Magnesian Skarn Research Articles

Mineral chemistry and garnet U-Pb dating in the Bizmişen iron skarn deposit, Erzincan, East-Central Türkiye

In Bizmişen area, Middle Eocene (46.3–42.0 Ma) plutonic rocks (quartz diorite) were intruded into Triassic-Cretaceous limestones and Upper Cretaceous ophiolites and caused to skarn zones containing prograde (garnet, clinopyroxene) and retrograde (amphibole, epidote, calcite, magnetite, phlogopite, serpentinite and chlorite) minerals. Due to contact relationships of quartz diorites with both serpentinized ultramafic rocks and limestone blocks, the mineralogical associations represent calcic (grossular/andradite, amphibole, chlorite and epidote) as well as magnesian (diopside, serpentine, phlogopite, talc) skarns. During the skarnization process, garnet, diopside, epidote, scapolite and amphibole minerals developed in the endoskarn zone within quartz-diorite, and diopside, tremolite, serpentine, phlogopite, talc, Mg-chlorite and calcite minerals developed in the exoskarn zones in ophiolites (serpantinite and listwaenite) and limestones. Skarn and magmatic clinopyroxenes in serpentinized ultramafic hosted exoskarn zone have a compositional range of Wo45-53En35-53Fs0–15 and Wo24-51En38-76Fs0–11, and classified as diopside and augite, respectively. The end members of garnets are Adr46–54Grs43–50Prp1–2Sps1.1–5 in amphibole-epidote-calcite-garnet skarn in endoskarn zone, whereas Adr40–93Grs4–57Prp0.2–2.3Sps0.9–2 in epidote-calcite-garnet skarn in exoskarn zone, and classified as andradite-rich grandite garnets. FeO, MnO and partially MgO contents gradually increase from the edges to the center in zoned garnet grains. Amphibole compositions represent to calcic (Ca >1 atoms per formula unit) group (pargasite) and indicate the high oxygen fugacity conditions which caused the increase in the rate of magnetite crystallization. Al2O3 and FeO contents of epidotes range 23.68–27.63 and 9.10–14.45 wt%, respectively, correspond to composition of epidote and clinozoisite. The iron oxide contents (FeO, wt%) of magnetites change from 91.72 to 98.36 correspond to structural Fe3+1.88–1.97 and Fe2+0.91–1.0 values. The contents of Ti, divalent and trivalent metal cations correspond to ulvospinel-magnetite compositional line at the magnetite end-member. The mineral chemistry of skarn minerals shows similarities to those of most iron skarn deposits. Garnet U-Pb ages (46.95–45.63 Ma) are consistent with the cooling ages of the Bizmişen pluton. The prograde stage of skarn should be occurred syn-intrusion, whereas retrograde stage should be developed later than youngest garnet age (45.6 Ma) and before the oldest late stage argillic alteration (37.5 Ma).

Oxoborates of the ludwigite group: Natural and mineral-like compounds as prospective materials

Research subject. Natural oxoborates of the ludwigite group, including azoproite, ludwigite, and vonsenite. Their empirical formulas based on five oxygen atoms have the following form: azoproite (Mg1.81Fe2+0.19)∑2.00(Fe3+0.36Ti0.26Mg0.26Al0.12)∑1.00 O2(BO3), ludwigite (Mg1.69Fe2+0.30Mn2+0.01)Σ2.00(Fe3+0.90Al0.07Mg0.02Sn0.01)Σ1.00O2(BO3) and vonsenite (Fe2+1.86Mg0.13)∑1.99 (Fe3+0.92Mn2+0.05Sn4+0.02Al0.02)∑1.01O2(BO3). Aim. To establish the relationship between the composition, crystal structure, and thermal behavior (293–1373 K) of the minerals. Materials and methods. Ludwigite was collected at the Iten’yurginskoe tin skarn deposit; vonsenite was collected at the Titovskoe magnesium-skarn boron deposit; azoproite was collected at magnesian skarns of the Tazheran alkaline massif. The methods of single crystal X-ray diffraction, energy dispersive X-ray spectroscopy, high-temperature X-ray diffraction, Mössbauer spectroscopy, and thermal analysis were used. Results. Low-charge cations (Fe2+, Fe2.5+, Mg2+) tend to occupy the M(1)–M(3) sites, and high-charge cations (Fe3+, Al3+, Ti4+, Sn4+) generally occupy the M(4) site. Azoproite is characterized by the highest melting temperature Tm > 1650 K. Due to the low Fe2+ content, azoproite does not undergo solid-phase decomposition across the investigated temperature range. The melting point of ludwigite exceeds 1582 K, which is due to the high Mg content; as a result of the Fe2+ → Fe3+ oxidation, it gradually decomposes with the formation of hematite, warwickite, and magnetite. The temperatures of oxidation and solid-phase decomposition in the Fe2+-rich vonsenite are approximately 100 K lower than those in ludwigite. The melting point of vonsenite is 1571 K. All the minerals are characterized by a weak degree of thermal expansion anisotropy. The main contribution to the thermal expansion anisotropy is due to the preferred orientation of the [BO3]3– triangles. Conclusions. The thermal properties of the oxoborates depend on their chemical composition. It was established that Tm increases with an increase in the Mg and Ti4+ content, and decreases with an increase in the Fe2+ content. The Fe2+ → Fe3+ oxidation is observed when the FeO component in the minerals exceeds 10 wt %, which leads to the solid-phase decomposition starting at temperatures of about 500–600 K. The values of the 293KαV volume thermal expansion of ludwigite and azoproite are comparable, while the largest values were observed for vonsenite. This is associated with the largest average bond lengths, primarily those of <Fe2+–O>6.

Nephrite from Xinjiang Qiemo Margou Deposit: Gemological and Geochemical Insights

The nephrite belt in the Altun Mountain–Western Kunlun Mountain region, which extends about 1300 km in Xinjiang, NW China, is the largest nephrite deposit in the world. The Qiemo region in the Altun Mountains is a crucial nephrite-producing area in China, with demonstrated substantial prospects for future exploration. While existing research has extensively investigated secondary nephrite deposits in the Karakash River and native black nephrite deposits in Guangxi Dahua, a comprehensive investigation of black nephrite from original deposits in Xinjiang is lacking. Margou black-toned nephrite was recently found in primary deposits in Qiemo County, Xinjiang; this makes in-depth research on the characteristics of this mine necessary. A number of technical analytical methods such as polarizing microscopy, Ultra-Deep Three-Dimensional Microscope, electron microprobe, back-scattered electron image analysis, X-ray fluorescence, and inductively coupled plasma mass spectrometry were employed for this research. An experimental test was conducted to elucidate the chemical and mineralogical composition, further clarifying the genetic types of the black and black cyan nephrite from the Margou deposit in Qiemo, Xinjiang. The results reveal that the nephrite is mainly composed of tremolite–actinolite, characterized by Mg/(Mg + Fe2+) ratios ranging from 0.86 to 1.0. Minor minerals include diopside, epidote, pargasite, apatite, zircon, pyrite, and magnetite. Bulk-rock rare earth element (REE) patterns exhibit distinctive features, such as negative Eu anomalies (δEu = 0.00–0.17), decreasing light REEs, a relatively flat distribution of heavy REEs, and low total REE concentrations (1.6–38.9 μg/g); furthermore, the Cr (6–21 μg/g) and Ni (2.5–4.5 μg/g) contents are remarkably low. The magmatic influence of granite appears to be a fundamental factor in the genesis of the magnesian skarn hosting Margou nephrite. The distinctive black and black cyan colors are attributed to heightened iron content, mainly associated with FeO (0.08~6.29 wt.%). Analyses of the chemical composition allow Margou nephrite to be classified as typical of magnesian skarn deposits.

Ammonium-Bearing Fluorapophyllite-(K) in the Magnesian Skarns from Aleului Valley, Pietroasa, Romania

An ammonium-bearing fluorapophyllite-(K) occurs as a late hydrothermal product in the outer endoskarn zone from Aleului Valley (N 46°37′04″, E 22°35′22″), located at the contact of the granodiorite laccolith from Pietroasa, of Upper Cretaceous age, with Anisian dolostones. Associated minerals are wollastonite, K feldspar, diopside, fluorapatite, talc, and pectolite. The chemical structural formula is [K0.985Na0.012(NH4)0.076]Σ=1.073(Ca4.009Mn0.001Fe2+0.003Mg0.002Ba0.001)Σ=4.016(Si7.953Al0.047) O20.029[F0.899(OH)0.101]·8.059H2O. The structure was successfully refined as tetragonal, space group P4/mnc, with cell parameters of a = 8.9685(1) Å and c = 15.7885(5) Å. The indices of refraction are ω = 1.534(1) and ε = 1.536(1). The calculated density is Dx = 2.381 g/cm3, in good agreement with the measured density, Dm = 2.379(4) g/cm3. The thermal analysis shows that the mineral completely dehydrates at up to 450 °C (endothermic effects at 330, 371, and 448 °C) and loses ammonium at 634 °C. In the infrared spectra, the multiplicity of the bands assumed to be silicate modes (1ν1 + 3ν3 + 2ν2 + 3ν4) agrees with the reduction in the symmetry of the SiO44− ion from Td to Cδ. Fluorapophyllite-(K) from Aleului Valley is of late hydrothermal origin and crystallized from F-rich fluids originating from the granodiorite intrusion, which mobilized K, Ca, and Si from the pre-existing feldspar.

Genetic features of tourmaline from the magnesian skarns of Kuhilal deposit, Southwestern Pamir

Background. Although the Kuhilal deposit of Mg skarns has been thoroughly studied, tourmaline in their composition has never been considered [5, 6, 16]. Uvite, a tourmaline variety, was mentioned in the list of rare minerals only with its crystallochemical formula [17]. L.N. Shabynin, a great connoisseur of skarns, noted the rarity of tourmaline in Mg skarns of various deposits. Tourmaline of this type is characterized by a strong variation in ferruginosity and a significant content of Ca. At the same time, Ca:Na varies from 2:3 to 20:1 [15]. According to N.N. Pertsev, another major specialist in skarns, tourmaline is a rare mineral of Mg skarn deposits [11]. The boron-iron ore deposit of Tayozhnoe, Aldan shield, is an exception. This deposit belongs to skarns, where a widespread development of tourmaline was noted [12]. Tourmaline (dravite) of this deposit was found only in silicate metamorphic rocks containing marbles and Mg skarns.Aim. To determine the paragenesis, crystal morphology, chemical composition, and genetic characteristics of tourmaline from Kuhilal Mg skarns.Materials and methods. Large aggregates (more than 10 cm across) and crystals of apple-green tourmaline from the Mg skarns of the Kuhilal deposit were investigated. Samples of Mg skarns containing tourmaline were collected and documented by the authors during fieldwork research at the Kuhilal deposit in 2017. The samples were examined by mineralogical and petrographic methods, X-ray diffraction analysis using a DRONE-3M (analyst A.V. Fedorov, Sergo Ordzhonikidze Russian State University for Geological Prospecting), microprobe analysis using a Cameca SX 100 in 15 kV 30 nA shooting mode (analyst V.I. Taskaev, IGEM RAS), and X-ray fluorescence analysis using an AXIOS advanced spectrometer with an X-ray tube equipped with a 3 kW Rh anode and Philips PW-2400 with a sensitivity of 10-4% (analyst A.I. Yakushev, IGEM RAS). The majority of studies were conducted at the Department of Mineralogy and Gemology of the Sergo Ordzhonikidze Russian State University for Geological Prospecting.Results. Tourmaline from the Mg skarns of the Kuhilal deposit has been studied for the first time. This mineral is rare for skarn rocks. Two tourmaline mineral associations were identified: with spinel and forsterite, and with chlorite and serpentine. In terms of chemical composition, tourmaline isattributed to fluorine-containing uvite with a close to zero ferruginosity. Uvite is characterized by a lenticular shape with a rarely observed, underdeveloped prism. Its mineralogical properties, chemical composition, and formation conditions were analyzed. Tourmaline can be used to make inexpensive jewelry inserts.Conclusion. Tourmaline crystallization occurred under the conditions of granulite facies of regional metamorphism. For boron formation, an apo-sedimentary, evaporite source is assumed.

Post-collisional magmatic-hydrothermal mineralization in the São Gabriel Terrane (southern Brazil): Insights from mineral chemistry, stable isotopes, and sulfide trace-elements of the Caçapava do Sul skarns

Prograde and retrograde magnesian skarns associated with the Caçapava do Sul Granitic Complex intrusion (central Dom Feliciano Belt, southern Brazil) host Cu–Fe (Mo–Au) mineralization. Vein and contact prograde skarns contain disseminated pyrite, pyrrhotite, molybdenite, and chalcopyrite formed from the interaction of mafic and felsic intrusions and dolomitic marbles at ca. 578 Ma. The prograde skarn mineralization is mainly localized in fold hinges and pinch-and-swell structures. Retrograde skarns host massive chalcopyrite and pyrite with chlorite and calcite associated with brittle structures at ca. 557 Ma. In this contribution, we provide mineral chemistry analyses of magmatic and skarn assemblages, calcite stable isotope analyses, and trace-element characterization of pyrite and chalcopyrite to assess ore-forming processes involved in the formation of the skarns. Amphibole-plagioclase geothermobarometry in granodiorite and monzonite apophyses of the Caçapava do Sul Granitic Complex yielded crystallization pressures between 4 and 5 kbar and temperatures from 680 to 750 °C. Biotite and amphibole composition of granodiorite, monzonite, and garnet-leucogranite apophyses suggest a trend of decreasing oxygen fugacity from early to late intrusions. Calcite-dolomite solvus thermometry in prograde skarns indicates temperatures between 580 and 630 °C whereas chlorite thermometry in retrograde skarn yields lower temperatures between 280 and 310 °C. Calcite from the retrograde skarns shows values of approximately −5.5‰ for δ13CVPDB and ∼9.0‰ for δ18OSMOW, indicating a major contribution of magmatic fluids during the retrograde stage whereas previous studies indicate a mixed igneous-sedimentary character of the calcite in prograde skarns. Our findings propose a multiphase magmatic-hydrothermal origin for the Cu–Fe (Mo–Au) skarn mineralization hosted by the Passo Feio Metamorphic Complex. The prograde and retrograde magnesian skarns of Caçapava do Sul were formed in the same age interval (578 - 557 Ma) as many other magmatic-hydrothermal base and precious metals mineralization in the São Gabriel Terrane. Hence, we suggest that the studied skarns belong to a multi-intrusive Cu-porphyry system in the São Gabriel Terrane formed during the post-collisional stage of the Dom Feliciano Belt.

Age and compositions of garnet in a magnesian skarn Au-Cu deposit, Tibet, implications for ore-fluid evolution

Compared to calcareous skarn Au-Cu deposits, magnesian skarn (Mg-skarn) Au-Cu deposits are scarce; hence the early evolution of the ore-fluids to late mineralization for the kinds of deposits has been inadequately investigated. Located at the southern margin of the Bangong-Nujiang metallogenic belt, the Galale Au-Cu deposit contains 32.59 tonnes of gold (average grade 2.04 g/t) and 105,600 tonnes of copper (average grade 0.66 %). The orebodies are hosted in an Mg-skarn with associated minerals, including olivine, pyroxene, garnet, and serpentine, which developed in the contact zone between the granodiorite and dolomite of the Jiega Formation. However, the genetic relationship between the Mg-skarn, granodioritic magma, and Au-Cu mineralization remains unclear. The contribution of early stage ore-forming fluids to late Au-Cu mineralization is still vague. In this study, we present the major and trace element compositions, and U–Pb isotope data for garnets obtained from the Galale deposit. We used the data to define the timing, nature, and evolution of early ore-forming fluid and described the genesis of the deposit. The color, at macro- and micro-scales, and chemical composition of the garnets can be used to divide them into two categories, namely early Al-rich Grt-I type garnets, and late stage Fe-rich Grt-II type garnets. In practice, Grt-I (And29.5∼56.1Gro41.3∼68.0Pra1.6∼2.8) and Grt-II (And96.7∼99.9Gro0∼2.7Pra0.1∼0.7) are grossular-andradite solid solution system garnets. Based on the chondrite-normalized REE patterns, Grt-I can be further divided into two sub-classes: Grt-I-1 domain in the core, enriched in HREEs and U, and Grt-I-2 material in the rim, relatively depleted in HREEs. Grt-II is enriched in LREEs and depleted in HREEs. Eu anomalies are slightly negative for the Grt-I-1 domain, weakly positive for the Grt-I-2 domain, and strongly negative for the Grt-II type garnets. The variations in texture and composition in garnets indicated that the formation of Grt-I garnets occurred during diffusive metasomatism in a relatively closed system, in a moderately oxidized ore-forming fluid setting. The formation of Grt-II occurred in a strongly oxidized setting during advective metasomatism in an open system. The enrichment of REE and U in Grt-I garnets was mainly controlled by a “menzerite” type substitution mechanism, partially explaining the strong positive correlation between Mg and REE concentrations. In the Grt-II type garnets, enrichment may also have been co-controlled by coupling substitution and adsorption. In situ U–Pb dating of garnet shows that Grt-I-1 and Grt-I-2 material has isotopic ages of 92 ± 2 Ma (2σ, MSWD = 0.85) and 91 ± 2 Ma (2σ, MSWD = 0.96), respectively. The results were consistent with the previous ages obtained from the granodiorite and Molybdenite using Re–Os isotopic dating within error. This indicates that magma, skarn alteration, and mineralization were spatially and temporally related. In addition, it indicates that the Galale deposit is a typical Mg-skarn Au-Cu deposit. In the earliest stages of deposit development, ore-forming fluids with a high oxygen fugacity (fO2) have inherited their characteristics from the magma. The crystallization of many magnetites during the oxide stage has decreased oxygen fugacity in the metallogenetic system. This has resulted in a relatively low fO2 fluid for Au-Cu precipitation. The study demonstrates that the ore-fluid fO2 plays a vital role in metal migration, hence Au-Cu mineralization in Mg-skarn deposits.

Petrogenesis of Jian forsterite jade solely composed of end-member forsterite (Fo 99.8): Constrained by trace element and oxygen isotope

The Jian forsterite jade, named for its enrichment of end-member forsterite, is a new type of jade discovered in Ji'an County (Jilin Province, Northeast China). The formation mechanism of this rare end-member forsterite remains unclear. In this study, we present the mineral chemistry and oxygen isotope analysis of end-member forsterite to elucidate the formation mechanism of the Jian forsterite jade. The Jian forsterite jade can be divided into three main types: yellowish-green, dark-green, and black. The Jian forsterite jade consists mainly of forsterite, serpentine, as well as minor brucite, spinel, phlogopite, dolomite, calcite, magnesite, and magnetite. The Fo% content (100 × Mg/[Mg + Fe], mol%) of forsterite varies from 96.69 to 99.82. All tested forsterite samples show low Ni, Mn, Cr, and Ca contents and very high B contents. The δ18O values of forsterite range from 13.79 ‰ to 18.57 ‰, which are significantly higher than those from the mantle and are similar to those from skarn, marble, and calc-silicate rocks. The oxygen isotope values of forsterite, coupled with a distinctive trace element signature, suggest that the genesis of end-member forsterite results from a siliceous fluid-mediated decarbonation of Mg-rich dolomite. The genesis of the Jian forsterite jade can be outlined in two main metamorphic stages: (1) high-temperature prograde stage related to the interaction of the gneiss-derived SiO2-rich fluids with overlying dolomite. High temperature leads to the formation of forsterite, spinel, and calcite mineral assemblage. (2) low-temperature retrograde stage characterized by the infiltration of hydrous fluids. Hydrous silicate minerals, mostly serpentine, phlogopite, and talc, are formed during this stage. Our work highlights and confirms the effectiveness of the trace element geochemistry of forsterite in identifying magnesian skarns, and classifies the forsterite in the Jian forsterite jade as an extreme example of this occurrence.

Garnet and scheelite chemistry of the Weijia tungsten deposit, South China: Implications for fluid evolution and W skarn mineralization in F-rich ore system

Fluid evolution is an essential subject in the studies of hydrothermal ore-forming processes. Garnet and scheelite prevail in W-bearing skarn deposits and record plentiful information on W skarn mineralization. In-situ LA-ICP-MS trace element analyses have been carried out on the garnet and scheelite from the F-rich Weijia W deposit in South China to constrain the processes of fluid evolution and W skarn mineralization. The Weijia W deposit mainly consists of calcic and magnesian skarns and was formed through six stages of alteration and mineralization. Two stages of fluid exsolution are recognized in the magmatic-hydrothermal system. The earlier exsolved fluids are Cl-rich with rightward-sloping REE patterns and result in pre-ore skarnization. The later exsolved fluids are F-rich with relatively flat REE patterns and are responsible for W mineralization. The pre-ore garnets are LREE-enriched and HREE-depleted whereas the syn-ore garnets are LREE-depleted and HREE-enriched with lower δEu values than the former, denoting a transition from wall rock-controlled to magmatic fluid-dominated fluid-rock interaction. Combined with the skarn occurrences, mineral assemblages, and garnet textures, it is revealed that the mechanism of skarn formation shifts from more diffusive metasomatism under lower water/rock ratios to more advective metasomatism at higher water/rock ratios. The advective metasomatism with a high flux of ore-forming fluids is hydrodynamically favorable for the consequent W mineralization. The earliest-formed scheelite is akin to the host granite porphyry in REE patterns and can reflect the features of initial mineralizing fluids. It has high ΣREE (1255–5059 ppm), Y (616–1416 ppm), Nb (585–2629 ppm), Ta (14–248 ppm), Mn (up to 1977 ppm) and low Mo (mostly < 1000 ppm) contents, indicating that the primary F-rich magmatic fluids are reduced and enriched in REEs, Y, Nb, and Ta. The contents of ΣREE, Y, Nb, and Ta in scheelite are decreasing with the evolution of the F-rich mineralizing fluids. The latest-formed scheelites have distinctly lower ΣREE (2.9–140 ppm), Y (0.01–4.1 ppm), Nb (1.7–77 ppm), and Ta (0.04–0.19 ppm) contents and higher (La/Yb)N ratios and δEu values. They show 1:1 positive correlation of EuN vs. EuN* and have high Mo (up to 129466 ppm) and low Mn (as low as 3.4 ppm) contents, implying involvement of meteoric waters in the evolved ore-forming fluids and an oxidizing condition. Fluid-rock interaction, mineral precipitation, and fluid mixing largely control the process of fluid evolution. Fluorine consumption due to the formation of fluorite and the other F-rich minerals is vital for the compositional evolution of F-rich mineralizing fluids. The decrease of F concentration in fluids will depress the solubilities of REEs, Y, Nb, and Ta and enhance the LREE/HREE fractionation. Greisenization and skarnization induced the neutralization of the acidic W-bearing fluids and the liberation of Ca from the granite porphyry and carbonate strata and then triggered the scheelite precipitation. The carbonate strata contain abundant Ca and the granite porphyry is poor in Ca, and thus the economic W mineralization dominantly occurs in the skarns.

Minerály coronaditové skupiny z Třebíče - Boroviny a Řípova (Morava, Česká republika)

Localities Třebíč - Borovina (GPS N 49° 12.400‘ E 015° 51.280‘) and nearby Řípov (N 49° 12.700‘ E 015° 50.850‘) are known since 19th century. They represent variegated residual rocks originated during Tertiary? weathering of marbles, dolomite marbles, calcic and magnesian skarns, quartzites and hornblendites intersected by aplites and granitic pegmatites. These rocks enveloped by the biotite gneisses and migmatites close to the contact with the Třebíč Pluton belong to the Moldanubian Zone of the Bohemian Massif. In the past, there was a short-time production of Fe-ore from the weathering zone at Třebíč - Borovina, as well as production of mineral raw-material for brickworks. Since the localities are inaccessible for a long time, we investigated 11 mineral samples of manganese oxidic minerals deposited in the museum collections (Museum Vysočina Třebíč, National Museum in Prague - Natural History Museum, Museum of the South-eastern Moravia in Zlín): 10 from Borovina and 1 from Řípov, labeled as pyrolusite, psilomelane, and wad. They usually form botryoidal black aggregates up to 20 cm in size. Powder X-ray diffraction proved the presence of the coronadite group minerals, accompanied by birnessite (one sample), kaolinite, quartz, gypsum, and minerals of the spinel and chlorite groups. Unit-cell parameters of the coronadite group minerals range as follows: a = 9.750 - 9.939 Å, b = 2.851 - 2.869 Å, c = 9.840 - 10.024 Å, and β = 88.66 - 90.77° (for the monoclinic space group 2/m). Scanning electron microscopy showed the botryoidal texture, where at least part of the zoning visible in back-scattered electrons is in fact the result of density of the mineral aggregate, alternating from massive to fibrous, sometimes with the atol microstructure. Empirical average mineral formulae, based on WDS analyses, are: hollandite from Borovina (Ba2+0.40 Ca2+0.16Mg2+0.13Cu2+0.03Zn2+0.02Pb2+0.01K+0.18Na+0.04)Σ0.98 [(Mn4+5.90Si4+0.06P5+0.04)Σ6.00 (Mn1.77Fe0.20Al0.11)3+Σ2.07] Σ8.07O16, cryptomelane from Borovina (K+0.51Na+0.04Ba2+0.20Ca2+0.09Zn2+0.05Cu2+0.03Mg2+0.02Pb2+0.02Co2+0.01)Σ0.97 [(Mn4+6.91 Si4+0.03P5+0.06)Σ7.00(Mn0.72Fe0.07Al0.06)3+Σ0.85]Σ7.85O16, and cryptomelane from Řípov (K+0.66Na+0.03Ba2+0.14Ca2+0.04 Zn2+0.03Cu2+0.01)Σ0.92[(Mn4+6.88Si4+0.03P5+0.09)Σ7.00 (Mn0.77Al0.11 Fe0.04)3+Σ0.93] Σ7.93O16. Most significant are substitutions Al3+ → Mn3+-1 and Fe3+ → Al3+-1 at the M3+ site, also Mg2+ → Ba2+-1 and Ca2+ → Ba2+-1 at the A2+ site in hollandite. Accessory minerals - baddeleyite and probable xenotime-(Y), present in the hollandite and cryptomelane aggregates, were identified only by EDS analyses.

Genesis and evolution of the San Manuel iron skarn deposit (Betic Cordillera, SW Spain)

The San Manuel magnesian skarn is an iron deposit hosted in dolomitic marbles from a tectonic slice imbricated within the Ronda peridotites, in the westernmost part of the Betic Cordillera, Spain. According to the dominant mineral assemblage, the skarn is subdivided into three different zones, (1) forsterite ± calcite skarn, (2) calcite ± chlorite ± serpentine skarn, and (3) Ca-amphibole skarn. The main ore in the skarn is a ∼ 2.5 m thick, massive ore body situated in the middle of the sequence. In this paper, we firstly report a comprehensive major to trace element composition, texture, microstructure, and mineralogy characterization for zoned magnesioferrite-magnetite grains of the San Manuel deposit using a combination of (1) laser ablation inductively coupled plasma mass spectrometer, (2) focused ion beam combined with transmission electron microscopy, and (3) electron back-scattered diffraction. We have defined four different magnesioferrite-magnetite generations. A complete sequence of zoning includes cores of magnesioferrite (Mag-1; MgO up to 10.6 wt%) overprinted by three successive generations of magnetite, namely Mag-2, Mag-3, Mag-4. Mag-2 (MgO < 4 wt%), hosts composite forsterite ± calcite ± chlorite inclusions, consistently with high Si, Ca, and Sr (average: 8204 ppm, 8980 ppm, and 49 ppm respectively) contents detected by in situ laser ablation inductively coupled plasma (LA-ICP-MS). Mag-3 replacing former Mag-1 and Mag-2 includes nanometric spinel and gahnite exsolutions detected by focused ion beam combined with a transmission electron microscope (FIB-TEM), which is consistent with its high Al, Ti, V, and Ga (average: 5073 ppm, 368 ppm, and 20 ppm, respectively) trace element concentration. Mag-4 is the Fe-richest magnetite (up to 94.16 wt% FeOtotal) forming the outermost rims in magnetite grains, and exhibiting the lowest total trace element contents. Approaches in temperature estimations employing magnetite-spinel exsolutions in Mag-3 suggest that the minimum temperature of the prograde stage reached temperatures below 700 °C, whereas Mag-4 should be formed during the retrograde stage. Magnetite microstructure studied by electron backscatter diffraction (EBSD) suggests Mag-4 formation under fluid-assisted dynamic conditions, which is consistent with the tectonic evolution of the emplacement. We propose that the San Manuel deposit formed by pulsed hydrothermal fluids derived from anatexis of crustal rocks during peridotite emplacement, promoting re-equilibration processes that led to the magnesioferrite-magnetite zoning.

Geology, mineralogy, and cassiterite geochronology of the Ayawilca Zn-Pb-Ag-In-Sn-Cu deposit, Pasco, Peru

The Ayawilca deposit in Pasco, Peru, represents the most significant recent base-metal discovery in the central Andes and one of the largest undeveloped In resources globally. As of 2018, it hosts an 11.7 Mt indicated resource grading 6.9% Zn, 0.16% Pb, 15 g/t Ag, and 84 g/t In, an additional 45.0 Mt inferred resource grading 5.6% Zn, 0.23% Pb, 17 g/t Ag, and 67 g/t In, and a separate Sn-Cu-Ag inferred resource of 14.5 Mt grading 0.63% Sn, 0.21% Cu, and 18 g/t Ag. Newly obtained U–Pb dates for cassiterite by LA-ICP-MS (22.77 ± 0.41 and 23.05 ± 2.06 Ma) assign the Ayawilca deposit to the Miocene polymetallic belt of central Peru. The polymetallic mineralization occurs as up to 70-m-thick mantos hosted by carbonate rocks of the Late Triassic to Early Jurassic Pucará Group, and subordinately, as steeply dipping veins hosted by rocks of the Pucará Group and overlying Cretaceous sandstones-siltstones of the Goyllarisquizga Group. Relicts of a distal retrograde magnesian skarn and cassiterite (stage pre-A) were identified in the deepest mantos. The volumetrically most important mineralization at Ayawilca comprises a low-sulfidation assemblage (stage A) with quartz, pyrrhotite, arsenopyrite, chalcopyrite, Fe-rich sphalerite, and traces of stannite and herzenbergite. Stage A sphalerite records progressive Fe depletion, from 33 to 10 mol% FeS, which is compatible with the observed transition from low- to a subsequent intermediate-sulfidation stage (B) marked by the crystallization of abundant pyrite and marcasite. Finally, during a later intermediate-sulfidation stage (C) sphalerite (up to 11 mol% FeS), galena, native bismuth, Cu-Pb-Ag sulfosalts, siderite, Mn-Fe carbonates, kaolinite, dickite, and sericite were deposited. This paragenetic evolution shows striking similarities with that at the Cerro de Pasco Cordilleran-type polymetallic deposit, even if at Ayawilca stage C did not reach high-sulfidation conditions. The occurrence of an early retrograde skarn assemblage suggests that the manto bodies at Ayawilca formed at the transition between distal skarn and skarn-free (Cordilleran-type) carbonate-replacement mineralization. Mineral assemblages define a T-fS2 evolutionary path close to the pyrrhotite-pyrite boundary. Buffering of hydrothermal fluids by underlying Devonian carbonaceous phyllites of the Excelsior Group imposed highly reduced conditions during stage A mineralization (logfO2 < − 30 atm). The low fO2 favored efficient Sn mobility during stages pre-A and A, in contrast to other known ore deposits in the polymetallic belt of central Peru, in which the occurrence of Sn minerals is minor. Subsequent cooling, progressive sealing of vein walls, and decreasing buffering potential of the host rocks promoted the shift from low- (stage A) to intermediate-sulfidation (stages B and C) states. LA-ICP-MS analyses reveal significant In contents in Fe-rich sphalerite (up to 1.7 wt%), stannite (up to 1908 ppm), and chalcopyrite (up to 1185 ppm). The highest In content was found in stage A sphalerite that precipitated along with chalcopyrite and stannite, thus pointing to the early, low-sulfidation assemblage as prospective for this high-tech metal in similar mineral systems. Indium was likely incorporated into the sphalerite crystal lattice via Cu+ + In3+ ↔ 2 Zn2+ and (Sn, Ge)4+ + (Ga, In)3+ + (Cu + Ag)+ ↔ 4 Zn2+ coupled substitutions. Indium incorporation mechanisms into the stannite and chalcopyrite crystal lattices remain unclear.

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 high-grade 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 °C 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 °C 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 °C 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 °C 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.

Geochemical characteristics and composition changes of tremolite at various stages in the mineralization process of nephrite from Tieli, Heilongjiang, Northeastern China

The quality of nephrite (jade) is directly related to the structural and compositional changes it undergoes during mineralization. This study is the first systematic analysis of the geochemical characteristics and composition changes of tremolite at various stages in the mineralization process of nephrite from Tieli, Heilongjiang, Northeastern China, using polarized light microscopy, electron probe microanalysis, X-ray diffraction, and backscatter and laser ablation inductively coupled plasma mass spectrometry. The results showed that the main mineral component of Tieli nephrite is tremolite, which contains diopside, serpentine, calcite, dolomite, quartz, and feldspar. Tieli nephrite belongs to the magnesian skarn deposit. The tremolite rare-earth element (REE) distribution curves showed obvious differences, suggesting that the ore body has different metallogenic sources and conditions. Tieli nephrite mineralization is divided into three stages: diopside formation, tremolite formation, and hydrothermal alteration. During tremolite formation, three series of tremolite are formed, and the content of the third series determines the quality of the nephrite produced. The composition and structure of Tieli nephrite are quite complex, however, which greatly affects the quality of nephrite.

Major and trace element composition of olivine from magnesian skarns and silicate marbles

Abstract Olivine is a major rock-forming mineral in various magmatic and metamorphic rocks and the upper mantle. In this paper, we present the first high-precision analyses of olivine from 15 samples of magnesian skarns and silicate marbles (MSSM) from the collection of the Fersman Mineralogical Museum (Moscow, Russia). Mg# [Mg/(Mg+Fe2+)·100, mol%] of olivine from the samples studied varies from 86 to nearly 100. The main distinctive features of the olivine are anomalously low contents of Co (&amp;lt;51 mg/g), Cr (&amp;lt;5 mg/g), and Ni (&amp;lt;44 mg/g) and high content of B (23–856 mg/g), which correlate with host-rock compositions. Phosphorus (5–377 mg/g) incorporation in olivine is charge balanced by the incorporation of Li (0.15–61 mg/g) and Na (&amp;lt;14.3 mg/g). Y and REE contents exhibit positive correlations with Na, which suggests that REE incorporation into MSSM olivine could occur via charge-balanced coupled substitution with Na at low temperature and low aSiO2 conditions during MSSM formation. The documented compositional features of olivine from magnesian skarns and silicate marbles can help reconstruct the genesis of the host-rocks and identify xenocrysts of MSSM olivine in magmatic rocks.

Types of metasomatic rocks: temperature conditions, buildups, features of composition, minerageny

The relevance of the work is due to the importance of metasomatic rocks associated many ore and non-metallic mineral resources. Purpose of the work: study of temperature conditions of formation, the characteristics of the chemical and mineral composition, the mineralogy of metasomatites. Results. The extended classification of the main types of metasomatic rocks (alkaline, basic, acidic) formed in the early alkaline and acid stages of the hydrothermal process is given. Temperature conditions of formation, features of chemical and mineral composition and metasomatite mineralogeny are considered. Alkaline metasomatites are subdivided into potassium (pyroxene phenites, microclinites, biotite-orthoclase metasomatites, gumbaites) and sodium (nepheline-pyroxene phenites, albites, sodic alterations). Deposits of tungsten, molybdenum, gold and uranium are associated with potassium metasomatites (gumbaites), and deposits of beryllium, lithium, tantalum, and niobium are associated with sodium metasomatites (albite). The main metasomatic rocks (basificates) include calcium and iron-magnesian metasomatites (calcareous and magnesian skarns, diopside-lapis lazuli metasomatites, rhodingites, kamaforites, carbonatites, apocarbonate calcites, dolomite-ankerite, magnesite and sideroplesite metasomatites). The formation of deposits of iron, boron, and phlogopite is associated with skarn; deposits of rare-earth elements, tantalum, niobium, and apatite are associated with carbonatites. Acid metasomatites are subdivided into aluminous and siliceous. Aluminous metasomatites include propylites, chloritolites, microcline-sericite and tourmaline-sericite metasomatites, secondary quartzites, argillizated rocks. Alumina deposits (kaolins, bentonites) are associated with secondary quartzites. Siliceous metasomatites include the largest number of species: uralite metasomatites, greisens, listvenites and berezites, chlorite-sericite-quartz and sericite-quartz metasomatites, charoitites, serpentinites, nephrites, anthophyllite metasomatites, carbonate-talc metasomatites and talcites, magnetite quartzites, jaspers, jasperoids. There is a group of metasomatites among them consisting of quartz in association with hydrous alumosilicates (muscovite, topaz, and chlorite). The other group includes low-alumina metasomatites, the mineral composition of which is dominated by hydrous calcium and magnesian silicates (charoite, serpentine, antophyllite, tremolite, talc). The third group is represented by metasomatites of quartz composition (magnetite quartzites, jaspers, jasperoids). The formation of deposits of iron, tin, tungsten, molybdenum, gold, polymetals, nonmetallic raw materials (asbestos, talc, charoite, nephrite, jasper) is associated with siliceous metasomatites. Conclusions. According to the formation temperature, high-temperature (above 500o С), medium-temperature (500–300о С) and low-temperature (below 300o С) metasomatic rocks are distinguished. The average compositions of alkaline metasomatites are characterized by high concentrations of potassium or sodium oxides, the predominance of feldspars (orthoclase, microcline, albite) in association with pyroxenes, carbonates. The main metasomatites are distinguished by high contents of calcium, magnesium and iron oxides at low silica concentrations prevailing in the mineral composition of silicates (pyroxenes and garnets) or carbonates (calcite, dolomite, magnesite, breunnerite). The composition of acid metasomatites is characterized by high concentrations of alumina or silica, the predominance of hydrous aluminosilicates, silicates and quartz.

A study of igneous rocks related to Zn–Pb mineralization in the Shinyemi and Gagok deposits of the Taebaeksan Basin, South Korea

AbstractThe Shinyemi and Gagok deposits, located in the Taebaeksan Basin, South Korea, display Zn–Pb mineralization along a contact between Cretaceous granitoids and Cambrian–Ordovician carbonates of the Joseon Supergroup. The Shinyemi mine is one of the largest polymetallic skarn‐type magnetite deposits in South Korea and comprises Fe and Fe–Mo–Zn skarns, and Zn–Cu–Pb replacement deposits. Both deposits yield similar Cretaceous mineralization ages, and granitoids associated with the two deposits displaying similar mineral textures and compositions, are highly evolved, and were emplaced at a shallow depth. They are classified as calc‐alkaline, I‐type granites (magnetite series) and were formed in a volcanic arc. Compositional variation is less in the Shinyemi granites and aplites (e.g., SiO2 = 74.4–76.6 wt% and 74.4–75.1 wt%, respectively) than in the Gagok granites and aplites (e.g., SiO2 = 65.6–68.0 wt% and 74.9–76.5 wt%, respectively). Furthermore, SiO2 vs K/Rb and SiO2 vs Rb/Sr diagrams indicate that the Shinyemi granitoids are more evolved than the Gagok granitoids. Shinyemi granitoids had been already differentiated highly in deep depth and then intruded into shallow depth, so both granite and aplite show the highly evolved similar chemical compositions. Whereas, less differentiated Gagok granitoids were separated into two phases in the last stage at shallow depth, so granite and aplite show different compositions. The amounts of granites and aplite are similar in the Shinyemi deposit, whereas the aplite appears in an amount less than the granite in the Gagok deposit. For this reason, the Shinyemi granitoids caused not only Fe enrichment during formation of the dolomite‐hosted magnesian skarn but also was associated with Mo mineralization in the Shinyemi deposit. Zn mineralization of the Gagok deposit was mainly caused by granite rather than aplite. Our data suggest that the variation in mineralization displayed by the two deposits resulted from differences in the compositions of their associated igneous intrusions.

Factors controlling the crystal morphology and chemistry of garnet in skarn deposits: A case study from the Cuihongshan polymetallic deposit, Lesser Xing'an Range, NE China

Abstract The grossular-andradite solid solutions in garnet from skarn deposits in relation to hydrothermal processes and physicochemical conditions of ore formation remain controversial. Here we investigate garnet occurring in association with calcic and magnesian skarn rocks in the Cuihongshan polymetallic skarn deposit of NE China. The calcic skarn rocks contain three types of garnets. (1) Prograde type I Al-rich anisotropic garnets display polysynthetic twinning and a compositional range of Grs18–80Adr10–75. This type of garnet shows markedly low rare earth element (REE) contents (3.27–78.26 ppm) and is strongly depleted in light rare earth elements (LREE, 0.57–44.65 ppm) relative to heavy rare earth elements (HREE, 2.31–59.19 ppm). They also display a significantly negative Eu anomaly (Eu/Eu* of 0.03–0.90). (2) Fe-rich retrograde type II garnets are anisotropic with oscillatory zoning and own wide compositional variations (Grs1–47Adr30–95) with flat REE (13.73–377.08 ppm) patterns. (3) Fe-rich retrograde type III isotropic garnets display oscillatory zoning and morphological transition from planar dodecahedral {110} crystal faces to {211} crystal faces in the margin. Types III garnets exhibit relatively narrow compositional variations of Grs0.1–12Adr85–97 with LREE-enrichment (0.80–51.87 ppm), flat HREE patterns (0.15–2.46 ppm) and strong positive Eu anomalies (Eu/Eu* of 0.93–27.07 with almost all &gt;1). The magnesian skarn rocks contain euhedral isotropic type IV Mn-rich garnet veins with a composition of Grs10–23Sps48–62Alm14–29. All calcic garnets contain considerable Sn and W contents. Type II garnet containing intermediate compositions of andradite and grossular shows the highest Sn contents (64.36–2778.92 ppm), albeit the lowest W range (1.11–468.44 ppm). Birefringence of garnet is probably caused by strain from lattice mismatch at a twinning boundary or ion substitution near intermediate compositions of grossular-andradite. The fine-scale, sharp, and straight garnet zones are probably caused by self-organization, but the compositional variations of zones from core to rim are probably caused by external factors. The zoning is likely driven by external factors such as composition of the hydrothermal fluid. REE concentrations are probably influenced by the relative proportion and temperature of the system. Moreover, the LREE-HREE fractionation of garnet can be attributed to relative compositions of grossular-andradite system. The W and Sn concentrations in garnet can be used as indicators for the exploration of W-Sn skarn deposits.

The Early Jurassic Fe–Sn metallogenic event and its geodynamic setting in South China: Evidence from Re–Os, U–Pb geochronology and geochemistry of the Dading magnesian skarn Fe–Sn deposit

The South China Block (SCB) is one of the largest W-Sn-polymetallic metallogenic district over the world, with most of the deposits formed during the Mesozoic. The Early Jurassic of SCB was considered as a magmatic and metallogenic quiescence stage, as response to the tectonic transition from the paleo-Tethyan to the paleo-Pacific geodynamic domains. The Dading Fe-Sn deposit is a quite rare Early Jurassic deposit recognized in SCB. SIMS Zircon U–Pb and molybdenite Re-Os dating indicate that the Dading Fe–Sn deposit (185.9 ± 4.9 Ma) and related Shibei granite (189.0 ± 1.5 Ma) formed at the Early Jurassic, which provides convincing evidence for a previously unrecognized Early Jurassic Fe–Sn metallogenic event in SCB. Geochemical data show that the Shibei granite has high SiO2, Nb, Zr + Nb + Ce + Y concentrations and high Ga/Al ratio, but low Y/Nb ratio, which are similar to those of A1-type granite. The large range of zircon εHf(t) values (−2.4 to +3.4), negative correlation between zircon εHf(t) and δ18O values, and unique whole-rock Sr–Nd isotopic compositions (εNd(t) = −3.3 to −3.7; ISr = 0.7063 – 0.7085) suggest that the Shibei granite is likely to originate from a mixed source of pre-existing crust and juvenile material with OIB-like isotopic composition. Combining with the spatial distribution of the volcanic–intrusive rocks, sedimentary basins, and tectonic deformation styles, we suggest that the Early Jurassic Fe–Sn mineralization occurred in an extensional environment, which was probably linked to the post-orogenic collapse of the Indosinian orogeny between the SCB and Indochina Block.

Contrasting types of boron-bearing deposits in magnesian skarns from Romania

Two types of boron-bearing deposits, displaying contrasting properties, were identified in five magnesian skarns from Romania, at Băiţa Bihor, Pietroasa, Cacova Ierii, Maşca Băişoara and Ocna de Fier. These should be defined as Fe-poor (Mg-B) and Fe-rich (Mg-Fe-B), respectively. The skarns are developed at the contact of igneous bodies of Upper Cretaceous age with dolomite sequences. They occur as metasomatic columns, since a roughly consistent zoning was found from core to rim in the skarn bodies. Borates (suanite, kotoite, ludwigite, szaibélyite, rarely fluoborite) occur in the outer skarn zones, whereas the inner zones typically contain magnesian silicates (e.g., forsterite, humite-group minerals, diopside, and phlogopite) and spinel. The Mg-B type of skarn deposit is typified by the abundance of suanite – szaibélyite and kotoite and by the scarcity of ludwigite and magnetite. The B-bearing portions of the Fe-rich skarns consist dominantly of bands of ludwigite alternating with magnetite. Small amounts of kotoite, forsterite and clinohumite are also present. The differentiation of the two types of deposits is further emphasized by the development of F-rich parageneses (i.e., fluoborite, fluorite, F-rich humites) only in the Fe-poor skarns. All B-bearing skarns in Romania experienced generally similar peak contact-metamorphic conditions of 400–650 °C and pressures up to 3 kbar. Borates have similar geochemical signatures with respect to minor elements as the contemporaneous silicates.