Preliminary mineralogical and petrological study of the Ortosa Au–Bi–Te ore deposit: a reduced gold skarn in the northern part of the Rio Narcea Gold Belt, Asturias, Spain

The Ortosa deposit (NW Spain) in the northern part of the Rio Narcea Gold Belt (RNGB) is located in the Cantabrian Zone of the Iberian Massif. This zone corresponds to the westernmost exposure of the European Hercynides. The deposit is hosted by marine shales, siltstones, calcareous siltstones and interbedded sandy limestones of the upper part of the Silurian Furada Formation. These rocks are intruded by a main stock and numerous sills and dikes consisting of a reduced, ilmenite-bearing quartz-monzodiorite (Ortosa intrusion). Skarn metasomatism and associated gold mineralization overprinted these sedimentary and igneous rocks, forming endo- and exoskarns.The earliest stage of alteration involved potassium metasomatism from which metasomatic biotite developed in the hornfels around the intrusion. In the endoskarn, the first metasomatic mineral to form is actinolite. Subsequently, quartz, pyroxene (Hd_30–45), and sulfides (mainly arsenopyrite and pyrrhotite) formed, followed by a second generation of amphibole (ferroactinolite and ferrohornblende). The exoskarn is a pyroxene-garnet skarn, which is often banded. The prograde minerals are pyroxene (Hd_10–30) and grossular garnet. The retrograde mineralogy consists of hedenbergite-rich pyroxene (Hd_50–87), amphibole (ferroactinolite–ferrohornblende), and the metallic minerals with minor fluorapatite, K-feldspar, albite, epidote–clinozoisite, vesuvianite and calcite. A final stage of retrograde alteration is characterized by calcite, quartz, and chlorite.Pyrrhotite and arsenopyrite are the more abundant metallic minerals, and löllingite, chalcopyrite, pyrite and sphalerite are present in smaller amounts. The gold occurs as native gold and maldonite, and is accompanied by hedleyite, native bismuth, and bismuthinite. These Au–Bi–Te mineral assemblages occupy cavities and fractures in the arsenopyrite or in the pyrrhotite.Estimated physiochemical conditions of formation based on the composition and stability fields of major calc-silicate and sulfide minerals indicate that the hedenbergite-rich pyroxene and the earliest sulfides (löllingite–pyrrhotite–arsenopyrite) crystallized at temperatures between 470 and 535°C at low log fS₂ between −10 and −6.5 and low log fO₂ of −22. The Ortosa skarns can be included in the reduced gold skarn subtype defined by Meinert (Mineralogical Association of Canada, Quebec city, Que., Canada, 1998, 26,359–414 ).     

Geochemical Characteristics,Origin, and Evolution of Ore‐Forming Fluids of the Khut Copper Skarn Deposit,West of Yazd in Central Iran

The Khut copper skarn deposit is located at about 50 km northwest of Taft City in Yazd province in the middle part of the Urumieh‐Dokhtar magmatic arc. Intrusion of granitoid of Oligocene–Miocene age into carbonate rocks of the Triassic Nayband Formation led to the formation of marble and a calcic skarn. The marble contains high grade Cu mineralization that occurs mainly as open space filling and replacement. Cu‐rich sulfide samples from the mineralized marble are also anomalous in Au, Zn, and Pb. In contrast, the calcic skarn is only weakly anomalous in Cu and W. The calcic skarn is divided into garnet skarn and garnet–pyroxene skarn zones. Paragenetic relationships and microthermometric data from fluid inclusions in garnet and calcite indicate that the compositional evolution of skarn minerals occurred in three main stages as follows. (i) The early prograde stage, which is characterized by Mg‐rich hedenbergite (Hd_53.7Di_42.3–Hd_86.1Di_9.5) with Al‐bearing andradite (69.8–99.5 mol% andradite). The temperature in the early prograde skarn varies from 400 to 500°C at 500 bar. (ii) The late prograde stage is manifested by almost pure andradite (96.2–98.4 mol% andradite). Based on the fluid inclusion data from garnet, fluid temperature and salinity in this stage is estimated to vary from 267 to 361°C and from 10.1 to 21.1 wt% NaCl equivalent, respectively. Pyrrhotite precipitation started during this stage. (iii) The retrograde stage occurs in an exoskarn, which consists of an assemblage of ferro‐actinolite, quartz, calcite, epidote, chlorite, sphalerite, pyrite, and chalcopyrite that partially replaces earlier mineral assemblages under hydrostatic conditions during fracturing of the early skarn. Fluids in calcite yielded lower temperatures (T < 260°C) and fluid salinity declined to ～8 wt% NaCl equivalent. The last stage mineralization in the deposit is supergene weathering/alteration represented by the formation of iron hydroxide, Cu‐carbonate, clay minerals, and calcite. Sulfur isotope data of chalcopyrite (δ³⁴S of +1.4 to +5.2‰) show an igneous sulfur source. Mineralogy and mineral compositions of the prograde assemblage of the Khut skarn are consistent with deposition under intermediately oxidized and slightly lower fS₂ conditions at shallow crustal levels compared with those of other typical Fe‐bearing Cu–Au skarn systems.     

Garnetization as a ground preparation process for copper mineralization: evidence from the Mazraeh skarn deposit, Iran

The Mazraeh Cu–Fe skarn deposit, NW Iran is the result of the intrusion of an Oligocene–Miocene granitic pluton into Cretaceous calcareous rocks. The pluton ranges in composition from monzonite to quartz monzonite, monzogranite, tonalite and granodiorite with I-type, calc-alkaline, and weakly peraluminous characteristics. The Mazraeh pluton was emplaced in a volcanic arc setting in an active continental margin at a depth of ~8 km. Pyroxene skarn, garnet skarn, and epidote skarn zones were formed during the intrusive phase. The garnet skarn developed as exoskarn and endoskarn from the calcareous wall rocks and the pluton, respectively, prior to mineralization. Garnet skarn from the exoskarn zone is identified by relict layering inherited from the precursor calcareous lithologies. Mass balance calculation of garnet skarn in the endoskarn zone indicates that hydrothermal fluids originating from the cooling magma introduced Si, Fe, Mn, Ca, Mg, P, Ag, Cu, Zn, La, Pb, Cd, Mo, and Y. The main mass loss in the garnet skarn was due to destruction of feldspars in the Mazraeh plutonic rocks and leaching of K₂O and Na₂O. Released Ca has been fixed in the andraditic garnet. Garnetization of the Mazraeh pluton was accompanied by mass and volume increase. The magnitude of these changes depends mainly on the degree of alteration and composition of the precursor. The brittle behavior of the endoskarn zone was increased due to formation of massive garnet which subsequently fractured. These fractures not only facilitated movement of hydrothermal fluids but also provided new locations for Cu mineralization. Therefore locating strongly garnetized zones may be a vector to ore in skarn deposits.     

南泥湖——三道庄钼(钨)矿床中矽卡岩的形成过程及其与钼钨矿化的关系

通过野外地质、光学显微镜以及背散射(BSE)电子图像的观察,南泥湖—三道庄钼(钨)矿床中矽卡岩的形成过程为:第一期流体首先与靠近岩体的大理岩发生反应生成硅灰石、钙铁榴石、钙铝榴石、钙铁辉石和透辉石,当流体继续向外运移遇到灰岩时,直接将其交代形成透辉石矽卡岩或曲卷纹层状透辉石矽卡岩;第二期流体则沿裂隙向围岩中呈面型分布,叠加交代第一期矽卡岩化过程。据此,石榴子石和辉石可以划分为两个世代,第一世代石榴子石(Gro_(3-82)And_(15-96))呈斑点状,第一世代辉石(Di_(18-86)Hd_(13-70)Jo_(0-13))可与斑点状石榴子石共生,也可与斜长石(Ab_(55-70)An_(30-44))共生;第二世代石榴子石(Gro_(23-58)And_(37-74))呈面型分布,第二世代辉石(Di_(0-68)Hd_(28-84)Jo_(3-16))沿裂隙呈面型向围岩中展布。第一世代石榴子石和辉石在空间上分布范围较第二世代广。钼钨矿化在矽卡岩的最早阶段即已开始,贯穿整个矽卡岩的形成过程,引起钼钨沉淀的原因可能是具有较高钼钨含量的流体与围岩发生反应时引起的局部还原性环境。     

Granite- and gabbrodiorite-associated skarn deposits of NW Iran

Field and laboratory studies show that there are two types of skarn deposits in NW Iran: granite-associated (type I) and gabbrodiorite-associated (type II). Granite-associated deposits are accompanied by Cu and Fe mineralisation, whereas Mn and Fe are the main ore metals in gabbrodiorite-associated skarn deposits. There are some differences in the mineralogy of these skarn deposits. Bixbyite, piemontite and Cr-bearing garnet are found only in gabbrodiorite-associated skarns, whereas idocrase occurs only in granite-associated deposits. Type II skarns show exoskarn features, whereas some type I skarns have developed endoskarn as well. Evidence of boiling of hydrothermal fluid can be seen in both types and seems to be a common mechanism of mineral deposition. Gabbrodiorite-associated skarns show higher fO₂ than granite-associated deposits. Based on mineralogical and textural evidence, mineralisation in both groups has started from about 550 °C. Early formed anhydrous minerals have begun to be replaced by hydrous minerals from about 400 °C.It seems that due to low fluid content in the gabbrodioritic magma, heated meteoritic water in the surrounding volcanoclastic and tuffaceous rocks was the main source of hydrothermal solution in the gabbrodiorite-associated skarn system.     

Geochemistry,fluid inclusion and stable isotope constraints (C and O) of the Sivrikaya Fe-skarn mineralization (Rize,NE Turkey)

The Sivrikaya Fe-skarn mineralization is hosted by dolomitic limestone layers of Late Cretaceous volcano-sedimentary unit, comprised of andesite, basalt and their pyroclastites, including, sandstone, shale and dolomitic limestone layers. Intrusion of the Late Cretaceous–Eocene İkizdere Granitoid in the volcano–sedimentary unit resulted in skarn mineralization along the granitoid–dolomitic limestone contact. The ore is associated with exoskarns, and mineralization is characterized by early anhydrous garnet and pyroxene with late hydrous minerals, such as epidote, tremolite, actinolite and chlorite. The ore minerals are mainly magnetite and hematite, with minor amounts of pyrite and chalcopyrite. The composition of garnet and pyroxene in the exoskarn is Adr_{79.45−99.03}Grs_0−17.9Prs_0.97−2.65 and Di_69.1−77.1Hd_22.2−29.8Jhn_0.6−1.4, respectively, and abundances of magnetite in the ore suggest that the Fe-skarn mineralization formed under relatively oxidized conditions.Homogenization temperatures (T_h) of all fluid inclusions and calculated salinity content are in the range of 166 °C–462 °C and 0.35–14.3 wt% NaCl equ., respectively. Well-defined positive correlation between Th and salinity values indicates that meteoric water was involved in the hydrothermal solutions. Eutectic temperatures (Te) between −40.8 °C and −53.6 °C correspond to the presence of CaCl₂ in the early stage of fluid inclusions. On the other hand, the Te temperatures of later-stage fluid inclusions, in the range of −38 °C and −21.2 °C, correspond to the presence of MgCl₂, FeCl₂, KCl and NaCl type salt combinations. None of the fluid inclusions were found to contain separated gas phases in microscopy observations. However, a limited amount of dissolved CH₄ was identified in the early stage, high temperature fluid inclusions using Raman spectroscopic studies.Δ¹⁸O values in both dolomitic limestone (10.8–12.5‰) and skarn calcite (7.6–9.8‰) were highly depleted compared to the typical δ¹⁸O values of marine limestones. Decreases in δ¹⁸O values are accepted as an indication of dilution by meteoric water because retrograde brecciation of garnet, magnetite and breccia filling epidote and quartz in volcanic host rocks are an indication of increasing permeability, allowing infiltration of meteoric water. Highly depleted δ¹³C isotopes (up to −6.5‰) of dolomitic limestone, indicate that organic matter in carbonates had an effect on the decreasing isotopic ratios. The presence of CH₄ and CH₂ in fluid inclusions can be explained by the thermal degradation of these organic materials.     

Skarn textures and a case study: the Ocna de Fier-Dognecea orefield, Banat, Romania

We address the question of the predictability of skarn textures and their role in understanding the evolution of a skarn system. Recent models of skarn formation show that skarns are ideal for application of self-organisation theory, with self-patterning the rule in fluid-rock interaction systems rather than the exception. Zonation in skarn deposits, a consequence of infiltration-driven metasomatism, can also be treated in terms of self-organisation. Other less commonly described features, such as scalloping, fingering and mineral banding, can be understood by application of reactive infiltration and hydrodynamics at the skarn front. Devolatilisation may trigger formation of back-flow fluxes that overprint previously formed skarn. The range of textures formed from such events can be used to discriminate between prograde and retrograde stages. Refractory minerals, such as garnet, magnetite and pyrite, readily retain overprinting events. Skarns are also composed largely of minerals from solid solution series (garnet, pyroxene, pyroxenoids, etc.) and therefore skarn mineralogy helps to establish trends of zonation and evolution. The same minerals can act as ‘chemical oscillators’ and record metasomatic trends.The Ocna de Fier-Dognecea deposit was formed in a 10 km deep skarn system. Zonation and evolution trends therefore represent only the result of interaction between magmatically derived fluids emerging at the source and limestone. From the same reason, the transition from prograde to retrograde regime is not influenced by interaction with external fluids. Thirdly, the mineralisation comprises Fe, Cu and Zn-Pb ores, thus facilitating comparison with skarn deposits that commonly are formed in shallower magmatic-hydrothermal environment. Copper-iron ores (magnetite+Cu-Fe sulphides), hosted by magnesian (forsterite+diopside) skarn, occur in the deepest and central part of the orefield, at Simon Iuda. Their petrological character allows interpretation as the core of the skarn system formed from a unique source of fluids emerging from the subjacent granodiorite. It formed first as a consequence of the local setting, where a limestone indented in the granodiorite permitted strong reaction at 650 °C and focussed the up-streaming, buoyant fluids. The first sharp front of reaction is seen at the boundary between the Cu-Fe core and Fe ores hosted by calcic skarn (Di_70-90-And_70-90), where Cu-Fe sulphides disappear, and forsterite gives way to garnet in the presence of diopside (Di₉₀). Following formation of forsterite, devolatilisation and transient plume collapse is interpreted from a range of piercing clusters and trails. We presume lateral flow to have been initiated at the source, as the emerging fluids are in excess to the fluids driven into reaction by the plume. Formation of the other orebodies, up to 5 km laterally downstream in both directions, is interpreted as skarn fingering at the limestone side. The metasomatic front is perpendicular to the flow along the channel of schists placed between the limestone base and the granodiorite.A metal zonation centred onto the source is defined, based on metal distribution: Cu-Fe/Fe/Zn-Pb. The second front of reaction, at the boundary between the Fe and Zn-Pb zone, has a sulphidation/oxidation character, with diopside giving way to a Fe-Mn-rich pyroxene, (HedJoh)_>60+pyroxmangite±bustamite; garnet is minor. Johannsenite-rich pyroxene (Di_20-40Hed_20-40Joh₄₀) is found in proximal skarn at the upper part of Simon Iuda, stable with Zn_0.95Fe_0.05S, at an inferred 570 °C. In distal skarn from Dognecea and Paulus, Mn-hedenbergite (Di_<10Hed₇₀Joh_20-30) formed at 400 °C is stable with Zn_0.84Fe_0.16S. Extensive compositional fields, eutectic decomposition and lamellar intergrowths characterise pyroxene in the Zn-Pb zone, formed at the magnetite-hematite buffer in the presence of pyrite. Distal skarn has a reducing character, in comparison with the proximal. A drop in both fS₂ and O₂, with the zoned system moving closer to the pyrite-pyrrhotite buffer, is induced from the temperature gradient. Based on pyroxene mineralogy and calculated fS₂, the metal zonation is confirmed as being formed upwards and outwards from the source.The Fe and Zn-Pb zones both have a patterned side coexisting with the unpatterned one. Patterning is seen at scales from macroscopic (rhythmic banding, nodular, spotted, orbicular, mossy, mottled textures) to microscopic scales (oscillatory zonation in garnet and silica-bearing magnetite). Following plume updraft, the path of decarbonation reaction controlled the motion of the skarn front until, towards the end of the prograde stage, a multiple steady state regime developed and produced rhythmic patterns on all scales. The activation of powerful patterning operators, represented by Liesegang banding alone, or coupled with competitive particle growth, show that the skarn front had the characteristics of an unstable coarsening front of reaction.A second retrograde event, carbofracturing, triggered by erratic decarbonation after cessation of infiltration, can be interpreted from overprinting textures in the Fe and Zn-Pb zone. A major drop in fO₂ is inferred from extensive, pseudomorphous replacement of hematite by magnetite. Textures show progressive destruction of prograde assemblages, i.e., piercing clusters, shock-induced, fluid-pressure assisted brecciation and deformation, followed by healing of the disrupted assemblages. Release of trace elements accompanies both retrograde events, with a Bi-Te-Au-Ag association common to both. The importance of shock-induced textures is emphasised in the context of Au enrichment, especially when the retrograde fluids cross the main buffers in fO₂-fS₂ space.The presence of Bi-sulphosalt polysomes in the Fe zone indicates that patterning extends down to the nanoscale. The key role played by polysomatism in stabilising compositional trends that cannot otherwise be formed at equilibrium is a fertile ground yet to be adequately explored.     

Geology of the Jiama porphyry copper–polymetallic system,Lhasa Region,China

The Jiama deposit, located in the eastern part of the well-known Gangdese Metallogenic Belt on the Tibetan Plateau, is the largest porphyry Cu–polymetallic system in the region, with the largest exploration budget, and is economically viable in the Gangdese Belt to undergo large-scale development. The deposit is well preserved and has experienced little erosion. The proven resources of the deposit are 7.4 Mt Cu, 0.6 Mt Mo, 1.8 Mt Pb + Zn, 6.65 Moz Au, and 360.32 Moz Ag. The results presented in this paper are based on geological and tectonic mapping, geological logging, and other exploration work performed by members of the Jiama Exploration Project Team over a period of 6 years. We propose that the Jiama porphyry Cu–polymetallic system is composed of skarn Cu–polymetallic, hornfels Cu–Mo, porphyry Mo ± Cu, and distal Au mineralization. The development of skarn Cu–polymetallic orebodies at the Jiama deposit was controlled mainly by the contact zone between porphyries and marbles, an interlayer detachment zone, and the front zone of a gliding nappe structure. The hornfels Cu–Mo and porphyry Mo ± Cu orebodies were controlled mainly by a fracture system related to intrusions, and the distal Au mineralization resulted from late-stage hydrothermal alteration.On the basis of field geological logging, optical microscopy, and chemical analysis, we verify that the alteration zones in the Jiama deposit include potassic, phyllic, propylitic, and argillic alteration, with a local lithocap, as well as endoskarn and exoskarn zones. The endoskarn occurs mainly as epidote alteration in quartz diorite porphyry and granite porphyry, and is cut by massive andradite veins. The exoskarn includes garnet–pyroxene and wollastonite skarn, in which the mineralogy and mineral chemical compositions display an outward zonation with respect to the source porphyry. From the proximal skarn to the intermediate skarn to the distal skarn, the garnet/pyroxene ratio varies from > 20:1 to ~ 10:1 to ~ 5:1, the garnet color varies from red-brown to brown-green to green-yellow, and the average composition of garnet varies from Ad_80.1Gr_18.9(Sp + Py)_1.0 to Ad_76.3Gr₂₃(Sp + Py)_0.7 to Ad_59.5Gr_39.5(Sp + Py)_1.0, respectively. The pyroxene is not as variable in composition as the garnet, and is primarily light green to white diopside with a maximum hedenbergite content of ~ 20% and an average composition of Di_88.6Hd_8.9Jo_2.5. From the proximal skarn to the intermediate skarn to the distal skarn, the mineralization changes from Cu–Mo to Cu ± Mo to Pb–Zn ± Cu ± Au ores, respectively. The wollastonite skarn displays no zonation and hosts mainly bornite mineralization. The Cu and Mo mineralization is closely related to the potassic and phyllic zones in the porphyry–hornfels.Zircons from four mineralized porphyries yield U–Pb ages of 15.96 ± 0.5 Ma, 15.72 ± 0.14 Ma, 15.59 ± 0.09 Ma, and 15.48 ± 0.08 Ma. The Re–Os ages of molybdenite from the skarn, hornfels, and porphyry are 15.37 ± 0.15 Ma, 14.67 ± 0.37 Ma, and 14.66 ± 0.27 Ma, respectively. The present results are consistent with the findings of previous research on fluid inclusions, isotopes, and other such aspects. On the basis of the combined evidence, we propose a porphyry Cu–polymetallic system model for the Jiama deposit and suggest a regional exploration strategy that can be applied to prospecting for porphyry-skarn mineralization in the Lhasa area.     

Skarn mineralogy and its geological significance for the Tayuan (Cu–Mo)–Pb–Zn deposit,northern Daxinganling metallogenic belt

The Tayuan (Cu–Mo)–Pb–Zn deposit is located in the northern part of Daxinganling, NE China. Lenticular ore body occurs in the skarn zone. The skarn minerals mainly include garnet, pyroxene, epidote and wollastonite. Electron microprobe analysis shows that the end member of garnet is mainly andradite (Ad_62–97Gr_11–45), the pyroxene is mainly diopside, and epidote is mainly clinozoisite. These characteristics indicate that the Tayuan polymetallic skarn deposit is mainly calcareous skarn. Sometimes the content zonation can be observed in garnets. With one garnet crystal, content is shifty from the core to the rim. In general, the iron content in the core is higher than in the edge. The content in the garnet shows that the garnet in the Tayuan deposit formed from weak oxidation in alkaline environment with the oxygen fugacity increasing, suggesting that the hydrothermal fluid evolved from an acidic to a slight alkaline state. In the Tayuan polymetallic deposit, the ratio of Mn/Fe in pyroxene is about 1.3, and of Mg/Fe, it is about 2. The components of garnet in the Tayuan deposit plot in the field of the typical skarn Zn, Cu, Mo deposits in the world.     

The Genesis of Zoned Skarns in the Sierra Nevada, California

Zoned skarns occur at plutonic-metamorphic contacts, in veinscutting marble, and at contacts between marble and interlayeredamphibolite and biotite-rich rocks. For P = 2 kb, fluid inclusionsand P-T-X_CO2 stability relations of calc-silicate assemblagessuggest T< 650 °C and a H₂O-rich fluid (X_CO2 < 0.1).Small-scale, Ca-rich endoskarns are common near exoskarns. Massbalance calculations suggest that: (a) the formation of exoskarnrequires the influx of solute in an aqueous solution from uncontaminatedmagma in addition to material derived from the endoskarn, (b)some ‘limestone assimilation’ is required to formendoskarns, and (c) skarn formation was essentially a constant-volumeprocess. Applying chromatographic theory, compositional profilesof garnet and pyroxene across zoned skarns suggest that infiltrationmetasomatism was an important process, although diffusion metasomatismappears to have produced local compositional gradients at theinfiltration ‘fronts’. Fluid flow calculations showthat thick exoskarns could readily form by intergranular infiltration of aqueous solutions. Reciprocal diffusional exchangeis suggested as a dominant mechanism in the formation of zonedskarns formed at contacts between interlayered metamorphic lithologies.     

The alteration, mineralogy and geochronology (SHRIMP U–Pb and 40Ar/39Ar) of copper-bearing Anjerd skarn, north of the Shayvar Mountain, NW Iran

A Cu-bearing skarn zone occurs north of the Shayvar Mountain in northwestern Iran. Skarn-type metasomatic alteration and mineralization occur along the contact between Upper Cretaceous impure carbonates and a Miocene Cu-bearing granitic stock. Both endoskarn and exoskarn developed in the rocks. Exoskarn is the principal skarn zone and is enclosed by a skarnoid–hornfelsic zone. Skarn formation occured during stages: (1) prograde, (2) middle stage and (3) late stage. In the prograde stage, there were two main processes: (a) metamorphic–bimetasomatic and (b) prograde metasomatic. The metamorphic process began immediately after intrusion of the pluton into the enclosing impure carbonates. The prograde metasomatic stage commenced with segregation and evolution of a fluid phase in the pluton and movement into fractures and micro-fractures in the skarnoid–hornfelsic rocks developed in a metamorphic zone. The introduction of considerable amounts of Fe, Si and Mg led to the development of voluminous medium- to coarse-grained anhydrous calc-silicates. During the middle stage, the previously formed skarn zones were affected by intense multiple hydrofracturing in the Cu-bearing stock. In addition to Fe, Si and Mg, substantial amounts of Cu, Pb and Zn, along with volatile components such as H₂S and CO₂ were added to the skarn system. Consequently, substantial amounts of hydrous calc-silicates (epidote, tremolite–actinolite), sulfides (pyrite, chalcopyrite and molybdenite), oxides (magnetite, hematite) and carbonates (calcite) replaced the anhydrous calc-silicates. The retrograde stage was synchronous with the incursion of relatively low-temperature, more oxidized fluids into skarn system, resulting in partial alteration of the early-formed calc-silicates and development of a series of very fine-grained aggregates of chlorite, clay, hematite and calcite. Zircon grains from the endoskarn zone provide constraints on the timing of solidification of the granite stock (9.91 ± 0.31 Ma) that caused mineralization in the Anjerd area. One sample of primary hornblende from the monzogranitic Shayvar batholith has an ⁴⁰Ar/³⁹Ar age of 26.54 ± 0.65 Ma and indicates that intrusion of the Miocene stock and associated Cu skarn formation occurred a considerable time after intrusion of the batholith.     

The origin and evolution of skarn-forming fluids from the Phu Lon deposit,northern Loei Fold Belt,Thailand: Evidence from fluid inclusion and sulfur isotope studies

The Phu Lon skarn Cu–Au deposit is located in the northern Loei Fold Belt (LFB), Thailand. It is hosted by Devonian volcano-sedimentary sequences intercalated with limestone and marble units, intruded by diorite and quartz monzonite porphyries. Phu Lon is a calcic skarn with both endoskarn and exoskarn facies. In both skarn facies, andradite and diopside comprise the main prograde skarn minerals, whereas epidote, chlorite, tremolite, actinolite and calcite are the principal retrograde skarn minerals.Four types of fluid inclusions in garnet were distinguished: (1) liquid-rich inclusions; (2) daughter mineral-bearing inclusions; (3) salt-saturated inclusions; and (4) vapor-rich inclusions. Epidote contains only one type of fluid inclusion: liquid-rich inclusions. Fluid inclusions associated with garnet (prograde skarn stage) display high homogenization temperatures and moderate salinities (421.6–468.5 °C; 17.4–23.1 wt% NaCl equiv.). By contrast, fluid inclusions associated with epidote (retrograde skarn stage) record lower homogenization temperatures and salinities (350.9–399.8 °C; 0.5–8 wt% NaCl equiv.). These data suggest a possible mixing of saline magmatic fluids with external, dilute fluid sources (e.g., meteoric fluids), as the system cooled. Some fluid inclusions in garnet contain hematite daughters, suggesting an oxidizing magmatic environment. Sulfur isotope determinations on sulfide minerals from both the prograde and retrograde stages show a uniform and narrow range of δ³⁴S values (?2.6 to ?1.1 ‰ δ³⁴S), suggesting that the ore-forming fluid contained sulfur of orthomagmatic origin. Overall, the Phu Lon deposit is interpreted as an oxidized Cu–Au skarn based on the mineralogy and fluid inclusion characteristics.     

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.     

The mineralogy of copper-bearing skarn to the east of the Sungun-Chay river, East-Azarbaidjan, Iran

A calcic copper-bearing skarn zone in East-Azarbaidjan, NW of Iran is located to the east of the Sungun-Chay river. Skarn-type metasomatic alteration and mineralization occurs along the contact between Upper Cretaceous impure carbonates and an Oligo-Miocene Cu-bearing granitoid stock. Both endoskarn and exoskarn are developed along the contact. Exoskarn is the principal skarn zone enclosed by a marmorized and skarnoid–hornfelsic zone. The skarnification process occurred two stages: (1) prograde and (2) retrograde. The prograde stage is temporally and spatially divided into two sub-stages: (a) metamorphic–bimetasomatic (sub-stage I) and (b) prograde metasomatic (sub-stage II). Sub-stage I began immediately after the intrusion of the pluton into the enclosing impure carbonates. Sub-stage II commenced with segregation and evolution of a fluid phase in the pluton and its invasion into fractures and micro-fractures of the marmorized and skarnoid–hornfelsic rocks developed during sub-stage I. The introduction of considerable amounts of Fe, Si and Mg led to the development of substantial amounts of medium- to coarse-grained anhydrous calc-silicates. From texture and mineralogy the retrograde metasomatic stage can be divided into two discrete sub-stages: (a) early (sub-stage III) and (b) late (sub-stage IV). During sub-stage III, the previously formed skarn zones were affected by intense multiple hydro-fracturing phases in the Cu-bearing stock. In addition to Fe, Si and Mg, substantial amounts of Cu, Pb, Zn, along with volatile components such as H₂S and CO₂ were added to the skarn system. Consequently considerable amounts of hydrous calc-silicates (epidote, tremolite–actinolite), sulfides (pyrite, chalcopyrite, galena, sphalerite, bornite), oxides (magnetite, hematite) and carbonates (calcite, ankerite) replaced the anhydrous calc-silicates. Sub-stage IV was concurrent with the incursion of relatively low temperature, more highly oxidizing fluids into skarn system, bringing about partial alteration of the early-formed calc-silicates and developing a series of very fine-grained aggregates of chlorite, clay, hematite and calcite.     

西藏列廷冈铁多金属矿床矽卡岩矿物学特征及其地质意义

西藏列廷冈铁多金属矿床位于冈底斯北缘弧背断隆带内,是近年来勘查评价的规模可达中型的接触交代矽卡岩型矿床。矿区矽卡岩主要呈层状、似层状,矽卡岩型铁多金属矿体赋存于下-中三叠统查曲浦组(T_(1-2)c)矽卡岩和大理岩中,矿体呈透镜状、囊状、似层状产出,矽卡岩矿物较发育。为进一步查明矿床矽卡岩矿物种属及矽卡岩类型,剖析矽卡岩形成环境及其与矿化类型之间的关系,基于对矽卡岩矿物系统的显微镜下观测,利用电子探针对矿床主要矽卡岩矿物化学成分进行了系统分析。矽卡岩矿物主要为石榴子石、透辉石、角闪石、绿帘石、绿泥石等,矿床矽卡岩具典型钙矽卡岩特征。根据矿物共生组合及交代关系推断成矿流体经历了5个阶段,分别为早期矽卡岩阶段、退化蚀变阶段、早期热液阶段、石英硫化物阶段和碳酸盐阶段。特征矿物的电子探针分析结果表明,石榴子石主要为钙铁榴石-钙铝榴石系列(And_(18.37~99.89)Gro_(0.24~79.05)Ura+Pyr+Spe_(0.98~6.63)),且发育环带结构;辉石主要为透辉石-钙铁辉石系列(Di_(53.56~99.91)Hd_(1.61~44.55)Jo_(0.08~5.11));角闪石主要为阳起石,次为铁、镁角闪石,均属钙质角闪石系列;绿泥石主要为富铁的铁镁绿泥石;绿帘石贫Fe、Mg。在矿床成矿演化过程中,其成矿环境是发生改变的,早期矽卡岩阶段到最晚期碳酸盐阶段,成矿环境至少经历了从高温、偏碱性的氧化环境到相对低温、偏酸性的还原环境的转变。     

江西永平铜矿矽卡岩矿物特征及其地质意义

永平铜矿含矿岩石主要为绿帘石透辉石石榴石矽卡岩,这种岩石类型是与斑岩体有关的矽卡岩铜矿的典型赋矿岩石。通过对这一主要赋矿矽卡岩的研究,我们发现石榴石生长分为两个阶段:(1)早期石榴石:主要分布在石榴石颗粒核部,XAdr=1.0,主要以钙铁榴石为主,说明早期流体中可能含有较多的铁,是在较氧化条件下形成的;(2)晚期石榴石,沿石榴石裂隙重新成核或者在靠近流体通道的早期石榴石表面生长,出现震荡环带,XAdr=0.46~0.99,为钙铁-钙铝石榴石系列。石榴石发生变化的期间也形成新的矿物,如绿帘石、萤石、方解石和石英等。共存石榴石和绿帘石矿物中存在Fe3+-Al3+之间的替代,说明流体的氧逸度、组分浓度或aFe3+/aAl3+可能发生了变化。金属矿物也可能是在这一阶段形成的。永平铜矿矽卡岩从接触带到大理岩空间上有分带现象。从岩体到围岩的变化趋势为:石榴石含量减少,颜色存在红棕色-棕色-棕绿色-黄绿色-浅黄色的变化趋势;矿石品位降低,这与石榴石中Al2O3含量的变化较一致。我们认为这种变化是含矿热液对早期矽卡岩进行再交代改造的结果,表现为石榴石和绿帘石中Fe3+-Al3+含量的变化,并将Cu等金属沉淀下来。根据矽卡岩矿物的这些特征,在矿床勘探时,可依据棕色石榴石来追踪主矿体的位置。     

Dating magmatic and hydrothermal processes using andradite-rich garnet U–Pb geochronometry

Andradite-rich garnet is a common U-bearing mineral in a variety of alkalic igneous rocks and skarn deposits, but has been largely neglected as a U–Pb chronometer. In situ laser ablation-inductively coupled plasma mass spectrometry U–Pb dates of andradite-rich garnet from a syenite pluton and two iron skarn deposits in the North China craton demonstrate the suitability and reliability of the mineral in accurately dating magmatic and hydrothermal processes. Two hydrothermal garnets from the iron skarn deposits have homogenous cores and zoned rims (Ad₈₆Gr₁₁ to Ad₉₈Gr₁) with 22–118 ppm U, whereas one magmatic garnet from the syenite is texturally and compositionally homogenous (Ad₇₀Gr₂₂ to Ad₇₇Gr₁₄) and has 0.1–20 ppm U. All three garnets have flat time-resolved signals obtained from depth profile analyses for U, indicating structurally bound U. Uranium is correlated with REE in both magmatic and hydrothermal garnets, indicating that the incorporation of U into the garnet is largely controlled by substitution mechanisms. Two hydrothermal garnets yielded U–Pb dates of 129 ± 2 (2σ; MSWD = 0.7) and 130 ± 1 Ma (2σ; MSWD = 0.5), indistinguishable from zircon U–Pb dates of 131 ± 1 and 129 ± 1 Ma for their respective ore-related intrusions. The magmatic garnet has a U–Pb age of 389 ± 3 Ma (2σ; MSWD = 0.6), consistent with a U–Pb zircon date of 388 ± 2 Ma for the syenite. The consistency between the garnet and zircon U–Pb dates confirms the reliability and accuracy of garnet U–Pb dating. Given the occurrence of andradite-rich garnet in alkaline and ultramafic magmatic rocks and hydrothermal ore deposits, our results highlight the potential utilization of garnet as a powerful U–Pb geochronometer for dating magmatism and skarn-related mineralization.     

Petrogenesis of the Platinova skarn in the Belmont domain (Composite Arc Belt, SE Ontario, Canada)

Summary The Platinova skarn is hosted by greenschist facies calcitic marble, contiguous to the hypersolvus Deloro pluton, in the Belmont domain, southeastern Ontario, Canada. The skarn is approximately 4 million tones grading 35% wollastonite. The contact between the pluton and the skarn is not exposed. The skarn is divided into wollastonite-rich and poor units. Garnet and pyroxene from the wollastonite-rich unit exhibit the composition Grs_67–89Adr_11–36Alm_0–3Sps_<2, and Di_50–90Hd_10–48Jo_0–2, and from the wollastonite-poor unit Grs_17–98Adr_0–82Alm_0–2Sps_<1.5 and Di_39–95Hd_3–59Jo_0.3–4, respectively. The skarn development is ascribed to the incursion of magmatogene, silica-rich, CO₂-poor (<0.15) fluids at temperatures of approximately 580 °C, and at pressures of 200 MPa. The genetic model proposed for skarn development, based on field and mineralogical evidence indicates addition of many components relative to essentially pure calcitic marble precursor, including Si, Al, Fe, Mg, Mn, B, Na, and loss of CO₂. Podiform fabrics of the wollastonite unit are interpreted as products of metasomatism rather than as relict sedimentary laminations or metamorphic structures. Present address: Department of Geology, University of Patras, Patras, Greece     

福建马坑矽卡岩型铁(钼)矿床稀土元素地球化学及地质意义

马坑铁(钼)矿是一个赋存于莒舟-大洋花岗岩外接触带黄龙组(C₂h)灰岩和林地组(C₁l)碎屑岩层间构造破碎带中的大型铁矿床。本文利用电感耦合等离子体质谱法(ICP-MS)对马坑的石榴子石、辉石、黄铁矿和磁铁矿矿石的稀土元素(REEs)开展研究。结果表明:石榴子石、辉石和磁铁矿单矿物的稀土分配模式具有相似性,多为轻稀土富集,正铕异常,基本无铈异常,表明其成矿环境为氧化环境,暗示它们之间存在成因联系。矿体附近大理岩和退化蚀变岩稀土元素特征出现规律性变化,表明它们受到岩浆期后热液的交代作用的影响,碎屑岩和褪色辉绿岩提供了部分铁质。     

The Carlés copper–gold–molybdenum skarn (Asturias, Spain): geometry, mineral associations and metasomatic evolution

This paper presents the petrographical, mineralogical and geochemical characteristics of the Carlés Cu–Mo–Au ore deposit, located in the Rio Narcea Gold Belt (Cantabrian zone of the Iberian Massif). It is related to a small postkinematic calc-alkaline monzogranite, which intrudes as a cedar-tree laccolith into the upper siliciclastic Furada Formation (late Silurian age) and the Nieva carbonates (early Devonian age). The Carlés deposit consists mainly of a well-developed exoskarn. The exoskarn is mostly calcic skarn made up of early garnet and pyroxene, and later amphibole, magnetite and sulfides. The presence of magnesian skarn has been recorded on the north side of the intrusion (roof of granitoid). Magnesian skarn consists of olivine, which is partially replaced by diopside and phlogopite and spinel. Close to the igneous rock, skarns are overprinted by strong potassic alteration. The ore is related to the skarn retrogradation and post-skarn veining and faulting. The skarn-related ore consists of earlier, uneconomic magnetite and Fe–As sulfide assemblages and economic Cu–Au–Ag (Bi–Te) assemblages on the eastern and western sides of the contact aureole, and uneconomic Mo and subeconomic Fe–As–Cu–Au–Ag on the northern side of the contact. Later subeconomic Fe–As–Sb–(Zn–Sn–Cu–Au–Ag) assemblages crosscut the granitoid, skarn, marbles and mineral associations developed previously, and are related to younger episodes of fracturing and faulting. Fluid inclusions in the first hydrothermal stage consist of an aqueous solution with significant contents of CO₂, which reach unmixing conditions as a result of a decrease in P–T conditions. This led to two types of solutions, aqueous solutions of moderate to high salinity and hydrocarbon solutions of low salinity. This unmixing phenomenon controlled the first stage of gold precipitation. During the late hydrothermal activity, primary low-salinity-aqueous-carbonic inclusions with contrasting densities are found. They homogenize into vapor, critical or liquid phase. Homogenization temperatures are practically the same in all inclusions, indicating a boiling phenomenon that could control a new precipitation of gold.