Pyrrhotite Inclusions Research Articles

New insights on the formation of the Jingchong Cu-Co-Pb-Zn deposit, South China: Evidence from sphalerite mineralogy and muscovite 40Ar-39Ar dating

The northeastern Hunan Province hosts numerous hydrothermal Pb-Zn(-Cu-Co) polymetallic deposits. As a representative example, the Jingchong Cu-Co-Pb-Zn deposit is characterized by the lower Cu-Co and upper Pb-Zn mineralization, whereas little is known about Pb-Zn mineralization. In this study, three generations of sphalerite were identified based on their textural and geochemical differences. The Sph-I exhibits the oscillatory zoning that consists of reddish-brown Sph-Ia (poor in chalcopyrite inclusion) alternating with dark Sph-Ib with zoned chalcopyrite inclusion. Sph-II is composed of honey-brown Sph-IIa (abundant chalcopyrite droplets) and white clean Sph-IIb (rare chalcopyrite inclusion). The black Sph-III is characterized by nano- to submicron-sized chalcopyrite inclusions with typical “dusting” or “watermelon” texture and crosscuts all other sphalerite generations in veinlets. The electron microprobe and laser ablation inductively coupled plasma mass spectrometry show that Sph-I has higher Fe and Mn contents, but lower Cd, Cu and Ag contents than Sph-II and Sph-III. Sphalerite geothermometry yields temperatures of 334–346 (±58)°C for Sph-I, 254–289 (±60)°C for Sph-II and 286 (±55) °C for Sph-III. The sulfur fugacity ranges from logfS2 values of −9.03 to −8.26 for Sph-I to −11.77 to −10.63 for Sph-II and −10.82 for Sph-III. The combined textural features and chemical compositions indicate that the self-organized mechanism forms Sph-I, and that the coupled dissolution and precipitation reactions triggered by the influx of Cu-elevated fluids are responsible for the formation of Sph-II and Sph-III. The associated pyrite and pyrrhotite inclusions in sphalerite are produced by the exsolution mechanism, while chalcopyrite inclusions are formed by co-precipitation due to local supersaturation at the interface of sphalerite with fluid. The 40Ar-39Ar dating of muscovite in the Jingchong deposit yields a mineralizing age of ca. 121.1 ± 2 Ma, consistent with the ca. 130–120 Ma Pb-Zn mineralizing events in the northeastern Hunan Province. The sulfur isotopic values (−3.0 to +3.5‰) of the Pb-Zn ores are similar to that of Cu-Co ores, indicating a magmatic sulfur origin. Together with the trace element affinity of sphalerite with magmatic-hydrothermal origin, it was proposed that the Jingchong Pb-Zn and Cu-Co mineralization were formed in the same magmatic-hydrothermal system. The placement of Pb-Zn orebodies at the upward zoning of Cu-Co orebodies could be attributed to the higher solubilities of Pb and Zn chloride complexes in hydrothermal fluids, relative to Cu chloride complex.

Mineralogical and sulfur isotopic characteristics of Archean greenstone belt‐hosted gold mineralization at the Tau deposit of the Mupane gold mine, Botswana

AbstractThe Mupane gold deposit, which is one of the numerous gold occurrences in the Tati Greenstone Belt in the northeastern part of Botswana, consists of four orebodies, namely Tau, Tawana, Kwena, and Tholo deposits. The present research, which focuses on the genesis of the Tau deposit, was based on ore petrography, mineral chemistry of sulfides, and sulfur isotope data. Mineralogical characteristics of the host rocks indicate that banded iron formation at the Tau deposit includes iron oxides (magnetite), carbonates (siderite and ankerite), silicates (chlorite and amphibole), and sulfides (arsenopyrite and pyrrhotite). The deposit features arsenopyrite‐rich zones associated with biotite‐chlorite veins, which are indicative of the precipitation of arsenopyrite concomitant with potassic alteration. The replacement of magnetite by pyrrhotite in some samples suggests that sulfidation was likely the dominant gold precipitation mechanism because it is considered to have destabilized gold‐thiocomplexes in the ore‐forming fluids. Based on textural relationships and chemical composition, arsenopyrite is interpreted to reflect two generations. Arsenopyrite 1 is possibly early in origin, sieve textured with abundant inclusions of pyrrhotite. Arsenopyrite 1 was then overgrown by late arsenopyrite 2 with no porous textures and rare inclusions of pyrrhotite. Gold mineralization was initiated by focused fluid flow and sulfidation of the oxide facies banded iron formation, leading to an epigenetic gold mineralization. The mineralogical assemblages, textures, and mineral chemistry data at the Tau gold deposit revealed two‐stage gold mineralizations commencing with the deposition of invisible gold in arsenopyrite 1 followed by the later formation of native gold during hydrothermal alteration and post‐depositional recrystallization of arsenopyrite 1. Laser ablation inductively coupled plasma mass spectrometric analysis of arsenopyrite from the Tau deposit revealed that the hydrothermal event responsible for the formation of late native gold also affected the distribution of other trace elements within the grains as evidenced by varying trace elements contents in arsenopyrite 1 and arsenopyrite 2. The range of δ34S of gold‐bearing assemblages from the Tau deposit is restricted from +1.6 to +3.9‰, which is typical of Archean orogenic gold deposits and indicates that overall reduced hydrothermal conditions prevailed during the gold mineralization process at the Tau deposit. The results from this study suggest that gold mineralization involved multi‐processes such as sulfidation, metamorphism, deformation, hydrothermal alteration, and gold remobilization.

On the provenance of GEMS, a quarter century post discovery

The provenance of GEMS (glass with embedded metal and sulfides) in cometary type interplanetary dust particles is investigated using analytical scanning transmission electron microscopy and secondary ion mass spectrometry. We review the current state of knowledge and closely examine the densities, elemental compositions and distributions, iron oxidation states, and isotopic compositions of a subset of GEMS in chondritic porous interplanetary dust. We find that GEMS are underdense with estimated densities that are 35–65% of compositionally equivalent crystalline aggregates. GEMS low densities result in a lower contribution to the bulk compositions of IDPs than has been assumed based on their volume fraction. We also find that element/Si ratios, assumed to be primary (indigenous), are instead perturbed by contamination and secondary alteration, including pulse heating during atmospheric entry. Fe in pyrrhotite inclusions was oxidized and Mg, S, Ca, and Fe were depleted relative to lithophile Al and Si, resulting in reduction in element/Si ratios. Because they trap outgassing elements, Fe-rich oxide rims that formed on the surface of GEMS are serendipitous “witness plates” to the changes in composition that accompany atmospheric entry. As a result of alteration, GEMS elemental compositions cannot reliably inform about their provenance. Except for highly anomalous oxygen isotope ratios measured in some large GEMS grains that indicate a contribution from circumstellar dust, oxygen isotope compositions are generally poor indicators of provenance. Prior work indicates that most GEMS fall close to the terrestrial oxygen isotope composition, which, however, does not exclude a presolar interstellar origin. Nitrogen isotopic compositions are more diagnostic. Elevated 15N/14N ratios indicate that GEMS accreted in conjunction with formation of organic matter by ion–molecule reactions in a cold (<50 K) presolar environment like the extreme outer nebula or interstellar medium. Considering all observations, we conclude that GEMS are most likely processed interstellar silicates.

VIS-IR Spectroscopy of Mixtures of Water Ice, Organic Matter, and Opaque Mineral in Support of Small Body Remote Sensing Observations

Visual-to-infrared (VIS-IR) remote sensing observations of different classes of outer solar system objects indicate the presence of water ice and organics. Here, we present laboratory reflectance spectra in the 0.5–4.2 μm spectral range of binary particulate mixtures of water ice, organics analogue (kerite), and an opaque iron sulphide phase (pyrrhotite) to investigate the spectral effects of varying mixing ratios, endmember grain size, and mixing modality. The laboratory spectra are also compared to different implementations of the Hapke reflectance model (Hapke, 2012). We find that minor amounts (≲1 wt%) of kerite (investigated grain sizes of 45–63 μm and &lt;25 μm) can remain undetected when mixed in coarse-grained (67 ± 31 μm) water ice, suggesting that organics similar to meteoritic insoluble organic matter (IOM) might be characterized by larger detectability thresholds. Additionally, our measurements indicate that the VIS absolute reflectance of water ice-containing mixtures is not necessarily monotonically linked to water ice abundance. The latter is better constrained by spectral indicators such as the band depths of water ice VIS-IR diagnostic absorptions and spectral slopes. Simulation of laboratory spectra of intimate mixtures with a semi-empirical formulation of the Hapke model suggests that simplistic assumptions on the endmember grain size distribution and shape may lead to estimated mixing ratios considerably offset from the nominal values. Finally, laboratory spectra of water ice grains with fine-grained pyrrhotite inclusions (intraparticle mixture) have been positively compared with a modified version of the Hapke model from Lucey and Riner (2011).

Phase relationships in the system ZnS-CuInS2: Insights from a nanoscale study of indium-bearing sphalerite

Abstract Micrometer- to submicrometer-scale indium-rich domains are preserved within sphalerite included in hornfels-hosted pyrrhotite from the Dulong polymetallic skarn, Yunnan, China. The nano-mineralogy of the ZnS-bearing blebs was investigated using scanning transmission electron microscopy on thinned foils extracted in situ from pyrrhotite. Indium incorporation in sphalerite occurs via the coupled substitution 2Zn2+ ↔ Cu+ + In3+; the results thus allow insights into phase relationships in the system ZnS-CuInS2 in which solubility limits are debated with respect to a cubic to tetragonal phase transition. The highest concentrations of In are measured in basket-weave domains from the smallest ZnS blebs or from un-patterned areas in coarser, irregular ZnS inclusions in pyrrhotite. Indium-rich domains contain 17–49 mol% CuInS2, whereas In-poor sphalerite contains &amp;lt;5 mol% CuInS2. Atomic-scale metal ordering observed in In-(Cu)-rich ZnS domains was modeled as mixed sites in a cubic structure with P43m symmetry and empirical formula [(Cu,In,Zn)3(Zn0.5Fe0.5)]4S4. This sphalerite modification is distinct from the cubic-tetragonal phase transition reported elsewhere for analogous, synthetic phases with abundant planar defects. The Zn1.5Fe0.5CuInS4 nanophase described here potentially represents a Fe-bearing polymorph of Zn2CuInS4, considered as an end-member in the sakuraiite solid-solution series. At ≤50 mol% CuInS2 in the ZnS-CuInS2 system, incorporation of In via coupled In+Cu substitution is promoted within a cubic ZnS phase with lower symmetry than sphalerite rather than into the spatially coexisting chalcopyrite of tetragonal symmetry. Solid-state diffusion accounts for phase re-equilibration resulting in the basket-weave textures typical of In-(Cu)-rich domains in the smallest blebs, whereas fluid percolation assists grain coarsening in the irregular inclusions. The results show evidence for the existence of a more complex phase transition than previously recognized from experimental studies, and, intriguingly, also to a potential eutectic in the system ZnS-CuInS2. Pyrrhotite-bearing hornfels in skarns may concentrate In and other critical metals hosted in sphalerite and related sulfides due to the efficient scavenging from fluid by these minerals and the subsequent preservation of those included phases by sealing within the pyrrhotite matrix.

Alaskan-type nature and PGE mineralization of the Wuxing mafic–ultramafic complex in eastern part of the Central Asian Orogenic belt

The Wuxing mafic–ultramafic complex is located in the eastern part of the Central Asian Orogenic Belt (CAOB). It consists of hornblende-olivine clinopyroxenite, hornblende clinopyroxenite, clinopyroxenite, gabbro and diorite. Hornblende occurs in all the rock types of the complex and is pargasite in composition. Clinopyroxene is diopsidic in composition with high CaO and low TiO2 contents. The flat REE and sub-parallel trace element patterns of both clinopyroxene and hornblende suggest that these rocks were formed by fractional crystallization from common magma with no significant crustal contamination. Enrichment in large ion lithophile elements relative to high field strength elements of the silicate minerals, together with the variable sulfur isotope compositions (δ34S = -2.55 ~ 11.01‰) of the sulfides, indicate the involvement of subducted oceanic materials into the mantle source. These petrological, mineralogical and geochemical features strongly suggest the Alaskan-type nature of the Wuxing complex. The hydrous parental magma of the Wuxing complex was derived from partial melting of the mantle wedge, which had been metasomatized by subducted melts/fluids.The Wuxing complex is a unique Pt-Pd-rich Ni-Cu sulfide deposit in the CAOB. The ore minerals, which are dominated by pyrite, pyrrhotite, pentlandite, chalcopyrite and platinum-group mineral (PGM), mainly occur in clinopyroxenite and hornblende clinopyroxenite. The sulfide ores are predominantly present as net-textured and disseminated textures. Pentlandite and chalcopyrite associated with pyrrhotite commonly occur in the marginal zone of the pyrrhotite grains. The PGMs occur as interstitial grains at the contact between base-metal sulfides and silicate minerals or along the crack of pyrrhotite or clinopyroxene, or as inclusions in pyrrhotite. The occurrences of sulfides and PGMs in the Wuxing complex, together with sulfur isotope compositions and PGE patterns, reveal that the PGE enrichment of the Alaskan-type complexes can be attributed to the high-degree partial melting of the mantle source, sulfur involvement in the source, and PGE transportation of hydrous melts.

Strusky a železo z experimentální tavby železa realizované na hradě Buchlově (jv. Chřiby) v roce 2018

During experimental smelting of iron in a replica of historical shaft furnace, which was held at the Buchlov Castle in 2018, charcoal and Mn-enriched pelosiderite-limonite iron ore from the locality Strážovice near Kyjov were used. The obtained furnace slag is practically completely formed by glass phase; only rare small domains also contain olivine. The glass phase is compositionally heterogeneous and contains 0.7 - 10.7 wt. % MnO, whereas olivine corresponds to fayalite with elevated contents of tephroite (ca. 12 mol. %), forsterite (ca. 4 mol. %) and dicalciumsilicate (1 mol. %) components. The produced metallic iron is also compositionally heterogeneous, rich in phosphorus and in places it contains small spherical inclusions of pyrrhotite. The phase composition of slag differs significantly from those of typical iron slags. The reason can be seen either in anomalous chemical composition of used ore (the elevated contents of Mn could potentially act as an inhibitor of crystallization), or in too high temperatures during smelting (the phase relations in metallic iron suggest temperatures exceeding 1500 °C) in combination with rapid cooling of the furnace content after finishing of smelting. Both phase composition of slag as well as chemical composition of individual slag phases and metallic iron are significantly different from those of local historical artefacts from the period of usage of technology of direct production of iron. These findings do not support the idea that local pelosiderite iron ores were used for production of iron already during this early period.

Sulfide Mineralization in the Carbonatites and Phoscorites of the Guli Massif, Polar Siberia, and Their Noble-Metal Potential

We report the first combined investigation (neutron activation, X-ray fluorescence, and electron microprobe analysis) of mineral forms of Au and Ag and noble metal distribution in the sulfide-bearing phoscorites and carbonatites of the Guli alkaline ultrabasic massif (Polar Siberia) and magnetite and sulfide separates from these rocks. The highest noble metal contents were observed in the sulfide separates from the carbonatites: up to 2.93 Pt, 61.6 Au, and 3.61 ppm Ag. Pyrrhotite, djerfisherite, chalcopyrite, and pyrite are the most abundant sulfides and the main hosts for Au and Ag. The latest assemblage of chalcopyrite, Ag-rich djerfisherite, lenaite, sternbergite, and native silver shows significant Ag concentrations. The wide occurrence of K sulfides and presence of multiphase inclusions in pyrrhotite consisting of rasvumite, K‒Na–Ca carbonate, carbocernaite, strontianite, galena, chalcopyrite, sternbergite, lenaite, and native silver suggest that the sulfides were formed at high activities of K, Na, Sr, LREE, F, Cl, and S. Chlorine shows high complex-forming capacity to Ag and could be an agent of noble metal transport in the carbonatites. Crystallization of the early djerfisherite–pyrrhotite assemblages of the phoscorites and carbonatites began at a temperature not lower than 500°C and continued up to the formation of late Ag-bearing sulfides at temperatures not higher than 150°C. The carbonatite-series rocks could be enriched in Au and Ag during late low-temperature stages and serve as a source for Au placers.

Sulfur isotope compositions of pyrite from high-pressure metamorphic rocks and related veins (SW Tianshan, China): Implications for the sulfur cycle in subduction zones

A detailed petrographic, microstructural and geochemical investigation of pyrites from four eclogites / blueschists and their veins in the Tianshan (NW China) have revealed the occurrence of four types of pyrites: δ34S values of the pyrites range from −24.7 to +13.2‰, whereby three populations can be distinguished that have distinct δ34S ranges corresponding to different paragenetic stages. Py1 pyrite grains contain micro- to nanoscale inclusions of pyrrhotite, chalcopyrite, bornite, sphalerite, galena, arsenopyrite, cobalt-pentlandite, enargite, titanite, biotite, barite, and have δ34S values of −3.8 to +2.7‰ (average δ34S = −0.6 ± 0.9‰), which is inherited from a magmatic and hydrothermal fluid input during alteration of the oceanic crust. Py2 pyrite occurs as inclusions within the cores of garnet where it coexists with fine-grained inclusions of rutile, glaucophane and rarely with omphacite. Thus, these pyrite inclusions likely formed during prograde evolution. Py2 is too small to be analyzed by SIMS and thus no isotopic compositions could be determined. The Py3 pyrite grains contain eclogite-facies mineral inclusions, such as omphacite, glaucophane, epidote, rutile and lawsonite, and are inferred to have formed during the late prograde evolution close to or at peak eclogite-facies conditions. Py3 pyrite display positive δ34S values ranging from +3.6 to +13.2‰ (average δ34S = +9.7 ± 2.8‰), suggesting the source of sulfur was either anhydrite incorporated during seafloor alteration or 34S-enriched sulfide from lower sections of the oceanic lithosphere. Py4 pyrite occurs as irregular patches, isolated euhedral to subhedral grains or as rims around Py1 or Py3 pyrites, associated with magnetite and ilmenite. Py4 grains have δ34S values of −24.7 to −3.9‰ (average δ34S = −5.0 ± 2.1‰), with the most likely source of sulfur being 32S-enriched pelagic sediments that in the Tianshan are interlayered with the metavolcanic lithologies and underwent amphibolite facies metamorphism during exhumation. This study provides insight into the sulfur cycle within subduction zones. We document that during subduction and exhumation fluids with distinct sulfur isotopic compositions driven by dehydration reactions in the downgoing slab cause metasomatism in the surrounding lithologies. In particular, we suggest that at least locally the plate interface is characterized by sediment-derived fluids that are characterized by 32S-enriched sulfur and comparatively higher oxygen fugacities.

Microchemical characterization of placer gold grains from the Meyos-Essabikoula area, Ntem complex, southern Cameroon

Gold occurs as a native metal, usually containing silver, and in some cases mercury, copper, and palladium. It may also occur as inclusions within sulfur-rich minerals, such as pyrite and arsenopyrite. The style and variety of gold mineralization is influenced by the geological setting, chemistry of the ore fluids, and the nature of their interactions with rocks. Gold grains liberated from bedrock into surficial sediments during weathering and erosion are chemically stable and may be characterized according to their mineralogy: i.e the alloy composition and suite of mineral inclusions revealed within polished sections, characteristics faithful to gold from the hypogene source. This approach has been applied to placer gold grains from the Meyos-Essabikoula area, Cameroon, where the source of gold is not yet confirmed due to poor outcrop exposure.A total of 221 alluvial gold grains from 10 sites, tributaries of Sing and Bivele River over the Ntem Complex have been studied using Electron Probe Micro-Analysis (EMPA) to determine the concentration of minor alloying metals, (notably Au, Ag, Cu, and Hg) and Scanning Electron Microscopy (SEM) in order to evaluate the assemblage of mineral inclusions within the gold. Most of the grains are sub-rounded with pitted surfaces and inclusions of pyrrhotite, acanthite, and chalcopyrite were observed. The grains are AuAg alloys ranging from 54.4 to 99.8 wt% Au, 0.1–48.4 wt% Ag, 0.1–0.8 wt% Hg and 0–0.3 wt% Cu. The presence of Fe oxide (magnetite) inclusions containing Cr and V (to around 5 wt %) has not been reported elsewhere and suggests a strong interaction between hot reducing ore fluids and local mafic lithologies.

Ore facies, mineral chemical and fluid inclusion characteristics of the Hossein-Abad and Western Haft-Savaran sediment-hosted Zn-Pb deposits, Arak Mining District, Iran

The Arak basin in the northern part of the Malayer-Esfahan metallogenic belt (MEMB) of Iran hosts 9 Zn-Pb sulfide deposits within a Jurassic sedimentary succession of black, fine-grained sandstone, siltstone and shale. This succession was deposited in an extensional back-arc environment between the Sanandaj- Sirjan Zone (SSZ) and the Central Iranian microcontinent. Two of the 9 deposits (Western Haft-Savaran and Hossein-Abad) are the focus of study. Here, three ore facies can be distinguished, based on the morphology of the orebodies and the sulfide mineralogy and textures: (a) stockwork, (b) massive, and (c) bedded mineralization. The stockwork and massive mineralization are interpreted to have formed in the subsurface, whereas bedded mineralization was sedimented on the seafloor. The Fe contents of sphalerites from massive and stockwork mineralization from the two deposits, together with the presence of pyrrhotite inclusions, indicate that sphalerite precipitated from relatively low fS2 (<10−11) fluid. Homogenization temperatures of fluid inclusions in sphalerite, quartz and siderite in massive mineralization range from 105 to 309 °C, and average 208 °C, with salinities between 4.03 and 11.1 wt% NaCl eq., and averaging 5.77 wt% NaCl eq. These widely ranging salinities and homogenization temperatures reflect mixing of shallow connate water with venting metalliferous fluid that is of deep basinal origin, and deposition of mineralization predominantly below the seafloor. Collectively, the host rock types, ore facies and textures, deposition in an reduced ambient environment, fluid inclusion temperatures and salinities, and mineralizing fluid behaviour at the seafloor are all compatible with a vent-proximal sedimentary exhalative (SEDEX) origin for the Western Haft-Savaran and Hossein-Abad deposits.

Jurassic magmatism related Pb-Zn-W-Mo polymetallic mineralization in the central Nanling Range, South China: Geochronologic, geochemical, and isotopic evidence from the Huangshaping deposit

The Nanling Range in South China is characterized by extensive Mesozoic magmatism and coeval nonferrous and rare metal mineralization. Huangshaping is a world-class Pb-Zn-W-Mo polymetallic skarn deposit in the central Nanling Range. Magmatic rocks occurring in this ore district include quartz porphyry, granite porphyry, granophyre, dacite porphyry, and aplite, with only the first three granitoids genetically associated with polymetallic mineralization. Most of the orebodies are constrained within the contact zones as skarn and veins between these granitic stocks and the carbonate wall rocks.Since the age of the quartz porphyry is still controversial, and studies of the dacite porphyry and aplite are absent, we focus on these magmatic rocks first. LA-ICP-MS zircon U-Pb dating suggests that the crystallization ages of the quartz porphyry, dacite porphyry, and aplite are 154.3±1.9Ma, 158.1±0.8Ma, and 148.4±3.4Ma, respectively. Combined with previously published age data, we infer the evolutionary sequence of magmatic rocks should be dacite porphyry→quartz porphyry→granite porphyry (granophyre)→aplite. The quartz porphyry, dacite porphyry, and aplite yield high contents of high field strength elements (Zr+Nb+Ce+Y=255–440ppm), high ratios of 10,000×Ga/Al (2.6–3.2), and prominent depletions in Ba, Sr, Eu, P, and Ti, indicating their crustal affinities to A-type granites. They have negative εNd(t) values (−9.4 to −7.0) and high initial Pb isotopic ratios (206Pb/204Pbi=18.307–18.644, 207Pb/204Pbi=15.689–15.742, 208Pb/204Pbi=38.589–38.986), suggesting that they were probably derived by partial melting of ancient granulitic crustal materials.The sulfide minerals exhibit a wide range of δ34SV-CDT values from −22.6 to 24.2‰, with 206Pb/204Pb of 17.669–19.708, 207Pb/204Pb of 15.492–15.714, and 208Pb/204Pb of 37.880–39.789, indicating that sulfur, lead, and other associated metals were derived from a mixture of magmatic components and the Carboniferous wall rocks. Fluid inclusions in pyrrhotite, sphalerite, and marmatite samples have 3He/4He ratios of 0.12 to 1.53 Ra, with calculated mantle helium proportions of 1.3 to 18.9%, indicating a predominantly crustal origin for the ore fluids, with minor inputs from the mantle. The Huangshaping deposit is a typical example of the genetic relationship both spatially and temporally between Jurassic magmatism and polymetallic metallogeny in the Nanling Range.

Unusual shape of pyrrhotite inclusions in scapolite of igneous rocks from the southernern Urals

The unique igneous rock (scapolite–diopside gabbro) from the Ilmeny Mountains in the southern Urals is described. Gabbro fills a segment of dike 1.3 m thick that cuts through calcite–dolomite carbonatite. Medium-grain pyroxenite with scapolite that occurs at selvages gradually passes to scapolite-bearing gabbro in the central part of the dike. Scapolite crystals display surfaces of concurrent growth, which are evidence of their magmatic origin. Scapolite (Me 63–70%) contains numerous pyrrhotite inclusions as platelets 0.001 mm thick oriented parallel to the cleavage plane {100}. The calculated pyrrhotite formula is consistent with its stoichiometry (Fe1–xS). The morphology of the platelets (hexagonal sections) and their optical properties indicate a hexagonal symmetry of pyrrhotite. As follows from the insignificant difference between scapolite grains with and without pyrrhotite inclusions, scapolite and pyrrhotite should be regarded as products of synchronous magmatic melt crystallization.

Release of arsenic from cyanidation tailings

At a gold mine in northern Sweden, gold occurring as inclusions in pyrrhotite and arsenopyrite is leached by cyanidation of the ore. The main sulphide minerals in the ore are pyrrhotite and arsenopyrite. Effluents from the cyanidation process are treated with Fe2(SO4)3 to form Fe-precipitates suitable for the co-precipitation of As. The aim of this study was to perform static and kinetic leaching tests on the ore and tailings to define geochemical processes governing As mobility. Sequential leaching tests suggested that the majority of dissolved As deriving from the sulphide fraction in the ore was incorporated in newly formed Fe-precipitates in the tailings. The mobility of As in the tailings was therefore mainly dependent on the stability of these As-bearing Fe-precipitates. Weathering cell tests (WCT) involving 31 weekly cycles of wetting and air exposure were conducted to assess the stability of the As in the tailings under accelerated weathering conditions. The first stage of the WCT was characterized by a pH≈5 and low As leaching, probably driven by the dissolution of amorphous Fe-As species. In the second stage of the WCT, leaching of Fe, S and As increased and the pH decreased to <3.5. An increase of the leachate’s molar Fe/S-ratio suggested that pyrrhotite oxidation was occurring. The falling pH destabilized As-bearing Fe-precipitates, causing further As release. The total As release during the WCT corresponded to only a small proportion of the tailings’ total As content. The accelerated As-leaching observed towards the end of the WCT could thus indicate that its release could increase progressively over time.

Mn- and Zn-bearing ilmenite in porphyries of the Central Urals

Ilmenite crystals incorporated into epidote phenocrysts of porphyry dikes contain up to 8.8 wt % ZnO and 20 wt % MnO. These crystals, less than 50 μm in size, are associated with rutile, pyrite, pyrrhotite inclusions and are characterized by nonuniform Zn distribution. Ilmenite microphenocrysts 100–200 μm in size that occur in the muscovite-epidote-quartz-feldspar groundmass contain up to 2.4 wt % ZnO and 10–20 wt % MnO. It is suggested that the formation of Mn- and Zn-bearing ilmenite is related to impact of hydrous oxidized melt on the sulfide-bearing crustal rocks, giving rise to sphalerite decomposition.

Multiphase evolution in the black-shale-hosted Ni–Cu–Zn–Co deposit at Talvivaara, Finland

The Talvivaara deposit contains 1550Mt of ore averaging 0.22% Ni, 0.13% Cu, 0.49% Zn and 0.02% Co. The precursors of the host rocks were deposited 2.1–1.9Ga ago in a stratified marine basin. Fractured talc-carbonate rocks delineate the eastern border of the deposit and serpentinites and talc-carbonate rocks occur along the rift-related sequence to the north and south of Talvivaara. Characteristic features are high concentrations of organic carbon and sulphur with median values of 7.6% and 8.2%, respectively. Organic carbon is graphitic at present and a variety of sulphide textures occur, representing multiphase evolution during diagenesis, tectonic deformation and medium-grade regional metamorphism. The main sulphides of the Talvivaara ore are pyrrhotite, pyrite, sphalerite, chalcopyrite and pentlandite. Sulphides occur both as fine-grained disseminations and coarse grains or aggregates. Chalcopyrite mainly occurs in joint surfaces and quartz-sulphide veins and pentlandite occur as inclusions in pyrrhotite. Alabandite (MnS) occurs in black shales and black metacarbonate rocks. The early low-T sulphide minerals were overprinted by later stage processes. No framboidal pyrite is any longer present, but spheroidal pyrite with a grain size of <0.01mm and containing up to 0.7% Ni occurs. During the deposition of the organic-rich mud the anoxic/euxinic bottom waters were enriched in Ni+, Cu+ and Zn2+. Sulphur isotope δ34S values indicate mixing of sulphur derived from different processes or fractionation by sulphate reduction in a restricted basin. Both thermochemical and bacterial sulphate reductions were important for the generation of reduced sulphur.

High-temperature conductivity of magnetite ores in relation to their genesis and mineral composition ( by the example of the Goroblagodatskoe skarn-magnetite deposit)

Samples of magnetite ores of different parageneses and mineral compositions from the Goroblagodatskoe skarn-magnetite deposit were studied by physical and mineralogo-petrographic methods. Electrical-resistance curves were obtained for an ore containing 80–90% magnetite for the temperature range 20–800 ºC. Three groups of samples were recognized according to the pattern of temperature curves and electrical resistance: sulfide-free, sulfide-containing (pyrrhotite), and variolitic ores. The parameters of high-temperature conductivity (activation energy E0 and coefficient of electrical resistance log R0) have been determined. A linear relationship between E0 and log R0 (log R0= a – bE0) has been established for magnetite ores of all mineral types. The coefficient a varies from 1.92 to 4.80 depending on the type and mineral composition of magnetite ores. The coefficient b is nearly constant for all studied samples, 6.65. The figurative points of the samples in the E0–log R0 coordinates lie in the field bounded by the straight lines log R0= 4.80 – 6.65 E0 and log R0= 1.92 – 6.65 E0. The samples of magnetite ores of the skarn and hydrosilicate paragenesis with visible pyrrhotite inclusions and samples of variolitic ores form an individual group in the above field. Within the group, the ores are also subdivided into garnet-magnetite (skarn paragenesis), epidote-chlorite-magnetite (hydrosilicate paragenesis), pyroxene-magnetite, and orthoclase-magnetite (variolitic ores).

Anatomy of a pressure-induced, ferromagnetic-to-paramagnetic transition in pyrrhotite: Implications for the formation pressure of diamonds

[1] Meteorites and diamonds encounter high pressures during their formation or subsequent evolution. These materials commonly contain magnetic inclusions of pyrrhotite. Because magnetic properties are sensitive to strain, pyrrhotite can potentially record the shock or formation pressures of its host. Moreover, pyrrhotite undergoes a pressure-induced phase transition between 1.6 and 6.2 GPa, but the magnetic signature of this transition is poorly known. Here we report room temperature magnetic measurements on multidomain and single-domain pyrrhotite under nonhydrostatic pressure. Magnetic remanence in single-domain pyrrhotite is largely insensitive to pressure until 2 GPa, whereas the remanence of multidomain pyrrhotite increases 50% over that of initial conditions by 2 GPa, and then decreases until only 33% of the original remanence remains by 4.5 GPa. In contrast, magnetic coercivity increases with increasing pressure to 4.5 GPa. Below ∼1.5 GPa, multidomain pyrrhotite obeys Neel theory with a positive correlation between coercivity and remanence; above ∼1.5 GPa, it behaves single domain–like yet distinctly different from uncompressed single-domain pyrrhotite. The ratio of magnetic coercivity and remanence follows a logarithmic law with respect to pressure, which can potentially be used as a geobarometer. Owing to the greater thermal expansion of pyrrhotite with respect to diamond, pyrrhotite inclusions in diamonds experience a confining pressure at Earth's surface. Applying our experimentally derived magnetic geobarometer to pyrrhotite-bearing diamonds from Botswana and the Central African Republic suggests the pressures of the pyrrhotite inclusions in the diamonds range from 1.3 to 2.1 GPa. These overpressures constrain the mantle source pressures from 5.4 to 9.5 GPa, depending on which bulk modulus and thermal expansion coefficients of the two phases are used.

Petrology and rock magnetism of the gabbro of Troodos ophiolite

In order to determine the nature of remanence carriers of the layered gabbro of the Troodos ophiolite, Cyprus, we report optical and electron microscopic observations, together with rock magnetic and paleomagnetic experiments. Above all, the study aims to understand and clarify the time of magnetic acquisition relative to the brittle deformation of the oceanic crust manifested by the ridge-transform intersection (Solea graben and the Arakapas transform). Petrographic examination of pyroxene grains revealed isolated magnetite inclusions ranging in size from single-domain (SD) to multi-domain (MD) and in addition, MD pyrrhotite inclusions residing in veins and cracks. Thermal demagnetization and thermomagnetic procedures indicate two components, low and high temperature. We argue that the low temperature component, <350 °C, and the high component, <580 °C, are the contribution of the pyrrhotite and magnetite, respectively. The SD magnetite inclusions exsolved in pyroxene are the dominant carriers of magnetic remanence in Troodos Gabbro. The initial formation of these inclusions occurred via exsolution reaction at temperatures between 520 and 850 °C, above the Curie temperature of pure magnetite during the solidification of the magma. Therefore, acquisition of remanent magnetization of the Troodos gabbro took place during the earliest stages of crustal accretion, before any brittle deformation associated with the spreading ridge and the transform fault occurred.

CONTAMINATION OF THE SOUTH MOUNTAIN BATHOLITH BY SULFIDES FROM THE COUNTRY ROCKS

Sulfide minerals (Po + Py + Ccp >> Sp + Gn + Apy) are common constituents of the Meguma Supergroup (MSG) country rocks, and are also common in the marginal facies of the South Mountain Batholith (SMB), Nova Scotia, relative to the interior of the batholith. The distribution and relative modal proportions of sulfides in the granites near the contact indicate that they are probably contaminants from the MSG country rocks. We trace the textural and chemical changes that occur in Py, Po, and Ccp from the country rocks through their xenoliths to the granite during their assimilation in the granite. Pyrrhotite in the country rock ranges from large polycrystalline porphyroblasts with many inclusions to small individual grains free of inclusions, all with low concentrations of Co and Ni. Chalcopyrite in the country rocks occurs mainly as anhedral inclusions in pyrrhotite, and as small isolated grains in the silicate matrix. Pyrite in the country rocks occurs as euhedral cubes or as anhedral cores to pyrrhotite grains. Relative to their occurrences in the MSG country rocks, characteristics of sulfide grains in the granitic rocks include generally smaller grain-sizes, Po grains with fewer silicate and oxide inclusions, development of some Po grains with an inclusion-rich core and an inclusion-free rim, Po grains that have a lower Fe:S ratio and contain higher concentrations of Co (up to 0.17 wt%) and Ni (up to 0.41 wt%), local increases in the Ccp:Po ratio, better development of crystal faces on Ccp inclusions in Po, development of micro-dropper or silicate-melt-displacing textures, and a general absence of Py except for its association with Ccp in microgranitoid enclaves. The grain-size reduction is consistent with disintegration of polycrystalline MSG sulfide grains, either in the solid state or in a partially melted state, as well as dissolution in the SMB magma. The higher concentrations of Co and Ni in the SMB pyrrhotite are consistent with cation exchange with the granitic melt. Most of the remaining characteristics are consistent with partial melting of the multiphase MSG sulfide blebs related to their incorporation in the SMB magma. From known phase-relations in the system Cu–Fe–S, we deduce that temperatures of the SMB magma exceeded the temperature of beginning of melting of the composition-dependent multiphase MSG sulfide aggregates, and thus at least some of them underwent partial melting. Other more refractory grains, which have undergone only textural (annealing, ductile deformation) and chemical modification in the solid state, are simply modified xenocrysts.