Cuspidine‐bearing skarn from Chesney Vale,Victoria

The rare calc‐silicate minerals cuspidine, bultfonteinite, foshagite and xonotlite occur in a calcsilicate skarn zone near Chesney Vale, in northern Victoria. They are associated with andradite-grossular garnet, vesuvianite, diopside, wollastonite, prehnite, epidote, fluorite, calcite, perovskite,sphene and possibly tobermorite. The calc‐silicate skarn zone has formed in thermally meta‐morphosed, Ordovician, deep‐marine sediments adjacent to an Early Devonian aplitic granite pluton. The assemblages are estimated to have formed at low pressure (<100 MPa) at temperaturesnot exceeding 600°C in the presence of a low‐X_co2 fluorine‐bearing fluid. The occurrence is the firstrecord of bultfonteinite and foshagite in Australia and the first record of cuspidine and xonotlite inVictoria.     

Timing and setting of skarn and iron oxide formation at the Smältarmossen calcic iron skarn deposit, Bergslagen, Sweden

Abundant iron oxide deposits including banded iron formations, apatite iron oxide ores, and enigmatic marble/skarn-hosted magnetite deposits occur in the Palaeoproterozoic Bergslagen region, southern Sweden. During the last 100 years, the latter deposit class has been interpreted as contact metasomatic skarn deposits, metamorphosed iron formations, or metamorphosed carbonate replacement deposits. Their origin is still incompletely understood. At the Smältarmossen mine, magnetite was mined from a ca. 50-m-thick calcic skarn zone at the contact between rhyolite and stratigraphically overlying limestone. A syn-volcanic dacite porphyry which intruded the footwall has numerous apophyses that extend into the mineralized zone. Whole-rock lithogeochemical and mineral chemical analyses combined with textural analysis suggests that the skarns formed by veining and replacement of the dacite porphyry and rhyolite. These rocks were added substantial Ca and Fe, minor Mg, Mn, and LREE, as well as trace Co, Sn, U, As, and Sr. In contrast, massive magnetite formed by pervasive replacement of limestone. Tectonic fabrics in magnetite and skarn are consistent with ore formation before or early during Svecokarelian ductile deformation. Whereas a syngenetic–exhalative model has previously been suggested, our results are more compatible with magnetite formation at ca. 1.89 Ga in a contact metasomatic skarn setting associated with the dacite porphyry.     

Defining trace-element alteration halos to skarn deposits hosted in heterogeneous carbonate rocks: Case study from the Cu–Zn Antamina skarn deposit,Peru

The presence of geochemical anomalies, defining haloes around hydrothermal ore deposits, can be used to vector towards mineralization, or identify ore bodies buried at depth. Several important types of ore deposits, including skarn deposits, are often hosted within carbonate-rich sedimentary rocks. Identifying anomalous trace-element concentrations in carbonate rocks is complicated by variable lithology (i.e. siliciclastic component) and volume loss during hydrothermal alteration. In this study of the world-class Antamina skarn deposit in Peru, we use the ratio of metals:immobile elements (e.g. La, Al₂O₃) to differentiate genuine and false geochemical anomalies in limestones and marbles surrounding the skarn deposit. Unaltered limestones are used to define threshold values for metal:immobile element ratios (through use of the median value ± 2 median absolute deviations). Genuine anomalies are identified when metal concentrations exceed those predicted using median + 2 median absolute deviations. In addition, comparison of “four acid” and lithium-borate fusion analytical techniques reveals that the lower cost four-acid techniques give reliable results. Our approach can be used to identify geochemical anomalies and halos related to hydrothermal alteration of carbonate-rich rocks, which have direct application to skarn deposits.     

The origin of skarn beds, Ryllshyttan Zn�CPb�CAg + magnetite deposit, Bergslagen, Sweden

Thin- to medium-bedded, stratiform calc-silicate deposits (banded skarns) are a peculiar, but important, component of the supracrustal successions in the Palaeoproterozoic Bergslagen mining district of central Sweden. They are referred to as ??skarn-banded leptites?? in the literature and are common in areas and at stratigraphic levels that contain iron oxide and base metal sulphide deposits. The stratigraphic hanging wall of the stratabound Ryllshyttan Zn?CPb?CAg + magnetite deposit at Garpenberg, contains approximately 100?C150?m of interbedded aluminous skarn beds and rhyolitic ash-siltstones. The skarn beds are mineralogically variable and dominantly composed of grandite, spessartine, epidote, actinolite, quartz, clinopyroxene, and locally magnetite. Integrated field-mapping, and whole-rock lithogeochemical, microscopic and mineral chemical analyses suggest that the stratiform skarn beds are the products of at least two discrete hydrothermal events and subsequent metamorphism. The first event comprised accumulation in a quiescent subaqueous environment, below wave base, of calcareous and ferruginous sediments rich in Fe, Mn, Ca, and Mg. These chemical sediments were deposited concurrently with rhyolitic ash-silt sedimentation, thus forming a (now metamorphosed) laminated calcareous Fe formation with both a detrital rhyolitic component and rhyolitic siltstone interbeds. Positive Eu-anomalies and negative Ce-anomalies for normalized rare earth element analyses of skarn beds suggest that the iron may have been derived from exhalation of hot and reduced hydrothermal fluids, which upon mixing with more oxidized seawater, precipitated Fe oxides and/or carbonates that settled from suspension to the seafloor. The size of the positive Eu-anomalies of the chemical sediments are modified by the content of rhyolitic volcaniclastic material, which has a negative Eu anomaly, such that positive Eu-anomalies are only observed in skarn beds that possess a minor volcaniclastic component. Subsequently, the calcareous Fe formations were subjected to post-depositional alteration by hydrothermal fluids, locally yielding more manganoan and magnesian assemblages. The Mn-alteration is manifested by lateral gradations from epidote-grandite-clinopyroxene±magnetite rocks into significantly more Mn-rich quartz-spessartine rocks and massive andradite rocks over distances of less than 10?cm within individual skarn beds. Magnesian alteration is manifested by the development of discordant zones of pargasite para-amphibolites and formation of stratiform pargasite rocks texturally similar to the interlaminated grandite-epidote-ferroan diopside rocks. The latter increase in abundance towards the Ryllshyttan deposit and are associated with pre-metamorphic/pre-tectonic K?CMg?CFe±Si alteration (now biotite-phlogopite-garnet-cordierite-pargasite rocks) that is related to base metal mineralization. The zone of Mn- and Mg-altered skarn beds extends beyond the zone of pervasive K?CMg?CFe±Si alteration around Ryllshyttan. This suggests that the skarn bed progenitors, or their sedimentary contacts against rhyolitic ash-siltstones, acted as conduits to outflowing hydrothermal fluids. The chemical and mineralogical imprint, imposed on affected beds by alteration, may serve as indicators of proximity to intense K?CMg?CFe±Si alteration envelopes around other base metal sulphide deposits in Bergslagen. The last recorded event comprised syn-tectonic veining of competent massive andradite skarn beds. The veins contain quartz-albite-epidote-ferroan diopside-actinolite assemblages.     

Geology and genesis of the post-collisional porphyry–skarn deposit at Bangpu,Tibet

Bangpu deposit in Tibet is a large but poorly studied Mo-rich (~ 0.089 wt.%), and Cu-poor (~ 0.32 wt.%) porphyry deposit that formed in a post-collisional tectonic setting. The deposit is located in the Gangdese porphyry copper belt (GPCB), and formed at the same time (~ 15.32 Ma) as other deposits within the belt (12 ~ 18 Ma), although it is located further to the north and has a different ore assemblage (Mo–Pb–Zn–Cu) compared to other porphyry deposits (Cu–Mo) in this belt. Two distinct mineralization events have been identified in the Bangpu deposit which are porphyry Mo–(Cu) and skarn Pb–Zn mineralization. Porphyry Mo–(Cu) mineralization in the deposit is generally associated with a mid-Miocene porphyritic monzogranite rock, whereas skarn Pb–Zn mineralization is hosted by lower Permian limestone–clastic sequences. Coprecipitated pyrite and sphalerite from the Bangpu skarn yield a Rb–Sr isochron age of 13.9 ± 0.9 Ma. In addition, the account of garnet decreases and the account of both calcite and other carbonate minerals increases with distance from the porphyritic monzogranite, suggesting that the two distinct phases of mineralization in this deposit are part of the same metallogenic event.Four main magmatic units are associated with the Bangpu deposit, namely a Paleogene biotite monzogranite, and Miocene porphyritic monzogranite, diabase, and fine-grained diorite units. These units have zircon U–Pb ages of 62.24 ± 0.32, 14.63 ± 0.25, 14.46 ± 0.38, and 13.24 ± 0.04 Ma, respectively. Zircons from porphyritic monzogranite yield ε_Hf(t) values of 2.2–8.7, with an average of 5.4, whereas the associated diabase has a similar ε_Hf(t) value averaging at 4.7. The geochemistry of the Miocene intrusions at Bangpu suggests that they were derived from different sources. The porphyritic monzogranite has relatively higher heavy rare earth element (HREE) concentrations than do other ore-bearing porphyries in the GPCB and plots closer to the amphibolite lithofacies field in Y–Zr/Sm and Y–Sm/Yb diagrams. The Bangpu diabase contains high contents of MgO (> 7.92 wt.%), FeOt (> 8.03 wt.%) but low K₂O (< 0.22 wt.%) contents and with little fractionation of the rare earth elements (REEs), yielding shallow slopes on chondrite-normalized variation diagrams. These data indicate that the mineralized porphyritic monzogranite was generated by partial melting of a thickened ancient lower crust with some mantle components, whereas the diabase intrusion was directly derived from melting of upwelling asthenospheric mantle. An ancient lower crustal source for ore-forming porphyritic monzogranite explains why the Bangpu deposit is Mo-rich and Cu-poor rather than the Cu–Mo association in other porphyry deposits in the GPCB because Mo is dominantly from the ancient crust.The Bangpu deposit has alteration zonation, ranging from an inner zone of biotite alteration through silicified and phyllic alteration zones to an outer propylitic alteration zone, similar to typical porphyry deposits. Some distinct differences are also present, for example, K-feldspar alteration at Bangpu is so dispersed that a distinct zone of K-feldspar alteration has not been identified. Hypogene mineralization at Bangpu is characterized by the early-stage precipitation of chalcopyrite during biotite alteration and the late-stage deposition of molybdenite during silicification. Fluid inclusion microthermometry indicates a change in ore-forming fluids from high-temperature (320 °C–550 °C) and high-salinity (17 wt.%–67.2 wt.%) fluids to low-temperature (213 °C–450 °C) and low-salinity (7.3 wt.%–11.6 wt.%) fluids. The deposit has lower δD_V-SMOW (− 107.1‰ to − 185.8‰) values compared with other porphyry deposits in the GPCB, suggesting that the Bangpu deposit formed in a shallower setting and is associated with a more open system than is the case for other deposits in this belt. Sulfides at Bangpu yield δ³⁴S_V-CDT values of − 2.3‰ to 0.3‰, indicative of mantle-derived S implying that coeval mantle-derived mafic magma (e.g., diabase) simultaneously supplied S and Cu to the porphyry system at Bangpu. In comparison, the Pb isotopic compositions (²⁰⁶Pb/²⁰⁴Pb = 18.79–19.28, ²⁰⁷Pb/²⁰⁴Pb = 15.64–15.93, ²⁰⁸Pb/²⁰⁴Pb = 39.16–40.45) of sulfides show that other metals (e.g., Mo, Pb, Zn) were likely derived mainly from an ancient crustal source. Therefore, the formation of the Bangpu deposit can be explained by a two-stage model involving (1) the partial melting of an ancient lower crust triggered by invasion of asthenospheric mantle-derived mafic melts that provide heat and metal Cu and (2) the formation of the Bangpu porphyry Mo–Cu system, formed by magmatic differentiation in the overriding crust in a post-collisional setting.     

Formation of the Vysoká–Zlatno Cu–Au skarn–porphyry deposit, Slovakia

The central zone of the Miocene Štiavnica stratovolcano hosts several occurrences of Cu–Au skarn–porphyry mineralisation, related to granodiorite/quartz–diorite porphyry dyke clusters and stocks. Vysoká–Zlatno is the largest deposit (13.4 Mt at 0.52% Cu), with mineralised Mg–Ca exo- and endoskarns, developed at the prevolcanic basement level. The alteration pattern includes an internal K- and Na–Ca silicate zone, surrounded by phyllic and argillic zones, laterally grading into a propylitic zone. Fluid inclusions in quartz veinlets in the internal zone contain mostly saline brines with 31–70 wt.% NaCl eq. and temperatures of liquid–vapour homogenization (Th) of 186–575°C, indicating fluid heterogenisation. Garnet contains inclusions of variable salinity with 1–31 wt.% NaCl eq. and Th of 320–360°C. Quartz–chalcopyrite veinlets host mostly low-salinity fluid inclusions with 0–3 wt.% NaCl eq. and Th of 323–364°C. Data from sphalerite from the margin of the system indicate mixing with dilute and cooler fluids. The isotopic composition of fluids in equilibrium with K-alteration and most skarn minerals (both prograde and retrograde) indicates predominantly a magmatic origin (δ¹⁸O_fluid 2.5–12.3‰) with a minor meteoric component. Corresponding low δD_fluid values are probably related to isotopic fractionation during exsolution of the fluid from crystallising magma in an open system. The data suggest the general pattern of a distant source of magmatic fluids that ascended above a zone of hydraulic fracturing below the temperature of ductile–brittle transition. The magma chamber at ∼5–6 km depth exsolved single-phase fluids, whose properties were controlled by changing PT conditions along their fluid paths. During early stages, ascending fluids display liquid–vapour immiscibility, followed by physical separation of both phases. Low-salinity liquid associated with ore veinlets probably represents a single-phase magmatic fluid/magmatic vapour which contracted into liquid upon its ascent.     

Geology and genesis of the giant Beiya porphyry–skarn gold deposit,northwestern Yangtze Block,China

The Beiya ore deposit is located in the northwestern Yangtze Block, to the southeast of the Tibetan Plateau, SW China. The deposit is hosted by a porphyritic monzogranitic stock that is cross-cut by a porphyritic granite and later lamprophyre dikes. The whole-rock geochemistry of the porphyritic monzogranite and granite intrusions is both potassic and adakite-like, as evidenced by high K₂O/Na₂O (2.2 to 24.8), Sr/Y (53.2 to 143.2), and (La/Yb)_N (4.9 to 28.9) ratios. Both intrusions have comparable zircon U–Pb ages of ca. 36 Ma and εHf(t) values of − 6.8 to + 2.7. Zircons within these intrusions have Hf isotope crustal model ages with a prominent peak at ca. 840 Ma, and both of the intrusions have similar Sr–Nd–Pb isotopic compositions that are comparable to the compositions of amphibolite xenoliths hosted by potassic felsic intrusions in western Yunnan. The contemporaneous lamprophyre dikes show Nb–Ta depletion, enriched (⁸⁷Sr/⁸⁶Sr)_i and εNd(t), and extremely low Nb/U ratios (1.6–3.6), suggesting that these dikes were formed from magmas generated by partial melting of a metasomatized subcontinental lithospheric mantle (SCLM). The geochemistry of the porphyritic intrusions and the lamprophyre dikes suggests that the Beiya porphyries formed as a result of partial melting of a thickened and K-rich region of the lower crust, triggered by melting of metasomatized SCLM. The ca. 840 Ma U–Pb ages and εHf(t) values (− 6.8 to + 2.7) of xenocrystic zircons within the porphyritic intrusions suggest that these zircons were produced in a continental arc setting at ca. 840 Ma. The peak Hf model age of the zircons crystallized from the intrusions and the U–Pb ages of the xenocrystic zircons within the intrusions suggest that these porphyritic intrusions formed from magmas sourced from a juvenile crust that formed at ca. 840 Ma. This juvenile crust is most likely the source for the metals within the porphyry–skarn deposits in the study area, as the SCLM-derived lamprophyre dikes in this area are barren.Massive Fe–Au orebodies (~ 99 million metric tons at an average grade of 2.61 g/t Au) within the study area are generally located within the skarn-altered boundary of the porphyritic monzogranite stock and along the faults in the surrounding Triassic carbonates. The Fe–Au orebodies are spatially and genetically associated with skarn comprising garnet and diopside. Petrographic observations show that the massive Fe–Au orebodies mainly consist of hematite and magnetite with disseminated pyrite that hosts native gold and electrum.The porphyritic granite contains porphyry-style mineralization in the form of disseminated and veinlet-hosted pyrite and chalcopyrite. Pyrite-hosted lattice-bound gold is present within both the massive Fe–Au and the porphyry-type mineralization in the study area, and is present at concentrations up to 10 ppm Au (as determined by in situ LA-ICP-MS analysis). Subsequent weathering altered the primary magnetite–hematite–sulfide assemblage in the Fe–Au orebody into a magnetite–limonite assemblage, and generated laterite-type mineralization in which gold is hosted by limonite.     

Dal’negosrk skarn deposit,Sikhote-Alin: Stages and sources of matter for borosilicate ores

The danburite orebody at the northeastern wall of the open pit of the Dal’negorsk borosilicate deposit is studied. The comparative mineralogical-, isotopic-, and thermobarogeochemical analyses of danburite from the Levoberezhnyi area and datolite of the late skarn stage from the Tsentral’nyi open pit confirms that danburite is a result of the early borosilicate stage of formation of the deposit. Combined with previously published data, it is concluded that marine sedimentary rocks or Early Cretaceous arkose sandstones from the matrix of the Taukhin accretionary prism could be the source of boron.     

Mineral compositions and fluid evolution of the Tonglushan skarn Cu–Fe deposit,SE Hubei,east-central China

The Tonglushan Cu–Fe deposit (1.12 Mt at 1.61% Cu, 5.68 Mt at 41% Fe) is located in the westernmost district of the Middle–Lower Yangtze River metallogenic belt. As a typical polymetal skarn metallogenic region, it consists of 13 skarn orebodies, mainly hosted in the contact zone between the Tonglushan quartz-diorite pluton (140 Ma) and Lower Triassic marine carbonate rocks of the Daye Formation. Four stages of mineralization and alterations can be identified: i.e. prograde skarn formation, retrograde hydrothermal alteration, quartz-sulphide followed by carbonate vein formation. Electron microprobe analysis (EMPA) indicates garnets vary from grossular (Ad_20.2–41.6Gr_49.7–74.1) to pure andradite (Ad_47.4–70.7Gr_23.9–45.9) in composition, and pyroxenes are represented by diopsides. Fluid inclusions identify three major types of fluids involved during formation of the deposit within the H₂O–NaCl system, i.e. liquid-rich inclusions (Type I), halite-bearing inclusions (Type II), and vapour-rich inclusions (Type III). Measurements of fluid inclusions reveal that the prograde skarn minerals formed at high temperatures (>550°C) in equilibrium with high-saline fluids (>66.57 wt.% NaCl equivalent). Oxygen and hydrogen stable isotopes of fluid inclusions from garnets and pyroxenes indicate that ore-formation fluids are mainly of magmatic-hydrothermal origin (δ¹⁸O = 6.68‰ to 9.67‰, δD = –67‰ to –92‰), whereas some meteoric water was incorporated into fluids of the retrograde alteration stage judging from compositions of epidote (δ¹⁸O = 2.26‰ to 3.74‰, δD= –31‰ to –73‰). Continuing depressurization and cooling to 405–567°C may have resulted in both a decrease in salinity (to 48.43–55.36 wt.% NaCl equivalent) and the deposition of abundant magnetite. During the quartz-sulphide stage, boiling produced sulphide assemblage precipitated from primary magmatic-hydrothermal fluids (δ¹⁸O = 4.98‰, δD = –66‰, δ³⁴S values of sulphides: 0.71–3.8‰) with an extensive range of salinities (4.96–50.75 wt.% NaCl equivalent), temperatures (240–350°C), and pressures (11.6–22.2 MPa). Carbonate veins formed at relatively low temperatures (174–284°C) from fluids of low salinity (1.57–4.03 wt.% NaCl equivalent), possibly reflecting the mixing of early magmatic fluids with abundant meteoric water. Boiling and fluid mixing played important roles for Cu precipitation in the Tonglushan deposit.     

The Dal’negorsk borosilicate skarn deposit,primorye, Russia: Composition of ore-bearing solutions and boron sources

The Dal’negorsk borosilicate skarn deposit (44° 34′ N and 135° 37′ E), located in the center of the ore field bearing the same name, is referred to the category of giant deposits. The currently predominant genetic concept assumes that ore mineralization at this deposit is related to a mantle source and that boron and ore-bearing alkaline fluids are derivatives of a juvenile source as well. The alternative model considered in this paper suggests that sedimentary sequences, probably, evaporites of a local basin, were immediate boron sources and hot subsurface water served as an agent of ore deposition. The authors’ conclusions are based on (1) mineralogical and geochemical features of alteration of premineral dikes as evidence for the composition of percolating ore-bearing fluids, (2) results of fluid inclusion study, and (3) boron and oxygen isotopic compositions of datolite.The latite bodies immediately predating deposition of economic datolite ore do not show mineralogical or geochemical attributes of their belonging to alkaline rock series. According to our data, these bodies are composed of Paleogene premineral basalts that intruded into the future borosilicate deposit close to the central channel of ore-bearing fluid, served as fluid conduits, and were altered to ultrapotassic rocks under the effect of such fluid. It is suggested that hot aqueous ore-bearing fluid was enriched in highly soluble compounds of Ba, K, and B and extremely depleted in poorly soluble compounds of Zr, Nb, Ta, La, and Ce. This suggestion does not contradict the properties and composition of primary and pseudosecondary two-phase fluid inclusions in danburite, datolite, quartz, and fluorite from orebodies. Judging from the boron isotopic composition of datolite (δ¹¹B = ?9 to ?31 ‰), the main amount of boron was extracted from metasedimentary rocks of the Mesozoic basement. The oxygen isotopic composition of datolite from the Dal’negorsk deposit (δ¹⁸O_SMOW = ?1.64 to ?2.97 and less frequently up to ?5‰) indicates a significant contribution of subsurface water to the transport of boron. A model of multistage accumulation of boron in ore of the Dal’negorsk borosilicate skarn deposit is proposed.     

P–T conditions during skarn formation in the Ocna de Fier ore district, Romania

P–T conditions during skarn formation in the 75.5 Ma old Ocna de Fier-Dognecea (SW Romania) ore district are assessed in this work using a combination of petrogenetic grids, Berman's TWEEQU programme, and several independent geothermobarometers. These were applied both to hornfelses surrounding the skarn and to the granodiorite which caused the skarn and contact metamorphism. The results are consistent and point to a peak metamorphic temperature of 700 ± 50 °C, decreasing away from the contact, and to a pressure of 2.8 ± 1 kbar, equivalent to ∼10 km depth in the region. These results quantify the qualitative idea that skarn mineralisation normally forms in a high T, low P contact metamorphic environment. Received: 13 February 1998 / Accepted: 8 April 1999     

Geochemistry,mineralogy and genesis of the Ayazmant Fe–Cu skarn deposit in Ayvalik, (Balikesir), Turkey

The Ayazmant Fe–Cu skarn deposit is located approximately 20 km SE of Ayval?k or 140 km N of Izmir in western Turkey. The skarn occurs at the contact between metapelites and the metabasites of the Early Triassic K?n?k Formation and the porphyritic hypabyssal intrusive rocks of the Late Oligocene Kozak Intrusive Complex. The major, trace, and rare earth-element geochemical analysis of the igneous rocks indicate that they are I-type, subalkaline, calc-alkaline, metaluminous, I-type products of a high-level magma chamber, generated in a continental arc setting. The ⁴⁰Ar–³⁹Ar isochron age obtained from biotite of hornfels is 20.3 ± 0.1 Ma, probably reflecting the age of metamorphic–bimetasomatic alteration which commenced shortly after intrusion into impure carbonates. Three stages of skarn formation and ore development are recognized: (1) Early skarn stage (Stage I) consisting mainly of garnet with grossular-rich (Gr_75–79) cores and andradite-rich (Gr_36–38) rims, diopside (Di_94–97), scapolite and magnetite; (2) sulfide-rich skarn (Stage II), dominated by chalcopyrite with magnetite, andraditic garnet (Ad₈₄–₈₉), diopside (Di₆₅–₇₅) and actinolite; and (3) retrograde alteration (Stage III) dominated by actinolite, epidote, orthoclase, phlogopite and chlorite in which sulfides are the main ore phases. ⁴⁰Ar–³⁹Ar age data indicate that potassic alteration, synchronous or postdating magnetite–pyroxene–amphibole skarn, occurred at 20.0 ± 0.1 Ma. The high pyroxene/garnet ratio, plus the presence of scapolite in calc-silicate and associated ore paragenesis characterized by magnetite (± hematite), chalcopyrite and bornite, suggests that the bulk of the Ayazmant skarns were formed under oxidized conditions. Oxygen isotope compositions of pyroxene, magnetite and garnet of prograde skarn alteration indicate a magmatic fluid with δ¹⁸O values between 5.4 and 9.5‰. On the basis of oxygen isotope data from mineral pairs, the early stage of prograde skarn formation is characterized by pyroxene (Di_94–97)-magnetite assemblage formed at an upper temperature limit of 576 °C. The lower temperature limit for magnetite precipitation is estimated below 300 °C, on the basis of magnetite–calcite pairs either as fracture-fillings or massive ore in recrystallized limestone-marble. The sulfide assemblage is dominated by chalcopyrite with subordinate molybdenite, pyrite, cubanite, bornite, pyrrhotite, galena, sphalerite and idaite. Gold–copper mineralization formed adjacent to andradite-dominated skarn which occurs in close proximity to the intrusion contacts. Native gold and electrum are most abundant in sulfides, as fine-grained inclusions; grain size with varying from 5 to 20 µm. Sulfur isotope compositions obtained from pyrrhotite, pyrite, chalcopyrite, sphalerite and galena form a narrow range between ? 4.8 and 1.6‰, suggesting the sulfur was probably mantle-derived or leached from magmatic rocks. Geochemical data from Ayazmant shows that Cu is strongly associated with Au, Bi, Te, Se, Cd, Zn, Pb, Ni and Co. The Ayazmant mineralizing system possesses all the ingredients of a skarn system either cogenetic with, or formed prior to a porphyry Cu(Au–Mo) system. The results of this study indicate that the Aegean Region of Turkey has considerable exploration potential for both porphyry-related skarns and porphyry Cu and Au mineralization.     

Malayaite and tin‐bearing silicates from a skarn at Doradilla via Bourke,New South Wales

An extensive complex zoned skarn is developed at the contact of a leucoadamellite intrusive at Doradilla, NW New South Wales. The skarn is a disequilibrium assemblage resulting from a progressive sequence of replacement of a carbonate precursor. Early grossular‐clinopyroxene rocks are replaced by andradite with 0.5–3.5 wt.% SnO₂ clinopyroxene and quartz. Later alteration along fractures and bedding planes of the garnet‐clinopyroxene quartz assemblage has produced calcite‐malayaite (CaSn0.95Ti0.05SiO₅) veins. The final replacement stage was the overprinting of the silicate phases by assemblages containing sulphides, cassiterite, magnetite, titanite, fluorite, biotite and chlorite. The tin content of garent increases with increasing andradite component suggesting replacement of Fe³⁺ by Sn⁴⁺. Associated clinopyroxenes contain 0.1% SnO₂. The coexistence of titanite and its tin isomorph malayaite with extremely limited solid solution indicates late stage skarn temperatures of less than 400°C.     

Geology,geochronology, and Hf isotope geochemistry of the Longtougang skarn and hydrothermal vein Cu–Zn deposit,North Wuyi area,southeastern China

The recently discovered Longtougang skarn and hydrothermal vein Cu–Zn deposit is located in the North Wuyi area, southeastern China. The intrusions in the ore district comprise several small porphyritic biotite monzonite, porphyritic monzonite, and porphyritic granite plutons and dikes. The mineralization is zoned from a lower zone of Cu-rich veins and Cu–Zn skarns to an upper zone of banded Zn–Pb mineralization in massive epidote altered rocks. The deposit is associated with skarn, potassic, epidote, greisen, siliceous, and carbonate alteration. Molybdenite from the Cu-rich veins yielded a Re–Os isochron age of 153.6 ± 3.9 Ma, which is consistent with U–Pb zircon ages of 154.0 ± 1.3 Ma for porphyritic monzonite, 154.0 ± 0.8 Ma for porphyritic biotite monzonite, and 152.0 ± 0.8 Ma for porphyritic granite. Geological observations suggest that the Cu mineralization is genetically related to the porphyritic biotite monzonite and porphyritic monzonite. All the zircons from intrusive rocks in the ore district are characterized by ε_Hf(t) values between − 13.41 and − 4.38 and Hf model ages (T_DM2) between 2054 and 1482 Ma, reflecting magmas derived mainly from a Proterozoic crustal source. Molybdenite grains from the deposit have Re values of 14.6–27.7 ppm, indicative of a mixed mantle–crust source. The porphyry–skarn abundant Cu and hydrothermal vein type Pb–Zn–Ag deposits in the North Wuyi area are related to the Late Jurassic porphyritic granites and Early Cretaceous volcanism, respectively. The Late Jurassic mineralization-related granites were derived from the crustal anatexis with some mantle input, which was triggered by asthenospheric upwelling induced by slab tearing during oblique subduction of the paleo-Pacific plate beneath the South China block, and the Early Cretaceous mineralization-related granitoids mainly from crust material formed within a series of NNE-trending basins during margin-parallel movement of the plate.     

High temperature gas–solid reactions in calc–silicate Cu–Au skarn formation; Ertsberg,Papua Province,Indonesia

The 2.7–3 Ma Ertsberg East Skarn System (Indonesia), adjacent to the giant Grasberg Porphyry Copper deposit, is part of the world’s largest system of Cu–Au skarn deposits. Published fluid inclusion and stable isotope data show that it formed through the flux of magma-derived fluid through contact metamorphosed carbonate rock sequences at temperatures well above 600° C and pressures of less than 50 MPa. Under these conditions, the fluid has very low density and the properties of a gas. Combining a range of micro-analytical techniques, high-resolution QEMSCAN mineral mapping and computer-assisted X-ray micro-tomography, an array of coupled gas–solid reactions may be identified that controlled reactive mass transfer through the ~ 1 km³ hydrothermal skarn system. Vacancy-driven mineral chemisorption reactions are identified as a new type of reactive transport process for high-temperature skarn alteration. These gas–solid reactions are maintained by the interaction of unsatisfied bonds on mineral surfaces and dipolar gas-phase reactants such as SO₂ and HCl that are continuously supplied through open fractures and intergranular diffusion. Principal reactions are (a) incongruent dissolution of almandine-grossular to andradite and anorthite (an alteration mineral not previously recognized at Ertsberg), and (b) sulfation of anorthite to anhydrite. These sulfation reactions also generate reduced sulfur with consequent co-deposition of metal sulfides. Diopside undergoes similar reactions with deposition of Fe-enriched pyroxene in crypto-veins and vein selvedges. The loss of calcium from contact metamorphic garnet to form vein anhydrite necessarily results in Fe-enrichment of wallrock, and does not require Fe-addition from a vein fluid as is commonly assumed.     

Chemical composition and evolution of the garnets in the Astamal Fe-LREE distal skarn deposit,Qara-Dagh–Sabalan metallogenic belt,Lesser Caucasus,NW Iran

The chemistry of garnet can provide clues to the formation of skarn deposits. The chemical analyses of garnets from the Astamal Fe-LREE distal skarn deposit were completed using an electron probe micro-analyzer. The three types of garnet were identified in the Astamal skarn are: (I) euhedral coarse-grained isotropic garnets (10–30 mm across), which are strongly altered to epidote, calcite and quartz in their rim and core, with intense pervasive retrograde alteration and little variation in the overall composition (Adr_94.3–84.4 Grs_8.5–2.7 Alm_1.9–0.2) (garnet I); (II) anhedral to subhedral brecciated isotropic garnets (5–10 mm across) with minor alteration, a narrow compositional range along the growth lines (Adr_82–65.4 Grs_21.9–11.7 Alm_11.1–2.4) and relatively high Cu (up to 1997 ppm) and Ni (up to 1283 ppm) (garnet II); and (III) subhedral coarser grained garnets (> 30 mm across) with moderate alteration, weak diffusion and irregular zoning of discrete grossular-almandine-rich domains (Adr_84.2–48.8 Grs_32.4–7.6 Alm_19.9–3.5) (garnet III). In the third type, the almandine content increases with increasing grossular/andradite ratio and increasing substitutions of Al for Fe^3 +.Almost all three garnet types have been replaced by fine-grained, dark-brown allanite that is typically disseminated and has the same relief as andradite. The Cu content increases while Ni content decreases slightly towards the rim of garnet II and garnet III. Copper in garnet II is positively correlated with increasing almandine content and decreasing andradite content, indicating that the almandine structure, containing relatively more Fe^2 +, is more suitable than andradite and grossular to host divalent cations such as Cu^2 +. Nickel in garnet II is positively correlated with increasing andradite content, total Fe, and decreasing almandine content. This is because Ni^2 + substitutes for Fe^3 + in the Y (octahedral) position. There are unusual discrete grossular-almandine rich domains within andraditic garnet III, indicating the low diffusivity of Ca compared to Fe at high temperatures.     

Combined garnet,scheelite and apatite U–Pb dating of mineralizing events in the Qiaomaishan Cu–W skarn deposit,eastern China

Determining the precise timing of mineralization and mineralizing events is crucial to understanding regional mineralizing and other geological events and processes. However, there are a number of mineralogical and analytical limitations to the approaches developed for the absolute dating of mineralizing systems, such as molybdenite Re–Os and zircon and garnet U–Pb, among others. This means that the precise and accurate dating of mineralizing systems that may not contain minerals suitable for dating using existing approaches requires the development of new (and ideally in situ) approaches to absolute dating. This study outlines a new in situ analytical approach that has the potential to rapidly and accurately evaluate the timing of ore formation. Our study employs a novel application of in situ scheelite U–Pb dating analysis using laser ablation–inductively coupled plasma–mass spectrometry (LA–ICP–MS) and samples from the Qiaomaishan deposit, a representative example of skarn mineralization within the Xuancheng ore district of eastern China. Our approach to scheelite dating of the deposit is verified by cross-comparison to dating of cogenetic garnet and apatite, proving the effectiveness of this approach. Our new approach to dating of scheelite-bearing geological systems is rapid, cheap, requires little sample preparation, and is undertaken in situ, allowing crucial geological and mineralogical context to be retained during analysis. The approaches outlined here not only allow the determination of the absolute timing of formation of the Qiaomaishan deposit through the U–Pb dating of scheelite [138.6 ± 3.2 Ma, N = 39, mean square weighted deviation (MSWD) = 1.17], garnet (138.4 ± 1.0 Ma, N = 40, MSWD = 1.3), and apatite (139.6 ± 3.3 Ma, N = 35, MSWD = 0.72), but also further supports the theoretical genetic links between this mineralization and the emplacement of a proximal porphyritic granodiorite intrusion (zircon U–Pb age: 139.5 ± 1.2 Ma, N = 23, MSWD = 0.3). Moreover, our research indicates that the higher the concentrations of U within scheelite, the more suitable that scheelite is for U–Pb dating, with the main factor controlling the U content of scheelite seemingly being variations in oxygen fugacity conditions. This novel approach provides a potentially powerful tool, not just for the dating of skarn systems but also with potential applications in orogenic and intrusion-related gold, porphyry W–Mo, and greisen mineralizing systems as well as other scheelite-bearing geological bodies or geological systems.     

Geology,mineralization, and fluid inclusion characteristics of the Chorukh-Dairon W–Mo–Cu skarn deposit in the Middle Tien Shan,Northern Tajikistan

The Chorukh-Dairon deposit is part of the metallogenic belt of WMo, CuMo, AuW, and Au deposits along the Late Paleozoic active continental margin of the Tien Shan. It is related to the Late Carboniferous multiphase pluton, with successive intrusive phases of early monzogabbro through monzonite-quartz monzonite to monzogranite and leucogranite, and the latest lamprophyre dikes. The deposit is an example of complex W–Mo–Cu magmatic-hydrothermal system related to magnetite-series shoshonitic igneous suite. It contains zones of W–Cu–Mo oxidized prograde and retrograde skarns, with abundant scapolite, plagioclase, K-feldspar, andradite garnet, magnetite, as well as molybdoscheelite and minor chalcopyrite, and molybdenite. Skarns are overprinted by hydrosilicate alteration assemblages, with amphibole, chlorite, epidote, quartz, calcite, scapolite, albite, scheelite, and chalcopyrite, and are cut by quartz-carbonate-barite-fluorite-sulfide veins.The fluid evolution included a release of high temperature (~ 400–500 °C), high pressure (900–1100 to 700–800 bars), high salinity magmatic-hydrothermal aqueous chloride fluid, with its direct separation from crystallizing magma and formation of prograde and retrograde skarns. Fluid enrichment in Ca (up to 15–22 wt.% CaCl₂) at the retrograde skarn stage was possibly related to magmatic differentiation and provided intense molybdoscheelite deposition from a homogenous fluid. In contrast, hydrosilicate alteration assemblages were formed at lower temperatures (~ 350–400 °C) initially from a homogenous and then from a boiling Ca-rich (20–22 wt.% CaCl₂) magmatic-hydrothermal fluid, with the latter contributing to the most intense scheelite deposition. The stable isotope data (δ¹³C_CO2 = − 3.0 ± 0.5‰ and δ¹⁸О_H2O = + 6.5 ± 0.5‰, δ³⁴S = + 7.5 to + 7.7‰) obtained for the hydrosilicate stage minerals suggest significant fluid sourcing from magmatic and meteoric waters as well as from sedimentary rocks enriched in seawater sulfate, possibly evaporites, although a strongly homogenous character of the isotopic composition reveals intense isotope homogenization in a magmatic chamber. Some light sulfur isotope enrichment of sulfides from the quartz-carbonate-barite-fluorite-sulfide veins (δ³⁴S = + 6.0 to + 6.1‰) may be linked to the evolution of the magmatic source toward more mantle-related sulfur species, as these veins were formed after emplacement of the late mafic (lamprophyre) dikes.