Fe-Cu Skarn Research Articles

Sulfur and Carbon–Oxygen Isotopic Geochemistry and Fluid Inclusion Characteristics of the Yolindi Cu-Fe Skarn Mineralization, Biga Peninsula, NW Turkey: Implications for the Source and Evolution of Hydrothermal Fluids

The current study sought to investigate the physiochemical conditions and fluid evolution within the Yolindi Cu-Fe skarn mineralization located in the Biga Peninsula, NW Turkey. This was accomplished through a comprehensive investigation of geological and mineralogical data, along with isotopic analyses of sulfur (δ34S), carbon (δ13C), and oxygen (δ18O) of sulfide and calcite minerals, respectively, as well as fluid inclusion data pertaining to various minerals (e.g., andradite, quartz, and calcite). The Yolindi area features a complex geological framework, including the Paleozoic Kalabak Group (which includes the Torasan, Yolindi, and Sazak formations) and the Triassic Karakaya Complex. These formations were subsequently intruded via Early Miocene Şaroluk granitoids and Hallaçlar volcanics. Skarn formation is zoned into endoskarn and exoskarn types (being categorized into proximal, intermediate, and distal zones), with distinct mineral assemblages indicating concentric and contact metamorphic alteration patterns around the western part of Şaroluk granitoid intrusion in contact with the Torasan formation. The ore mineralogy and paragenesis suggest three distinct stages of evolution: an initial phase of prograde metasomatism characterized by the formation of magnetite and pyrite alongside anhydrous calc-silicate minerals; a subsequent phase of retrograde alteration marked by the formation of epidote, actinolite, and scapolite, accompanied by the occurrence of chalcopyrite and specular hematite; and finally, a post-metasomatic stage involving oxidation processes that led to the development of secondary mineral assemblages containing cerussite, covellite, and malachite. Sulfur isotopes (δ34S) of sulfides from endoskarn (from +0.27 to +0.57‰VCDT) to intermediate exoskarn (from −9.44 to −5.46‰VCDT) zones indicate a diverse sulfur source, including magmatic, sedimentary, and possibly organic matter. δ34S values in hydrothermal fluids suggest a magmatic–hydrothermal origin, with endoskarn and proximal zone fluids showing a slight negative signature and intermediate zone fluids indicating a strong influence from organic-rich or metamorphic sulfur reservoirs. Carbon and oxygen isotopic compositions (δ13C and δ18O) of calcite revealed a progression from marine carbonate signatures in marble samples (from +1.89 to +2.23‰VPDB; from +21.61 to +21.73‰VSMOW) to depleted values in prograde (from −6.0 to +0.09‰VPDB; from +6.22 to +18.14‰VSMOW) and retrograde skarns (from −3.8 to −2.25‰VPDB; from +0.94 to +3.62‰VSMOW), reflecting interactions with high-temperature magmatic fluids and meteoric water mixing. The fluid inclusions in prograde minerals generated under the conditions of fluid boiling exhibited high temperatures, reaching up to 412 °C, and salinities up to 26 wt.% NaCl equivalent. Conversely, the fluid inclusions in retrograde minerals, which were generated due to fluid mixing, exhibited lower temperatures (with an average of 318 °C) and salinities with an average of 4.9 wt.% NaCl equivalent. This indicated that the cooler and more diluted fluids mix with meteoric waters and interact with organic materials in the host rocks. This suggests a multifaceted origin involving various sources and processes. Therefore, this study concluded that the skarn mineralization in the Yolindi area resulted from complex interactions between magmatic, metamorphic, and meteoric fluids, reflecting a dynamic ore-forming environment with implications for the regional metallogeny of Cu-Fe skarn deposits.

Significant mobilization of REE from calc-alkaline melt into fluid during fluid exsolution: Insights from magmatic amphibole composition from Tieshan skarn Fe-Cu deposit (Hubei Province, China)

Hydrothermal fluids associated with carbonatites and peralkaline silicate rocks typically exhibit high REE content, but this is generally not the case for calc-alkaline rocks. However, the Tieshan skarn Fe-Cu deposit in the Edong district of Hubei Province in China demonstrates economic REE mineralization potential linked to calc-alkaline rocks. To investigate the presence of REE enrichment in the fluid, we present textural and compositional data of rock-forming mineral amphibole from the quartz diorite in the Tieshan deposit. Three distinct types of amphibole are identified in the Tieshan quartz diorite, namely Early amphibole, Main-stage amphibole, and Late amphibole, following the crystallization sequence. Early amphibole (813–864 °C, 115–152 MPa) crystallized when the magma was emplaced at a depth of approximately 4.8 km. Main-stage amphibole (741–806 °C, 58–103 MPa) crystallized at a depth of roughly 3 km. Between the early and main-stage amphibole crystallization, the magma experienced fractional crystallization of pyroxene, amphibole, and plagioclase, resulting in a REE enrichment in the residual melt. Late amphibole crystallized subsequent to the transition from lithostatic to hydrostatic stress states (656–729 °C, 27–52 MPa). Significantly, the transport of REE from the magma system initiated towards the end of Main-stage amphibole crystallization. A comparison with the Tonglvshan granitic rocks in the same district indicates an elevated F content and extended fractional crystallization history in the Tieshan magma, contributing to REE enrichment in its melt. Furthermore, the high F content lowered the solidus temperature of the Tieshan magma, thereby facilitating the more efficient removal of REE into the fluid. The assimilation of evaporate into the magma possibly led to heightened sulfur and chlorine levels in the fluid, enabling the transport of a significant amount of REE.

Genesis and Evolution of the Yolindi Cu-Fe Skarn Deposit in the Biga Peninsula (NW Turkey): Insights from Genetic Relationships with Calc-Alkaline Magmatic Activity

The current work investigates the impact of magmatic fluids and metasomatic processes on the Yolindi Cu-Fe skarn deposit in the Biga Peninsula, Turkey. It traces the stages of skarn evolution, from prograde to retrograde alterations, and investigates findings within a broader geological, mineralogical, and geochemical framework. Additionally, it assesses the evolutionary history of the Yolindi deposit in relation to calc-alkaline magmatic activity in an island-arc environment and compares its mineral compositions and genesis with other global and regional Cu-Fe skarn deposits. The Yolindi Cu-Fe skarn deposit in the Biga Peninsula was formed by the intrusion of Şaroluk quartz monzonite pluton into Upper Paleozoic Torasan Formation rocks such as phyllite, schists, hornfels, marble, and serpentinites. During skarnification, reactions between the magmatic fluids from the Şaroluk quartz monzonite pluton and the Torasan Formation produced skarn minerals associated with metals such as Fe and Cu. Initially, these reactions formed prograde skarn minerals such as augite-rich pyroxenes and andradite garnets with magnetite and pyrite. As the system cooled, these initial minerals underwent retrograde alteration, leading to the formation of minerals such as epidote, actinolite, and chlorite, as well as other copper and iron minerals including chalcopyrite, bornite, secondary magnetite, and specular hematite. Therefore, four main stages influenced the formation of the Yolindi Cu-Fe deposit: metamorphic bimetasomatic, prograde metasomatic, and retrograde metasomatic stages. Later, oxidation and weathering resulted in supergene minerals such as cerussite, malachite, and goethite, which serve as examples of the post-metamorphic stage. The mineralogical shifts, such as the andradite–grossular transition, reflect changing hydrothermal fluid compositions and characteristics due to the addition of meteoric fluids. Importantly, the formation of magnetite after garnet and clinopyroxene during the retrograde stage is evidenced by magnetite crystals within garnet. The mineral associations of the Yolindi Cu-Fe skarn deposit align with the global skarn deposits and specific Turkish skarns (e.g., Ayazmant Fe-Cu and Evciler Cu-Au skarn deposits). The Yolindi Cu-Fe skarn deposit, in association with ore-bearing solutions having magmatic origins, developed in an island-arc setting.

Fluid evolution and genesis of the Sankuanggou Fe[sbnd]Cu skarn deposit, Duobaoshan ore field, Northeast China: Evidence from fluid inclusions and H-O-S-Pb isotopes

The Sankuanggou FeCu skarn deposit is located in the Duobaoshan ore field in the northern Great Xing'an Range, Notheast China. The ore bodies occurred in the skarn of the contact zone between the Yanshanian granodiorite and the middle Ordovician Duobaoshan Formation marble. According to the field investigations and mineral crosscutting relationships, five paragenetic stages were identified: the anhydrous skarn (Stage I); hydrous skarn (Stage II); chalcopyrite-pyrite-quartz-molybdenite (Stage III); sphalerite-quartz stage (Stage IV) and quartz-calcite (Stage V). In the Stage I and II, the assemblage of fluid inclusions (FIs) in quartz is characterized by the development of daughter mineral-bearing three-phase FIs (S-type), vapor-rich two-phase aqueous FIs (LV-type) and liquid-rich two-phase aqueous FIs (VL-type). VL- and LV-type FIs were found in the Stage III quartz, whereas only VL-type FIs were present in the Stage IV quartz and Stage V calcite. The homogeneous temperatures of the FIs in Stages I to V were 364–495, 295–405, 243–360 and 135–207 °C, respectively, with salinities of 4.16–58.42, 4.17–47.99, 3.37–14.2, 1.03–11.11 and 3.53–8.4 wt% NaCl eqv., respectively. In general, the ore-forming fluids changed from high-temperature NaCl-H2O system fluids, that contained negligible amounts of CO2 and CH4 and exhibited obvious boiling, to a medium- to low-temperature and low-salinity NaCl–H2O system with fluid mixing. According to the HO isotopic analysis of Stages I and II (δ18OH2O = 0.3–6.3 ‰, δ18D = −112.6 to −79.9 ‰), the ore-forming fluid was identified as magmatic fluid. In contrast, the δ18OH2O and δ18D values in Stages III and IV gradually decreased (δ18OH2O = −9.6 to −2.3 ‰, δ18D = −133.1 to −118.9 ‰), implying a gradual meteoric water input into the fluid. The S isotopic analysis (δ34S range from −4 to −0.8 ‰) revealed that S mainly originates from the magma during the mineralization process. Further, the Pb isotopic (208Pb/204Pb = 37.64–38.725, 207Pb/204Pb = 15.45–15.606 and 206Pb/204Pb = 18.115 to 19.786) investigations indicated that the ore-forming materials of this deposit are derived from the crust-mantle mixing. Based on the previously reported geochronologic and geodynamic data, we can conclude that the Sankuanggou deposit is a typical FeCu skarn deposit and formed during the Early Jurassic Paleo-Pacific Plate subduction.

Discrimination of Mineralization Types of Skarn Deposits by Magnetite Chemistry

There are different mineralization types for skarn deposits with various origins and ore-forming conditions. Magnetite is one of the main ore minerals in skarn deposits, but whether chemical compositions of magnetite can be used to discriminate different mineralization types remains unknown. This paper collects the published magnetite electron probe microanalysis (EPMA) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) data of skarn deposits and investigates the relationship between magnetite geochemistry and mineralization types of skarn deposits using the partial least squares-discriminant analysis (PLS-DA). For EPMA data, magnetite from Fe-Zn skarn deposits can be roughly separated from that of Cu-Fe-Pb-Zn, Fe, Fe-Co-Bi-Ag, Fe-Cu, and Fe-Zn-Pb skarn deposits due to the relative enrichment of Al and Mn for the former. For LA-ICP-MS data, magnetite from Fe-Sn, Fe-Zn, and W-Mo-Pb-Zn-Fe-Cu skarn deposits can be roughly separated from that of other skarn deposits due to positive correlation with Mn, Zn, and Sn and the negative correlation with V for the former. The relative depletion of V for these mineralization types likely reflects higher oxygen fugacity than the other types of skarn deposits. Magnetite from Fe-Au skarn deposits is separated due to the relatively high Cr and Ga contents, whereas magnetite from Fe-Cu skarn deposits can be discriminated because of the relative enrichment of Mg and Co. The discrimination between different types of skarn deposits in the plot of Mg + Mn vs. (Si + Al)/(Mg + Mn) indicates that the chemical composition of magnetite is significantly affected by the fluid–rock interaction, where magnetite from Fe-Au skarn deposit shows the lowest fluid–rock ratios. The PLS-DA discrimination based on LA-ICP-MS data is better than that of EPMA data, and the main discriminant elements for the different mineralization types are Mg, Al, Ti, V, Mn, Co, Zn, Ga, and Sn. Based on the discriminant elements, we propose a plot of Mg+Mn vs. Ga+Sn to discriminate different mineralization types of skarn deposits.

Geology, fluid inclusions and S-Pb-C-O isotopes of the Kuokuqueke Fe-Cu skarn deposit in Western Tianshan, China

The late Paleozoic Boluokenu island arc belt, located on the northern margin of Western Tianshan, Xinjiang, hosts a series of epithermal Au, hydrothermal vein-type Pb-Zn and porphyry-skarn Fe-Cu polymetallic deposits and is one of the most important metallogenic belts in China. The Kuokuqueke skarn deposit is located in the middle of the Boluokenu metallogenic belt. Skarn and Fe-Cu orebodies crop out along the contact between the lower Silurian Nilekehe Formation and the Kenaxia-Kekeqiaoke granitic intrusions. Based on field investigations and petrographic observations, four main paragenetic stages of skarn formation and ore deposition are identified: the prograde skarn stage (I), retrograde skarn stage (II), quartz-sulfide stage (III), and quartz-calcite stage (IV). Ore minerals mainly consist of magnetite and hematite, with lesser amounts of pyrite, chalcopyrite, sphalerite and galena. Four types of fluid inclusions were identified in garnet, epidote, quartz, and calcite at different stages, i.e., bi-phase (liquid and vapor) aqueous inclusions (L-dominated homogenized to liquid phase and V-dominated homogenized to vapor phase), tri-phase (liquid, vapor and solid) aqueous inclusions (S-bearing) and liquid-only aqueous inclusions. From the early to late stages, ore-forming fluids show an evolutionary trend from high temperature and medium–high salinity to low temperature and low salinity. The fluid inclusions were trapped at pressures of 400∼600 bars and 100∼300 bars for the prograde and retrograde skarn stage, respectively, corresponding to depths of 1.6∼2.4 km (under lithostatic conditions) and 1∼2 km (under hydrostatic conditions), respectively. The δ34S values of sulfides range from −5.2 to 0.5‰, indicating a magmatic origin of the sulfur in ore-forming fluids. The 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb values of the sulfides vary from 17.893 to 18.242, 15.550 to 15.591 and 37.996 to 38.175, respectively, indicating that lead was derived from a mixed crust-mantle source of subduction; the δ13CV-PDB values and δ18OV-SMOW values of calcite range from −0.6 to 2.4 and 8.1 to 13.3, respectively, indicating that carbon in fluids was mainly sourced from the mixture of ore-related granite and host carbonate rocks. Comprehensive studies indicate that the Kuokuqueke deposit is a typical skarn deposit, in which fluid boiling occurred locally in the pre-ore stage (I) and boiling in the main ore stage (II∼III) was the main cause of ore mineral deposition, while meteoric water may have been involved in the post-ore stage (IV).

Fluid inclusions, isotopes and mineralogy of the Kuruer epithermal Cu-Au deposit, Chinese Western Tianshan: Implications for ore genesis and exploration

The Kuruer Cu-Au deposit is located in the Wusun Range of Yili Block, Chinese Western Tianshan, where numerous epithermal Au, skarn Fe-Cu and porphyry Mo-Cu deposits have been recognized. Petrography, fluid inclusions, S-Pb-H-O isotopes, field emission-scanning electron microscopy (FE-SEM) plus energy dispersive spectrometer (EDS) and electron microprobe analysis (EMPA) have been carried out to constrain the genesis of the Kuruer deposit and its implication for further exploration. The minerlization is hosted by volcanic rocks and occur as veins and veinlets structurally controlled by NW-trending faults. Three ore-forming stages were recognized, including quartz-sulfides-bismuth-gold stage (I), quartz-chalcopyrite stage (II) and calcite-chlorite-chalcopyrite stage (III).Six types of fluid inclusions were identified in stage I quartz, including monophase vapor inclusions (type 1), liquid-rich biphase inclusions (type 2), vapor-rich biphase inclusions (type 3), H2O-rich CO2-H2O triphase inclusions (type 4), CO2-rich CO2-H2O triphase inclusions (type 5) and solid halite-bearing triphase inclusions (type 6), whereas only type 2 inclusions were recognized in stage II quartz and stage III calcite. Types 2, 3, 4 and 6 inclusions in stage I have homogenization temperature (Th) ranges of 184–359 °C, 209–252 °C, 250–319 °C and 229–263 °C, with salinity ranges of 4.1–8.5 wt% NaCleq, 5.9–6.9 wt% NaCleq, 1.0–6.0 wt% NaCleq and 32.7–33.9 wt% NaCleq, respectively. Type 2 inclusions in stages II and III have Th varying from 144 to 212 °C and 114 to 163 °C, with salinities of 0.2–6.7 wt% NaCleq and 0.1–3.1 wt% NaCleq, respectively.The in-situ δ34S values of sulfides in stage I range from −4.66 to 0.34‰. The 206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb ratios of stage I chalcopyrite vary from 18.295 to 18.954, 15.568 to 15.673 and 38.109 to 38.817, respectively, which are consistent with those of Early Carboniferous Dahalajunshan Formation volcanic rocks and granitoids from the Wusun Range. The values of δ18OH2O-VSMOW calculated from δ18Oquartz and δDH2O-VSMOW of stage I quartz range from 0.0 to 2.4‰ and −118.6 to −109.3‰, respectively. These isotopic compositions indicate that both metals and sulfur were sourced from the hosting volcanic rocks and hidden causative pluton, while the initial ore-forming fluids were magmatic in origin, with increasing involvement of meteoric water with time.Evidence from mineralogy, mineral geochemistry and fluid inclusions indicates that the initial fluid phase separation triggered the precipitation of “invisible” gold within pyrite and chalcopyrite during stage I. Subsequently, the decrease of fS2 due to the escape of H2S(g) and sulfide precipitation and cooling caused the formation of liquid bismuth from solutions. The bismuth melts have scavenged Au in situ from the residual solutions, resulting in the formation of Bi-Au inclusions within the fractures and intergranular spaces of earlier pyrite. For stages II and III, dilution and cooling due to input of meteoric water facilitated the chalcopyrite precipitation. The Kuruer Cu-Au deposit is classified as a subepithermal mineralization associated with porphyries. Porphyry Cu-Au mineralization could have developed beneath the Kuruer and its vicinity.

Eocene magmatism and associated Fe-Cu mineralization in northeastern Turkey: a case study of the Karadağ skarn

ABSTRACT The metallogenic belt containing numerous skarn mineralized systems starting from Eastern Europe continues through Turkey and Iran. The study area in the Eastern Pontides is within this metallogenic belt. The 44.39 ± 0.53 Ma Karadağ Intrusion sourced skarn mineralization is located along the granitoid-to-limestone contact. The Karadağ Intrusion is an arc-like pluton with medium–high K calc-alkaline and peraluminous–metaluminous affinity. The Karadağ Fe–Cu skarn mineralization (Gümüşhane, Turkey), an exoskarn, is hosted by Late Cretaceous limestone and consists of early garnet, clinopyroxene, and orthoclase with late epidote and chlorite. Primary ore minerals are magnetite and haematite, accompanied by minor amounts of chalcopyrite and pyrite. Pyroxene comprises mostly diopside and less hedenbergitic diopside and johannsenite. Wollastonite is very rare. Garnet is andradite and grossular–andradite. Thus, all these results imply that the Karadağ Fe–Cu skarn mineralization formed under relatively oxidized and Fe-rich conditions. The homogenization temperatures of the fluid inclusions vary from 189°C to 405°C for quartz and 186°C to 430°C for calcite. The salinity contents in the fluid inclusions are within 0.2–9 wt% NaCl equivalent for quartz and 0.4–14.8 wt% NaCl equivalent for calcite. First melting temperatures between −36.5 and −47.4°C were attained with the presence of NaCl–FeCl2± CaCl2 in the initial phase of fluid inclusions. The first melting in the later stage of fluid inclusions is between −3.8 and −17.2°C, thereby, supporting the existence of NaHCO3-Na2CO3-KCl-type salt composition. The δ18O values of minerals are 1.7–10.3‰ for garnet, 11.1–14.6‰ for quartz, 6.4 to 6.8‰ for epidote, and 2.8–3.8‰ for magnetite in the Karadağ skarn mineralization. The δ18O value of epidote indicates magmatic fluid, whereas those of garnet, magnetite, and quartz suggest magmatic fluids together with less meteoric effect. The δ18O values in limestone (18.7 to 22.3‰), marble (8.7‰), and calcite (10.5 to 12.2‰) were depleted relative to typical δ18O contents of marine carbonates (20 to 30‰). Moreover, the C isotope values of calcite (−5.4 to −1.4‰), marble (−2.1‰), and limestone (1.0 to 1.2‰) reflect those of metamorphic rocks and skarns (−4.0 to 3‰ and −18 to 2‰). Mineral paragenesis, fluid inclusion, and stable isotopic signatures are consistent with ore mineralization caused by the interaction of magmatic fluids with carbonate host rocks. Karadağ Fe-Cu skarn mineralization, associated with Karadağ postcollisional magmatism, is an example of skarn mineralized system in the Eastern Pontides.

Iron Isotope Fractionation during Skarn Cu-Fe Mineralization

Fe isotopes have been applied to the petrogenesis of ore deposits. However, the behavior of iron isotopes in the mineralization of porphyry-skarn deposits is still poorly understood. In this study, we report the Fe isotopes of ore mineral separations (magnetite, pyrite, chalcopyrite and pyrrhotite) from two different skarn deposits, i.e., the Tonglvshan Cu-Fe skarn deposit developed in an oxidized hydrothermal system and the Anqing Cu skarn deposit developed in a reduced hydrothermal system. In both deposits, the Fe isotopes of calculated equilibrium fluids are lighter than those of the intrusions responsible for the skarn and porphyry mineralization, corroborating the “light-Fe fluid” hypothesis. Interestingly, chalcopyrite in the oxidized-Tonglvshan skarn deposit has lighter Fe than chalcopyrite in the reduced-Anqing skarn deposit, which is best understood as the result of the prior precipitation of magnetite (heavy Fe) from the ore fluid in the oxidized-Tonglvshan systems and the prior precipitation of pyrrhotite (light Fe) from the ore fluid in the reduced-Anqing system. The δ56Fe for pyrite shows an inverse correlation with δ56Fe of magnetite in the Tonglvshan. In both deposits, the Fe isotope fractionation between chalcopyrite and pyrite is offset from the equilibrium line at 350 °C and lies between the FeS-chalcopyrite equilibrium line and pyrite-chalcopyrite equilibrium line at 350 °C. These observations are consistent with the FeS pathway towards pyrite formation. That is, Fe isotopes fractionation during pyrite formation depends on a path from the initial FeS-fluid equilibrium towards the pyrite-fluid equilibrium due to the increasing extent of Fe isotopic exchange with fluids. This finding, together with the data from other deposits, allows us to propose that the pathway effect of pyrite formation in the Porphyry-skarn deposit mineralization is the dominant mechanism that controls Fe isotope characteristics.

Mafic microgranular enclaves from the Tieshan batholith, eastern China: Implications for petrogenesis of magma associated with Fe-Cu skarn mineralization

Mineralogy, geochemistry, and geochronology of the mafic microgranular enclaves (MMEs) and their host diorite from the Tieshan batholith, Edong district, eastern China, were studied to constrain their petrogenesis and relationship with Fe-Cu skarn mineralization. The MMEs are diorite in composition and characterized by mixed apatite morphologies (elongated thin needles and stubby prismatic form) and bladed biotite, as well as clots of host diorite and megacrystic alkali-feldspar xenocrysts. The MMEs have similar zircon U-Pb age as their host diorite (~139 Ma). Most of the major and trace elements of the MMEs show a linear trend on Harker diagrams and plot along the low-silica trend of the host diorite. They are also characterized by enrichment of LREE and large ion lithophile elements (LILE), but are depleted in high field strength elements (HFSE). The MMEs display similar initial Sr isotopes and εNd(t), and slightly lower εHf(t) compared to that of host diorite. These results indicate that the Tieshan batholith formed via partial melting of an enriched lithospheric mantle, which is believed to be in equilibrium with a garnet-bearing residue (>50 km), followed by contamination of low crustal materials and fractional crystallization, whereas the MMEs appear to be the products of magma mixing. The presence of Cu- and Ni-bearing minerals in the MMEs probably indicates upper mantle or lower crust accumulation of sulfide which may have played a key role in controlling the formation of the parental magma associated with the skarn-porphyry Cu deposit (148 to 135 Ma) from the Middle-Lower Yangtze River metallogenic belt (MLYRMB). In contrast, the thinner, normal crust (~30 km) at ~ 130 Ma, believed to be in equilibrium with a plagioclase-rich residue, was either unsuitable for producing Cu-bearing accumulations or failed to transfer the deep accumulations to shallower levels to form Cu-bearing skarn systems, resulting in Fe-only mineralization. This may imply that skarn-porphyry Cu deposits prefer to form under > 50 km crustal settings, whereas Fe skarns may preferentially occur under normal (~30 km) crustal thickness.

Establishment of a research workflow for occurrence state of critical metal in ore concentrate powder: A case study of the cobalt-rich sulfur ore concentrate powder from the Middle-Lower Yangtze River Valley Metallogenic Belt, China

长江中下游成矿带作为我国矿床学研究程度和矿产利用技术水平最高的成矿带之一，大部分矿床中除了主要成矿元素铜、金、铁和硫等，还伴生潜在可利用的关键金属资源镉、钴、硒、碲和铼等。由于目前矿山主要选矿回收铜、铁、硫、铅、锌、金和银等主要矿种，在不改变选矿工艺的条件下，矿山产品矿精粉中关键金属的分布特征和可利用性是当前关键金属资源利用的核心问题之一。本文对成矿带内玢岩型铁矿床、矽卡岩型铁矿床、矽卡岩型铁铜矿床、矽卡岩型铜金矿床、斑岩型铜金矿床和角砾岩筒型铜金矿床等六类矿床的矿山产品（铜金粉、硫精粉、铁精粉和金精粉）进行了系统化学成分分析，发现目前的矿山产品中关键金属元素含量普遍不高，但矽卡岩型铁矿床中的龙桥铁矿床硫精粉中富集钴，具有综合回收利用钴资源的潜力。在此基础上，本次工作利用综合矿物分析技术（TIMA），扫描电镜（SEM）和激光剥蚀-等离子体质谱仪（LA-ICP-MS）三种测试方法，系统开展了富钴硫精粉中钴的赋存状态研究。结果表明，龙桥硫精粉中钴矿物为辉砷钴矿、铁硫砷钴矿和硫铜钴矿，分别占硫精粉中总钴含量的9.93%、0.64%和0.01%。黄铁矿晶格中类质同象形式产出的钴占总量的81.97%，此外还有7.46%的钴赋存在其他矿物中。通过对比研究，初步建立了矿精粉中关键金属元素赋存状态的研究方法流程，为矿精粉中钴的回收利用提供了依据。;The Middle-Lower Yangtze River Valley Metallogenic Belt is one of the metallogenic belts with well-studied economic geology research and comprehensive mineral utilization technology in China. In addition of the main ore-forming elements Cu, Au, Fe and S, most deposits are associated with potentially available critical element resources, such as Cd, Co, Se, Te and Re. At present, the mines processed and recovered Cu, Fe, S, Pb, Zn, Au, Ag and other major products. Without changing the mineral process, the key problems in the utilization of critical element resources are the understanding of the occurrence of critical metals in ore concentrations. We have conducted a systematic chemical composition analysis of the mine products (i.e., copper concentrate powder, sulfur concentrate powder, iron concentrate powder and gold concentrate powder) of six types of deposits in the metallogenic belt, including apatite-magnetite Fe deposit, skarn Fe deposit, skarn Fe-Cu deposit, skarn Cu-Au deposit, porphyry Cu-Au deposit and breccia-hosted Au deposit. It is found that the contents of critical elements (Cd, Co, Se, Te and Re) in those mine products are generally low, except Co enriched in sulfur concentrate powder of Longqiao skarn iron deposit, which has the possibility of recovery and utilization of cobalt resources. In this study, the occurrence of cobalt in Co-rich sulfur concentrate powder was analyzed by Tescan Integrated Mineral Analyzer (TIMA), Scanning Electron Microscope (SEM) and Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS). The analyses results show that the cobalt independent minerals in Longqiao sulfur concentrate powder are cobaltite, glaueodot and carrollite, which account for 9.93%, 0.64% and 0.01% of the total cobalt in sulfur concentrate powder, respectively. The amount of cobalt occurs as isomorphic form in pyrite lattice accounts for 81.97% of the total. In addition, 7.46% of cobalt exists in other unknown minerals. Research workflow of critical elements deportments in ore concentrate powder is established initially, which provides a theoretical basis for the recovery and utilization of cobalt in ore concentrate powder.

Geochemistry, microthermometry, and C and O isotope constraints on the origin of the Düzköy Fe-Cu skarn deposit (Gümüşhane, NE Turkey)

The Fe-Cu-type Duzkoy skarn deposit occurs along the contact between the Lower Cretaceous Berdiga limestone and the Eocene-aged Harsit granitoid. The endoskarn zone is characterized by the presence of granular pyroxenes, while garnet, epidote, quartz, and calcite are commonly defined in the exoskarn. Fe-Cu-type skarns were identified according to the mineralogical properties, garnet (Ad0-8.81Gr59.69-78.65Py21.35-38.11) and pyroxene (Hd0.29-38.64Di61.09-99.02Jo0.06-1.26) compositions, and Mn/Fe ratios (in the range of < 0.1 to 3.75) of pyroxenes. The geochemistry of the Harsit granitoid is also compatible with Fe-Cu-type skarns according to the high MgO (2.41 wt%) and low K2O (2.05 wt%), as well as Rb-Sc and Rb/Sr-Zr contents. Therefore, the coexistence of both oxide and sulfide phases was found to be closely associated with the geochemical features of the Harsit granitoid. Higher homogenization temperatures (Th, up to 483 °C) and salinity (up to 44.4 wt% NaCl equ.) of the early-stage fluids correspond to magmatic-dominated fluids. In contrast, the decreasing Th and salinity as low as 168 °C and 1.1 wt% NaCl equ., respectively, refer to a mixture of meteoric water through the later stages. The δ13C isotopes of skarn calcites (between − 1.62 and 2.77‰) are compatible with marine carbonates, while their δ18O rates, ranging from 9.04 and 24.5‰, are highly depleted. Further depletion of δ18O isotopes (down to 3.47‰), calculated from the equilibrated fluids with calcites, while δ13C isotopes were stable, is indicative of the mixing of magmatic and meteoric waters, and these results comply well with the fluid inclusion data.

In situ LA-ICP-MS study of garnets in the Makeng Fe skarn deposit, eastern China: Fluctuating fluid flow, ore-forming conditions and implication for mineral exploration

Most garnets in Fe-Cu skarn deposits have simple petrographic textures, LREE-enriched geochemical patterns, are enriched in Fe, and are distinguished from garnets of typical W or W-Mo skarn deposits by their extremely low W, Sn, and Mo contents. However, little is known about the garnets in Fe skarn systems that have more complex textures and high concentrations of W, Sn, and Mo. Here we describe diverse textures and LA-ICP-MS data for garnets in the largest Fe skarn deposit (Makeng) in eastern China, and we discuss the dynamics of the mineralizing fluids and the significance of garnet for W-Mo exploration. Garnets from the Makeng deposit fall into four main types, corresponding to four-stage garnet growth based on their textural characteristics and trace element contents: Stage 1, Al-rich relatively homogeneous garnets (Adr51-55) with a portion (Adr17-48) and HREE-enriched patterns and weak negative Eu anomalies; Stage 2, Fe-rich garnet with LREE-enriched or flat patterns and weak negative or positive Eu anomalies, represented by oscillatory zoned rims (Adr50-90) with dodecahedral faces and oscillatory zones (cores Adr54-68, rims Adr65-80) with composite dodecahedral-trapezohedral faces; Stage 3, nearly pure andradite garnets with significantly LREE-enriched patterns and strong positive Eu anomalies, as represented by irregular zones (Adr70-99) in oscillatory zoned rims and relatively homogeneous garnets (Adr95-100) with extremely weak zoning; and Stage 4, Al-rich garnet with HREE-enriched patterns and weak negative or weak positive Eu anomalies, as represented by garnet veinlets (Adr45-77) with weak zoning. These four stages of garnet were formed by periodic fluctuations in the fluid flux which can be explained by a kinetic dispersion model: a low flux responsible for the Al-rich garnet, a high flux responsible for the Fe-rich garnets, the highest flux responsible for the nearly pure andradite garnet, and a low flux responsible for the veins of Al-rich garnet. Relative to garnet in Fe-Cu skarn deposits, all garnet types in the Makeng Fe skarn deposit are rich in trace elements such as W, Sn, and Mo, especially the pure andradite garnet in stage 3, which has the highest contents of W, Sn, and Mo. These elemental enrichments are closely correlated with Fe, LREE/HREE, and fO2 signatures. The W and Mo signatures are identical to those of garnets in typical W or W-Mo skarn deposits, and they are useful geochemical indicators during exploration for W-Mo ore deposits.

Zircon geochemistry of Edong granitoids in the Middle-Lower Yangtze Metallogenic Belt (Eastern China): Constraints on W-Cu-Fe skarn mineralization

It has long been established that skarn deposits of different metals are associated with intrusions of different compositions. Intermediate-felsic granitoids in the Edong district of the Middle-Lower Yangtze Metallogenic Belt host skarn deposits with varying W-Cu-Fe proportions, yet previous whole-rock geochemical studies could not distinguish between the magmatic suites that formed the different skarn deposits. In this study, LA-ICP-MS zircon geochemical data are presented for the Ruanjiawan W skarn (60300 t WO3), Tongshankou Cu skarn (0.6 Mt Cu), Tonglushan Cu-Fe skarn (1.1 Mt Cu and 56.8 Mt Fe) and Jinshandian Fe skarn (200 Mt Fe) deposits in the Edong district. Zircons from the ore-forming intrusions of these skarn deposits are all characterized by heavy rare earth element (HREE) enrichments and light rare earth element (LREE) depletions, with positive Ce anomalies and slightly negative Eu anomalies. Tungsten contents in zircons from the W ore-forming intrusion (0.02–3.16 ppm W; avg. 1.14 ppm) are generally higher than in zircons from the Cu ore-forming intrusion (0.00–0.24 ppm W; avg. 0.03 ppm). Copper content in zircons from the Cu ore-forming intrusion is higher than in those from the W ore-forming intrusion. Fertile intrusive rocks from the four skarn deposits contain zircons with high calculated Ce4+/Ce3+ ratios (Ruanjiawan: 71.7; Tongshankou: 207.5; Tonglushan: 263.6; Jinshandian: 189.0. Fluorine content of the Ruanjiawan intrusion is higher than the Tonglushan and Jinshandian intrusions, followed by the Tongshankou intrusion. Chlorine contents show the opposite trend. We propose that the different source regions for the ore-fertile intrusions is the critical factor that controls the metal content, oxygen fugacity and volatile components. Our studies suggest that zircon geochemistry is a good indicator to distinguish tungsten causative intrusions from copper- and iron ore related intrusions (i.e. W content ≧ 1.14 ppm and Ce4+/Ce3+ ratios ≦ 207.5).

Analysis of the infiltrative metasomatic relationships controlling skarn mineralization at the Abbas-Abad Fe-Cu Deposit, Isfahan, north Zefreh Fault, Central Iran

The Abbas-Abad volcano-sedimentary-hosted Fe-Cu skarn deposit, NE Isfahan, is one of the most important skarns in the central Urumieh-Dokhtar magmatic arc. It was formed along the contact with the Dorojin granitoid massif next to the Zefreh Fault. The plutonic rocks are of I-type, volcanic arc affinity with normal-K, metaluminous, calc-alkaline to calcic quartz diorite, tonalite, and granodiorite, similar to many other Fe-type skarn-related granitoids worldwide. The parent magma involved in this skarn system is high temperature and relatively oxidized. Amphibole geobarometery in quartz diorite yielded a crystallization pressure lower than 200 MPa (2 kb, ~7 km) at 724° to 785 °C. Granitoid compositions around the ore deposit are mainly granodiorite. U-Pb zircon dating yields Early Miocene ages of 23.0 ± 1.6 Ma for a quartz dioritic rock and 21.3 ± 1.5 Ma for a tonalitic sample. The injection and cooling of the granodiorite produced a hornblende hornfels aureole with endoskarn.Paragenetic relationships and microprobe data indicate that Abbas-Abad calcic skarn evolution can be subdivided into three stages as follow: (I) Prograde skarn associated andradite-rich garnet (Adr93-98Grs0-4Spe1-2) and pyroxene, (II) Retrograde skarn starting with garnet (Adr53-69Grs28-43Spe2-4), magnetite, and sulfide minerals associated with calcic-alteration, and (III) Post-ore with pyrite, chalcedony, epidote, quartz, calcite, and zeolite veinlets. Textural and compositional studies of garnet and magnetite from the garnet-bearing exoskarn zone reveal the multiple events associated with skarn formation. Garnets are characterized by low TiO2 and relatively high CaO that are indicative of a calcareous wall-rock among Eocene volcaniclastic rocks. They are grouped into garnet-1 (low w/r) and garnet-2 (inverse zoning at high w/r) with notable Cu-contents (up to 743 ppm). Petrographically, magnetite morphology is divided into fine-grained granular, needle-like, and polycrystalline aggregates. Mineral chemistry of needle-like type reveals impure components (Al2O3, CaO, and SiO2). This type formed from dissolution-reprecipitation processes during a stage of reequilibration in the skarn system. Mixing with cooler external fluid (rich in oxygen and poor in Fe2+) is reflected in individual features during infiltration metasomatism during garnet and magnetite growth, such as oscillatory zoning and needle-like textures. Thus, we infer increasing pH (decreasing acidity) and decreasing T related to carbonate neutralization reactions affecting Fe- and Cu-chloride complexing as the main controls on mineralization.The structural studies of the area show that movement of the dextral transtensional Zefreh Fault provide local zones for emplacement of Dorojin granitoid during the Early Miocene. Consequently, the dextral transtensional Zefreh Fault and dextral transpression associated with the Marbin-Rangan Fault uplifted the skarn and host units and Dorojin body under the roughly N-S directed maximum compression direction. Furthermore, the interplay of Zefreh and Marbin-Rangan faults within the N-S regional compressional regime formed an anticlinal structure that exposed the Dorojin body within the core.

The Lavrion Pb-Zn-Ag–Rich Vein and Breccia Detachment-Related Deposits (Greece): Involvement of Evaporated Seawater and Meteoric Fluids During Postorogenic Exhumation

AbstractThe formation of ore deposits in the Lavrion Pb-Zn-Ag district was associated with Miocene detachment that accommodated orogenic collapse and exhumation of high-grade nappes across the ductile-brittle transition. This district consists of (1) low-grade porphyry Mo style, (2) Cu-Fe skarn, (3) high-temperature carbonate replacement Pb-Zn-Ag, and (4) vein and breccia Pb-Zn-Ag mineralization. The vein and breccia mineralization locally contains high-grade silver in base metal sulfides that are cemented by fluorite and carbonate gangue. The rare earth element contents of these gangue minerals, chondrite-normalized patterns, and fluid inclusion studies suggest that they precipitated from a low-temperature hydrothermal fluid. Primary and pseudosecondary fluid inclusions in fluorite and calcite are characterized by a wide range of homogenization temperatures (92°–207°C) and salinities of up to 17.1 wt % NaCl equiv. Secondary fluid inclusions only represent &lt;5 vol % of the total fluid trapped. Fluids extracted from inclusions in fluorite have values of δD = –82.1 to –47.7‰ (Vienna-standard mean ocean water [V-SMOW]) and δ18O = –10.4 to –5.1‰ (V-SMOW). These data and low ratios of Cl/Br measured by crush-leach analyses for fluids in fluorite (102–315) and calcite (162–188) are compatible with the ore fluid being the result of mixing of meteoric water with evaporated seawater. These data suggest that fluids leading to the deposition of late Pb-Zn-Ag–rich vein- and breccia-style mineralization in Lavrion were related to circulation of mixed evaporated seawater and meteoric fluids that was enhanced by brittle deformation. This contrasts with the fluids of magmatic origin related to the formation of low-grade porphyry Mo, Cu-Fe skarn, and high-temperature carbonate replacement deposits spatially related to the Plaka granodiorite.

Comparison of 3D prospectivity modeling methods for Fe-Cu skarn deposits: A case study of the Zhuchong Fe-Cu deposit in the Yueshan orefield (Anhui), eastern China

Three-dimensional (3D) metallogenic prospectivity modeling has become increasingly important in deep Fe-Cu skarn mineralization prospecting. The selection of prediction models and their comparison are of great significance. In this paper, we integrated the geological and geophysical data from the Zhuchong Fe-Cu deposit in the Yueshan orefield (Anhui, eastern China) to establish the local 3D geological framework. We extracted the 3D ore-controlling factors quantitatively by means of 3D spatial analysis methods, and compared the 3D mineralization locations predicted by the weight of evidence method and the artificial neural network method. The results show that both methods can locate most of the known orebodies, suggesting that both are relatively reliable. In addition, the weight of evidence method performed distinctly better than the artificial neural network method in terms of both prediction effectiveness and efficiency. Therefore, the weight of evidence method may be more applicable in 3D prospectivity modelling for Fe-Cu skarn deposits in the region. Finally, the composite area predicted by the two methods is taken as the final prediction result of the mineralization area of the deposit. And it is suggested that in the quantitative 3D prediction, multiple selection of different methods with good adaptability should be involved in the prediction at the same time, and compound prediction method should be used to delineate the target area. Our work has guiding significance for future deep prospecting and exploitation for other similar Fe-Cu skarn deposits.

Petrogenesis and mineralization of the porphyry and skarn mineralization-related Husite intrusion in the Boluokenu metallogenic belt, Western Tianshan Orogenic Belt, NW China

Many porphyry and skarn Cu (Fe, Mo, Au, Zn) deposits have been discovered along the western Tianshan Orogenic Belt within the Central Asian Orogenic Belt. Generally, these Cu polymetallic deposits are considered to be linked to porphyries that formed in an arc setting, e.g., in a continental magmatic arc and island magmatic arc, but an agreement on their source region has not been reached. The Husite granitic complex and associated Kekesala skarn Fe-Cu deposit from the Boluokenu metallogenic belt provide significant insights into a comprehensive study of the ore-forming porphyries in Boluokenu. The ore-forming porphyries are mainly granodiorites and belong to calc-alkaline and high-K calc-alkaline series. LA-ICP-MS zircon U-Pb dating on the granodiorites yields ages of 368 Ma. The trace element compositions of the granodiorites are characterized by enrichment in large ion lithophile elements (LILE) and light rare earth elements (LREE), depletion in high field strength elements (HFSE) and heavy rare earth elements (HREE), and slightly negative Eu anomalies and are similar to rocks that form in a continental arc setting. These rocks also show large variations in their εHf (t) (+4.1 to +9.7) and Mg# (38–69) values, alongside low Ba/Th (4–230) and high Th/Yb (3.77–7.41) and Th/La (0.21–0.71) ratios, suggesting that the granodiorite magma originated from the partial melting of mafic lower crust with a mantle wedge component and involved signals of subduction-zone sediments and fluids. The Husite mafic microgranular enclaves (MMEs) exhibit high Mg# (50–62), MgO (3.25–6.93 wt%) and low SiO2 (48.8–59.5%) contents, with positive εHf(t) from +3.3 to +7.4. The zircon LA-ICP-MS U-Pb ages of the MMEs (373 Ma) indicate nearly coeval formation between the MMEs and HMPs during the Late Devonian. These features with the petrological and mineralogical characteristics (such as needle-like apatite and disequilibrium feldspar xenocrysts) suggest that the Husite MMEs formed from the mixing of felsic magma from the partial melting of mafic lower crust and mafic magma that was derived from mantle wedge, rather than restite, xenoliths or fractional crystallization of magma. Thus, the skarn Fe-Cu mineralization were probably related to hybrid intermediate-acid magma that is characterized by high water and oxygen contents and high sulfur fugacity. It can be inferred that the response to ongoing slab roll-back during the Junggar plate’s subduction beneath the Yili Block, including the underplating of mantle-derived mafic magmas from the metasomatism of subduction-zone melts, led to the partial melting of the mafic lower crust to form felsic magma. Then, the continuous reaction between the mafic and felsic magmas further increased the Fe-Cu concentrations and was closely related to the subsequent Fe-Cu mineralization.

Mineralization, Mineralogy and Geochemistry of Saheb Fe-Cu Deposit of Saqqez (Kurdestan), NW Iran

The Saheb Fe-Cu skarn deposit is located in the Sanandaj-Sirjan metamorphic belt, SE Saqqez, western Iran and has been formed along the contact between the Oligo-Miocene aged Saheb granitoid and the Permian aged impure calcareous rocks and includes endoskarn and exoskarn. Exoskarn is widely developed and includes garnet and epidote skarn zones. The majority of mineralized zones are concentrated in garnet skarn. The relatively oxidizing mineralogical assemblage of the Saheb skarn includes garnet (andradite-grossular), pyroxene (diopside-hedenbergite), magnetite and hematite. Magnetite is the main and abundant ore mineral throughout the ore deposit. Based on field evidences and microscopic studies of skarn zone samples, two stages of prograde and retrograde alteration are distinguishable. According to the results of sample analysis of Saheb skarn intrusive body by XRF and ICP-MS techniques, the combination of this body is chiefly granite to granodiorite-diorite and belongs to the I-type granitoids, metaluminous and K-rich calc-alkaline series. The Saheb granitoid is related to the VAG (Volcanic Arc Granite) tectonic setting.

REEs mineralization in a Fe-Cu skarn deposit associated with calc-alkaline magmatism

REEs mineralization in a Fe-Cu skarn deposit associated with calc-alkaline magmatism