Minerals of the beudantite–segnitite series from the oxidation zone of the Berezovskoe gold deposit,middle Urals: Chemical variations,behavior of admixtures,and antimonian varieties

In the oxidation zone of the Berezovskoe gold deposit in the middle Urals, Russia, minerals of the beudantite–segnitite series (idealized formulas PbFe₃ ³⁺ AsO₄)(SO₄)(OH)₆ and PbFe₃ ³⁺ AsO₄)(AsO₃OH)(OH)₆, respectively) form a multicomponent solid solution system with wide variations in the As, S, Fe, Cu, and Sb contents and less variable P, Cr, Zn, Pb, and contents K. The found minerals of this system correspond to series from beudantite with 1.25 S apfu to S-free segnitite, with segnitite lacking between 1.57 and 1.79 As apfu. Segnitite at the Berezovskoe deposit contains presumably pentavalent Sb (up to 15.2 wt % Sb₂O₅ = 0.76 Sb apfu, the highest Sb content in the alunite supergroup minerals), which replaces Fe³⁺. The Sb content increases with increasing As/S value. On the contrary, beudantite is free of or very poor in Sb (0.00–0.03 Sb apfu). Many samples of segnitite are enriched in Cu (up to 8.2 wt% CuO = 0.83 Cu apfu, uncommonly high Cu content for this mineral) and/or in Zn (up to 2.0 wt% ZnO = 0.19 Zn apfu). Both Cu and Zn replace Fe. The generalized formula of a hypothetic end member of the segnitite series with 1 Sb apfu is Pb(Fe³⁺ M ²⁺Sb⁵⁺)(AsO₄)₂(OH)₆, where M = Cu, Zn, Fe²⁺. The chemical evolution of beudantite–segnitite series minerals at the Berezovskoe deposit is characterized by an increase in the S/As value with a decrease in the Sb content from early to late generations.     

Structural changes in the FeAl2O4–FeCr2O4 solid solution series and their consequences on natural Cr-bearing spinels

The influence of Al–Cr substitution on the spinel structure was studied in synthetic single crystals belonging to the FeCr₂O₄–FeAl₂O₄ series produced by flux growth at 1,000–1,300 °C in controlled atmosphere. Samples were characterized by single-crystal X-ray diffraction, electron microprobe analyses and Mössbauer spectroscopy. Crystals of sufficient size and quality for single-crystal X-ray diffraction were obtained in the ranges Chr_0–0.45 and Chr_70–100 but not for intermediate compositions, possibly due to a reduced stability in this range. The increase in chromite component leads to an increase in the cell edge from 8.1534 (6) to 8.3672 (1) Å and a decrease in the u parameter from 0.2645 (2) to 0.2628 (1). Chemical analyses show that Fe²⁺ is very close to 1 apfu (0.994–1.007), Al is in the range 0.0793–1.981 apfu, Cr between 0 and 1.925 apfu. In some cases, Fe³⁺ is present in amounts up to 0.031 apfu. Spinels with intermediate Cr content (Chr component between 40 and 60) are strongly zoned with Cr-rich cores and Cr-poor rims. Mössbauer analyses on powdered spinels of the runs from which single crystal has been used for X-ray structural data show values of Fe³⁺/Fe_tot consistently larger than that calculated by EMPA on single crystals, presumably due to chemical variation between single crystals from the same runs. The synthesis runs ended at a temperature of 1,000 °C, but it is possible that cation ordering continued in the Cr-poor samples towards lower temperatures, possibly down to 700 °C.     

Cu- and Mn-bearing tourmalines from Brazil and Mozambique: crystal structures, chemistry and correlations

Cu- and Mn-bearing tourmalines from Brazil and Mozambique were characterised chemically (EMPA and LA-ICP-MS) and by X-ray single-crystal structure refinement. All these samples are rich in Al, Li and F (fluor-elbaite) and contain significant amounts of CuO (up to ~1.8 wt%) and MnO (up to ~3.5 wt%). Structurally investigated samples show a pronounced positive correlation between the <Y-O> distances and the (Li + Mn²⁺ + Cu + Fe²⁺) content (apfu) at this site with R ² = 0.90. An excellent negative correlation exists between the <Y-O> distances and the Al₂O₃ content (R ² = 0.94). The samples at each locality generally show a strong negative correlation between the X-site vacancies and the (MnO + FeO) content. The Mn content in these tourmalines depends on the availability of Mn, on the formation temperature, as well as on stereochemical constraints. Because of a very weak correlation between MnO and CuO we believe that the Cu content in tourmaline is essentially dependent on the availability of Cu and on stereochemical constraints.     

Hydrothermal synthesis of pyrochlores and their characterization

Pyrochlores, microlites, and U-betafites of pyrochlore group minerals were obtained from mixing experiments of the corresponding oxides and fluorides by hydrothermal synthesis at T = 800 °C and P = 200 MPa in the solution of 1.0 M NaF. The presence of U⁴⁺ in pyrochlore does not affect the cell parameter, which for the phases of pyrochlore–microlite series is 10.42 ± 0.01 Å. In a system with an excess of UO₂, pyrochlores and microlites, containing uranium up to 0.2–0.3 atoms per formula unit (apfu), are formed. In the uranium-free system of betafites composition, perovskites and Ti-bearing pyrochlores are formed. U-pyrochlores of betafite series, containing 2Ti = Nb + Ta in moles, have cubic cell parameters of 10.26 ± 0.02 Å and U⁴⁺ isomorphic capacity of 0.4–0.5 apfu. In the pyrochlore structure, U⁴⁺ may substitute for Ca²⁺ and Na⁺ cations in the eightfold site. In pyrochlores of pyrochlore–microlite series, Ca²⁺ is replaced by U⁴⁺, while in pyrochlores of betafite series, U⁴⁺ replaces Na⁺. Phases with pyrochlore structure, containing U⁵⁺ and U⁶⁺ in the sixfold site, usually occupied by Nb⁵⁺, Ta⁵⁺, and Ti⁴⁺, are formed under oxidizing conditions (Cu–Cu₂O buffer). They are characterized by low content of Nb⁵⁺, Ta⁵⁺ (<0.1 apfu), and anomalous behavior of the crystal lattice (compression, instead of expansion). Under natural conditions, the formation of pyrochlores containing a significant amount of U⁵⁺ and U⁶⁺ is unlikely.     

Structural changes and valence states in the MgCr<Subscript>2</Subscript>O<Subscript>4</Subscript>–FeCr<Subscript>2</Subscript>O<Subscript>4</Subscript> solid solution series

The influence on the structure of Fe²⁺ Mg substitution was studied in synthetic single crystals belonging to the MgCr₂O₄–FeCr₂O₄ series produced by flux growth at 900–1200 °C in controlled atmosphere. Samples were analyzed by single-crystal X-ray diffraction, electron microprobe analyses, optical absorption-, infrared- and Mössbauer spectroscopy. The Mössbauer data show that iron occurs almost exclusively as ^IVFe²⁺. Only minor Fe³⁺ (<0.005 apfu) was observed in samples with very low total Fe. Optical absorption spectra show that chromium with few exceptions is present as a trivalent cation at the octahedral site. Additional absorption bands attributable to Cr²⁺ and Cr³⁺ at the tetrahedral site are evident in spectra of end-member magnesiochromite and solid-solution crystals with low ferrous contents. Structural parameters a₀, u and T–O increase with chromite content, while the M–O bond distance remains nearly constant, with an average value equal to 1.995(1) Å corresponding to the Cr³⁺ octahedral bond distance. The ideal trend between cell parameter, T–O bond length and Fe²⁺ content (apfu) is described by the following linear relations: a₀=8.3325(5) + 0.0443(8)Fe²⁺ (Å) and T–O=1.9645(6) + 0.033(1)Fe²⁺ (Å) Consequently, Fe²⁺ and Mg tetrahedral bond lengths are equal to 1.998(1) Å and 1.965(1) Å, respectively.     

Combining in situ isotopic, trace element and textural analyses of quartz from four magmatic-hydrothermal ore deposits

This study couples in situ ¹⁶O, ¹⁷O and ¹⁸O isotope and in situ trace element analyses to investigate and characterize the geochemical and textural complexity of magmatic-hydrothermal quartz crystals. Euhedral quartz crystals contemporaneous with mineralization were obtained from four magmatic-hydrothermal ore deposits: El Indio Au–Ag–Cu deposit; Summitville Au–Ag–Cu deposit; North Parkes Cu–Au deposit and Kingsgate quartz-Mo–Bi–W deposit. The internal features of the crystals were imaged using cathodoluminescence and qualitative electron microprobe maps. Quantitative isotopic data were collected in situ using 157 nm laser ablation inductively coupled plasma mass spectrometry (for 40 trace elements in quartz) and sensitive high-resolution ion microprobe (for 3 isotopes in quartz). Imaging revealed fine oscillatory zoning, sector zoning, complex “macromosaic” textures and hidden xenocrystic cores. In situ oxygen isotope analyses revealed a δ¹⁸O range of up to 12.4 ± 0.3 ‰ in a single crystal—the largest isotopic range ever ascribed to oscillatory zonation in quartz. Some of these crystals contain a heavier δ¹⁸O signature than expected by existing models. While sector-zoned crystals exhibited strong trace element variations between faces, no evidence for anisotropic isotope fractionation was found. We found: (1) isotopic heterogeneity in hydrothermal quartz crystals is common and precludes provenance analysis (e.g., δD–δ¹⁸O) using bulk analytical techniques, (2) the trace element signature of quartz is not an effective pathfinder toward noble metal mineralization and (3) in three of the four samples, both textural and isotopic data indicate non-equilibrium deposition of quartz.     

Fahlore thermochemistry: Gaps inside the (Cu,Ag)<Subscript>10</Subscript>(Fe,Zn)<Subscript>2</Subscript>(Sb,As)<Subscript>4</Subscript>S<Subscript>13</Subscript> cube

Possible topologies of miscibility gaps in arsenian (Cu,Ag)₁₀(Fe,Zn)₂(Sb,As)₄S₁₃ fahlores are examined. These topologies are based on a thermodynamic model for fahlores whose calibration has been verified for (Cu,Ag)₁₀(Fe,Zn)₂Sb₄S₁₃ fahlores, and conform with experimental constraints on the incompatibility between As and Ag in (Cu,Ag)₁₀(Fe,Zn)₂(Sb,As)₄S₁₃ fahlores, and with experimental and natural constraints on the incompatibility between As and Zn and the nonideality of the As for Sb substitution in Cu₁₀(Fe,Zn)₂(Sb,As)₄S₁₃ fahlores. It is inferred that miscibility gaps in (Cu,Ag)₁₀(Fe,Zn)₂As₄S₁₃ fahlores have critical temperatures several °C below those established for their Sb counterparts (170 to 185°C). Depending on the structural role of Ag in arsenian fahlores, critical temperatures for (Cu,Ag)₁₀(Fe,Zn)₂(Sb,As)₄S₁₃ fahlores may vary from comparable to those inferred for (Cu,Ag)₁₀(Fe,Zn)₂As₄S₁₃ fahlores, if the As for Sb substitution stabilizes Ag in tetrahedral metal sites, to temperatures approaching 370°C, if the As for Sb substitution results in an increase in the site preference of Ag for trigonal-planar metal sites. The latter topology is more likely based on comparison of calculated miscibility gaps with compositions of fahlores from nature exhibiting the greatest departure from the Cu₁₀(Fe,Zn)₂(Sb,As)₄S₁₃ and (Cu,Ag)₁₀(Fe,Zn)₂Sb₄S₁₃ planes of the (Cu,Ag)₁₀(Fe,Zn)₂(Sb,As)₄S₁₃ fahlore cube.     

Mineralogy and Mineral Chemistry of the Cretaceous Duolong Gold‐Rich Porphyry Copper Deposit in the Bangongco Arc,Northern Tibet

The Early Cretaceous Duolong gold‐rich porphyry copper deposit is a newly discovered deposit with proven 5.38 Mt Cu resources of 0.72% Cu and 41 t gold of 0.23 g t^?1 in northern Tibet. Granodiorite porphyry and quartz diorite porphyrite are the main ore‐bearing porphyries. A wide range of hydrothermal alteration associated with these porphyries is divided into potassic, argillic and propylitic zones from the ore‐bearing porphyry center outward and upward. In the hydrothermal alteration zones, secondary albite (91.5–99.7% Ab) occurs along the rim of plagioclase phenocryst and fissures. Secondary K‐feldspar (75.1–96.9% Or) replaces plagioclase phenocryst and matrix or occurs in veinlets. Biotite occurs mainly as matrix and veinlet in addition to phenocryst in the potassic zone. The biotite are Mg‐rich and formed under a highly oxidized condition at temperatures ranging from 400°C to 430°C. All the biotites are absent in F, and have high Cl content (0.19–0.26%), with log (X_Cl/X_OH) values of ?2.74 to ?2.88 and IV (Cl) values of ?3.48 to ?3.35, suggesting a significant role of chloride complexes (CuCl₂^‐ and AuCl₂^‐) in transporting and precipitating copper and gold. Chlorites are present in all alteration zones and correspond mainly to pycnochlorite. They have similar Fe/(Fe+Mg), Mn/(Mn+Mg) ratios, and a formation temperature range of 280–360°C. However, the formation temperature of chlorite in the quartz‐gypsum‐carbonate‐chlorite vein is between 190°C and 220°C, indicating that it may have resulted from a later stage of hydrothermal activity. Fe³⁺/Fe²⁺ ratios of chlorites have negative correlation with Al^IV, suggesting oxygen fugacity of fluids increases with decreasing temperature. Apatite mineral inclusions in the biotite phenocrysts show high SO₃ content (0.44–0.82%) and high Cl content (1–1.37%), indicating the host magma had a high oxidation state and was enriched in S and Cl. The highest Cl content of apatite in the propylitic zone may have resulted from pressure decrease, and the lowest Cl content of apatite in the argillic zone may have been caused by a low Cl content in the fluids. The low concentration of SO₃ content in the hydrothermal apatite compared to the magmatic one may have resulted from the decrease of oxygen fugacity and S content in the hydrothermal fluid, which are caused by the abundant precipitation of magnetite.     

Distinct local environments for Ca along the non-ideal pyrope–grossular solid solution: A new model based on crystallographic and EXAFS analysis

A multi-technique approach (based on electron microprobe analysis, structure refinement, and EXAFS analysis at the Ca K-edge) was used to characterise the local geometry of Ca in synthetic and natural garnet compositions referable to the pyrope–grossular solid solution. Multi-shell fits of the EXAFS data indicate that Ca assumes the standard [4 + 4]-fold coordination (the polyhedral shape being a triangular dodecahedron with Ca1–O = 2.30–2.31(1) and Ca2–O = 2.45–2.46(1) Å) when Ca > 1.50 atoms per formula unit (apfu), but assumes a nearly regular [8]-fold coordination with Ca–O = 2.35–2.36 (1) Å when (Mg, Fe²⁺, Mn²⁺) > 1.50 apfu. Therefore, in the pyrope-dominant structure the Ca1–O distance lengthens and the Ca2–O distance shortens to converge towards the value observed for the Mg2–O bond in pyrope. This finding is consistent with many distinct structural features observed in solid solution terms with (Mg, Fe²⁺, Mn²⁺) > 1.50 apfu or Ca > 1.50 apfu, as well as with the anomalous properties of the intermediate terms observed both in the short-range and in the long-range perspective. The presence of two distinct Ca coordinations in the pyrope (almandine, spessartine)-like and in the grossular-like structure, and thus of an isosymmetric transition at the intermediate composition, can help to explain both the strong and asymmetric non-ideality of the solid solution between pyrope (almandine) and grossular, as well as the differences in the ability to incorporate some trace elements (such as REE and actinides) which are commonly used as process-specific indicators. This feature must be taken into account when building theoretical models of the garnet solid solutions, which are at the moment the most promising approach for calculating thermodynamic properties or for interpreting and predicting trace-element behaviour in this crucial mineral phase.     

An experimental study of amphibole stability in low-pressure granitic magmas and a revised Al-in-hornblende geobarometer

We report new experimental data on the composition of magmatic amphiboles synthesised from a variety of granite (sensu lato) bulk compositions at near-solidus temperatures and pressures of 0.8–10 kbar. The total aluminium content (Al^tot) of the synthetic calcic amphiboles varies systematically with pressure (P), although the relationship is nonlinear at low pressures (<2.5 kbar). At higher pressures, the relationship resembles that of other experimental studies, which suggests of a general relationship between Al^tot and P that is relatively insensitive to bulk composition. We have developed a new Al-in-hornblende geobarometer that is applicable to granitic rocks with the low-variance mineral assemblage: amphibole + plagioclase (An_15–80) + biotite + quartz + alkali feldspar + ilmenite/titanite + magnetite + apatite. Amphibole analyses should be taken from the rims of grains, in contact with plagioclase and in apparent textural equilibrium with the rest of the mineral assemblage at temperatures close to the haplogranite solidus (725 ± 75 °C), as determined from amphibole–plagioclase thermometry. Mean amphibole rim compositions that meet these criteria can then be used to calculate P (in kbar) from Al^tot (in atoms per formula unit, apfu) according to the expression:

$${\textit{P }}\left( {\text{kbar}} \right) = 0.5 + 0.331\left( 8 \right) \times {\text{Al}}^{\text{tot}} + 0.995\left( 4 \right) \times \left( {{\text{Al}}^{\text{tot}} } \right)^{2}$$

This expression recovers equilibration pressures of our calibrant dataset, comprising both new and published experimental and natural data, to within ±16 % relative uncertainty. An uncertainty of 10 % relative for a typical Al^tot value of 1.5 apfu translates to an uncertainty in pressure estimate of 0.5 kbar, or 15 % relative. Thus the accuracy of the barometer expression is comparable to the precision with which near-solidus amphibole rim composition can be characterised.

     

Blue, complexly zoned, (Na,Mg,Fe,Li)-rich beryl from quartz-calcite veins in low-grade metamorphosed Fe-deposit Sk��ly near Ryma?ov, Czech Republic

Syn-tectonic quartz-calcite veins containing blue beryl are enclosed in hematite > magnetite-rich portions of the low-grade metamorphosed Fe-deposit Skály near Ryma?ov, Czech Republic. Aggregates of pale to deep blue beryl, up to 2?cm in diameter, are associated with euclase, clinochlore, hematite, albite and dravite. Complexly zoned beryl crystals consist of skeletal aggregates of beryl I randomly distributed within volumetrically dominant beryl II with narrow rims of beryl III. All types of beryl have similar contents of Na (0.32?C0.49 apfu) and Mg (0.31?C0.41 apfu) but variable contents of Fe_tot (0.05?C0.34 apfu) and Al (1.20?C1.62 apfu). The LA-ICP-MS study yielded elevated contents of Li, up 1,314?ppm (0.28?wt.% Li₂O) in beryl I. The quartz-calcite veins represent an unusual type of low-T metamorphic-hydrothermal vein related to Fe-ore deposit characterized by single-stage fracturing and mobilization in a closed system at T~200?C300°C and CO ₃ ^2- as a major complexing agent for the mobility of Be.     

Dehydration and partial melting of tremolitic amphibole coexisting with zoisite, quartz, anorthite, diopside, and water in the system H2O-CaO-MgO-Al2O3-SiO2

The greenschist to amphibolite transition as modeled by the reaction zoisite+tremolite + quartz= anorthite+diopside+water has been experimentally investigated in the chemical system H₂O−CaO− MgO−Al₂O₃−SiO₂ over the range of 0.4–0.8 GPa. This reaction is observed to lie within the stability fields of anorthite + water and of zoisite + quartz, in accord with phase equilibrium principles, and its position is in excellent agreement with the boundary calculated from current internally-consistent data bases. The small dP/dT slope of 0.00216 GPa/K (21.6 bars/K) observed for this reaction supports the pressure-dependency of this transition in this chemical system. Experimental reversals of the Al content in tremolitic amphibole coexisting with zoisite, diopside, quartz, and water were obtained at 600, 650, and 700^°C and indicated Al total cations (atoms per formula unit, apfu) of only up to 0.5±0.08 at the highest temperature. Thermodynamic analysis of these and previous compositional reversal data for tremolitic amphibole indicated that, of the activity/composition relationships considered, a two-site-coupled cation substitution model yielded the best fit to the data and a S ⁰ (1 bar, 298 K) of 575.4±1.6 J/K · mol for magnesio-hornblende. The calculated isopleths of constant Al content in the amphibole are relatively temperature sensitive with Al content increasing with increasing temperature and pressure. Finally, several experiments in the range of 1.0–1.3 GPa were conducted to define the onset of melting, and thus the upper-thermal limit, for this mineral assemblage, which must involve an invariant point located at approximately 1.05 GPa and 770^°C. Received: 24 January 1997 / Accepted: 2 October 1997     

A Raman spectroscopic study on the structural disorder of monazite–(Ce)

This study addresses whether Raman spectra can be used to estimate the degree of accumulated radiation damage in monazite-(Ce) samples whose chemical composition was previously determined. Our results indicate that the degree of disorder in monazite–(Ce), as observed from increasing Raman band broadening, generally depends on both the structural state (i.e., radiation damage) and the chemical composition (i.e., incorporation of non-formula elements). The chemical effects were studied on synthetic orthophosphates grown using the Li-Mo flux method, and non radiation-damaged analogues of the naturally radiation-damaged monazite–(Ce) samples, produced by dry annealing. We found that the “chemical” Raman-band broadening of natural monazite–(Ce) can be predicted by the empirical formula, $$ {\hbox{FWHM}} {\hbox{[c}}{{\hbox{m}}^{ - {1}}}{]} = {3}{.95} + {26}{.66} \times {\hbox{(Th}} + {\hbox{U}} + {\hbox{Ca}} + {\hbox{Pb)}} {\hbox{[apfu]}} $$ where, FWHM = full width at half maximum of the main Raman band of monazite–(Ce) (i.e., the symmetric PO₄ stretching near 970?cm^?1), and (Th+U+Ca+Pb) = sum of the four elements in apfu (atoms per formula unit). Provided the chemical composition of a natural monazite–(Ce) is known, this “chemical band broadening” can be used to estimate the degree of structural radiation damage from the observed FWHM of the ν₁(PO₄) band of that particular sample using Raman spectroscopy. Our annealing studies on a wide range of monazite–(Ce) reference materials and other monazite–(Ce) samples confirmed that this mineral virtually never becomes highly radiation damaged. Potential advantages and the practical use of the proposed method in the Earth sciences are discussed.     

Diffusion in single crystal of melilite: interdiffusion of Al + Al vs. Mg + Si

Interdiffusion coefficients of Al + Al vs. Mg + Si in the gehlenite–åkermanite system of melilite were determined by coupled annealing of synthesized end-member single crystals. The observed diffusion coefficients for a couple-annealed sample vary for about 2 orders of magnitude, showing strong dependence on the gehlenite–åkermanite composition: diffusion coefficient observed at 1350 °C, for example, is 3 × 10^?13 cm² s^?1 at 5 mol% åkermanite composition (Ak₅), increases to 2 × 10^?11 cm² s^?1 at Ak₈₀, and then decreases to 1 × 10^?12 cm² s^?1 at Ak₉₅. The diffusion coefficient–temperature relation indicates high activation energy of diffusion of about 420 kJ mol^?1 for gehlenite-rich melilite. The observed diffusion coefficient–composition relation may be explained by a combination of (1) the diffusion coefficient–melting temperature relation (Flynn's rule) and (2) the feasibility of local charge compensation, which can possibly be maintained more easily in the intermediate chemical composition. The high activation energy value for gehlenitic melilite appears to correspond to the complex diffusion mechanism. The observed highly variable diffusion coefficients suggest that gehlenite–åkermanite zoning in the melilite crystals in Ca, Al-rich inclusions in the carbonaceous meteorites may provide a sensitive indicator for the thermal history of the inclusions.     

Enrichment pattern of leachable trace metals in roadside soils of Miri City,Eastern Malaysia

This article presents the results on distribution and enrichment pattern of acid-leachable trace metals (ALTMs) from roadside soil of Miri city, Sarawak, East Malaysia. The city is one of the fastest developing in the Malaysian region with huge petroleum resources. ALTMs Fe, Mn, Cr, Cu, Ni, Co, Pb, Zn and Cd along with organic carbon and carbonates (CaCO₃) were analyzed in 37 soil sediments collected from roadside. The enrichment of ALTMs [especially Cu (0.4–13.1 μg g^?1), Zn (9.3–70.7 μg g^?1), Pb (13.8–99.1 μg g^?1)] in the roadside soils indicate that these metals are mainly derived from sources related to traffic exhausts, forest fires and oil refineries. The comparative study and enrichment pattern of elements indicates that Mn, Cu, Zn and Pb are enriched multi-fold than the unpolluted soil and Ni, Pb, Cd in some samples compared to Sediment Quality Guidelines like Lowest Effect Level (LEL) and Effects Range Low (ERL) in the region which is mainly due to the recent industrial developments in the region.     

The Tiger Sulfide Chimney,Yonaguni Knoll IV Hydrothermal Field,Southern Okinawa Trough,Japan: The First Reported Occurrence of Pt–Cu–Fe‐Bearing Bismuthinite and Sn‐Bearing Chalcopyrite in an Active Seafloor Hydrothermal System

A sulfide chimney ore sampled from the flank of the active Tiger vent area in the Yonaguni Knoll IV hydrothermal field, south Okinawa trough, consists of anhydrite, pyrite, sphalerite, galena, chalcopyrite and bismuthinite. Electron microprobe analysis indicates that the chalcopyrite contains up to 2.4 wt% Sn, whereas bismuthinite contains up to 1.7 wt% Pt, 0.8 wt% Cu and 0.5 wt% Fe. The Sn‐rich chalcopyrite and Pt–Cu–Fe‐bearing bismuthinite are the first reported occurrence of such minerals in an active submarine hydrothermal system. The results confirm that Sn enters the chalcopyrite as a solid solution towards stannite by the coupled substitution of Sn⁴⁺Fe²⁺ for Fe³⁺Fe³⁺, whereas Pt, Cu and Fe enter the bismuthinite structure as a solid solution during rapid nucleation. The fluid inclusions homogenization temperatures in anhydrite (220–310°C) and measured end‐member temperature of the vent fluids on‐site (325°C) indicate that Sn‐bearing chalcopyrite and Pt–Cu–Fe‐bearing bismuthinite express the original composition of the minerals that precipitated as metastable phases at a temperature above 300°C. The result observed in this study implies that sulfides in ancient volcanogenic massive sulfide deposits have similar trace element distribution during nucleation but it is remobilised during diagenesis, metamorphism or supergene enrichment processes.     

Alkali in phlogopite and amphibole and their effects on phase relations in metasomatized peridotites: a high-pressure study

Subsolidus phase relations for a K-doped lherzolite are investigated in the model system K₂O–Na₂O–CaO–FeO–MgO–Al₂O₃–SiO₂–H₂O at 1.5–6.0 GPa and 680–1,000°C. Phlogopite is ubiquitous and coexists with Ca-amphibole up to 3.2 GPa and 900°C. High-pressure phlogopites show a peculiar mineral chemistry dependent on pressure: e.g., at 5.5 GPa and 680°C, excess of Si (up to 3.4 apfu) coupled with deficiency in Al (as low as 0.58 apfu) and K + Na (as low as 0.97 apfu), suggest a significant amount of a talc/10 Å phase component ([v]^XIISi₁K_?1Al _?1 ^IV , where [v]^XII is interlayer vacancy). Mixed layering or solid solution relations between high-pressure phlogopites and the 10 Å phase, Mg₃Si₄O₁₀(OH)₂ nH₂O, are envisaged. Phlogopite modal abundance, derived by weighted least squares, is maximum at high-pressure and relative low-temperature conditions and therefore along the slab–mantle interface (10.3 ± 0.7 wt.%, at 4.8 GPa, 680°C). In phlogopite-bearing systems, Ca-amphibole breaks down between 2.5 and 3.0 GPa, and 1,000°C, through the water conservative reaction 5(pa + 0.2 KNa_?1) + 17en + 15phl = (10di + 4jd) + 5py + 12fo + 20(phl + 0.2 talc), governed by bulk composition and pressure-dependent variations of K/OH in K-bearing phases and as a result, it does not necessarily imply a release of fluid.     

Fahlore and Sphalerite from the Darasun Gold Deposit in the Eastern Transbaikal Region,Russia: I. Mineral Assemblages and Intergrowths,Chemical Composition,and Its Evolution

The mineral assemblages, mode of occurrence, and chemical compositions of coexisting fahlore and sphalerite from the Darasun gold deposit have been described. Three generations of fahlore and three generations of sphalerite have been recognized. The FeS content in sphalerite coexisting with fahlore ranges from 0.8 to 9.4 mol %. The complete solid solution series Fe-tetrahedrite–Zn-tetrahedrite–Fe-tennantite–Zn-tennantite reflected in Sb/(Sb + As) and Fe/(Fe + Zn) ratios ranging from 0 to 0.97 and from 0.07 to 1.00, respectively, with a predominant negative relationship between these ratios has been identified for the first time at the deposit. Stepped, oscillatory, and combined stepped-oscillatory growth zonings within fahlore grains and heterogeneous aggregates of fahlore have been found. Fahlore is enriched in As with respect to Sb, and Zn-tetrahedrite is followed by Fe- and Zn-tennantite from early to late generation; Zn-tetrahedrite is followed by Fe-tennantite in zoned grains and overgrown rims; sphalerite crystallized at decreased temperature and sulfur fugacity. The evolution of the chemical composition of fahlores was caused by the evolving temperature, fluid salinity, and conditions of metal migration.     

Sulphur source and genesis of polymetallic sulphide occurrences of the Ofoten district in the Central–North Norwegian Caledonides: evidence from sulphur isotopic studies

Fourteen stratiform, stratabound and vein-type sulphide occurrences in the Upper Allochthon of the Central–North Norwegian Caledonides have been studied for their sulphur, oxygen and hydrogen isotope composition. Depositional ages of host rocks to the stratabound and stratiform sulphide occurrences range from 590 to 640?Ma. The sulphides and their host rocks have been affected by polyphase deformation and metamorphism with a peak temperature of 650?°C dated to 432?Ma. A total of 104 sulphide and 2 barite samples were analysed for δ³⁴S, 16 whole-rock and quartz samples for δ¹⁸O and 12 samples of muscovite for δD. The overall δ³⁴S values range from ?14 to +31‰ with the majority of sampled sulphides lying within a range of +4 to +15‰. In most cases δ³⁴S within each hand specimen behaves in accordance with the equilibrium fractionation sequence, δ³⁴S_gn<δ³⁴S_cp<δ³⁴S_sph<δ³⁴S_py. A systematic increase in δ³⁴S from the vein sulphides (?8‰) through schist/amphibolite-hosted (+6‰) and schist-hosted (+7 to +12‰) to dolomite-hosted (+12 to +31‰) occurrences is documented. The δ³⁴S averages of the stratiform schist-hosted sulphides are 17 to 22‰ lower than in the penecontemporaneous seawater sulphate. The Bjørkåsen (+4 to +6‰) occurrence is a volcanogenic massive sulphide (VMS) transitional to sedimentary massive sulphide (SMS), exhalative, massive, pyritic deposit of Cu–Zn–Pb sulphides formed by fluids which obtained H₂S via high-temperature reduction of seawater sulphate by oxidation of Fe²⁺ during the convective circulation of seawater through underlying rock sequences. The Raudvatn, volcanic-hosted, disseminated Cu sulphides (+6 to +8‰) obtained sulphur via a similar process. The Balsnes, stratiform, ‘black schist’-hosted, pyrite–pyrrhotite occurrence (?6 to ?14‰) is represented by typical diagenetic sulphides precipitated via bacteriogenic reduction of coeval (ca. 600?Ma) seawater sulphate (+25 to +35‰) in a system open to sulphate supply. The δ³⁴S values of the Djupvik–Skårnesdalen (+7 to +12‰), Hammerfjell (+5 to 11‰), Kaldådalen (+10 to +12‰) and Njallavarre (+7 to +8‰) stratiform, schist-hosted, massive and disseminated Zn–Pb (±Cu) sulphide occurrences, as well as the stratabound, quartzite-hosted, Au-bearing arsenopyrite occurrence at Langvatnet (+7 to +11‰), suggest that thermochemically reduced connate seawater sulphate was a principal sulphur source. The Sinklien and Tårstad, stratabound, dolomite- and dolomite collapse breccia-hosted, Zn (±Cu–Pb) sulphides are marked by the highest enrichment in ³⁴S (+20 to +31‰). The occurrences ?are?assigned to the Mississippi-Valley-type deposits.?High δ³⁴S values require reduction/replacement of contemporaneous (ca. 590?Ma) evaporitic sulphate (+23 to +34‰) with C_org-rich fluids in a closed system. The Melkedalen (+12 to +15‰), stratabound, fault-controlled, Cu–Zn sulphide deposit is hosted by the ca. 595?Ma dolomitised Melkedalen marble. The deposit is composed of several generations of ore minerals which formed by replacement of host dolomite. Polyphase hydrothermal fluids were introduced during several reactivation episodes of the fault zone. The positive δ³⁴S values with a very limited fractionation (<3‰) are indicative of the sulphide-sulphur generated through abiological, thermochemical reduction of seawater sulphate by organic material. The vein-type Cu (±Au–W) occurrences at Baugefjell, Bugtedalen and Baugevatn (?8 to ?4‰) are of hydrothermal origin and obtained their sulphur from igneous sources with a possible incorporation of sedimentary/diagenetic sulphides. In a broad sense, all the stratiform/stratabound, sediment-hosted, sulphide occurrences studied formed by epigenetic fluids within two probable scenarios which may be applicable separately or interactively: (1) expulsion of hot metal-bearing connate waters from deeper parts of sedimentary basins prior to nappe translation (late diagenetic/catagenetic/epigenetic fluids) or (2) tectonically driven expulsion in the course of nappe translation (early metamorphic fluids). A combination of (1) and (2) is favoured for the stratabound, fault-controlled, Melkedalen and Langvatnet occurrences, whereas the rest are considered to have formed within option (1). The sulphides and their host rocks were transported from unknown distances and thrust on to the Fennoscandian Shield during the course of the Caledonian orogeny. The displaced/allochthonous nature of the Ofoten Cu–Pb–Zn ‘metallogenetic province’ would explain the enigmatically high concentration of small-scale Cu–Pb–Zn deposits that occur only in this particular area of the Norwegian Caledonides.