In-situ LA–ICP-MS trace elemental analyses of magnetite: The late Palaeoproterozoic Sokoman Iron Formation in the Labrador Trough,Canada

The Sokoman Iron Formation in the Labrador Trough, Canada, a typical granular iron formation (GIF), is coeval with the ~ 1.88 Ga Nimish volcanic suites in the same region. It is composed of the Lower, Middle and Upper Iron Formations. In addition to primary and altered magnetite in iron formations of the Hayot Lake, Rainy Lake and Wishart Lake areas, magnetite in volcanic breccia associated with the iron formation is identified for the first time in the stratigraphy. Trace elemental compositions of the most primary, altered and volcanic brecciated magnetite of the Sokoman Iron Formation were obtained by LA–ICP-MS. Commonly detected trace elements of magnetite include Ti, Al, Mg, Mn, V, Cr, Co and Zn. These three types of magnetite have different trace elemental compositions. Primary magnetite in the iron formation has a relatively narrow range of compositions with the depletion of Ti, Pb, Mg and Al. Magnetite from volcanic breccia is rich in Ti, Al, V, Mn, Mg, Zn, Cu and Pb, indicative of crystallization from mantle-derived magmas. Altered magnetite in the iron formation shows a relatively wide range of trace elemental compositions. Mineralizing fluids associated with magmas that generated the ~ 1.88 Ga Nimish volcanic suites circulated through the sedimentary piles to further enrich the iron formations and to form magnetite with variable compositions. The comparisons of different types of primary and altered magnetite in the iron formation in the region show distinct provenance discrimination. Our findings also support the origin of iron formations in association with multiple stages of exhalative volcanic and hydrothermal processes.     

In–situ LA–ICP–MS trace elemental analyzes of magnetite: The Tieshan skarn Fe–Cu deposit,Eastern China

The Tieshan Fe–Cu deposit is located in the Edong district, which represents the westernmost and largest region within the Middle–Lower Yangtze River Metallogenic Belt (YRMB), Eastern China. Skarn Fe–Cu mineralization is spatially associated with the Tieshan pluton, which intruded carbonates of the Lower Triassic Daye Formation. Ore bodies are predominantly located along the contact between the diorite or quartz diorite and marbles/dolomitic marbles. This study investigates the mineral chemistry of magnetite in different skarn ore bodies. The contrasting composition of magnetite obtained are used to suggest different mechanisms of formation for magnetite in the western and eastern part of the Tieshan Fe–Cu deposit. A total of 178 grains of magnetite from four magnetite ore samples are analyzed by LA–ICP–MS, indicating a wide range of trace element contents, such as V (13.61–542.36 ppm), Cr (0.003–383.96 ppm), Co (11.12–187.55 ppm) and Ni (0.19–147.41 ppm), etc. The Ti/V ratio of magnetite from the Xiangbishan (western part of the Tieshan deposit) and Jianshan ore body (eastern part of the Tieshan deposit) ranges from 1.32 to 5.24, and 1.31 to 10.34, respectively, indicating a relatively reduced depositional environment in the Xiangbishan ore body. Incorporation of Ti and Al in magnetite are temperature dependent, which hence propose that the temperature of hydrothermal fluid from the Jianshan ore body (Al = 3747–9648 ppm, with 6381 ppm as an average; Ti = 381.7–952.0 ppm, with 628.2 ppm as an average) was higher than the Xiangbishan ore body (Al = 2011–11122 ppm, with 5997 ppm as an average, Ti = 302.5–734.8, with 530.8 ppm as an average), indicating a down–temperature precipitation trend from the Jianshan ore body to the Xiangbishan ore body. In addition, in the Ca + Al + Mn versus Ti + V diagram, magnetite is plotted in the skarn field, consideration with the ternary diagram of TiO₂–Al₂O₃–MgO, proposing that the magnetite ores are formed by replacement, instead of directly crystallized from iron oxide melts, which provide a better understanding regarding the composition of ore fluids and processes responsible for Fe mineralization in the Tieshan Fe–Cu deposit.     

In-situ LA-ICP-MS trace elemental analyses of magnetite and Re–Os dating of pyrite: The Tianhu hydrothermally remobilized sedimentary Fe deposit,NW China

The Tianhu Fe deposit (> 104 Mt at 42% TFe) in the Eastern Tianshan (NW China) is hosted in the schist, quartzite, marble, and amphibolite of the Neoproterozoic Tianhu Group. The deposit consists of disseminated, banded and massive ores. Metallic minerals are dominantly magnetite and pyrite, with minor titanite, pyrrhotite, chalcopyrite, and sphalerite. Gangue minerals include dolomite with minor forsterite, diopside, apatite, biotite, chlorite, tourmaline, tremolite, talc, calcite, and magnesite. Pyrite separates from ores have 10.7 to 54.7 ppb Re and 0.033 to 0.175 ppb common Os. Those from the massive ores have a model 1 isochron age of 535 ± 36 Ma (2σ), in agreement with the isochron age (528 ± 18 Ma) of pyrite from the banded ores by regression of seven Re–Os analyses. The Re–Os age of ~ 530 Ma reflects the timing of a hydrothermal event that remobilized the Tianhu deposit. Magnetite has Mg, Al, Ti, V, Mn, Zn, and Ga contents ranging from ~ 5 to 3500 ppm and Cr, Co, Ni, and Sn contents ranging from ~ 1 to 200 ppm. Most magnetite grains have Ca + Al + Mn and Ti + V contents similar to those of the banded iron formation (BIF). Some grains have elevated Ti and V contents, indicating that that magnetite was formed by sedimentary process and overprinted by hydrothermal activity. Pyrite has δ³⁴S_CDT values from − 9.23 to 10.96‰, indicating that the sulfur was reduced from the marine sulfates either by bacterial or thermochemical processes. Pyrite has relatively high Co (~ 346 to 3274 ppm) but low Ni (~ 5.6 to 35.4 ppm) with Co/Ni ratios ranging from ~ 10 to 270, indicating remobilization from a volcanic–hydrothermal fluid. Therefore, the Tianhu Fe deposit was originally a sedimentary type deposit but was overprinted by a hydrothermal event related to volcanic activity.     

In-situ LA-ICP-MS trace elemental analyses of magnetite: Fe–Ti–(V) oxide-bearing mafic–ultramafic layered intrusions of the Emeishan Large Igneous Province,SW China

The Taihe, Baima, Hongge, Panzhihua and Anyi intrusions of the Emeishan Large Igneous Province (ELIP), SW China, contain large magmatic Fe–Ti–(V) oxide ore deposits. Magnetites from these intrusions have extensive trellis or sandwich exsolution lamellae of ilmenite and spinel. Regular electron microprobe analyses are insufficient to obtain the primary compositions of such magnetites. Instead, laser ablation ICP-MS uses large spot sizes (~ 40 μm) and can produce reliable data for magnetites with exsolution lamellae. Although magnetites from these deposits have variable trace element contents, they have similar multi-element variation patterns. Primary controls of trace element variations of magnetite in these deposits include crystallography in terms of the affinity of the ionic radius and the overall charge balance, oxygen fugacity, magma composition and coexisting minerals. Early deposition of chromite or Cr-magnetite can greatly deplete magmas in Cr and thus Cr-poor magnetite crystallized from such magmas. Co-crystallizing minerals, olivine, pyroxenes, plagioclase and apatite, have little influence on trace element contents of magnetite because elements compatible in magnetite are incompatible in these silicate and phosphate minerals. Low contents and bi-modal distribution of the highly compatible trace elements such as V and Cr in magnetite from Fe–Ti oxide ores of the ELIP suggest that magnetite may not form from fractional crystallization, but from relatively homogeneous Fe-rich melts. QUILF equilibrium modeling further indicates that the parental magmas of the Panzhihua and Baima intrusions had high oxygen fugacities and thus crystallized massive and/or net-textured Fe–Ti oxide ores at the bottom of the intrusive bodies. Magnetite of the Taihe, Hongge and Anyi intrusions, on the other hand, crystallized under relatively low oxygen fugacities and, therefore, formed net-textured and/or disseminated Fe–Ti oxides after a lengthy period of silicate fractionation. Plots of Ge vs. Ga + Co can be used as a discrimination diagram to differentiate magnetite of Fe–Ti–(V) oxide-bearing layered intrusions in the ELIP from that of massif anorthosites and magmatic Cu–Ni sulfide deposits. Variable amounts of trace elements of magmatic magnetites from Fe–Ti–(P) oxide ores of the Damiao anorthosite massif (North China) and from Cu–Ni sulfide deposits of Sudbury (Canada) and Huangshandong (northwest China) demonstrate the primary control of magma compositions on major and trace element contents of magnetite.     

In-situ LA-ICPMS trace elements and U–Pb analysis of titanite from the Mesozoic Ruanjiawan W–Cu–Mo skarn deposit,Daye district,China

In this paper, we present U–Pb ages and trace element compositions of titanite from the Ruanjiawan W–Cu–Mo skarn deposit in the Daye district, eastern China to constrain the magmatic and hydrothermal history in this deposit and provide a better understanding of the U–Pb geochronology and trace element geochemistry of titanite that have been subjected to post-crystallization hydrothermal alteration. Titanite from the mineralized skarn, the ore-related quartz diorite stock, and a diabase dike intruding this stock were analyzed using laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS). Titanite grains from the quartz diorite and diabase dike typically coexist with hydrothermal minerals such as epidote, sericite, chlorite, pyrite, and calcite, and display irregular or patchy zoning. These grains have low LREE/HREE and high Th/U and Lu/Hf ratios, coupled with negative Eu and positive Ce anomalies. The textural and compositional data indicate that titanite from the quartz diorite has been overprinted by hydrothermal fluids after being crystallized from magmas. Titanite grains from the mineralized skarn are texturally equilibrated with retrograde skarn minerals including actinolite, quartz, calcite, and epidote, demonstrating that these grains were formed directly from hydrothermal fluids responsible for the mineralization. Compared to the varieties from the quartz diorite stock and diabase dike, titanite grains from the mineralized skarn have much lower REE contents and LREE/HREE, Th/U, and Lu/Hf ratios. They have a weighted mean ²⁰⁶Pb/²³⁸U age of 142 ± 2 Ma (MSWD = 0.7, 2σ), in agreement with a zircon U–Pb age of 144 ± 1 Ma (MSWD = 0.3, 2σ) of the quartz diorite and thus interpreted as formation age of the Ruanjiawan W–Cu–Mo deposit. Titanite grains from the ore-related quartz diorite have a concordant U–Pb age of 132 ± 2 Ma (MSWD = 0.5, 2σ), which is 10–12 Ma younger than the zircon U–Pb age of the same sample and thus interpreted as the time of a hydrothermal overprint after their crystallization. This hydrothermal overprint was most likely related to the emplacement of the diabase dike that has a zircon U–Pb age of 133 ± 1 Ma and a titanite U–Pb age of 131 ± 2 Ma. The geochronological results thus reveal two hydrothermal events in the Ruanjiawan deposit: an early one forming the Wu–Cu–Mo ores related to the emplacement of the quartz diorite stock and a later one causing alteration of the quartz diorite and its titanite due to emplacement of diabase dike. It is suggested that titanite is much more susceptible to hydrothermal alteration than zircon. Results from this study also highlight the utilization of trace element compositions in discriminating titanite of magmatic and hydrothermal origins, facilitating a more reasonable interpretation of the titanite U–Pb ages.     

Metallogeny of the Handagai skarn Fe–Cu deposit,northern Great Xing'an Range,NE China: Constraints on fluid inclusions and skarn genesis

The newly discovered Handagai skarn Fe–Cu deposit is located in the northern Great Xing'an Range of NE China and is hosted by the Ordovician Luohe Formation. The orebodies that form the deposit are generally concordant with the bedding within these sediments, and are spatially related to areas of skarn development. The Fe–Cu mineralization in this area records four stages of paragenesis, namely prograde skarn, retrograde skarn, quartz–sulfide, and quartz–carbonate stages. The Handagai deposit is a calcic skarn that is dominated by an andradite–diopside–epidote–actinolite assemblage. The mineralogy and geochemistry of the skarn indicate that it formed from a hydrothermal fluid that altered the carbonate units in this area to a garnet (And_42–95Grs_4–53) and pyroxene (Di_71–78Hd_22–29Jo_0–2) bearing skarn. The epidote within the skarn has an epidote end-member composition, with the chlorite in the skarn dominantly Fe-rich, indicating that these minerals formed in an Fe-rich environment. The petrographic, microthermometric, and Raman spectroscopic analysis of fluid inclusions within garnet, epidote, actinolite, quartz, and calcite precipitated at different stages of formation of the Handagai deposit indicate that mineralization-related fluid inclusions are either liquid-rich two-phase H₂O–NaCl (type I), gas-rich two-phase H₂O–NaCl (type II), three-phase (liquid + vapor + solid) H₂O–NaCl (type III), or CO₂–H₂O–NaCl inclusions (type IV). The early stages of mineralization are associated with all four types of inclusion, whereas the later stages of mineralization are only associated with type I and II inclusions. Inclusion homogenization temperatures vary between the four stages of mineralization (370 °C–530 °C and > 600 °C, 210 °C–290 °C, 190 °C–270 °C, and 150 °C–230 °C, from early to late, respectively), with salinities also varying between the earlier and later stages of mineralization (11–18 and > 45, 7–15, 6–9, and 3–7 wt.% NaCl equivalent (equiv.), respectively). The majority of the inclusions within the Handagai deposit have homogenization temperatures and salinities of 200 °C–350 °C and 4–14 wt.% NaCl equiv., respectively, indicating that this is a medium–high temperature and medium–low salinity type deposit. The fluid inclusions were trapped at pressures of 11 to 72 MPa, corresponding to depths of 0.4 to 2.9 km. The geology, mineralogy, geochemistry, and fluid inclusions microthermometry indicate that the Handagai deposit formed as a result of contact infiltration metasomatism, with the deposition of ore minerals resulting from a combination of factors that include boiling as a result of reduced pressure, cooling, and fluid mixing.     

In-situ LA–ICP–MS U–Pb geochronology and trace elements analysis of polygenetic titanite from the giant Beiya gold–polymetallic deposit in Yunnan Province,Southwest China

The Beiya gold–polymetallic deposit, located in the middle of the Jinshajiang–Ailaoshan alkaline porphyry metallogenic belt, is one of the largest gold deposits in China. The mineralization mainly occurs in skarn along the intrusive contacts between the alkaline porphyries and Middle Triassic limestone. In this paper, we present U–Pb age as well as major and trace element geochemistry of titanite from the Beiya deposit, and distinguish the titanite into a magmatic- and a hydrothermal suite. Our study indicates that the titanite from the ore-related porphyry and from the mineralized skarn is texturally and geochemically very different. The euhedral, envelope-shaped titanite from the ore-related porphyry has lower FeO, F, HFSEs, Nb/Ta and Lu/Hf, together with higher TiO₂ and Th/U than the subhedral titanite from the mineralized skarn. The titanite from the porphyry also displays higher LREE/HREE and more subtle negative Eu anomaly than its mineralized skarn counterpart. This suggests a magmatic- and a hydrothermal origin for, respectively, the titanite from the ore-related porphyry and from the mineralized skarn. In-situ magmatic titanite U–Pb dating has yielded an Eocene age of 36.0 ± 5.9 Ma, consistent with the porphyry zircon U–Pb age (36.07 ± 0.43 Ma) obtained in previous studies. Hydrothermal titanite has yielded a weighted average ²⁰⁶Pb/²³⁸U age of 33.1 ± 1.0 Ma (MSWD = 2.0), which represents the age of the retrograde skarn alteration and the maximum age for the gold mineralization. Together with the previous molybdenite Re–Os age, we have further constrained the Beiya gold–polymetallic metallogeny to 33.1–34.1 Ma. The mineralization age is slightly younger than the porphyry emplacement, indicating that the Beiya metallogeny was likely to be a post-magmatic hydrothermal product of the Himalayan orogenic event. The REE characteristics of hydrothermal titanite also reveal that the ore forming fluids may have been derived from a highly oxidized magma.     

In-situ SIMS uraninite U–Pb dating and genesis of the Xianshi granite-hosted uranium deposit,South China

The southeastern part of the Nanling metallogenic province, China is host to numerous granite-hosted vein-type hydrothermal uranium deposits. The geology and geochemistry of these deposits have been extensively studied. However, accurate and precise ages for the uranium mineralization are scarce because the uranium minerals in these deposits are usually fine grained, and may have formed in several stages. Therefore, the ages previously obtained by the bulk dating techniques are possibly a mixed age.The Xianshi uranium deposit, located in the southeastern part of the Guidong granite complex, is a major uranium deposit in South China. The uranium mineralization from this deposit is mainly fine grained uraninite in quartz or calcite veins which are spatially associated with the Cretaceous mantle-derived mafic dykes. Micro-Raman spectroscopy and X-ray diffraction analyses indicate that the dominant uranium mineral occurs as a rare form of uraninite (U₃O₇). Three distinct generations of uranium minerals have been identified based on petrographic and field relations. Stage 1 uraninite has the lowest UO₂ and highest PbO contents whereas Stage 3 uraninite has the highest UO₂ and lowest PbO contents.Uraninite from the Xianshi deposit was dated using an in-situ SIMS U–Pb dating technique. The results show three distinct age groups: 135 ± 4 Ma, 113 ± 2 Ma and 104 ± 2 Ma, which are in excellent agreement with the ages of three episodes of mantle-derived mafic dykes. Therefore, the Xianshi uranium deposit has experienced at least three hydrothermal events that are responsible for the deposition of uranium ores, which are genetically related to the emplacement of three sets of mafic dykes.     

Genetic relationship between silver–lead–zinc mineralization in the Wutong deposit,Guangxi Province and Mesozoic granitic magmatism in the Nanling belt,southeast China

More than 50 % of the world's total reserves of tungsten are in China and most tungsten deposits are located in the Nanling range in southeast China. This study explores the potential genetic relationship between tungsten–tin (W–Sn) mineralization and shallower Ag–Pb–Zn deposits in the Nanling range based on data from the Wutong deposit, Guangxi Province. The lead, oxygen, carbon, sulfur, and strontium isotopic compositions of minerals at Wutong indicate that a single crustal-derived fluid was responsible for mineralization. Wutong likely formed at relatively low temperatures (～200–300 °C) and low pressures, as indicated by the similarity between homogenization temperatures of fluid inclusions and those estimated from S isotopic compositions of minerals. The hübnerite age (92.3–104.4 Ma) indicates that the Wutong mineralization is likely related to nearby Late Yanshanian (Cretaceous) S-type granites derived from Proterozoic crust. This mineralization event coincides with the last W–Sn mineralization event and the Cretaceous peak of mineralization in the Nanling range.     

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

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

The late Mesozoic–Cenozoic tectonic evolution of the South China Sea: A petrologic perspective

This paper presents a review of available petrological, geochonological and geochemical data for late Mesozoic to Recent igneous rocks in the South China Sea (SCS) and adjacent regions and a discussion of their petrogeneses and tectonic implications. The integration of these data with available geophysical and other geologic information led to the following tectono-magmatic model for the evolution of the SCS region. The geochemical characteristics of late Mesozoic granitic rocks in the Pearl River Mouth Basin (PRMB), micro-blocks in the SCS, the offshore continental shelf and Dalat zone in southern Vietnam, and the Schwaner Mountains in West Kalimantan, Borneo indicate that these are mainly I-type granites plus a small amount of S-type granites in the PRMB. These granitoids were formed in a continental arc tectonic setting, consistent with the ideas proposed by Holloway (1982) and Taylor and Hayes, 1980, Taylor and Hayes, 1983, that there existed an Andean-type volcanic arc during later Mesozoic era in the SCS region. The geochonological and geochemical characteristics of the volcanics indicate an early period of bimodal volcanism (60–43 Ma or 32 Ma) at the northern margin of the SCS, followed by a period of relatively passive style volcanism during Cenozoic seafloor spreading (37 or 30–16 Ma) within the SCS, and post-spreading volcanism (tholeiitic series at 17–8 Ma, followed by alkali series from 8 Ma to present) in the entire SCS region. The geodynamic setting of the earlier volcanics was an extensional regime, which resulted from the collision between India and Eurasian plates since the earliest Cenozoic, and that of the post-spreading volcanics may be related to mantle plume magmatism in Hainan Island. In addition, the nascent Hainan plume may have played a significant role in the extension along the northern margin and seafloor spreading in the SCS.     

Constraints on the mineralization processes of the Makeng iron deposit,eastern China: Fluid inclusion,H–O isotope and magnetite trace element analysis

The Makeng iron deposit is located in the Yong’an-Meizhou depression belt in Fujian Province, eastern China. Both skarn alteration and iron mineralization are mainly hosted within middle Carboniferous-lower Permian limestone. Five paragenetic stages of skarn formation and ore deposition have been recognized: Stage 1, early skarn (andradite–grossular assemblage); Stage 2, magnetite mineralization (diopside–magnetite assemblage); Stage 3, late skarn (amphibole–chlorite–epidote–johannsenite–hedenbergite–magnetite assemblage); Stage 4, sulfide mineralization (quartz–calcite–fluorite–chlorite–pyrite–galena–sphalerite assemblage); and Stage 5, carbonate (quartz–calcite assemblage). Fluid inclusion studies were carried out on inclusions in diopside from Stage 2 and in quartz, calcite, and fluorite from Stage 4.Halite-bearing (Type 1) and coexisting two-phase vapor-rich aqueous (Type 3) inclusions in the magnetite stage display homogenization temperatures of 448–564 °C and 501–594 °C, respectively. Salinities range from 26.5 to 48.4 and 2.4 to 6.9 wt% NaCl equivalent, respectively. Two-phase liquid-rich aqueous (Type 2b) inclusions in the sulfide stage yield homogenization temperatures and salinities of 182–343 °C and 1.9–20.1 wt% NaCl equivalent. These fluid inclusion data indicate that fluid boiling occurred during the magnetite stage and that fluid mixing took place during the sulfide stage. The former triggered the precipitation of magnetite, and the latter resulted in the deposition of Pb, Zn, and Fe sulfides. The fluids related to magnetite mineralization have δ¹⁸O_fluid-VSMOW of 6.7–9.6‰ and δD of −96 to −128‰, which are interpreted to indicate residual magmatic water from magma degassing. In contrast, the fluids related to the sulfide mineralization show δ¹⁸O_fluid-VSMOW of −0.85 to −1.04‰ and δD of −110 to −124‰, indicating that they were generated by the mixing of magmatic water with meteoric water. Magnetite grains from Stage 2 exhibit oscillatory zoning with compositional variations in major elements (e.g., SiO₂, Al₂O₃, CaO, MgO, and MnO) from core to rim, which is interpreted as a self-organizing process rather than a dissolution-reprecipitation process. Magnetite from Stage 3 replaces or crosscuts early magnetite, suggesting that later hydrothermal fluid overprinted and caused dissolution and reprecipitation of Stage 2 magnetite. Trace element data (e.g., Ti, V, Ca, Al, and Mn) of magnetite from Stages 2 and 3 indicate a typical skarn origin.     

Re–Os isotopic ages of pyrite and chemical composition of magnetite from the Cihai magmatic–hydrothermal Fe deposit, NW China

The Eastern Tianshan Orogenic Belt of the Central Asian Orogenic Belt and the Beishan terrane of the Tarim Block, NW China, host numerous Fe deposits. The Cihai Fe deposit (>90 Mt at 45.6 % Fe) in the Beishan terrane is diabase-hosted and consists of the Cihai, Cinan, and Cixi ore clusters. Ore minerals are dominantly magnetite, pyrite, and pyrrhotite, with minor chalcopyrite, galena, and sphalerite. Gangue minerals include pyroxene, garnet, hornblende and minor plagioclase, biotite, chlorite, epidotite, quartz, and calcite. Pyrite from the Cihai and Cixi ore clusters has similar Re–Os isotope compositions, with ～14 to 62 ppb Re and ≤10?ppt common Os. Pyrrhotite has ～5 to 39 ppb Re and ～0.6 ppb common Os. Pyrite has a mean Re–Os model age of 262.3?±?5.6 Ma (n?=?13), in agreement with the isochron regression of ¹⁸⁷Os vs. ¹⁸⁷Re. The Re–Os age (～262 Ma) for the Cihai Fe deposit is within uncertainty in agreement with a previously reported Rb–Sr age (268?±?25 Ma) of the hosting diabase, indicating a genetic relationship between magmatism and mineralization. Magnetite from the Cihai deposit has Mg, Al, Ti, V, Cr, Co, Ni, Mn, Zn, Ga, and Sn more elevated than that of typical skarn deposits, but both V and Ti contents lower than that of magmatic Fe–Ti–V deposits. Magnetite from these two ore clusters at Cihai has slightly different trace element concentrations. Magnetite from the Cihai ore cluster has relatively constant trace element compositions. Some magnetite grains from the Cixi ore cluster have higher V, Ti, and Cr than those from the Cihai ore cluster. The compositional variations of magnetite between the ore clusters are possibly due to different formation temperatures. Combined with regional tectonic evolution of the Beishan terrane, the Re–Os age of pyrite and the composition of magnetite indicate that the Cihai Fe deposit may have derived from magmatic–hydrothermal fluids related to mafic magmatism, probably in an extensional rift environment.     

The Distribution of Trace Elements in Granitoids in the Nanling Region of China

Granitoids are widely spread in the Nanling Region of China.Four rockbodies in the region the been studied for their REE,Rb,Sr,Ba and Sc distributions.The four rockbodies occurred in different locations and are characterized as being different in age and type.The rock types are presented as follows:Qinghu monzonite,Guangxi;Fuxi granodiorite,Guangdong;Jiufeng monzonitic granite,Hunan;Zudong K-feldspar granite,Jiangxi.From the major and trace element distributions in these granitoids it is clearly shown that Rb/Sr ratios in the rocks tend to increase with increasing SiO2 content and differentiation index(DI),but LREE/HREE,La/Yb and K/Rb ratios tend to decrease,suggesting a correlation between trace element distribution and major element composition for the granitoids.The distribution characteristics of trace elements in each of the rockbodies are described in detail.From the comparative analysis of the Qinghu monzonite and Fuxi granodiorite it is evidenced that the REE distribution is closely related to the sequence of crystallization for the minerals,and also to the petrochemical types of these granitoids in addition to their crystal chemistry.     

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.     

Silver–bearing minerals in the Xinhua hydrothermal vein-type Pb-Zn deposit,South China

Mineralogy and Petrology - Electron probe microanalysis (EPMA) results are reported for newly identified silver–bearing minerals from the Xinhua deposit, Yunkaidashan area, South China. The...     

Metallogeny of the Shilu Fe–Co–Cu deposit,Hainan Island,South China: Constraints from fluid inclusions and stable isotopes

The Shilu deposit is a world-class Fe–Co–Cu orebody located in the Changjiang area of the western part of Hainan Island, South China. The distribution of Fe, Co, and Cu orebodies is controlled by strata of the No. 6 Formation in the Shilu Group and the Beiyi synclinorium. Based on a petrological study of the host rocks and their alteration assemblages, and textural and structural features of the ores, four mineralization stages have been identified: (1) the sedimentary ore-forming period; (2) the metamorphic ore-forming period; (3) the hydrothermal mineralization comprising the skarn and quartz–sulfide stage; and (4) the supergene period. The fluid inclusions in sedimentary quartz and/or chert indicate low temperatures (ca. 160 °C) and low salinities from 0.7 to 3.1 wt.% NaCl_eq, which corresponds to densities of 0.77 to 0.93 g/cm³. CO₂-bearing or carbonic inclusions have been interpreted to result from regional metamorphism. Homogenization temperatures of fluid inclusions for the skarn stage have a wide range from 148 °C to 497 °C and the salinities of the fluid inclusions range from 1.2 to 22.3 wt.% NaCl_eq, which corresponds to densities from 0.56 to 0.94 g/cm³. Fluid inclusions of the quartz–sulfide stage yield homogenization temperatures of 151–356 °C and salinities from 0.9 to 8.1 wt.% NaCl_eq, which equates to fluid densities from 0.63 to 0.96 g/cm³.Sulfur isotopic compositions indicate that sulfur of the sedimentary anhydrite and Co-bearing pyrite, and the quartz–sulfide stage, was derived from seawater sulfate and thermochemical sulfate reduction of dissolved anhydrite at temperatures of 200 °C and 300 °C, respectively. H and O isotopic compositions of the skarn and quartz–sulfide stage demonstrate that the ore-forming fluids were largely derived from magmatic water, with minor inputs from metamorphic or meteoric water. The Shilu iron ore deposit has an exhalative sedimentary origin, but has been overprinted by regional deformation and metamorphism. The Shilu Co–Cu deposit has a hydrothermal origin and is temporally and genetically associated with Indosinian granitoid rocks.     

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

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