The chromian spinels of the Lyavaraka ultrabasic complex, Serpentinite Belt, Kola Peninsula, Russia: Patterns of zoning, hypermagnesian compositions, and early oxidation

ABSTRACT The maximum value of Mg# [= 100Mg/(Mg + Fe2+ + Mn)] in chromium-bearing spinel-group minerals (Chr) in the Ultrabasic Core Zone (UCZ) of the Lyavaraka orthopyroxenite – harzburgite – dunite complex of the Serpentinite Belt in the Kola Peninsula is 54.5–67.5. Such highly magnesian compositions of spinel are associated with notable enrichments of ferric iron (Fe3+# 58–63). There are two generations of accessory Chr in the UCZ unit. The first generation occurs as inclusions in olivine that is not unusually magnesian (Mg# 90.3), and the second is closely associated with serpentine. The compositional series of Chr at Lyavaraka attains more aluminous compositions than was observed in nearby intrusive bodies. The anomalously high level of Mg in Chr, also manifest in ilmenite, is mainly a result of the high intrinsic fugacity of oxygen attained locally in the melt. A progressive buildup in H2O and increase in fO2 likely resulted from efficient vesiculation and selective loss of H2 from the Al-undepleted komatiitic magma crystallizing in a shallow setting. The chromian spinel forming in such a modified magma is virtually unzoned in Mn, and a minor quantity of Mn is also present in olivine and orthopyroxene. In contrast, zinc is strongly partitioned in the core of Chr, as it is relatively incompatible in the coexisting olivine and orthopyroxene at that stage. Zinc efficiently partitioned into the H2O-enriched melt, which crystallized as the pegmatitic orthopyroxenite near the contacts at Lyavaraka. A high potential of oxidation appears to be characteristic of all orthopyroxenite – harzburgite – dunite suites of the Serpentinite Belt formed from a primitive melt of komatiitic composition.

Insights into the Crystal Chemistry of the Serandite–Schizolite–Pectolite Series

ABSTRACT The compositional series {Na} [[M1+M2](Ca2XMn2–2X)Si3O8(OH)] includes the minerals serandite (X = 0), schizolite (X = 0.5), and pectolite (X = 1). Six crystals are structurally and chemically characterized in detail (four from Ilímaussaq, Greenland; two from Mont Saint-Hilaire, Québec, Canada): one serandite, one pectolite, and four schizolite crystals. Those originating from Greenland show up to 0.05 apfu LREE3+ (La + Ce + Pr + Nd + Eu + Gd). For each, all H atoms were located, and final R1 factors were below 4.4% (<R1> = 2.35%). The results are compared with previously published crystal structure data from an additional 16 samples, originating from worldwide (mostly) igneous environments. Across the series, for all investigated samples, Ca and Mn order preferentially at the octahedral M1 and M2 sites, respectively, following the exchange M2Ca + M1Mn ↔ M1Ca + M2Mn. Site-occupancies closely adhere to a two-site distribution coefficient, calculated here to be K = 20.0(5), for ideal mixing where activity coefficients approach unity. For the above order-disorder exchange, ΔHex is calculated to be –1.77 kcal. With knowledge of K, site assignment and species determination may be accurately made solely with compositional data, where 0 ≤ ΣCa < 0.55 apfu, serandite; 0.55 ≤ ΣCa < 1.45 apfu, schizolite; and 1.45 ≤ ΣCa ≤ 2 apfu, pectolite, with the dominant-constituent rule mandating M1Ca < M1Mn (M2Ca < M2Mn), serandite; M1Ca > M1Mn (M2Ca < M2Mn), schizolite; and M1Ca > M1Mn (M2Ca > M2Mn), pectolite. Polyhedral distortion and structural strain at the M1 and M2 sites, calculated using the equations of Robinson et al. (1971) and solutions to Kirchhoff network equations, respectively, show a predictable, cooperative variation across the entire compositional series; however, prominent discontinuities in distortion and strain behavior are observed for the schizolite composition.

Contribution to the chemical composition of minerals of the mimetite-pyromorphite series from the Guatomo mine near Tham Thalu, Bannang Sata District, Yala Province (Thailand)

The Guatomo mine is considered as one of the classic localities of mimetite worldwide. The chemical composition of six samples of minerals of mimetite-pyromorphite series from the Guatomo mine, representing different morphologies, colours as well as various geological environments/host rocks, was studied in detail by EMPA-WDS. This study revealed that both mimetite as well as pyromorphite are present at the Guatomo mine, representing rather variable compositional series ranging from the nearly end member mimetite (sample M1 - up to 0.03 apfu of P, sample M4 - up to 0.23 apfu of P and sample M5 with up to 0.18 apfu of P), through P-enriched mimetite (with 0.38 apfu of P) and As-rich pyromorphite (with 0.82 apfu of As, sample M2) up to As-enriched pyromorphite (sample M3 with As content reaching up to 1.03 apfu and sample M6 with up to 0.80 apfu of As). Besides of Pb, As, P and Cl only negligible amounts of Ca, V and S were detected in studied samples.

Variations of Major and Minor Elements in Pt–Fe Alloy Minerals: A Review and New Observations

Compositional variations of major and minor elements were examined in Pt–Fe alloys from various geological settings and types of deposits, both lode and placer occurrences. They included representatives of layered intrusions, Alaskan-Uralian-(Aldan)-type and alkaline gabbroic complexes, ophiolitic chromitites, and numerous placers from Canada, USA, Russia, and other localities worldwide. Pt–Fe alloy grains in detrital occurrences are notably larger in size, and these are considered to be the result of a special conditions during crystallization such as temperature, pressure, geochemistry or time. In addition, the number of available statistical observations is much greater for the placer occurrences, since they represent the end-product of, in some cases, the weathering of many millions of tonnes of sparsely mineralized bedrock. Typically, platinum-group elements (PGE) present in admixtures (Ir, Rh, and Pd) and minor Cu, Ni are incorporated into a compositional series (Pt, PGE)2–3(Fe, Cu, Ni) in the lode occurrences. Relative Cu enrichment in alloys poor in Pt implies crystallization from relatively fractionated melts at a lower temperature. In contrast to the lode deposits, the distribution of Ir, Rh, and Pd is fairly chaotic in placer Pt–Fe grains. There is no relationship between levels of Ir, Rh, and Pd with the ratio Σ(Pt + PGE):(Fe + Cu + Ni). The compositional series (Pt, PGE)2–3(Fe, Cu, Ni) is not as common in the placer occurrences; nevertheless, minor Cu and Ni show their maximums in members of this series in the placer grains. Global-scale datasets yield a bimodal pattern of distribution in the Pt–Fe diagram, which is likely a reflection of the miscibility gap between the ordered Pt3Fe structure (isoferroplatinum) and the disordered structure of native or ferroan platinum. In the plot Pt versus Fe, there is a linear boundary due to ideal Pt ↔ Fe substitution. Two solid solution series are based on the Ir-for-Pt and Pd-for-Pt substitutions. The incorporation of Ir is not restricted to Pt3Fe–Ir3Fe substitution (isoferroplatinum and chengdeite, plus their disordered modifications). Besides, Ir0 appears to replace Pt0 in the disordered variants of (Pt–Ir)–Fe alloys. There is a good potential for the discovery of a new species with a Pd-dominant composition, (Pd, Pt)3Fe, most likely in association with the alkaline mafic-ultramafic or gabbroic complexes, or the mafic units of layered intrusions. The “field of complicated substitutions” is recognized as a likely reflection of the crystallochemical differences of Pd and Ir, extending along the Ir-Pd axis of the Ir–Pd–Rh diagram. The inferred solid solution extends approximately along the line Ir–(Pd:Rh = 2:3). Minor Pd presumably enters the solid solution via a coupled substitution in combination with the Rh. An Ir-enrichment trend in Pt–Fe alloys typically occurs in the Alaskan-type complexes. The large size of the Pt–Fe nuggets associated with some of these complexes is considered to be related to an ultramafic-mafic pegmatite facies, whereas significant Pd-enrichment is characteristic of gabbroic source-rocks (e.g., Coldwell Complex), resulting in a markedly different trend for the Pt versus Fe (wt.%). However, based on our examination of a large dataset of Pt–Fe alloys from numerous origins, we conclude that they exhibit compositional overlaps that are too large to be useful as reliable index-minerals.

Structural Study of Lithium Strontium Borophosphate Crystal Using X-Ray Diffraction and Infrared Spectroscopy

In order to study the influence of deionized water and heat treatment on the structure of the crystal, a compositional series of 20Li2O:20SrO:30B2O3:30P2O5 with deionized water and without de-ionized water as a solvent were prepared at 800ᵒC for different sintering time from 7 to 24 h. The crystalline phase and structural of 20Li2O:20SrO:30B2O3:A 30P2O5 crystal was studied using X-ray powder diffraction (XRD) and Infrared (IR) Spectroscopy. From the XRD result, samples prepared with deionized water as solvent displayed better crystalline respond. The samples showed a better crystalline structure when it was sintered for 24 h as compared to 7 h. The infrared spectra of the samples showed three distinctive regions around 1200 – 650 cm-1, 650 – 360 cm-1 and 360 cm-1 showing clear signs of boron units as the major host structure.

Structure and Properties of Selected Zirconia Silicate Glasses

Viscosity, density, thermal expansion, glass transition temperature, refractive index, molar refraction, and chemical durability of selected compositional series of Na2O-K2O-ZnO-CaOZrO2- SiO2 glasses containing 1 and 3 mol. % ZrO2 were measured and interpreted according to the network-forming / -modifying activities of particular oxides. The influence of ZrO2 / SiO2, ZnO / CaO, and K2O / Na2O substitution on measured physical and chemical properties was discussed.

Study of Lithium-Lead Phosphate and Borophosphate Glasses

Lithium-lead phosphate and borophosphate glasses were studied in compositional series of xLi2O-(50-x)PbO-50P2O5, xLi2O-(50-x)PbO-10B2O3-40P2O5 and xLi2O-(50-x)PbO-20B2O3- 30P2O5. All glasses crystallize on heating within the range of 400-610oC. Their glass transition temperature decreases with increasing Li2O content in the region of x = 0-30 mol% Li2O and then slowly increases in all series of glasses reflecting thus changes in the bond strength of the glass structural network. Density, molar volume and chemical durability of the glasses decrease with increasing Li2O content. The 31P MAS NMR and Raman spectra show that at all glass series with the replacement of PbO by Li2O the ratio of Q2/Q1 units, present in the structure, slightly increase. The 11B MAS NMR spectra of glasses with 10 mol% B2O3 reveal the presence of only BO4 units in the glass structure, whereas the spectra of the glasses with 20 mol% B2O3 reveal also the presence of small amount of BO3 units.

OPTICAL PROPERTIES OF BORO-GERMANATE GLASS SYSTEMS

Three samples of boro-germanate glass system ( GeO 2– B 2 O 3) were prepared by cooling the melt from 1473°K in the compositional series containing 40, 35 and 30 mol% B 2 O 3. For these glasses the optical absorbance, % transmission, optical band gap, relative permittivity (ε r ), index of refraction (n) and index of dispersion (Abbe No., V d ) have been determined. The position of the absorption edge and hence the optical band gap (E opt ) was found to depend on glass composition. The absorption edge was attributed to indirect transitions. The values of E opt and n d were observed to decrease with increasing B 2 O 3 content while ε r and V d increased with increasing B 2 O 3 content.