution indicates a ratio of Cu: Sb = 2.28: 1 in the entire captured volume, which is similar to the ratio calculated by EPMA, yet with inhomogeneities at the nanometer-scale. Analysis of the solute distribution shows two distinct sizes of clusters that are rich in Cu, Sb and Ag.

Micro- and nano-size hydrogarnet clusters and proton ordering in calcium silicate garnet: Part I. The quest to understand the nature of “water” in garnet continues

The calcium-silicate garnets, grossular (Ca3Al2Si3O12), andradite (Ca3Fe23+Si3O12), and their solid solutions [Ca3(Alx,Fe1−x3+)2Si3O12], can incorporate various amounts of structural OH–. This has important mineralogical, petrological, rheological, and geochemical consequences and extensive experimental investigations have focused on the nature of “water” in these phases. However, it was not fully understood how OH- was incorporated and this has seriously hampered the interpretation of different research results. IR single-crystal spectra of several nominally anhydrous calcium silicate garnets, both “end-member” and solid-solution compositions, were recorded at room temperature and 80 K between 3000 and 4000 cm–1. Five synthetic hydrogarnets in the system Ca3Al2(SiO4)3-Ca3Al2(H4O4)3-Ca3Fe23+(SiO4)3-Ca3Fe23+(H4O4)3 were also measured via IR ATR powder methods. The various spectra are rich in complexity and show several OH- stretching modes at wavenumbers between 3500 and 3700 cm–1. The data, together with published results, were analyzed and modes assigned by introducing atomic-vibrational and crystal-chemical models to explain the energy of the OH- dipole and the structural incorporation mechanism of OH-, respectively. It is argued that OH- is located in various local microscopic- and nano-size Ca3Al2H12O12- and Ca3Fe23+H12O12-like clusters. The basic substitution mechanism is the hydrogarnet one, where (H4O4)4– ↔ (SiO4)4–, and various local configurations containing different numbers of (H4O4)4– groups define the cluster type. Some spectra also possibly indicate the presence of tiny hydrous inclusion phases, as revealed by OH- modes above about 3670 cm–1. They were not recognized in earlier studies. Published proposals invoking different hypothetical “defects” and coupled-substitution mechanisms involving H+ are not needed to interpret the IR spectra, at least for OH- modes above about 3560 cm–1. Significant mineralogical, petrological, and geochemical consequences result from the analysis and are discussed in the accompanying Part II (this issue) of the investigation.

Coupled Substitutions of Minor and Trace Elements in Co-Existing Sphalerite and Wurtzite

The nature of couple substitutions of minor and trace element chemistry of expitaxial intergrowths of wurtzite and sphalerite are reported. EPMA and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analyses display significant differences in the bulk chemistries of the two epitaxial intergrowth samples studied. The sample from the Animas-Chocaya Mine complex of Bolivia is Fe-rich with mean Fe levels of 4.8 wt% for wurztite-2H and 2.3 wt% for the sphalerite component, while the sample from Merelani Hills, Tanzania, is Mn-rich with mean Mn levels in wurztite-4H of 9.1 wt% and for the sphalerite component 7.9 wt% In both samples studied the wurtzite polytype is dominant over sphalerite. LA-ICP-MS line scans across the boundaries between the wurtzite and sphalerite domains within the two samples show significant variation in the trace element chemistries both between and within the two coexisting polytypes. In the Merelani Hills sample the Cu+ + Ga3+ = 2Zn2+ substitution holds across both the wurztite and sphalerite zones, but its levels range from around 1200 ppm of each of Cu and Ga to above 2000 ppm in the sphalerite region. The 2Ag+ + Sn4+ = 3Zn2+ coupled substitution does not occur in the material. In the Animas sample, the Cu+ + Ga3+ = 2Zn2+ substitution does not occur, but the 2(Ag,Cu)+ + Sn4+ = 3Zn2+ substitution holds across the sample despite the obvious growth zoning, although there is considerable variation in the Ag/Cu ratio, with Ag dominant over Cu at the base of the sample and Cu dominant at the top. The levels of 2(Ag,Cu)+ + Sn4+ = 3Zn2+ vary greatly across the sample from around 200 ppm to 8000 ppm Sn, but the higher values occur in the sphalerite bands.

Sulfur-bearing monazite-(Ce) from the Eureka carbonatite, Namibia: oxidation state, substitution mechanism, and formation conditions

Sulfur-bearing monazite-(Ce) occurs in silicified carbonatite at Eureka, Namibia, forming rims up to ~0.5 mm thick on earlier-formed monazite-(Ce) megacrysts. We present X-ray photoelectron spectroscopy data demonstrating that sulfur is accommodated predominantly in monazite-(Ce) as sulfate, via a clino-anhydrite-type coupled substitution mechanism. Minor sulfide and sulfite peaks in the X-ray photoelectron spectra, however, also indicate that more complex substitution mechanisms incorporating S2– and S4+ are possible. Incorporation of S6+ through clino-anhydrite-type substitution results in an excess of M2+ cations, which previous workers have suggested is accommodated by auxiliary substitution of OH– for O2–. However, Raman data show no indication of OH–, and instead we suggest charge imbalance is accommodated through F– substituting for O2–. The accommodation of S in the monazite-(Ce) results in considerable structural distortion that may account for relatively high contents of ions with radii beyond those normally found in monazite-(Ce), such as the heavy rare earth elements, Mo, Zr and V. In contrast to S-bearing monazite-(Ce) in other carbonatites, S-bearing monazite-(Ce) at Eureka formed via a dissolution–precipitation mechanism during prolonged weathering, with S derived from an aeolian source. While large S-bearing monazite-(Ce) grains are likely to be rare in the geological record, formation of secondary S-bearing monazite-(Ce) in these conditions may be a feasible mineral for dating palaeo-weathering horizons.