Dualistic distribution coefficients of trace elements in the system mineral–hydrothermal solution. III. precious metals (Au and Pd) in magnetite and manganmagnetite

Distribution coefficients D of Au and Pd between magnetite (manganmagnetite) and ammonium chloride hydrothermal solution and the structural D^str and surface-related D^sur terms of these coefficients were determined at 450 and 500°С and a pressure of 1 kbar using internal sampling techniques. Quantitative data on the speciation of precious metals are obtained using the technique of statistical selections of analytical data on single crystals SSADSC and compared with LA-ICP-MS data. Both Pd and Au are elements compatible with magnetite and its manganoan variety: D^str is ≈3 for Pd and ≈1 for Au, although Au seems to weakly enrich fluid at 500°C: D^str ≈ 0.5–0.8. The trends of postmagmatic Pd and Au fractionation can thus strongly depend on the presence of spinel-group minerals, first of all, magnetite and its solid solutions. The dualistic nature of the distribution coefficients provides sound grounds to believe that both elements are highly compatible, with regard not only for the structural but also for the surface-related modes of their occurrence (D^sur ≈ 17 and ≈50–70 for Au and Pd, respectively). The maximum concentrations of structural modes of the elements are 5.3 ppm for Au and 5.1 ppm for Pd and were found in the solid solution whose jacobsite mole fractions were 0.82 and 0.49, respectively. The principal distribution patterns of the elements in crystals are confirmed by LA-ICP-MS data. Data on this system testify that the distribution coefficients of minor and trace elements are geochemically dualistic because of the abnormal absorption properties of nanometer-sized nonautonomous phases on the surface of ore minerals, and this dualism plays an important geochemical role.     

Partitioning of trace elements in co-crystallized sphalerite–galena–chalcopyrite hydrothermal ores

There is an abundance of published trace element data for sphalerite, galena and chalcopyrite in natural systems, yet for a co-crystallized assemblage comprising these base metal sulphides, there is no detailed understanding of the preferred host of many trace elements. Laser-ablation inductively-coupled plasma mass spectrometry trace element maps and spot analyses were generated on 17 assemblages containing co-crystallized sphalerite and/or galena and/or chalcopyrite from 9 different ore deposits. These deposits are representative of different ore types, geologic environments and physiochemical conditions of ore formation, as well as superimposed syn-metamorphic remobilisation and recrystallization. The primary factors that control the preferred base metal sulphide host of Mn, Fe, Co, Cu, Zn, Ga, As, Se, Ag, Cd, In, Sb, Te, Tl and Bi are element oxidation state, ionic radius of the substituting element, element availability and the maximum trace element budget that a given sulphide mineral can accommodate. Temperature, pressure, redox conditions at time of crystallization and metal source, do not generally appear to influence the preferred base metal sulphide host of all the trace elements. Exceptions are Ga, In and Sn recrystallized at high metamorphic grades, when the preferred host of Ga and Sn usually becomes chalcopyrite. In more typical lower temperature ores, the preferred host of Ga is sphalerite. Indium concentrations also increase in chalcopyrite during recrystallization. At lower temperatures the partitioning behaviour of Sn remains poorly constrained and shows little predictable pattern among the data here. The results obtained may be used as a tool to assess co-crystallization. If trace element distributions in a given base metal sulphide assemblage match those reported here, and assuming those distributions have not been significantly altered post (re-) crystallization, then it may be suggestive of a co-crystallized assemblage. Such information provides a foundation for novel attempts to develop trace element-in-sulphide geothermometers.     

Geochemical background of potentially toxic trace elements in reclaimed soils of the abandoned pyrite–uranium mine (south-central Poland)

Spatial distribution patterns of As, Ba, Cd, Cr, Cu, Mn, Ni, Pb, U and Zn were determined in topsoil samples collected after 40 years of chemical remediation conducted in the inoperative “Staszic” pyrite–uranium mine in the Holy Cross Mountains, south-central Poland. Soil samples were taken from 58 sites using a systematic random sampling design. Selected samples were subjected to an X-ray diffractometry analysis on bulk soils and separated clay fractions. Hematite, goethite and gypsum are common mineral phases in soil samples. Technogenic soils developed on reclaimed mine spoils show uniform spatial element distribution patterns and additionally a distinct enrichment in As, Pb, Mn, U and Zn. Mineral and chemical composition of soils vs. rocks points to the lithogenic source of the determined elements. The results of chemical analysis have been used for evaluation of geochemical background of trace elements in the study area with the iterative 2σ-technique. This investigation shows that using mean crustal element concentrations (Clarke values) as proxies of threshold values in soils are not useful for determination of strongly positive geochemical anomalies. A modified enrichment factor, i.e. a local enrichment factor, is proposed for identification of sites where soils are contaminated.     

Water qualitiy and distribution of trace elements in the Doñana aquifer (SW Spain)

The variations of groundwater quality in the unconfined zone of the Almonte-Marismas aquifer, upon which Doñana National Park is located, are analysed. Most sampled points are multiple piezometers, allowing for the vertical distribution study of the hydrogeochemical characteristics in the aquifer. Temperature, pH, electrical conductivity, dissolved oxygen and redox potential were determined in the field. A large number of parameters, including major ions and a large amount of minor and trace elements, were analysed. In the southern zone, where aeolian sands crop out, water composition in the shallower part of the aquifer is of the sodium chloride type, with low pH (5.5–6) and mineralization (<200 μS/cm) values. As water circulates through the aquifer, bicarbonate and calcium concentrations increase slightly. In agricultural or urban zones, nitrates and sulphates present their highest contents in the upper part of the aquifer. In zones with low pH levels (around 6), concentration of many trace metals (Al, Co, Cr, Cu, Ni, Zn, etc.) also shows a distribution similar to that of sulphates and nitrates, which indicates its fertilizer-linked origin. In zones with neutral or alkaline pH, regardless of high nitrate content, concentration of the above mentioned metals is very low due to its immobilisation by surface adsorption processes. The distribution of Br contents also shows the effects of agricultural pollution.     

Evolution of the magmatic–hydrothermal system and formation of the giant Zhuxi W–Cu deposit in South China

The Zhuxi deposit is a recently discovered W–Cu deposit located in the Jiangnan porphyry–skarn W belt in South China. The deposit has a resource of 3.44 million tonnes of WO3, making it the largest on Earth,however its origin and the evolution of its magmatic–hydrothermal system remain unclear, largely because alteration–mineralization types in this giant deposit have been less well-studied, apart from a study of the calcic skarn orebodies. The different types of mineralization can be classified into magnesian skarn, calcic skarn, and scheelite–quartz–muscovite(SQM) vein types. Field investigations and mineralogical analyses show that the magnesian skarn hosted by dolomitic limestone is characterized by garnet of the grossular–pyralspite(pyrope, almandine, and spessartine) series, diopside, serpentine,and Mg-rich chlorite. The calcic skarn hosted by limestone is characterized by garnet of the grossular–andradite series, hedenbergite, wollastonite, epidote, and Fe-rich chlorite. The SQM veins host highgrade W–Cu mineralization and have overprinted the magnesian and calcic skarn orebodies. Scheelite is intergrown with hydrous silicates in the retrograde skarn, or occurs with quartz, chalcopyrite, sulfide minerals, fluorite, and muscovite in the SQM veins.Fluid inclusion investigations of the gangue and ore minerals revealed the evolution of the ore-forming fluids, which involved:(1) melt and coexisting high–moderate-salinity, high-temperature, high-pressure(>450 ℃and >1.68 kbar), methane-bearing aqueous fluids that were trapped in prograde skarn minerals;(2) moderate–low-salinity, moderate-temperature, moderate-pressure(~210–300 ℃and ~0.64 kbar),methane-rich aqueous fluids that formed the retrograde skarn-type W orebodies;(3) low-salinity,moderate–low-temperature, moderate-pressure(~150–240 ℃and ~0.56 kbar), methane-rich aqueous fluids that formed the quartz–sulfide Cu(–W) orebodies in skarn;(4) moderate–low-salinity,moderate-temperature, low-pressure(~150–250 ℃and ~0.34 kbar) alkanes-dominated aqueous fluids in the SQM vein stage, which led to the formation of high-grade W–Cu orebodies. The S–Pb isotopic compositions of the sulfides suggest that the ore-forming materials were mainly derived from magma generated by crustal anatexis, with minor addition of a mantle component. The H–O isotopic compositions of quartz and scheelite indicate that the ore-forming fluids originated mainly from magmatic water with later addition of meteoric water. The C–O isotopic compositions of calcite indicate that the ore-forming fluid was originally derived from granitic magma, and then mixed with reduced fluid exsolved from local carbonate strata. Depressurization and resultant fluid boiling were key to precipitation of W in the retrograde skarn stage. Mixing of residual fluid with meteoric water led to a decrease in fluid salinity and Cu(–W) mineralization in the quartz–sulfide stage in skarn. The high-grade W–Cu mineralization in the SQM veins formed by multiple mechanisms, including fracturing, and fluid immiscibility, boiling, and mixing.     

Characteristics of trace elements in contaminated rivers and their environmental significance

Several rivers researched around Taihu Lake in Chinese eastern plain are distributed to the west of the lake. Pollutants of different types from tributaries and inlets flow directly into the main rivers and finally into the lake. They change trace elements of rivers fi＇om which we can analyze. Researches about trace elements are helpful for understanding the pollutant characteristics, industrial structure and agricultural cultivation in the area of network rivers in the plain of China. Samples of water column, suspended matter and sediment were collected fi＇om the west rivers of Taihu Lake, which represent three typical rivers. Observation in the field and the primary composition analysis showed the Caoqiao River was mainly contaminated by industrial wastewater, the Liangxi River was discharged by domestic sewage and the Dapu River was principally input by farmland runoff. REE concentrations and their normalized curves showed obvious characters for rivers discharged by different sewages. The contents of total REE in water column followed the order of the Caoqiao River, the Dapu River and the Liangxi River fi＇om high to low. TREEs in suspended matter and sediments follow the order of the Dapu River 〉 the Caoqiao River 〉 the Liangxi River. REE normalized curves （for Australia shale） suggested that significant diversities were presented in water column, suspended matter and sediments, i.e., heavy REE enrichment in water, middle REE enrichment in suspended matter, and smooth curves for sediments. But the heavy pollution resulted in several anomalous curves in the same rivers. Some element ratios were selected as indices for polluted rivers based on their geochemical properties and diversities between rivers. The results displayed the discriminative indices for water column, suspended matter and sediment. The effective indices were Pb/Fe, Cr/Fe, Ni/Fe, Pb/Ni, Zn/Ni for water column, Cu/Al, Cu/Fe, Zn/Fe, K/Ca, K/Na, Pb/Co, Zn/Co for suspend matter and Pb/Fe, K/Ca, Ca/Mg, Zn/Ni for sediment, respectively. In general, rivers mainly discharged by industrial sewage have high ratios of Pb/Ni, K/Ca, are enriched in the middle REE and have positive Gd anomaly. The domestic sewage flowing into rivers reveals high ratios of Zn/Ni, Pb/Fe, and is enriched in the heavy REE, and has the positive Eu anomaly. If runoff of farmland enters into the rivers, it will have high ratios of Ca/Mg, K/Na, high lanthanum, and show the smooth normalized curves of REE.     

Selenium and other trace elements in phosphate rock of Bayovar–Sechura (Peru)

Selenium is an essential trace element in regard to human and other animals' health, but it presents a narrow range of dietary deficiency and toxic excess. Some phosphate rocks are rich in selenium. Furthermore it is necessary to control selenium's and other trace elements’ compositions in the phosphate rocks, because phosphorite ores of different geographical sites are varied, and even ores from the same outcrop can vary substantially in trace element levels.     

Visible and “invisible” forms of gold and silver in the crystallization products of melts in the Fe–S–Ag–Au system: experimental data

The forms of Au and Ag occurrence in the crystallization products of melts in the Fe–S–Ag–Au system depending on the proportions of Fe/S and Ag/Au have been studied at (Fe + S)/(Ag + Au) = 0.1. It is shown that the S-rich systems with S/Fe = 2 contain Au–Ag sulfides and Au–Ag alloys. The systems depleted in S with S/Fe = 1 contain only Au–Ag alloys. The results of XPS provide evidence for the sulfide and metallic components of Au and Ag among the crystallization products of melts in the system studied at S/Fe = 2 and a metallic component with S/Fe = 1. According to the data of electron microprobe analysis, the content of “invisible” forms of noble metals in pyrite and pyrrhotite is < 0.024 wt % for Au and <0.030 wt % for Ag; the contents of “invisible” Au and Ag in troilites are 0.040 ± 0.013 wt % Au and 0.079 ± 0.016 wt % Ag.     

The mechanisms of paragenesis and separation of silver, lead and zinc in hydrothermal solutions

On the basis of an experimental study and thermodynamic calculation, the mechanisms of paragenesis and separation of silver, lead and zinc in the hydrothermal system have been studied. At acidic to nearly neutral pH, their chloride complexes are stable, and among them the chloride complexes of zinc are most stable. And the sulfide complexes are the dominant species at nearly neutral to alkaline pH,while the sulfide complexes of silver are most stable. With decreasing temperature, [ Cl^-] ,fO2, and increasing pH, the solubilities of silver, lead and zinc will decrease, leading to their deposition and separation. For sulfide complexes, the concentrations of reduced sulfur and pH are two important factors affecting their stabilities. Complexes of different forms and stabilities respond to the variation of conditions to different extents, which gave rise to the paragenesis and separation of silver, lead and zinc in the whole ore-forming process of dissolution, transport and deposition.     

Diffusion and partition coefficients of minor and trace elements in San Carlos olivine at 1,300°C with some geochemical implications

Lattice diffusion coefficients have been determined for 19 elements (Li, Be, Na, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Y, Zr, Eu, Gd, Lu and Hf) in a single crystal of San Carlos olivine as a function of crystallographic orientation, at 1,300°C, 1 bar and fO₂ = 10^−8.3 bars, by equilibration with a synthetic silicate melt. Results for Li, Na, V, Cr, Fe and Zn are from diffusion of these elements out of the olivine, starting from their indigenous concentrations; those for all other elements are from diffusion into the olivine, from the silicate melt reservoir. Our 25-day experiment produced diffusion profiles 50 to > 700 μm in length, which are sufficiently long that precise analyses could be achieved by scanning laser ablation inductively coupled plasma mass spectrometry, even at concentration levels well below 1 μg g⁻¹. For the divalent cations Ca, Mn, Fe and Ni, profiles were also obtained by electron microprobe analysis. The results of the two methods agree well with each other, and are consistent with divalent cation diffusion coefficients previously determined using different experimental methodologies. Olivine/melt partition coefficients retrieved from the data are also consistent with other published partitioning data, indicating that element incorporation and transport in olivine in our experiment occurred via mechanisms appropriate to natural conditions. Most of the examined trace elements diffuse through olivine at similar rates to the major octahedral cations Fe and Mg, showing that cation charge and radius have little direct influence on diffusion rates. Aluminium and P remain low and constant in the olivine, implying negligible transport at our analytical scale, hence Al and P diffusion rates that are at least two orders of magnitude slower than the other cations studied here. All determined element diffusivities are anisotropic, with diffusion fastest along the [001] axis, except Y and the REEs, which diffuse isotropically. The results suggest that element diffusivity in olivine is largely controlled by cation site preference, charge balance mechanisms and point-defect concentrations. Elements that are present on multiple cation sites in olivine (e.g. Be and Ti) and trivalent elements that are charge-balanced by octahedral site vacancies tend to diffuse at relatively fast rates.     

U–Pb–Hf isotopes and trace elements of metasomatic zircon delimit the evolution of neoproterozoic Capané ophiolite in the southern Brasiliano Orogen

The Capané ophiolite is a fragment of oceanic lithosphere obducted into the Ediacaran Porongos fold and thrust belt, southern Brasiliano Orogen. A studied rodingite blackwall contained in serpentinite has metasomatic zircon that displays multiple U–Pb ages from Tonian to Cryogenian (793 ± 0.9, 757 ± 2.1, 715 ± 2.2 Ma). The ages are interpreted as corresponding to multiple alteration events in the mantle. Multiple U–Pb–Hf isotopes and trace element analyses on the same crystals by laser ablation were controlled by backscatered electron images. Hf isotopes indicate zircon origin from a depleted mantle (εHf = +15 to +10.7), and trace elements point to an oceanic origin. The Capané ophiolite thus marks the evolution of the Adamastor ocean during the Tonian and Cryogenian, a significant result for the reconstruction of Rodinia and Gondwana supercontinents.     

Formation of gold–silver sulfides and native gold in Fe–Ag–Au–S system

We carried out experiments on crystallization of Fe-containing melts FeS₂Ag_0.1–0.1xAu_0.1x (x = 0.05, 0.2, 0.4, and 0.8) with Ag/Au weight ratios from 10 to 0.1. Mixtures prepared from elements in corresponding proportions were heated in evacuated quartz ampoules to 1050 ºC and kept at this temperature for 12 h; then they were cooled to 150 ºC, annealed for 30 days, and cooled to room temperature. The solid-phase products were studied by optical and electron microscopy and X-ray spectroscopy. The crystallization products were mainly from iron sulfides: monoclinic pyrrhotite (Fe_0.47S_0.53 or Fe₇S₈) and pyrite (Fe_0.99S_2.01). Gold–silver sulfides (low-temperature modifications) are present in all synthesized samples. Depending on Ag/Au, the following sulfides are produced: acanthite (Ag/Au = 10), solid solutions Ag_2–xAu_xS (Ag/Au = 10, 2), uytenbogaardtite (Ag/Au = 2, 0.75), and petrovskaite (Ag/Au = 0.75, 0.12). They contain iron impurities (up to 3.3 wt.%). Xenomorphic micro- (<1–5 μm) and macrograins (5–50 μm) of Au–Ag sulfides are localized in pyrite or between the grains of pyrite and pyrrhotite. High-fineness gold was detected in the samples with initial ratio Ag/Au ≤ 2. It is present as fine and large rounded microinclusions or as intergrowths with Au–Ag sulfides in pyrite or, more seldom, at the boundary of pyrite and pyrrhotite grains. This gold contains up to 5.7 wt.% Fe. Based on the sample textures and phase relations, a sequence of their crystallization was determined. At ~1050 ºC, there are probably iron sulfide melt L₁ (Fe,S ? Ag,Au), gold–silver sulfide melt L₂ (Au,Ag,S ? Fe), and liquid sulfur L_S. On cooling, melt L₁ produces pyrrhotite; further cooling leads to the crystallization of high-fineness gold (macrograins from L₁ and micrograins from L₂) and Au–Ag sulfides (micrograins from L₁ and macrograins from L₂). Pyrite crystallizes after gold–silver sulfides by the peritectic reaction FeS + L_S = FeS₂ at ~743 ºC. Elemental sulfur is the last to crystallize. Gold–silver sulfides are stable and dominate over native gold and silver, especially in pyrite-containing ores with high Ag/Au ratios.     

The distribution of trace elements and Sr isotopes across the coal and its partings in the Wyodak sea, Powder River Basin, Wyoming, USA

The spatial distribution of major, minor and trace elements in a coal basin is important for exploitation strategy and for the understanding of processes of coal formation and diagenesis. The 35400 km2 intermontane Powder River Basin, NW USA, is a major s…     

Evolution of hydrothermal fluids of HS and LS type epithermal Au–Ag deposits in the Seongsan hydrothermal system of the Cretaceous Haenam volcanic field,South Korea

The Haenam volcanic field was formed in the southern part of the Korean peninsula by the climactic igneous activity of the Late Cretaceous. The volcanic field hosts more than nine hydrothermal clay deposits and two epithermal Au–Ag deposits. This study focuses on the relationship between hydrothermal clay alteration and epithermal Au–Ag mineralization based on the geology, alteration mineralogy, geochronology, and mineralization characteristics.These clay and epithermal Au–Ag deposits are interpreted to have formed by the same hydrothermal event which produced two distinct types of mineral systems: 1) Au-dominant epithermal Au–Ag deposit and 2) clay-dominant hydrothermal clay deposit. The two types of mineral systems show a close genetic relationship as suggested by their temporal and spatial relationships. The Seongsan hydrothermal system progressively evolved from a low-intermediate sulfidation epithermal system with Au–Ag mineralization and phyllic alteration to an acid–sulfate high-sulfidation system with Au–Ag mineralization and/or barren advanced argillic/argillic alteration. The Seongsan system evolved during post volcanic hydrothermal activity for at least 10 Ma in the Campanian stage of the late Cretaceous.The Seongsan hydrothermal system shows the rare and unique occurrence of superimposed high to low (intermediate) sulfidation episodes, which persisted for about 10 Ma.     

Sediment recycling and crustal growth in the Central Asian Orogenic Belt: Evidence from Sr–Nd–Hf isotopes and trace elements in granitoids of the Chinese Altay

Felsic igneous rocks are common constituents of volcanic arcs, and contain valuable information about subduction-related magmatism. In this study we investigate nine granitoids with S-type volcanic arc affinity from the Chinese Altay, emplaced from 507 to 391 Ma in an active subduction zone during the early–middle Paleozoic. These granitoids are characterized by moderate to high SiO₂ contents (61.01–75.30 wt.%), moderate total alkalis (Na₂O + K₂O, 3.43–7.64 wt.%), and high Al₂O₃ contents (13.29–17.18 wt.%). Negative εNd(t) values (− 6.1 to − 1.0), the wide range of εHf(t) values (− 7.0 to + 9.0), and enrichment of LILEs such as Pb, Th and U, all suggest that the granitoids were probably derived from the partial melting of subducting oceanic sediments and the associated mantle wedge. This inference is further supported by the Nd-isotope data. The high initial ⁸⁷Sr/⁸⁶Sr ratios (0.703963–0.719428), low Ba/Th ratios (7.00–118.93), and uniformly negative εNd(t) values (− 6.1 to − 1.0) indicate that slab-derived aqueous fluids were vital in generating the initial magma of these granitoids, and assimilation played only a minor role. Our data demonstrate that residual zircon retains a substantial amount of Hf during the partial melting of oceanic sediments, therefore, Hf may not be an effective tracer for the input of recycled sediments. We conclude that sediment recycling played an important role in the generation of arc magmatism and the growth of the Central Asian Orogenic Belt (CAOB).     

Texture and chemistry of pyrite at Chah Zard epithermal gold–silver deposit,Iran

Gold mineralization at Chah Zard, Iran, is mostly concentrated in breccia and veins, and is closely associated with pyrite. Optical and scanning electron microscopy-backscattered electron observations indicate four different pyrite types, each characterized by different textures: porous and fractured py1, simple-zoned, oscillatory-rimmed, framboidal and fibrous py2, colloform py3, and inclusion-rich py4. Laser ablation ICP–MS analysis and elemental mapping reveal the presence of invisible gold in all pyrite types. The highest concentrations (161–166 ppm Au) are found in py2 and py4, which correlate with the highest As concentrations (73,000–76,000 ppm). In As-poor grains, Au concentrations decrease by about two orders of magnitude. Copper, Pb, Zn, Te, Sb, and Ag occur with invisible gold, suggesting that at least part of the gold occurs in nanoparticles of sulfosalts of these metals and metalloids. Gold distribution patterns suggest that only negligible Au was originally trapped in py1 from the initial ore fluids. However, most, if not all, Au was transported and deposited during subsequent overprinting hydrothermal fluid flow in overgrowth rims around the margins of the py2 and within microfractures of py4 grains. Oscillatory zonation patterns for Co, Ni, Sb, Cu, Pb, and Ag in pyrite reflect fluctuations in the hydrothermal fluid chemistry. The LA-ICP–MS data reveal that Cu, Pb and Ag show systematic variations between different pyrite types. Thus, Cu/Pb and Pb/Ag ratios in pyrite may provide a potentially powerful exploration vector to epithermal gold mineralization at Chah Zard district and elsewhere.     

Re–Os isotopic ages of pyrite and chemical composition of magnetite from the Cihai magmatic–hydrothermal Fe deposit, NW China

The Eastern Tianshan Orogenic Belt of the Central Asian Orogenic Belt and the Beishan terrane of the Tarim Block, NW China, host numerous Fe deposits. The Cihai Fe deposit (>90 Mt at 45.6 % Fe) in the Beishan terrane is diabase-hosted and consists of the Cihai, Cinan, and Cixi ore clusters. Ore minerals are dominantly magnetite, pyrite, and pyrrhotite, with minor chalcopyrite, galena, and sphalerite. Gangue minerals include pyroxene, garnet, hornblende and minor plagioclase, biotite, chlorite, epidotite, quartz, and calcite. Pyrite from the Cihai and Cixi ore clusters has similar Re–Os isotope compositions, with ～14 to 62 ppb Re and ≤10?ppt common Os. Pyrrhotite has ～5 to 39 ppb Re and ～0.6 ppb common Os. Pyrite has a mean Re–Os model age of 262.3?±?5.6 Ma (n?=?13), in agreement with the isochron regression of ¹⁸⁷Os vs. ¹⁸⁷Re. The Re–Os age (～262 Ma) for the Cihai Fe deposit is within uncertainty in agreement with a previously reported Rb–Sr age (268?±?25 Ma) of the hosting diabase, indicating a genetic relationship between magmatism and mineralization. Magnetite from the Cihai deposit has Mg, Al, Ti, V, Cr, Co, Ni, Mn, Zn, Ga, and Sn more elevated than that of typical skarn deposits, but both V and Ti contents lower than that of magmatic Fe–Ti–V deposits. Magnetite from these two ore clusters at Cihai has slightly different trace element concentrations. Magnetite from the Cihai ore cluster has relatively constant trace element compositions. Some magnetite grains from the Cixi ore cluster have higher V, Ti, and Cr than those from the Cihai ore cluster. The compositional variations of magnetite between the ore clusters are possibly due to different formation temperatures. Combined with regional tectonic evolution of the Beishan terrane, the Re–Os age of pyrite and the composition of magnetite indicate that the Cihai Fe deposit may have derived from magmatic–hydrothermal fluids related to mafic magmatism, probably in an extensional rift environment.     

Formation of a solid solution in the MgSiO3–MnSiO3 perovskite system

Experiments using laser-heated diamond anvil cells combined with synchrotron X-ray diffraction and SEM–EDS chemical analyses have confirmed the existence of a complete solid solution in the MgSiO₃–MnSiO₃ perovskite system at high pressure and high temperature. The (Mg, Mn)SiO₃ perovskite produced is orthorhombic, and a linear relationship between the unit cell parameters of this perovskite and the proportion of MnSiO₃ components incorporated seems to obey Vegard’s rule at about 50 GPa. The orthorhombic distortion, judged from the axial ratios of a/b and \( \sqrt{2}\,a/c, \) monotonically decreases from MgSiO₃ to MnSiO₃ perovskite at about 50 GPa. The orthorhombic distortion in (Mg_0.5, Mn_0.5)SiO₃ perovskite is almost unchanged with increasing pressure from 30 to 50 GPa. On the other hand, that distortion in (Mg_0.9, Mn_0.1)SiO₃ perovskite increases with pressure. (Mg, Mn)SiO₃ perovskite incorporating less than 10 mol% of MnSiO₃ component is quenchable. A value of the bulk modulus of 256(2) GPa with a fixed first pressure derivative of four is obtained for (Mg_0.9, Mn_0.1)SiO₃. MnSiO₃ is the first chemical component confirmed to form a complete solid solution with MgSiO₃ perovskite at the P–T conditions present in the lower mantle.