Dissolution–reprecipitation process of magnetite from the Chengchao iron deposit: Insights into ore genesis and implication for in-situ chemical analysis of magnetite

Magnetite formed in different environments commonly has distinct assemblages and concentrations of trace elements that can potentially be used as a genetic indicator of this mineral and associated ore deposits. In this paper, we present textural and compositional data of magnetite from the Chengchao iron deposit, Daye district, China to provide a better understanding in the formation mechanism and genesis of the deposit and shed light on analytical protocols for in-situ chemical analysis of hydrothermal magnetite. Magnetite grains from the ore-related granitoid pluton, mineralized endoskarn, magnetite-dominated exoskarn, and vein-type iron ores hosted in marine carbonate intruded by the pluton were examined using scanning electron microscopy and analyzed for major and trace elements using electron microprobe. Back-scattered electron images reveal that primary magnetite from the mineralized skarns and vein-type ores were all partly reequilibrated with late-stage hydrothermal fluids, forming secondary magnetite domains that are featured by abundant porosity and have sharp contact with the primary magnetite. These textures are interpreted as resulting from a dissolution–reprecipitation process of magnetite, which, however, are mostly obscure under optically.Primary magnetite grains from the mineralized endoskarn and vein-type ores contain high SiO₂ (0.92–3.21 wt.%), Al₂O₃ (0.51–2.83 wt.%), and low MgO (0.15–0.67 wt.%), whereas varieties from the exoskarn ores have high MgO (2.76–3.07 wt.%) and low SiO₂ (0.03–0.23 wt.%) and Al₂O₃ (0.54–1.05 wt.%). This compositional contrast indicates that trace-element geochemical composition of magnetite is largely controlled by the compositions of magmatic fluids and host rocks of the ores that have reacted with the fluids. Compared to its precursor mineral, secondary magnetite is significantly depleted in most trace elements, with SiO₂ deceasing from 1.87 to 0.47 wt.% (on average) and Al₂O₃ from 0.89 to 0.08 wt.% in mineralized endoskarn and vein type ores, and MgO from 2.87 to 0.60 wt.% in exoskarn ores. On the contrary, average content of iron is notably increased from 69.2 wt.% to 71.9 wt.% in the secondary magnetite grains. The results suggest that the dissolution–reprecipitation process has been important in significantly removing trace elements from early-stage magnetite to form high-grade, high-quality iron ores in hydrothermal environments. The textural and compositional data confirm that the Chengchao iron deposit is of hydrothermal origin, rather than being crystallized from immiscible iron oxide melts as previously suggested. This study also highlights the importance of textural characterization using various imaging techniques before in-situ chemical analysis of magnetite, as is the case for texturally complicated UTh-bearing accessory minerals that have been widely used for UPb geochronology study.     

In-situ LA-ICP-MS trace elemental analyses of magnetite: Cu-(Au,Fe) deposits in the Khetri copper belt in Rajasthan Province,NW India

Magnetite is common in many ore deposits and their host rocks, and is useful for petrogenetic studies. In the Khetri copper belt in Rajasthan Province, NW India, there are several Cu-(Au, Fe) deposits associated with extensive Cu ± Fe ± Au ± Ag ± Co ± REE ± U mineralization hosted in phyllites, schists and quartzites of the Paleoproterozoic Delhi Supergroup. Ore bodies of these deposits comprise dominantly disseminated and vein-type Cu-sulfide ores composed of chalcopyrite, pyrite, and pyrrhotite intergrown with minor magnetite. There are also Fe-oxide ores with minor or no Cu-sulfides, which are locally overprinted by the mineral assemblage of the Cu-sulfide ores. In addition to the Fe-oxide and Cu-sulfide ores, the protolith of the Delhi Supergroup includes banded iron formations (BIFs) with original magnetite preserved (i.e. magnetite-quartzites) and their sheared counterparts. In the sheared magnetite-quartzites, their magnetite and quartz are mobilized and redistributed to magnetite and quartz bands. Trace elemental compositions of magnetite from these types of ores/rocks were obtained by LA-ICP-MS. The dataset indicates that different types of magnetite have distinct concentrations of Ti, Al, Mg, Mn, V, Cr, Co, Ni, Zn, Cu, P, Ge and Ga, which are correlated to their forming environments. Magnetite grains in magnetite-quartzites have relatively high Al (800–8000 ppm), Ti (150–900 ppm) and V (300–600 ppm) contents compared to those of BIFs in other regions such as the Yilgarn Craton, Western Australia and Labrador, Canada. The high Al, Ti and V contents can be explained by precipitation of the magnetite from relatively reduced, Al–Ti-rich water possibly involving hotter, seafloor hydrothermal fluids derived from submarine mafic volcanic rocks. Magnetite in sheared magnetite-quartzites is generally irregular and re-crystallized, and has Ni, Mn, Al, Cu and P contents lower than the magnetite from the unsheared counterparts, suggesting that the shearing-related mobilization is able to extract these elements from original magnetite. However, elevated contents of Ti, V, Co, Cr, Ge and Mg of the magnetite in the sheared magnetite-quartzites can be ascribed to involvement of external hydrothermal fluids during the shearing, consistent with occurrence of some hydrothermal minerals in the samples.Compositions of magnetite from the Fe-oxide and Cu-sulfide ores are interpreted to be controlled mainly by fluid compositions and/or oxygen fugacity (fO₂). Other potential controlling factors such as temperature, fluid–rock interaction and co-precipitating minerals have very limited impacts. Magnetite in the Cu-sulfide ores has higher V but lower Ni contents than that of the Fe-oxide ores, likely indicating its precipitation from relatively reduced, evolved fluids. However, it is also indicated that the two types of magnetite do not show large distinctions in terms of concentrations of most elements, suggesting that they may have precipitated from a common, evolving fluid. We propose a combination of Ge versus Ti/Al and Cr versus Co/Ni co-variation plots to discriminate different types of magnetite from the Khetri copper belt. Our work agrees well with previous studies that compositions of magnetite can be potentially useful for provenance studies, but also highlights that discrimination schemes would be more meaningful for deposits in a certain region if fluid/water chemistry and specific formation conditions reflected in compositions of magnetite are clearly understood.     

Iron isotope fractionation during skarn-type alteration: Implications for metal source in the Han-Xing iron skarn deposit

The Han-Xing iron mineralization in the central North China Craton is a typical Fe skarn deposit associated with altered diorites. Here we report the Fe isotopic compositions of whole rocks and mineral separates from this deposit with a view to evaluate the Fe isotope fractionation during the formation of Fe skarn deposit, and to constrain the metal source. The Fe isotopes show a large variation both in whole rocks and mineral separates. Altered diorites show a wide range in δ⁵⁶Fe values (− 0.07‰ to + 0.21‰ relative to the Fe isotope standard IRMM-014) which positively correlate with their TFe₂O₃/TiO₂ ratios (Fe₂O₃ and FeO calculated as TFe₂O₃). The positive correlation indicates that heavy Fe isotopes were preferentially leached from diorites during the skarn-type alteration. Among the metallic minerals, pyrite and pyrrhotite are isotopically heavier (+ 0.12‰ to + 0.48‰) than the magnetite (+ 0.07‰ to + 0.21‰). Fe isotope fractionation between mineral pairs demonstrates that magnetite did not attain Fe isotopic equilibrium with pyrite and pyrrhotite, whereas pyrite and pyrrhotite might have attained isotopic equilibrium. Petrological observations and major element data also suggest that iron was leached from the diorites during the skarn-type alteration. If the leached iron provides the main Fe budget of the Han-Xing Fe skarn deposit, magnetite in ores would be isotopically heavier than the unaltered diorite. However, our results are in contrast with the magnetite being isotopically lighter than the unaltered diorite. This suggests that the major Fe source of the Han-Xing Fe skarn deposit is not from the leaching of diorites, and might be from magmatic fluid which is isotopically lighter than the silicate melt. Our data demonstrate that Fe isotopes can be used as important tracers in deciphering the metal source of Fe skarn deposits.     

Geology and genesis of Kafang Cu–Sn deposit,Gejiu district,SW China

Kafang is one of the main ore deposits in the world-class Gejiu polymetallic tin district, SW China. There are three main mineralization types in the Kafang deposit, i.e., skarn Cu–Sn ores, stratiform Cu ores hosted by basalt and stratiform Cu–Sn ores hosted by carbonate. The skarn mainly consists of garnet and pyroxene, and retrograde altered rocks. These retrograde altered rocks are superimposed on the skarn and are composed of actinolite, chlorite, epidote and phlogopite. Major ore minerals are chalcopyrite, pyrrhotite, cassiterite, pyrite and scheelite. Sulfur and Pb isotopic components hint that the sources of different types of mineralization are distinctive, and indicate that the skarn ore mainly originated from granitic magma, whereas the basalt-hosted Cu ores mainly derived from basalt. Microthermometry results of fluid inclusions display a gradual change during the ore-forming process. The homogenization temperature of different types of inclusions continuously decreases from early to late mineralization stages. The salinities and freezing temperatures exhibit similar evolutionary tendencies with the T _{homogenization}, while the densities of the different types keep constant, the majority being less than 1. Oxygen and hydrogen isotopic values (δ¹⁸O and δD) of the hydrothermal fluids fall within ranges of 3.1 to 7.7‰ with an average of 6.15‰, calculated at the corresponding homogenization temperature, and − 73 and − 98‰ with an average of − 86.5‰, respectively. Microthermometry data and H–O isotopes indicate that the ore-forming fluid of the Kafang deposit is mainly derived from magma in the early stage and a mixture of meteoric and magmatic water in late stage. Molybdenite Re–Os age of the skarn type mineralization is 83.4 ± 2.1 Ma, and the stratiform ores hosted by basalt is 84.2 ± 7.3 Ma, which are consistent with the LA-ICP-MS zircon age of the Xinshan granite intrusion (83.1 ± 0.4 Ma). The evidence listed above reflects the fact that different ore styles in the Kafang deposit belong to the same mineralization system.     

Fluid types and their genetic meaning for the BIF-hosted iron ores,Krivoy Rog,Ukraine

This paper contributes to the understanding of the genesis of epigenetic, hypogene BIF-hosted iron deposits situated in the eastern part of Ukrainian Shield. It presents new data from the Krivoy Rog iron mining district (Skelevatske–Magnetitove deposit, Frunze underground mine and Balka Severnaya Krasnaya outcrop) and focuses on the investigation of ore genesis through application of fluid inclusion petrography, microthermometry, Raman spectroscopy and baro-acoustic decrepitation of fluid inclusions. The study investigates inclusions preserved in quartz and magnetite associated with the low-grade iron ores (31–37% Fe) and iron-rich quartzites (38–45% Fe) of the Saksaganskaya Suite, as well as magnetite from the locally named high-grade iron ores (52–56% Fe). These high-grade ores resulted from alteration of iron quartzites in the Saksaganskiy thrust footwall (Saksaganskiy tectonic block) and were a precursor to supergene martite, high-grade ores (60–70% Fe). Based on the new data two stages of iron ore formation (metamorphic and metasomatic) are proposed.The metamorphic stage, resulting in formation of quartz veins within the low-grade iron ore and iron-rich quartzites, involved fluids of four different compositions: CO₂-rich, H₂O, H₂O–CO₂(± N₂–CH₄)–NaCl(± NaHCO₃) and H₂O–CO₂(± N₂–CH₄)–NaCl. The salinities of these fluids were relatively low (up to 7 mass% NaCl equiv.) as these fluids were derived from dehydration and decarbonation of the BIF rocks, however the origin of the nahcolite (NaHCO₃) remains unresolved. The minimum P–T conditions for the formation of these veins, inferred from microthermometry are T_min = 219–246 °C and P_min = 130–158 MPa. The baro-acoustic decrepitation analyses of magnetite bands indicated that the low-grade iron ore from the Skelevatske–Magnetitove deposit was metamorphosed at T = ~ 530 °C.The metasomatic stage post-dated and partially overlapped the metamorphic stage and led to the upgrade of iron quartzites to the high-grade iron ores. The genesis of these ores, which are located in the Saksaganskiy tectonic block (Saksaganskiy ore field), and the factors controlling iron ore-forming processes are highly controversial. According to the study of quartz-hosted fluid inclusions from the thrust zone the metasomatic stage involved at least three different episodes of the fluid flow, simultaneous with thrusting and deformation. During the 1^st episode three types of fluids were introduced: CO₂–CH₄–N₂(± C), CO₂(± N₂–CH₄) and low salinity H₂O–N₂–CH₄–NaCl (6.38–7.1 mass% NaCl equiv.). The 2^nd episode included expulsion of the aqueous fluids H₂O–N₂–CH₄–NaCl(± CO₂, ± C) of moderate salinities (15.22–16.76 mass% NaCl equiv.), whereas the 3^rd event involved high salinity fluids H₂O–NaCl(± C) (20–35 mass% NaCl equiv.). The fluids most probably interacted with country rocks (e.g. schists) supplying them with CH₄ and N₂. The high salinity fluids were most likely either magmatic–hydrothermal fluids derived from the Saksaganskiy igneous body or heated basinal brines, and they may have caused pervasive leaching of Fe from metavolcanic and/or the BIF rocks. The baro-acoustic decrepitation analyses of magnetite comprising the high-grade iron ore showed formation T = ~ 430–500 °C. The fluid inclusion data suggest that the upgrade to high-grade Fe ores might be a result of the Krivoy Rog BIF alteration by multiple flows of structurally controlled, metamorphic and magmatic–hydrothermal fluids or heated basinal brines.     

Mineralogy,fluid inclusions,and isotopes of the Cihai iron deposit,eastern Tianshan,NW China: Implication for hydrothermal evolution and genesis of subvolcanic rocks-hosted skarn-type deposits

Most skarn deposits are closely related to granitoids that intruded into carbonate rocks. The Cihai (>100 Mt at 45% Fe) is a deposit with mineral assemblages and hydrothermal features similar to many other typical skarn deposits of the world. However, the iron orebodies of Cihai are mainly hosted within the diabase and not in contact with carbonate rocks. In addition, some magnetite grains exhibit unusual relatively high TiO₂ content. These features are not consistent with the typical skarn iron deposit. Different hydrothermal and/or magmatic processes are being actively investigated for its origin. Because of a lack of systematic studies of geology, mineral compositions, fluid inclusions, and isotopes, the genetic type, ore genesis, and hydrothermal evolution of this deposit are still poorly understood and remain controversial.The skarn mineral assemblages are the alteration products of diabase. Three main paragenetic stages of skarn formation and ore deposition have been recognized based on petrographic observations, which show a prograde skarn stage (garnet-clinopyroxene-disseminated magnetite), a retrograde skarn stage (main iron ore stage, massive magnetite-amphibole-epidote ± ilvaite), and a quartz-sulfide stage (quartz-calcite-pyrite-pyrrhotite-cobaltite).Overall, the compositions of garnet, clinpyroxene, and amphibole are consistent with those of typical skarn Fe deposits worldwide. In the disseminated ores, some magnetite grains exhibit relatively high TiO₂ content (>1 wt.%), which may be inherited from the diabase protoliths. Some distinct chemical zoning in magnetite grains were observed in this study, wherein cores are enriched in Ti, and magnetite rims show a pronounced depletion in Ti. The textural and compositional data of magnetite confirm that the Cihai Fe deposit is of hydrothermal origin, rather than associated with iron rich melts as previously suggested.Fluid inclusions study reveal that, the prograde skarn (garnet and pyroxene) formed from high temperature (520–600 °C), moderate- to high-salinity (8.1–23.1 wt.% NaCl equiv, and >46 wt.% NaCl equiv) fluids. Massive iron ore and retrograde skarn assemblages (amphibole-epidote ± ilvaite) formed under hydrostatic condition after the fracturing of early skarn. Fluids in this stage had lower temperature (220°–456 °C) and salinity (8.4–16.3 wt.% NaCl equiv). Fluid inclusions in quartz-sulfide stage quartz and calcite also record similar conditions, with temperature range from 128° to 367 °C and salinity range from 0.2 to 22.9 wt.% NaCl equiv. Oxygen and hydrogen isotopic data of garnet and quartz suggest that mixing and dilution of early magmatic fluids with external fluids (e.g., meteoric waters) caused a decrease in fluid temperature and salinity in the later stages of the skarn formation and massive iron precipitation. The δ¹⁸O values of magnetite from iron ores vary between 4.1 and 8.5‰, which are similar to values reported in other skarn Fe deposits. Such values are distinct from those of other iron ore deposits such as Kiruna-type and magmatic Fe-Ti-V deposits worldwide. Taken together, these geologic, geochemical, and isotopic data confirm that Cihai is a diabase-hosted skarn deposit related to the granitoids at depth.     

Mineral and stable isotope compositions,phase equilibria and 40Ar–39Ar geochronology from the iron skarn deposit in Sangan,northeastern Iran

The Sangan iron skarn deposit is located on the eastern edge of the Sabzevar-Doruneh Magmatic Belt, northeastern Iran. Mineralization occurs at the contact between Eocene igneous rocks and Cretaceous carbonates. The silicate-dominant prograde skarn stage consists of garnet and clinopyroxene, whereas the retrograde stage is dominated by magnetite associated with minor hematite, phlogopite, pyrite, and chalcopyrite. Phase equilibria and mineral chemistry studies reveal that the skarn formed within a temperature range of ∼375° to 580 °C and that the mineralizing fluid evolved from a hot, low oxygen fugacity, alkaline fluid during the silicate-dominant stage to a fluid of relatively lower temperature and higher oxygen fugacity at the magnetite-dominant stage. The δ¹⁸O values of magnetite and garnet vary from +3.1 to +7.5‰ and +7.7 to +11.6‰, respectively. The calculated δ¹⁸O_H2O values of fluid in equilibrium with magnetite and garnet range from +9.8 to +11.1‰ and +10.1 to +14.8‰, respectively. These elevated δ¹⁸O_H2O values suggest interaction of magmatic water with ¹⁸O-enriched carbonates. The high δ³⁴S values (+10.6 to +17.0‰) of pyrite separates from the Sangan iron ore indicate that evaporites had an important role in the evolution of the hydrothermal fluid. Phlogopite separates from the massive ores yield ⁴⁰Ar/³⁹Ar plateau ages of 41.97 ± 0.2 and 42.47 ± 0.2 Ma, indicating that the skarn formation and associated iron mineralization was related to the oldest episode of magmatism in Sangan at ∼42 Ma. Eocene time marked a peak of magmatic activity and associated skarn in the post-collisional setting in northeastern Iran, whereas Oligo-Miocene magmatic activity and associated skarn in the Urumieh-Dokhtar Magmatic Belt are related to subduction. In addition, skarn mineralization in northeastern and eastern Iran is iron type, but skarn mineralization in the Urumieh-Dokhtar magmatic belt is copper – iron and copper type.     

Geological characteristics and metallogenesis of iron deposits in western Tianshan,China

The western Tianshan metallogenic belt is one of the most significant polymetallic iron metallogenic belts in China. Important advances have been achieved recently in iron exploration in the Awulale Mountain in western Tianshan, China. These newly-discovered iron deposits are mainly hosted in the basic-medium andesitic lavas and volcaniclastics, often comprising a number of high-grade ores. Magnetite is predominated in ore mineral assemblages, and pyrite, chalcopyrite, pyrrhotite or sphalerite increase in certain deposits. Wallrock alterations are intensively developed, exemplified as sodic–calcic and potassic alterations which display in different patterns as country rocks and ore-controlled structures vary. Skarn assemblages are commonly developed in ore districts like Beizhan, Dunde and Chagangnuoer, and pyroxene + albite + K-feldspar − epidote + actinolite alterations are dominated around ore bodies in Zhibo deposit, whereas the Shikebutai deposit develops alteration assemblages comprising of jasper, barite, sericite, and chlorite. Thus, iron deposits can be divided into three types including volcanic-sedimentary type, volcanic magmatic-hydrothermal type and iron skarn type. Our preliminary interpretation about the tectonic background of this iron mineralization in this area is in the late stage of a collisional–accretional orogenic belt around Carboniferous, with some extrusional–extensional tectonic transition locally. Iron mineralization is likely to have a close genetic relationship with volcanic–subvolcanic activity, syn- or slightly post- the volcanism which took place besides continental arc. Volcanic eruption contributes to majority of mineralizing iron, with minor extracted from hydrothermal replacement from wall rocks.     

The post-collisional Cihai iron skarn deposit,eastern Tianshan,Xinjiang, China

The Cihai iron skarn deposit is located in the southern part of the eastern Tianshan, Xinjiang, northwestern China. The major iron orebodies are banded and nearly parallel to each other. The iron ores are hosted in an early diabase dike and in skarn. Post-ore diabase dikes cut the iron ores and their hosting diabase. Hydrothermal activity can be divided into four stages based on geological and petrographic observations: initial K–Na alteration (stage I), skarn-minor magnetite event (II), retrograde skarn-magnetite main ore event (III), and quartz–calcite–sulfide veining (IV). Zircon U–Pb dating yields ages of 286.5 ± 1.8 Ma for early diabase and 275.8 ± 2.2 Ma for post-ore diabase dikes. Amphibole separated from massive magnetite ore gives a ⁴⁰Ar–³⁹Ar plateau age of 281.9 ± 2.2 Ma and is the time of ore formation. Formation of the Cihai iron deposit is closely related to post-collisional magmatism and associated Cu–Ni–Au polymetallic mineralization in the eastern Tianshan.     

A new genetic model for the Triassic Yangyang iron-oxide–apatite deposit,South Korea: Constraints from in situ U–Pb and trace element analyses of accessory minerals

The Yangyang iron-oxide–apatite deposit in South Korea has undergone multiple episodes of igneous activity, deformation, hydrothermal alteration, and iron-oxide–apatite (IOA) mineralization. The iron orebodies occur as concordant- to discordant-layered lenticular or massive magnetite and/or magnetite–pyrite ores. The iron mineralization occurs along a N–S-trending shear zone within the Yangyang syenite, which experienced both early ductile and later brittle deformations. Alteration was caused mainly by the injection of hydrothermal fluid through the shear zone, leading to Fe–P mineralization. We recognize multiple stages of alteration in the Yangyang deposit, based on a paragenesis that is defined by distinct mineral assemblages including Na–Ca–K alteration phases (e.g., albite, diopside, actinolite, and biotite) and accessory minerals containing high field strength elements (e.g., apatite, sphene, allanite, and monazite). The alteration around the magnetite ore body shows an evolutionary trend from Ca (–Na) alteration, through K to phyllic alterations. The Fe–P mineralization is associated with the Ca–K and K alteration products. The iron orebodies are hosted by deformed and altered syenite, which intruded the Paleoproterozoic gneiss complexes at 233 ± 1 Ma (SHRIMP U–Pb zircon age) in a post-collisional tectonic setting. LA-ICP-MS U–Pb dating of REE-rich sphene and apatite from the iron ores and alteration products yields Fe mineralization ages of 216 ± 3 Ma (sphene) and 212 ± 13 Ma (apatite). This is the first time, which IOA-type mineralization in the Korean Peninsula was dated as Triassic age related to post-collisional magmatism within the Gyeonggi Massif, South Korea. The U–Pb system was subsequently reset (208 ± 3 Ma–sphene and 151 ± 13 Ma–apatite) by Jurassic and Cretaceous magmatism. This unique geological evolution was responsible for Mesozoic metal enrichment and remobilization into suitable structural traps in the Yangyang district.     

In-situ LA-ICP-MS trace elemental analyses of magnetite: The Bayan Obo Fe-REE-Nb deposit,North China

The Bayan Obo Fe-REE-Nb deposit in northern China is the world's largest light REE deposit, and also contains considerable amounts of iron and niobium metals. Although there are numerous studies on the REE mineralization, the origin of the Fe mineralization is not well known. Laser ablation (LA) ICP-MS is used to obtain trace elements of Fe oxides in order to better understand the process involved in the formation of magnetite and hematite associated with the formation of the giant REE deposit. There are banded, disseminated and massive Fe ores with variable amounts of magnetite and hematite at Bayan Obo. Magnetite and hematite from the same ores show similar REE patterns and have similar Mg, Ti, V, Mn, Co, Ni, Zn, Ga, Sn, and Ba contents, indicating a similar origin. Magnetite grains from the banded ores have Al + Mn and Ti + V contents similar to those of banded iron formations (BIF), whereas those from the disseminated and massive ores have Al + Mn and Ti + V contents similar to those of skarn deposits and other types of magmatic-hydrothermal deposits. Magnetite grains from the banded ores with a major gangue mineral of barite have the highest REE contents and show slight moderate REE enrichment, whereas those from other types of ores show light REE enrichment, indicating two stages of REE mineralization associated with Fe mineralization. The Bayan Obo deposit had multiple sources for Fe and REEs. It is likely that sedimentary carbonates provided original REEs and were metasomatized by REE-rich hydrothermal fluids to form the giant REE deposit.     

A combined fluid inclusion and S–Pb isotope study of the Neoproterozoic Pingshui volcanogenic massive sulfide Cu–Zn deposit,Southeast China

The Pingshui Cu–Zn deposit is located in the Jiangshan–Shaoxing fault zone, which marks the Neoproterozoic suture zone between the Yangtze block and Cathaysia block in South China. It contains 0.45 million tons of proven ore reserves with grades of 1.03 wt.% Cu and 1.83 wt.% Zn. This deposit is composed of stratiform, massive sulfide ore bodies, which contain more than 60 vol.% sulfide minerals. These ore bodies are hosted in altered mafic and felsic rocks (spilites and keratophyres) of the bimodal volcanic suite that makes up the Neoproterozoic Pingshui Formation. Metallic minerals include pyrite, chalcopyrite, sphalerite, tennantite, tetrahedrite and magnetite, with minor galena. Gangue minerals are quartz, sericite, chlorite, calcite, gypsum, barite and jasper. Three distinct mineralogical zones are recognized in these massive sulfide ore bodies: a distal zone composed of sphalerite + pyrite + barite (zone I); an intermediate zone characterized by a pyrite + sphalerite + chalcopyrite assemblages (zone II); and a proximal zone containing chalcopyrite + pyrite + magnetite (zone III). A thin, layer of exhalative jaspilite overlies the sulfide ore bodies except in the proximal zone. The volcanic rocks of the Pingshui Formation are all highly altered spilites and keratophyres, but their trace element geochemistry suggests that they were generated by partial melting of the depleted mantle in an island arc setting. Homogenization temperatures of the primary fluid inclusions in quartz from massive sulfide ores are between 217 and 328 °C, and their salinities range from 3.2 to 5.7 wt.% NaCl equivalent. Raman spectroscopy of the fluid inclusions showed that water is the dominant component, with no other volatile components. Fluid inclusion data suggest that the ore-forming fluids were derived from circulating seawater. The δ³⁴S values of pyrite from the massive sulfide ores range from − 3.6‰ to + 3.4‰, indicating that the sulfur was primarily leached from the arc volcanic rocks of the Pingshui Formation. Both pyrite from the massive sulfide ores and plagioclase from the spilites have similar lead isotope compositions, implying that the lead was also derived from the Pingshui Formation. The low lead contents of the massive sulfide ores and the geochemistry of their host rocks are similar to many VMS Cu–Zn deposits in Canada (e.g., Noranda) and thus can be classified as belonging to the bimodal-mafic subtype. The presence of magnetite and the absence of jaspilite and barite at the − 505 m level in the Pingshui deposit suggest that this level is most likely the central zone of the original lateral massive sulfide ore bodies. If this interpretation is correct, the deep part of the Pingshui Cu–Zn deposit may have significant exploration potential.     

Geology,geochemistry and genesis of the Qianfanling quartz-vein Mo deposit in Songxian County,Western Henan Province,China

The Qianfanling Mo deposit, located in Songxian County, western Henan province, China, is one of the newly discovered quartz-vein type Mo deposits in the East Qinling–Dabie orogenic belt. The deposit consists of molybdenite in quartz veins and disseminated molybdenite in the wall rocks. The alteration types of the wall rocks include silicification, K-feldspar alteration, pyritization, carbonatization, sericitization, epidotization and chloritization. On the basis of field evidence and petrographic analysis, three stages of hydrothermal mineralization could be distinguished: (1) pyrite–barite–quartz stage; (2) molybdenite–quartz stage; (3) quartz–calcite stage.Two types of fluid inclusions, including CO₂-bearing fluid inclusions and water-rich fluid inclusions, have been recognized in quartz. Homogenization temperatures of fluid inclusions vary from 133 °C to 397 °C. Salinity ranges from 1.57 to 31.61 wt.% NaCl eq. There are a large number of daughter mineral-CO₂-bearing inclusions, which is the result of fluid immiscibility. The ore-forming fluids are medium–high temperature, low to moderate salinity H₂O–NaCl–CO₂ system. The δ³⁴S values of pyrite, molybdenite, and barite range from − 9.3‰ to − 7.3‰, − 9.7‰ to − 7.3‰ and 5.9‰ to 6.8‰, respectively. The δ¹⁸O values of quartz range from 9.8‰ to 11.1‰, with corresponding δ¹⁸O_fluid values of 1.3‰ to 4.3‰, and δ¹⁸D values of fluid inclusions of between − 81‰ and − 64‰. The δ¹³C_V-PDB values of fluid inclusions in quartz and calcite have ranges of − 6.7‰ to − 2.9‰ and − 5.7‰ to − 1.8‰, respectively. Sulfur, hydrogen, oxygen and carbon isotope compositions show that the sulfur and ore-forming fluids derived from a deep-seated igneous source. During the peak collisional period between the North China Craton and the Yangtze Craton, the ore-forming fluids that derived from a deep igneous source extracted base and precious metals and flowed upwards through the channels that formed during tectonism. Fluid immiscibility and volatile exsolution led to the crystallization of molybdenite and other minerals, and the formation of economic orebodies in the Qianfanling Mo deposit.     

The geology and genesis of the iron skarns of the Turgai belt,northwestern Kazakhstan

The magnetite deposits of the Turgai belt (Kachar, Sarbai and Sokolov), in the Valerianovskoe zone of the southern Urals, Kazakhstan, contain a combined resource of over 3 Gt of iron oxide ore. The deposits are hosted by carbonate sediments and volcaniclastic rocks of the Carboniferous Valerianovka Supergroup, and are spatially related to the gabbroic to granitoid composition intrusive rocks of the Sarbai–Sokolov intrusive series. The magnetite deposits are developed dominantly as metasomatic replacement of limestone, but also, to a lesser extent, of volcanic rocks. Pre-mineralisation metamorphism and alteration resulted in the formation of wollastonite and the silicification of limestone. Magnetite mineralisation is associated with the development of a high temperature skarn assemblage of diopside, grossular–andradite garnet, actinolite, epidote and apatite. Sub-economic copper-bearing sulphide mineralisation overprints the magnetite mineralisation and is associated with deposition of hydrothermal calcite and the formation of an extensive sodium alteration halo dominated by albite and scapolite. Chlorite formation accompanies this stage and further later stage hydrothermal overprints. The replacement has in places resulted in preservation of primary features of the limestone, including fossils and sedimentary structures in magnetite, skarn calc-silicates and sulphides.Analysis of Re–Os isotopes in molybdenite indicates formation of the sulphide mineral assemblage at 336.2 ± 1.3 Ma, whilst U–Pb analyses of titanite from the skarn alteration assemblage suggests skarn alteration at 326.6 ± 4.5 Ma with re-equilibration of isotope systematics down to ~ 270 Ma. Analyses of mineral assemblages, fluid inclusion microthermometry, O and S isotopes suggest initial mineralisation temperatures in excess of 600 °C from hypersaline brines (45–50 wt.% NaCl eq.), with subsequent cooling and dilution of fluids to around 150 °C and 20 wt.% NaCl eq. by the time of calcite deposition in late stage sulphide-bearing veins. δ¹⁸O in magnetite (− 1.5 to + 3.5‰) and skarn forming silicates (+ 5 to + 9‰), δ¹⁸O and δ¹³C in limestone and skarn calcite (δ¹⁸O + 5.4 to + 26.2‰; δ¹³C − 12.1 to + 0.9‰) and δ³⁴S in sulphides (− 3.3 to + 6.6‰) and sulphates (+ 4.9 to + 12.9‰) are all consistent with the interaction of a magmatic-equilibrated fluid with limestone, and a dominantly magmatic source for S. All these data imply skarn formation and mineralisation in a magmatic–hydrothermal system that maintained high salinity to relatively late stages resulting in the formation of the large Na-alteration halo. Despite the reported presence of evaporites in the area there is no evidence for evaporitic sulphur in the mineralising system.These skarns show similarities to some members of the iron oxide–apatite and iron oxide–copper gold deposit classes and the model presented here may have implications for their genesis. The similarity in age between the Turgai deposits and the deposits of the Magnitogorsk zone in the western Urals suggests that they may be linked to similar magmatism, developed during post-orogenic collapse and extension following the continent–continent collision, which has resulted in the assembly of Laurussian terranes with the Uralide orogen and the Kazakh collage of the Altaids or Central Asian Orogenic Belt. This model is preferred to the model of simultaneous formation of very similar deposits in arc settings at either side of an open tract of oceanic crust forming part of the Uralian ocean.     

Investigation on mineralogy,geochemistry and fluid inclusions of the Goushti hydrothermal magnetite deposit,Fars Province,SW Iran: A comparison with IOCGs

The Goushti iron deposit from Dehbid area located in the Sanandaj-Sirjan metamorphic Belt (SSB), SW Iran is hosted by the Early Mesozoic silicified dolomite. Mineralized zones are lithostructurally controlled and oriented NW-SE parallel to the Zagros Orogenic Belt (ZOB). Magnetite, the major ore mineral, occurs as open space fillings and is accompanied by the secondary mineral phases hematite, goethite and martite. Gangue minerals mainly include quartz, dolomite and K-feldspar are associated with minor hydrosilicates. Calc-silicates such as wollastonite and diopside, minerals typical of skarns, are virtually absent from the ore zones. Fe₂O₃ content in the mineralized zones varies in the range of 38–75 wt%. The concentrations of Au, Cu, P, Ti, Cr and V as well as Co/Ni, Cr/V, (LREE)/(HREE), Eu/Sm and La/Lu values and Eu-Ce anomalies of the studied ores indicate that the Goushti deposit is a hydrothermal magnetite type. The subvolcanic rhyolite and basalt in this area are regarded as the source of iron and heat in the mineralizing system. The fluid inclusion data showed that magnetite deposited from the ore-bearing fluid with salinities 1–7 wt% NaCl equivalent at temperatures of 130–200 °C. A decrease in temperature and pressure, supplemented by fluid mixing, is the major controlling factor in iron oxide precipitation. The field relationships and mineralogical–geochemical characteristics of iron ores indicate that the Goushti hydrothermal deposit could not be classified as a member of the IOCG (Iron Oxide-Copper-Gold) deposits.     

Origin and evolution of hydrothermal fluids in the Taochong iron deposit,Middle–Lower Yangtze Valley,Eastern China: Evidence from microthermometric and stable isotope analyses of fluid inclusions

The Middle–Lower Yangtze River Valley is one of the most important metallogenic belts in China, hosting numerous Cu–Fe–Au–Mo deposits. The Taochong deposit is located in the northern part of the Fanchang iron ore district of the Middle–Lower Yangtze River metallogenic belt. The Fe-orebody is hosted by Middle Carboniferous to Lower Permian limestones. Skarns and Fe-orebodies occur as tabular bodies along interlayer-gliding faults, at some distance from the inferred granitic intrusions. Field evidence and petrographic observations indicate that the three stages of hydrothermal activity—the skarn, iron oxide (main mineralization stage), and carbonate stages—all contributed to the formation of the Taochong iron deposit. The skarn stage is characterized by the formation of garnet and pyroxene, with high-temperature, hypersaline hydrothermal fluids with isotopic compositions similar to those of typical magmatic fluids. These fluids were probably generated by the separation of brine from a silicate melt instead of the product of aqueous fluid immiscibility. The iron oxide stage coincides with the replacement of garnet and pyroxene by actinolite, chlorite, quartz, calcite and hematite. The hydrothermal fluids at this stage are represented by saline fluid inclusions that coexist with vapor-rich inclusions with anomalously low δD values (− 66‰ to − 94‰). The decrease in ore fluid δ¹⁸O_water with time and decreasing depth is consistent with the decreases in fluid salinity and temperature. The fluid δD values also show a decreasing trend with decreasing depth. Both fluid inclusion and stable isotopic data suggest that the ore fluid during the main period of mineralization was evolved by the boiling of various mixtures of magmatic brine and meteoric water. This process was probably induced by a drop in pressure from lithostatic to hydrostatic. The carbonate stage is represented by calcite veins that cut across the skarn and orebody, locally producing a dense stockwork. This observation indicates the veins formed during the waning stages of hydrothermal activity. The fluids from this stage are mainly represented by a variety of low-salinity fluid inclusions, as well as fewer high-salinity inclusions. These particular fluids have the lowest δ¹⁸O_water values (− 2.2‰ to 0.4‰) and a wide of range of δD values (− 40‰ to − 81‰), which indicate that they were originated from a mixture of residual fluids from the oxide stage, various amounts of meteoric water, and possibly condensed vapor. Low-temperature boiling probably occurred during this stage.We also discuss the reasons behind the anomalously low δD values in fluid inclusion water extracted by thermal decrepitation from quartz at high temperatures, and suggest that calcite data provide a possible benchmark for adjusting low δD values found in quartz intergrown with calcite.     

S,Pb, and Sr isotope geochemistry and genesis of Pb–Zn mineralization in the Huangshaping polymetallic ore deposit of southern Hunan Province,China

The Huangshaping Pb–Zn–W–Mo polymetallic deposit, located in southern Hunan Province, China, is one of the largest deposits in the region and is unique for its metals combination of Pb–Zn–W–Mo and the occurrence of significant reserves of all these metals. The deposit contains disseminated scheelite and molybdenite within a skarn zone located between Jurassic granitoids and Carboniferous sedimentary carbonate, and sulfide ores located within distal carbonate-hosted stratiform orebodies. The metals and fluids that formed the W–Mo mineralization were derived from granitoids, as indicated by their close spatial and temporal relationships. However, the source of the Pb–Zn mineralization in this deposit remains controversial.Here, we present new sulfur, lead, and strontium isotope data of sulfide minerals (pyrrhotite, sphalerite, galena, and pyrite) from the Pb–Zn mineralization within the deposit, and these data are compared with those of granitoids and sedimentary carbonate in the Huangshaping deposit, thereby providing insights into the genesis of the Pb–Zn mineralization. These data indicate that the sulfide ores from deep levels in the Huangshaping deposit have lower and more consistent δ³⁴S values (− 96 m level: + 4.4‰ to + 6.6‰, n = 13) than sulfides within the shallow part of the deposit (20 m level: + 8.3‰ to + 16.3‰, n = 19). The δ³⁴S values of deep sulfides are compositionally similar to those of magmatic sulfur within southern Hunan Province, whereas the shallower sulfides most likely contain reduced sulfur derived from evaporite sediments. The sulfide ores in the Huangshaping deposit have initial ⁸⁷Sr/⁸⁶Sr ratios (0.707662–0.709846) that lie between the values of granitoids (0.709654–0.718271) and sedimentary carbonate (0.707484–0.708034) in the Huangshaping deposit, but the ratios decreased with time, indicating that the ore-forming fluids were a combination of magmatic and formation-derived fluids, with the influence of the latter increasing over time. The lead isotopic compositions of sulfide ores do not correlate with sulfide type and define a linear trend in a ²⁰⁷Pb/²⁰⁴Pb vs. ²⁰⁶Pb/²⁰⁴Pb diagram that is distinct from the composition of the disseminated pyrite within sedimentary carbonates and granitoids in the Huangshaping deposit, but is similar to the lead isotopic composition of sulfides within coeval skarn Pb–Zn deposits in southern Hunan Province. In addition, the sulfide ores have old signatures with relative high ²⁰⁷Pb/²⁰⁶Pb ratios, suggesting that the underlying Paleoproterozoic basement within southern Hunan Province may be the source of metals within the Huangshaping deposit.The isotope geochemistry of sulfide ores in the Huangshaping deposit shows a remarkable mixed source of sulfur and ore-forming fluids, and the metals were derived from the basement. These features are not found in representative skarn-type Pb–Zn mineralization located elsewhere. The ore-forming elements (S, Pb, and Zn) from the granitoids made an insignificant contribution to sulfide precipitation in this deposit. However, the emplacement of granitoids did provide large amounts of heat and fluids to the hydrothermal system in this area and extracted metals from the basement rocks, indicating that the Jurassic magmatism associated with the Huangshaping deposit was crucial to the Pb–Zn mineralization.     

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 possible synglaciogenic Ediacaran hematitic banded iron salt formation (BISF) at Hormuz Island,southern Iran: Implications for a new style of exhalative hydrothermal iron-salt system

The Ediacaran BISF at Hormuz Island is a newly identified glaciogenic iron-salt deposit in the Tethyan margin of Gondwana. The BISF was formed by synchronous riftogenic A-type submarine felsic volcanism and evaporate deposition. The mineralization occurs in a proximal felsic tuff cone and jaspilitic distal zones and contains 1 million tonne of hematite-rich ore with an average grade of 58% Fe. The ore structure shows cyclicity of macrobandings, mesobandings and microbandings of anhydrite, halite, hematite and chert, which marks a new record in BIFs geohistory. The alteration minerals in the proximal and distal zones are actinolite, ripidolite, epidote, sericite, tourmaline, clinochlore, anhydrite and clay minerals. The occurrence of metamorphosed polygenetic bullet-shape dropstones in BISF attests that there was probably a continuous process of ice melting, episodic submarine volcanism and exhalative hydrothermal banded iron salt formation during the Late Ediacaran time. The non-metamorphosed Neoproterozoic stratigraphy, the presence of genus Collenia, U-Pb dating (558 ± 7 Ma) and the marked negative δ¹³C excursion in cap carbonates are representative of Late Ediacaran glaciation, which has been identified worldwide. The REE+Y display light REE enrichment, unusually strong Tb-Tm anomaly, a weak positive Y anomaly, but no distinguished Eu and Ce anomalies, reflecting the glaciogenic nature of the BISF. The contents of Zr, Hf, Nb, Ta, Th, La, Ce and Y in BISF, dropstones, halite and cap carbonates are similar to those of the Neoproterozoic glaciogenic BIFs. Also, the Ni/Fe, P/Fe ratios and Fe/Ti – Al/Al + Fe + Mn + Ca + Na + K diagram suggest an exhalative hydrothermal Ediacaran-type BISF. The absence of brecciated magnetite in the ore association and the low contents of copper (9–493 ppm) and gold (<5–8 ppb) are not in favor of the IOCG – Kiruna-type iron oxide ores. The co-paragenesis of hematite with several alteration minerals, in particular actinolite, tourmaline and anhydrite, indicates that the exhalative hydrothermal fluids were generated by the interaction of seawater with the felsic rocks and sediments at about 200–500 °C. The interaction of seawater with felsic magma and sediments led to the formation of Mg-rich alteration minerals, leaching Si, Fe, Mn and other elements and forming the potential ore fluids. It is highlighted that the A-type alkaline submarine felsic volcanism could be considered as an exploration target for BISF.     

The nappe-hosted Hoshbulak MVT Zn–Pb deposit,Xinjiang, China: A review of the geological,elemental and stable isotopic constraints

The Hoshbulak Zn–Pb deposit is located in South Tianshan, Xinjiang, China. The Zn–Pb orebody is tabular and stratoid in form and it is hosted in calcareous rocks of the Upper Devonian Tan'gaitaer Formation which were thrust over the Carboniferous system. The ores are mineralogically simple and composed mainly of sphalerite, galena, pyrite, calcite, dolomite and exhibit massive, banded, veinlets, colloidal, metasomatic, eutectic, concentric ring and microbial-like fabrics. The Co/Ni ratios of pyrite in the ores range from 0.46 to 0.90 by electron microprobe, which suggested that the Hoshbulak Zn–Pb mineralization was formed in a sedimentary environment. The REE patterns of the hydrothermal calcite coincide well with those of recrystallized micritic limestones, suggesting that the Hoshbulak Pb–Zn mineralization was closely genetically related to limestones of the Tan'gaitaer Formation. The C-, H- and O-isotopic compositions of hydrothermal calcite and dolomite in the ores yield δ¹³C(VPDB) values ranging from − 1.9‰ to + 2.6‰ (mean 0.79‰), δ¹⁸O(VSMOW) values from 22.41‰ to 24.67‰ (mean 23.04‰) and δD values from − 77‰ to − 102‰ for fluid inclusions. It is suggested that the ore-forming fluids, including CO₂, were derived from the calcareous strata of the Tan'gaitaer Formation in association with hydrocarbon brines. The δ³⁴S(VCDT) ranges from − 22.3‰ to − 8.5‰ for early ore-stage sulfides and from 5.9‰ to 24.2‰ with a cluster between 14.4‰ and 24.2‰ for the sulfides (pyrite, sphalerite, galena) in the main ore-stage. The ore sulfur may have been derived from evaporite rocks by thermochemical sulfate reduction (TSR) as the predominant mechanism for H₂S generation. The Pb-isotopic compositions of the sulfide minerals from the Hoshbulak ores yield ²⁰⁶Pb/²⁰⁴Pb ratios from 17.847 to 18.173, ²⁰⁷Pb/²⁰⁴Pb ratios from 15.586 to 15.873 and ²⁰⁸Pb/²⁰⁴Pb ratios from 37.997 to 38.905, which indicate that the metals were sourced mainly from the Tan'gaitaer Formation. We conclude that the genesis of the Hoshbulak Mississippi Valley-type deposit was closely related to thrust faulting in the South Tianshan orogen of China.