Source Of Hydrothermal Fluids Research Articles

Re-distribution and upgrade of metals induced by the superimposition of later magmatic fluids in the Archean Hongtoushan VMS deposit, NE China

The Hongtoushan copper-zinc deposit is a highly metamorphosed Archean volcanogenic massive sulfide deposit (VMS) in China. After metamorphism, the deposit underwent later fluid superimposition, which is of significance for the re-distribution of metals and upgrading ores. However, the hydrothermal modification mechanism and fluid source remain unclear due to the difficulties in accurately recognizing the mineral textures and assemblages formed by hydrothermal modification. In this study, the mineral texture was investigated to identify the modification mechanism of later fluid and in situ sulfur isotope and trace elements of chalcopyrite were tested to track the source of later fluid and metals. The dominant assemblage formed by superimposed fluid consisted of pyrite, chalcopyrite, sphalerite, minor galena, magnetite, calcite, anhydrite, and hydrothermal alteration minerals, i.e. sericite and chlorite. These minerals infilled the fractures in early pyrite porphyroblasts or precipitated along the grain boundary. Additionally, the pre-existing sulfides were corroded by these minerals. They exhibited replacement and porous textures, indicating that the superimposed fluids resulted in a dissolution-reprecipitation process and formed new sulfides. The hydrothermal metasomatism produced the sericitization of plagioclase and chlorization of biotite, which concurrently liberated silica to form silicification. These interactions suggested that the hydrothermal fluid is acid fluid. The chlorite geothermometer defined the formation temperature of 226–279°C, implying that the superimposed fluid has a moderate temperature. The chalcopyrite precipitated from superimposed fluid either coexisted with pyrite (Ccp 2a) or magnetite (Ccp 2b). The sulfur isotope of Ccp 2a defined a closing zero range (0.75–2.41‰), demonstrating the superimposed fluids were derived from magmatic fluids. In contrast, the Ccp 2b enriched heavy sulfur with a δ34S range of 4.10–8.63‰, which was attributed to the oxidation of fluids. Partial ferrous ions were oxidized to ferric iron, and ferrous and ferric iron precipitated as magnetite. The mineral assemblage changed from chalcopyrite + pyrite, followed by magnetite + chalcopyrite + pyrite, to magnetite + pyrrhotite, representing the local increase of the oxidation state of hydrothermal systems. During the oxidation process, the oxygen fugacity of the superimposed fluid decreased, whereas the pH increased. These results provide crucial evidence on the re-distribution pattern of metals and the post-hydrothermal modification process in the Hongtoushan Cu-Zn deposit.

Biotite chemistry as an indicator of hydrothermal deposit types and fluid sources: Insights from big data compilation, multivariate statistical analysis, and machine learning

Identification of a deposit type in an early stage of exploration can save money and time. However, despite several studies, there is a lack of simple deposit classifiers based exclusively on the major and trace element chemistry of minerals, which is relatively easier to measure. Furthermore, the identification of fluid source is crucial for any ore-genetic study, as it exerts a first order control on physicochemical characteristics of fluid, which ultimately control the alteration mineralogy, metal solubility and mobilization, and metal association in a deposit. The stable isotope composition (e.g., δ34S, δ13C, δ18O, δ11B, etc.) of rocks and minerals is conventionally used to constrain the source of ore-forming fluids, however, the potential of mineral chemistry for constraining fluid source is not well-explored. In this study, we compile the major element composition (wt% of oxides) of a large number (n = 1932) of hydrothermal biotite from various ore settings and execute multivariate statistical analysis and machine learning-based predictive modeling to explore the potential of using biotite chemistry as an indicator of deposit type and fluid sources. The atoms per formula units (i.e., apfu values), and calculated parameters (e.g., Xphl, chlorine intercept value, log(fH2O/fHCl)fluid) is used to perform principle component analysis (PCA) and partial least square discriminant analysis (PLS-DA). The results show that among the different ore settings, iron-oxide copper‑gold, Archean gold, porphyry, and magmatic-hydrothermal rare earth metals deposits and among the fluid sources, (meta-)evaporitic, magmatic-hydrothermal, and metamorphic fluid sources can be reliably discriminated using biotite chemistry. We also show that skarn, hydrothermal platinum group elements, and carbonatite-related rare earth elements deposits may not be discriminated using biotite chemistry. Similarly, mafic rock-derived, carbonatite-derived, and meteoric fluid sources may not be discriminated by biotite chemistry. We propose multiple binary and ternary classifier diagrams, which can be used as discriminator of deposit types and fluid sources. Furthermore, we have developed four different PLS-DA predictive modeling, two for deposit types and two for fluid sources, which can predict deposit types and fluid sources with good accuracy. We provide a Windows© based program that can be used to discriminate deposit types using our PLS-DA predictive modeling. The binary and ternary classifiers and the Windows© programs are tested with recently published biotite data, and it has been shown that these classifiers and programs can efficiently separate deposit types and fluid sources. We also discuss about the limitations of the classifiers.

Hydrogeochemical and geothermal features of thermal springs along the Ganzi-Yushu fault, eastern Tibetan Plateau and its geological implications

Important fault zone processes can be discerned from the hydrothermal fluid circulation associated with active seismic sources. This study focused on the geochemical and isotopic features of the thermal waters along the Ganzi-Yushu fault (GZYSF) located in the eastern Tibetan Plateau. 22 spring samples were collected to characterize the chemical compositions and calculate the geothermal reservoir temperatures. The hydrothermal waters are mainly recharged by meteoric water based on the δ18O and δ2H values. Immature waters with a Na + -HCO3- or Ca2+(Mg2+)-HCO3- composition were recognized in the study area, combined with the poor correlation between K+, Na+, Mg2+, HCO3− and Cl− suggesting a shallow hydrothermal fluid source. The 87Sr/86Sr ratios and high concentrations of B (from 20.3 to 9445 μg/L) and Li (from 3.04 to 2380 μg/L) show a dissolution of silicate minerals containing calcium and magnesium during fluid circulation. The geothermometry in the silicon-enthalpy system suggested equilibrium temperatures up to 146 °C, whereas most are low temperatures. The shallow geothermal fields along GZYSF show that most large earthquakes (M＞5) were distributed in the transitional zone between high-value area and low-value area of the shallow geothermal field, suggesting a potential genetic link between geothermal field structure and earthquake nucleation along active faults. In conclusion, we proposed a conceptual model to portray the fluid circulation process. Such work can provide insights into the potential geothermal resource in Tibetan Plateau, and also investigate the processes controlling the fluid chemistry and the correlation with occurrence of earthquakes in the region.

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

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

Magmatic fluids responsible for lode gold mineralization in the giant Linglong deposit at Jiaodong, North China Craton: Constraints from Li[sbnd]O isotopes

The Jiaodong Peninsula, located in the eastern margin of the North China Craton, contains numerous world-class lode gold deposits that combined have a proven gold reserve of >5000 t. Despite a large amount of research, the source and evolution of hydrothermal fluids responsible for the gold mineralization in this region remains highly debated. The Linglong gold deposit is one of the largest deposits in the Jiaodong Peninsula. Gold lodes at Linglong are predominantly hosted within the Late Jurassic Linglong granite and structurally controlled by NE-trending faults. They are closely associated with large-scale hydrothermal alteration, which is paragenetically characterized by hydrothermal K-feldspar in pre-ore stage I, and sericite-quartz-pyrite in syn-ore stages II and III. The syn-ore alteration mineral assemblage is distributed within and around the gold lodes, whereas the K-feldspar alteration remains mainly distal to the gold lodes. From the unaltered to progressively intensifying K-feldspar-altered Linglong granites, there are decreasing trends for both whole-rock Li concentrations and δ7Li values, which are attributed to Rayleigh fractionation. The two values increase covariantly within the sericite-quartz-pyrite alteration zone towards the mineralization center, suggesting that further fluid-rock interaction and buffering of the ore fluid accounts for the observed Li elemental and isotopic variations. Fluid inclusion assemblages in quartz of stages I-III have homogenization temperatures of 349°-312 °C, 318°-272 °C, and 307°-246 °C, respectively. In-situ oxygen isotopic analysis on stage I quartz reveals δ18OQ values of 10.9–14.7 ‰, corresponding to δ18OW values of 4.3–9.2 ‰ for the equilibrated fluid. The δ18OW values of the equilibrated fluids of stages II and III are 5.6–8.9 ‰ and 5.2–8.8 ‰, respectively. The oxygen isotopic compositions indicate that magmatic fluid is prevailing for the K-feldspar and sericite-quartz-pyrite alterations. A binary mixing model using Li concentrations and δ7Li values further implies that the hydrothermal fluid was mainly sourced from coeval mafic magmas derived from the metasomatized lithospheric mantle. Our study highlights that lithium and in-situ oxygen isotopes can be used effectively to fingerprint the source of hydrothermal fluids and fluid-rock interactions.

Halogen fractionation during vapor-brine phase separation revealed by in situ Cl, Br, and I analysis of scapolite from the Yixingzhai gold deposit, North China Craton

Abstract Halogens (Cl, Br, and I) are major complexing agents for metal ions, and their ratios (Br/Cl and I/Cl) have been used to determine the source and evolution of hydrothermal fluid. Halogen fractionation during hydrothermal fluid evolution, however, has been inferred from several studies, which poses problems in using halogen ratios as a fluid tracer. The Br/Cl and I/Cl ratios of scapolite are consistent with those ratios present in the coexisting fluid during scapolite formation, making this mineral particularly useful for understanding hydrothermal fluid evolution. To better understand halogen fractionation during vapor-brine phase separation, we conducted fluid inclusion microthermometry, major elements, and in situ halogens and Sr isotope analysis of scapolite formed from a high-salinity hydrothermal fluid during the vapor-brine phase separation at the Yixingzhai gold deposit, North China Craton. The studied scapolite has 1.84–3.41 wt% Cl, 389–806 ppm Br, 8.4–24.4 ppm I, and significantly high Br/Cl (6.1–14.7 × 10–3) and high I/Cl (91–302 × 10–6) molar ratios that likely result from the preferential incorporation of Br and I into the brine phase compared to Cl entering the vapor phase during fluid phase separation. Based on fluid inclusion microthermometry results, the Rayleigh fractionation simulation shows that the Br/Cl and I/Cl ratios of the brine are estimated to be up to 18 × 10–3 and 500 × 10–6 during the formation of scapolite. These results reveal halogen fractionation during the vapor-brine phase separation of hydrothermal fluids. This view has implications for interpreting the halogen systematics of scapolite and other minerals formed in similar environments, particularly when they are used as a fluid tracer.

Fluid source and physicochemical conditions of the polymetallic mineralization in Gawuch Formation, Kohistan Island Arc, NW Pakistan

The Cu-Sb-Pb polymetallic vein deposit is hosted by metavolcanics rocks of the Gawuch Formation at the Kaldom Gol area of the northwest Kohistan arc terrain in northern Pakistan. The mineralization is closely associated with the dioritic to granodioritic rocks of the Lowari pluton, which was intruded into the Gawuch metavolcanics. Details of ore characterization and processes of ore genesis of this evidently hydrothermal mineralization are not well documented. Integrating petrographic, mineral-chemical and isotopic investigations, this study aims to comprehend the source of hydrothermal fluids, geochemical evolution, mineral inclusions and physicochemical conditions of the Cu-Sb-Pb polymetallic vein deposit in Gawuch metavolcanics in the Kohistan arc terrain in northern Pakistan. The mineralization is distinguished into three types of ore-gangue associations: Type Ia, Type Ib, and Type II. The textural study revealed two pyrite generations: (i) Py1 displaying euhedral to subhedral habits and containing scarce inclusions, and (ii) Py2 occurring as anhedral grains hosting abundant inclusions. Type Ia is characterized by Py1 associated with abundant quartz (Qz) showing comb texture, sericite (Ser), and minor chlorite (Chl). Type Ib comprises Qz + Ser + Chl and Py2, chalcopyrite (Ccp), and magnetite (Mag). Type II is represented by mosaic quartz, rhombic adularia, and bladed calcite, and the ore minerals fahlore and galena. Alteration zones composed of Qz-Ser ± Chl and Qz-Ser-Chl, surround Type I (a, b) and Type II veins, respectively. Fahlore and galena mostly replace pyrite of Type Ia and chalcopyrite of Type Ib. In addition, malachite, azurite, hematite and covellite occur as secondary (supergene) minerals. The Co/Ni ratios (>1) of Kaldom Gol pyrites suggest that the ore-forming fluids were hydrothermal in origin and Py1 and Py2 solidified at 221–304 °C and 225–261 °C, respectively. The LA-ICP-MS time-resolved depth profiles confirm the existence of sphalerite, and chalcopyrite inclusions in pyrite (Py1 and Py2) and millerite, bravoite, vaesite, Au-tellurides, native Au and galena inclusions in chalcopyrite and fahlore. Sulfur isotope compositions of pyrites (δ34S = Py1, −0.58 to +2 ‰; δ34S = Py2, −0.24 to +2.04 ‰) indicate that the ore-forming fluids were derived from magmatic source (s). The mineral assemblage, hydrothermal alterations, textures, temperature and δ34S of pyrites suggest that the Cu-Sb-Pb polymetallic mineralization at Kaldom Gol represents an intermediate-sulfidation type of epithermal deposit.

Tracing the Source of Hydrothermal Fluid in Ophiolite-Related Volcanogenic Massive Sulfide Deposits: A Case Study from the Italian Northern Apennines

The Italian Northern Apennines contain several Fe-Cu-Zn-bearing, Cyprus-type volcanogenic massive sulfide (VMS) deposits, which significantly contribute to the Cu resources of Italy. The massive sulfide lenses and related stockwork mineralizations are hosted by several levels (from basalt to serpentinite) of the unmetamorphosed ophiolitic series; therefore, this region offers perfect locations to study the ore-forming hydrothermal system in detail. A combination of fluid inclusion microthermometry, Raman spectroscopy, electron probe analyses (chlorite thermometry) and stable and noble gas isotope geochemistry was used to determine the fluid source of the VMS system at Bargone, Boccassuolo, Campegli, Casali–Monte Loreto, Corchia, Reppia and Vigonzano. This question of the fluid source is the focus of modern VMS research worldwide, as it has a direct influence on the metal content of the deposit. The obtained temperature and compositional data are both in the typical range of VMS systems and basically suggest evolved seawater origin for the mineralizing fluid. Modification of seawater was most commonly due to fluid–rock interaction processes, which happened during long-lasting circulation in the crust. The role of a small amount of magmatic fluid input was traced only at the lower block of Boccassuolo, which may be responsible for its higher ore grade. This fluid origin model is evidenced by O, H and C stable isotopic as well as He, Ne and Ar noble gas isotopic values.

Origin of microbial–hydrothermal bedded dolomites in the Permian Lucaogou Formation lacustrine shales, Junggar Basin, NW China

Dolomite is widely developed in the shale sequences of saline lakes and has significance in paleoenvironmental, paleoclimatic, and petroleum geology research. In this study, a new end-member type of dolomite is discovered from the Permian Lucaogou Formation in the Junggar Basin, northwest China, along with its geological significance. The microbial–hydrothermal origin of the bedded dolomite is evident from the development of hydrothermal minerals (including barite and cubic pyrite) and methanogenic micro-organisms. In terms of geochemistry, the bedded dolomite has high (Ba/La)N ratios (~2.8) and Sr contents (~594.9 ppm) and positive Sr anomalies (Sr/Sr* ~3.8). Chondrite-normalized rare earth element (REE) patterns exhibit light REE enrichment, heavy REE depletion, slightly positive Ce anomalies, and negative Eu anomalies. The bedded dolomite has relatively low 87Sr/86Sr ratios (~0.705283), high δ13C values (~6.63‰ ), and low δ18O values (~−9.92‰ ). All these indicate that the dolomitizing fluid is a mixed source of hydrothermal fluids and lake waters, and the hydrothermal fluids and microbial methanogenesis provided the Mg2+ and C, respectively. The combination of microbial and hydrothermal activity overcame the limitation of dolomitization hydration shells around Mg2+. In terms of geological significance, the studied Lucaogou Formation was deposited in an extensional tectonic setting under hot–arid climatic conditions, which controlled the high-frequency interbedding and meter-scale cyclicity of sediment deposition of dolomites and shales. The combined effects of tectonism and paleoclimate may be important factors for the formation of bedded dolomite, enrichment of organic matter and hydrocarbons in saline lacustrine shales.

The Ulug-Sair Gold Occurrence (Western Tuva, Russia): Mineralogy, Ore Genesis, and S-O Isotope Systematics

Ulug-Sair Au-Bi-Te-Se mineralization is one prospect for native Au in the Western Tuva, and its origin remains debated. Mineralization consists of gold–sulfide–quartz veins in the host sedimentary rocks (conglomerates, siltstones, shales), quartz–tourmaline, and quartz–carbonate–sericite–altered rocks. To determine its origin, we examined the mineralogical–geochemical features, formation conditions, and fluid sources of the Ulug-Sair ore. A mineralogical–geochemical investigation outlines two substages with Au: an early gold–sulfide–quartz with pyrite, chalcopyrite, galena, gold, and electrum; and a late gold–telluride–sulfide–quartz, characterized by the presence of Bi-bearing minerals (AgBiTe, Bi2Te2Se, Cu3BiS3, Bi), tellurides (Au and Ag), Se-tellurides (Ag and Bi), and selenides (Au, Ag, and Hg). The paragenesis of Au–Ag tellurides, and fluid inclusion study data (microthermometry, Raman spectroscopy, LA-ICP-MS, and crush leach analysis (gas and ion chromatography, ICP-MS) in quartz showed that quartz–tourmaline-altered rocks were formed by an aqueous Mg–Na–K-chloride fluid with a salinity of 8–10 wt % NaCl eq. at 325–370 °C, whereas the host quartz–carbonate–sericite-altered rocks were formed from CO2–H2O fluid containing CH4 and N2, with a salinity of 0.18–6.1 wt % NaCl eq. at 200–400 °C. Gold-bearing mineral assemblages were formed at P ~ 0.75–1.0 kbar (~2.3–3 km) due to CO2–H2O chloride (Na–K ± Fe, Mg) fluid with CH4, Na2SO4, and Na2B2O5, and salinities 1.7–12.5 wt % NaCl eq. at temperatures decreasing from 360 up to 115 °C (gold–sulfide–quartz veins—360–130 °C, and gold–telluride–sulfide–quartz veins—330–115 °C), and variable fO2, fS2, fSe2, and fTe2. Results of the investigation of the isotope composition of S in pyrites indicates the magmatic origin of the fluid (δ18SH2S fluid from −0.4 to +2.5‰). The stable O isotope data in quartz indicates that, at an early substage, the formation of ore involved a fluid of magmatic and metamorphic origin (from +8.2 to +11.6‰), and, in the later substage, multiple sources of hydrothermal fluids (from +3.1 to +10.4‰), including magmatic-derived, metamorphic-derived, and meteoric waters. These data, in conjunction with structurally controlled mineralization, point towards similarities of the Ulug-Sair ore system with orogenic gold deposits.

Sources of Hydrothermal Fluids Inferred from Oxygen and Carbon Isotope Composition of Calcite, Keweenaw Peninsula Native Copper District, Michigan, USA

The Mesoproterozoic North American Midcontinent Rift hosts the world’s largest accumulation of native copper in Michigan’s Keweenaw Peninsula. During a regional metamorphogenic-hydrothermal event, native copper was deposited along with spatially zoned main-stage minerals in a thermal high. This was followed by deposition of late-stage minerals including minor copper sulfide. Inferences from the oxygen and carbon isotopic composition of main-stage hydrothermal fluids, as calculated from 296 new and compiled isotopic measurements on calcite, are consistent with existing models that low-sulfur saline native copper ore-forming fluids were dominantly derived by burial metamorphic processes from the very low sulfur basalt-dominated rift fill at depth below the native copper deposits. Co-variation of oxygen and carbon isotopic compositions are consistent with mixing of metamorphic-derived fluids with two additional isotopically different fluids. One of these is proposed to be evolved seawater that provided an outside source of salinity. This fluid mixed at depth and participated in the formation of a well-mixed hybrid metamorphic-dominated ore-forming fluid. Secondary Ion Mass Spectrometry in-situ isotopic analyses of calcite demonstrate a high degree of variability within samples that is attributed to variable degrees of shallow mixing of the hybrid ore-forming fluid with sulfur-poor, reduced evolved meteoric water in the zone of precipitation. The oxygen and carbon isotopic compositions of 100 new and compiled measurements on late-stage calcite are mostly isotopically different than the main-stage hydrothermal fluids. The late-stage hydrothermal fluids are interpreted as various proportions of mixing of evolved meteoric water, main-stage hybrid ore-forming fluid, and shallow, evolved seawater in the relatively shallow zone of precipitation.

Geochemical constraints of hydrothermal alteration of dolostones: An example of Lower Cretaceous Qamchuqa Formation, Kurdistan Region, northern Iraq

This paper integrates major, minor, trace and rare-earth element (REE) data into C-, O-, Sr-isotopes, fluid-inclusions microthermometry of replacive matrix dolomite and vug/fracture-filling saddle dolomite and calcite of the Lower Cretaceous Qamchuqe Formation, the Kurditan Region of Iraq, in order to get further insights into the origin and geochemical evolution of their parent diagenetic fluids. Multiple generations of dolomite have been observed. These dolomites constitute replacive matrix dolomite and saddle dolomite cement, dominantly poorly ordered, non-ferroan, non-stoichiometric, with an average of 59.4 and 60 mol% CaCO3, respectively, and have low Sr, Fe and Mn concentrations. Replacive matrix dolomites display fairly comparable REE patterns to saddle dolomite, but with light REE (LREE) enrichment, and moderate low (∑REEs) contents (18.9–1111.5 and 16.6–593.4 ppb, respectively). Saddle dolomite has moderately positive Eu anomalies while replacive matrix dolomite has slightly less positive Eu anomalies and negative Dy, Ho and Yb anomalies. Both dolomites are characterized by slightly radiogenic 87Sr/86Sr ratios ranging from 0.707702 to 0.707839, overlapping, wide-ranging and negative δ18O values from −10.43 to −4.47 and −12.87 to −7.79 ‰VPDB, and δ13C values ranging from 0.38 to 3.57 and −3.45 to 3.11‰VPDB, respectively. The primary fluid inclusions microthermometry of replacive matrix and saddle dolomites yield homogenization temperatures (Th) ranging from 71.3 to 228.3 °C and 82–188 °C, respectively, and salinity values ranging between 14.4 to 25.4 and 15.6 to 27.9 wt% NaCl eq., respectively. These data suggest multiple hydrothermal fluid fluxes during and post Zagros orogeny. The geochemical data also show that these fluids derived from similar source of mixed hydrothermal and marine fluids, which caused the dolomitization of host rock and precipitation of dolomite cements.

Metallogenetic Mn-model of the Rhyacian-aged Buritirama Formation, Carajás domain (Amazon Craton)

The Mn-bearing Buritirama Formation is composed of clastic and chemical metasedimentary rocks representing a Rhyacian platformal basin (ca. 2.18–2.06 Ga) that limits the northern border of the Archean-Paleoproterozoic Carajás domain with the Paleoproterozoic Bacajá domain in the southern Amazon Craton, northern Brazil. The Buritirama Formation is divided into three main stratigraphic units. The Lower and Upper units consist of a basal quartzite followed by carbonate–silicate rocks (marls), dolomitic marbles (dolostone) and minor biotite schist while the Intermediate Unit consists of Mn-carbonate rocks topped by a supergene Mn-oxide deposit (Cenozoic age). These rocks were deformed and metamorphosed during the Transamazonian event (ca. 2.06 Ga).Geochemical data from dolomitic marbles (Lower Unit) exhibit negative Ce anomalies, high Y/Ho ratios (ca. 48) and seawater-like REE + Y patterns that reinforce an open platform setting for the Buritirama basin. Positive δ13C values (+3.2‰ to +5.0‰ V-PDB) for dolomitic marbles are considered to be an expression of the Lomagundi Carbon Isotopic Excursion. The metallogenesis of Mn-carbonate rocks is evaluated based on redox-sensitive trace elements (e.g. Zn and Ni), PAAS-normalized REE + Y patterns and δ13C values (−2.56‰ to +0.15‰ V-PDB) and point out to a classical multi-stage redox-controlled Mn-model involving: i) a primary hydrothermal fluid source related to ocean vents and/or normal faults; ii) microbially-mediated reduction of Mn-oxides particles at the ocean bottom; and iii) reactions between Mn2+ and CO32− (organic matter and seawater related), giving rise to diagenetic Mn-carbonates. The Rhyacian age, Mn deposits, and presence of Lomagundi-like δ13C allows to correlate the Buritirama Formation with the Águas Claras Formation within the Carajás domain further south, thus establishing an important metalliferous event that was up to now largely overlooked within the southern Amazon Craton.

Hypozonal gold mineralization in shear zone-hosted deposits driven by fault valve action and fluid mixing: the Nalunaq deposit, Greenland

Analyses of fluid inclusions in quartz from the Nalunaq gold deposit, Greenland, use to interpret hydrothermal fluid sources and gold transport and deposition mechanisms.

Fluid source, element mobility and physicochemical conditions of porphyry-style hydrothermal alteration-mineralization at Mirkhani, Southern Chitral, Pakistan

The Cretaceous calc-alkaline granodioritic rocks in north-western Kohistan island arc host porphyry-type mineralization at Mirkhani in the Khyber Pakhtunkhwa province of Pakistan. In this paper, we present whole-rock geochemistry, mass-change calculations, and type and degree of element mobility regarding the hydrothermal mineralization-alteration processes. There are two distinct types of pyrite mineralization: (1) euhedral to subhedral pyrite (Py1) and cataclastic pyrite (Py2). To comprehend the source of hydrothermal fluids and their physicochemical conditions, trace element and S (sulfur) isotope compositions of the two types of pyrite were determined. Besides, the pyrite and silicate minerals were investigated through electron probe microanalysis (EPMA).The average low Ni (46), Zn (5), Cd (below detection level), and Bi (1) contents (in ppm), high Co/Ni ratio (>10) of both Py1 and Py2, and the range of sulfur isotope values for Py1 (−0.84‰ to 1.49‰) and Py2 (−0.93‰ to 1.84‰) indicate affiliation of the mineralization with felsic magma-derived hydrothermal fluids. The average low and high contents (ppm) of Se (0.7), As (2.6) and Zn (2), and Co (1089), respectively, in Py1 than Py2 (Se = 1.3, As = 4, Zn = 6 and Co = 747) indicates that former pyrite grains crystallized at a higher temperature than the latter, however, both types of pyrites were formed in medium to high-temperature conditions.The observed strong mobility of REE (rare earth elements) and HFSE (high field strength elements), high La/Yb ratios (avg. 23), and low (<1) Nb/La and Th/La ratios in the altered rocks reflect mobilization by slightly acidic solutions dominated by chloride and fluoride-rich complexes (±SO4 and OH). The gain-loss calculations reveal that SiO2, CaO, and TiO2 were leached out, whereas Al2O3, Fe2O3, MgO, P2O5, K2O, Cu, As, Mo, Ag, Au, Bi, and REE, HFSE, and LILE (large-ion lithophile elements) were variably added to the rocks during the hydrothermal process.Temperature calculation for chlorite formation and the type of gangue and ore mineral assemblage (epidote + sericite + albite + pyrite) implies a mineralization temperature range between ~ 215 °C and ~ 322 °C. The porphyry style of hydrothermal alteration-mineralization, trace element and S isotope composition of pyrite, and elemental gain and loss indicates that the mineralization at Mirkhani could be a part of a major porphyry Cu-Au system.

Apatite Texture, Composition, and O-Sr-Nd Isotope Signatures Record Magmatic and Hydrothermal Fluid Characteristics at the Black Mountain Porphyry Deposit, Philippines

AbstractThe trace elemental and isotopic signatures in apatite can be modified during hydrothermal alteration. This study investigates the suitability of apatite as an indicator of the source, chemistry, and evolution of magma and hydrothermal fluids. In situ textural, elemental, and O-Sr-Nd isotope analyses were performed on apatite in thin sections, from fresh and propylitically altered pre- and synmineralized dioritic porphyries from the Black Mountain porphyry Cu deposit in the Philippines.All studied apatite crystals have similar subhedral to euhedral shapes and are homogeneous in the grayscale in backscattered electron images. In cathodoluminescence images, the apatite in fresh and altered rocks displays yellow to yellow-green and green to brown luminescence, respectively. Apatite in fresh rocks has a higher Cl and Mn content, and lower Fe, Mg, Sr, Pb, and calculated XOH-apatite, compared to apatite in altered rocks. The content of F, rare earth elements (REEs), Y, U, Th, and Zr, and the Sr-Nd isotope signatures of apatite from fresh and altered rocks are similar in all apatite grains (87Sr/86Sr = 0.7034–0.7042 vs. 0.7032–0.7043, εNd(t) = 5.3–8.0 vs. 5.1–8.4). The X-ray maps and elemental and oxygen isotope signatures across individual apatite crystals are typically homogeneous in apatite from both fresh and altered rocks. The distinct luminescence colors, coupled with distinct mobile element compositions (Cl, OH, Mn, Mg, Fe, Sr, Pb), indicate modification of primary magmatic apatite during interaction with hydrothermal fluids. The similarities in Sr isotope ratios (87Sr/86Sr = 0.7032–0.7043) but slight differences in O isotope signatures (δ18O = 6.0 ± 0.3‰ vs. 6.6 ± 0.3‰) in apatite from fresh and altered rocks are consistent with the magma and hydrothermal fluids having the same source and suggest significant phase separation in the hydrothermal fluids given that 18O preferentially fractionates into the residual liquid relative to 16O during phase separation. The similarity of immobile element (REE, Y, U, Th, and Zr) contents in both populations of apatite, consistency of textures and Nd isotope compositions, and absence of obvious dissolution-reprecipitation features all suggest that altered apatite retains some magmatic characteristics. The apatite in fresh rocks has oxygen isotope compositions similar to that of zircons from the same sample (δ18O = 5.9 ± 0.3‰), indicating little to no oxygen isotope fractionation between zircon and apatite and that apatite can be a good proxy for the oxygen isotope composition of the magma. Based on the Cl contents of the magmatic and replacement apatite, and assuming their equilibrium with high-temperature magma fluid and replacement hydrothermal fluid, respectively, the calculated Cl content of the early magmatic fluid and the later replacement fluid can be estimated to be 6.4 to 15.1 wt % and ~0.25 ± 0.03 wt %, respectively. This indicates a depletion of Cl from the early high-temperature fluid to the replacement fluid, consistent with phase separation.This study demonstrates that cathodoluminescence, elemental compositions (such as Cl, Mn, Mg, Fe, Sr, Pb) and Sr-O isotope signatures in apatite can be modified during hydrothermal alteration, whereas other components (REE, Y, U, Th, and Zr) and the Nd isotope composition are preserved. These features can be used to constrain the origin, chemistry, and evolution of the primary magma and ore-forming hydrothermal fluids.

Ore genesis of the Yadu carbonate-hosted Pb–Zn deposit in Southwest China: Evidence from rare earth elements and C, O, S, Pb, and Zn isotopes

The Yadu Pb–Zn deposit is hosted in Permian limestone in the Sichuan–Yunnan–Guizhou (SYG) Pb–Zn metallogenic province, Southwest China. The ore genesis was investigated in this study based on rare earth element (REE) geochemistry and C, O, S, Pb, and Zn isotopes. The REE contents imply that basement fluid may has been one source of hydrothermal fluids, and the mineralization environment changed from acidic and reducing to alkaline and oxidizing during the mineralization process. The C and O isotopes show that the carbon in mineralizing fluids mainly comes from marine carbonate, and that basin fluid was one of the metallogenic fluids. S isotopic compositions (δ34S = +7.91–13.02‰) of sulfides revealed that S2− originated from high-solubility sulfate within the ore-hosting strata through thermochemical reduction (TSR) processes. The Pb isotopic ratios of sulfides (206Pb/204Pb = +18.7396–18.7542, 207Pb/204Pb = +15.7588–15.7616, and 208Pb/204Pb = +39.3817–39.4080) are similar to those of Proterozoic basement rocks in the region, and the Zn isotope values of sphalerite are relatively narrow, ranging from +0.53 to +0.65‰, close to that of the basement rocks (δ66Zn: +0.62‰); imply that the basement may have been the key source of mineralizing metals. In addition, the Zn isotope values showed an obvious linear relationship with Pb isotopic ratios, rather than the S isotope values, which suggests that the mineralizing metals and sulfur may have come from different sources. Based on comprehensive analysis of the geology, mineralogy, REE contents, and C–O–S–Pb–Zn isotopes, this study proposes that the mineralization of the Yadu Pb–Zn deposit may have resulted from mixing between basement fluid and basin fluid. According to the proposed model, the metal-rich fluids of the basement were driven into specific structural units of the sedimentary rocks (for example, fault–fold tectonic systems) and mixed with sulfate-rich fluids at the mineralization sites. Through TSR processes, there was continuous and abundant precipitation of hydrothermal minerals, which formed the high-grade Pb–Zn deposit. Overall, these geological and geochemical characteristics of the Yadu Pb–Zn deposit are consistent with those of the MVT deposits; thus we propose that the Yadu Pb–Zn deposit is MVT deposit, The determination of the genetic type of this deposit is conducive to the research and exploration of similar Pb–Zn deposits in SYG Pb–Zn metallogenic province.

Genetic relationship between greisenization and Sn–W mineralization in vein and greisen deposits: Insights from the Panasqueira deposit (Portugal)

The W–Sn Panasqueira ore deposit is a magmatic-hydrothermal system, which includes a high-grade quartz-vein type mineralization and a disseminated greisen-type mineralization occurring in the upper part of the Panasqueira two-mica granite. We investigated the genetic and chronological relationships between the greisenization of the Panasqueira granite and the formation of ore-bearing quartz veins by monitoring major and trace elements variations in quartz-white mica assemblages composing the two-mica granite, greisen and W–Sn-bearing quartz veins. The greisen is characterized by an overall depletion in Mg, Ti, Ca, Na, Ba, Sr, REE and enrichment in Fe, Li, Rb, Cs, Sn, W which reflect the breakdown of feldspars and fluid-rock interactions with W–Sn-bearing fluids. White-mica from greisen and mineralized quartz veins are enriched in granophile elements (F, Rb, Cs, Li, Sn, W and Zn) compared to magmatic muscovite from the two-mica granite. Trace elements contents in quartz depict trends which show the progressive enrichment in Ge and B and depletion in Al, Ti and Li from magmatic to hydrothermal quartz that emphasize the progressive evolution and cooling of the magmatic-hydrothermal system of Panasqueira. Geochemical similarities between quartz-white mica assemblages from greisen and wolframite-bearing veins suggest that greisenization and the formation of mineralized veins result from the same hydrothermal event and derived from the same source of hydrothermal fluids. Apatite from greisen and quartz vein yielded U–Pb ages of 292 ± 10 Ma and 295 ± 5 Ma respectively confirming that greisenization and the formation of mineralized veins occurred roughly at the same time. These ages also overlap with the emplacement age of the Panasqueira granite (296 ± 4 Ma), indicating a temporal link between greisenization, W–Sn mineralization and granite crystallization. Temperatures of the magmatic-hydrothermal system constrained by Ti-in quartz thermometry depicts a cooling trend from magmatic quartz of granite (700–600 °C) to hydrothermal quartz of greisen (500–400 °C) and veins (450–350 °C). These results suggest that greisenization and the formation of W–Sn bearing quartz veins occurred at the magmatic-hydrothermal transition, during which orthomagmatic fluids rich in volatils, incompatible elements and W–Sn were exsolved during the final solidification stage of the Panasqueira two-mica granite.

Epithermal mineralization of the Bonanza-Sandy vein system, Masara Gold District, Mindanao, Philippines

The Masara Gold District in southeastern Mindanao island is an area of prolific hydrothermal copper and gold mineralization. This study documents the mineralization characteristics of the NW-trending Bonanza-Sandy epithermal veins to constrain possible hydrothermal fluid sources and ore-forming mechanisms. Epithermal mineralization in the NW veins is divided into three main stages: Stage 1 - massive quartz-sulfide; Stage 2 - massive to amorphous quartz-carbonate (calcite); and Stage 3 - colloform-cockade quartz-carbonate (bladed rhodochrosite). Stage 1 is the main gold mineralization phase, with chalcopyrite, pyrite, sphalerite and galena occurring with native gold and tellurides. Stages 2 and 3 contain invisible gold in the sphalerite, galena, pyrite and chalcopyrite. The deposit exhibits mineralization characteristics typical of intermediate sulfidation epithermal deposits based on the dominant chalcopyrite-pyrite mineral assemblage; illite-muscovite-chlorite alteration mineralogy that point to neutral pH conditions; and sphalerite composition of 2.26 to 8.72 mol% FeS in Stage 1 and 0.55 to 1.13 mol% FeS in Stage 2. The K-Ar age date of illite separates from highly altered diorite porphyry of the Lamingag Intrusive Complex yielded an Early Pliocene age (5.12 ± 0.16 Ma). Hydrothermal fluid exsolved from the magma that formed the Lamingag Intrusive Complex probably formed the ore-forming Stage 1 veins. Stages 2 and 3 involved the deposition of quartz and carbonate veins possibly by boiling hydrothermal fluids. Precious and base metal deposition was controlled by the Masara Fault Zone. Exploration markers for gold mineralization in the Masara Gold District and vicinity include the presence of Lamingag Intrusive Complex and massive sulfide veins.

Mineral paragenesis and hydrothermal evolution of the Dabaiyang tellurium-gold deposit, Hebei Province, China: Constraints from fluid inclusions, H-O-He-Ar isotopes, and physicochemical conditions

The Dabaiyang deposit is a typical Te-Au deposit hosted in Archean metamorphic rock in the Zhangjiakou district, northern margin of the North China Craton. It is located close to the famous Dongping Te-Au deposit; however, few researches have performed on the Archean metamorphic rock hosted Te-Au deposits, which precludes the studies on enrichment processes and mechanisms of Te-Au deposits in the Zhangjiakou district. In this contribution, four mineralization stages have been recognized in the Dabaiyang deposit: (1) K-feldspar-quartz veins; (2) quartz-pyrite veins; (3) polymetallic sulfide-quartz veins; and (4) calcite and quartz veins. Metallic minerals in this deposit include pyrite, chalcopyrite, galena, sphalerite, bornite, altaite, hessite, petzite, tetradymite, tellurobismuthite, native gold and electrum, and most of them were precipitated in stage III. Petrography, fluid inclusion microthermometry, and laser Raman spectroscopy revealed that the ore-forming fluid was a medium temperature H2O-NaCl hydrothermal system. Fluid temperatures evolved from 264–337 °C to 233–323 °C to 209–268 °C to 130–245 °C, and salinities varied from 1.2 to 10.3 wt% to 1.2–8.8 wt% to 4.3–10.5 wt% to 3.8–8.3 wt% NaCl equivalent. Ore-forming fluids yield H and O isotope compositions of −2.4‰ to 4.9‰ and −101.2‰ to −75.5‰, respectively, and 3He/4He and 40Ar/36Ar ratios of 1.31–1.58 and 3489.0–21824.1, respectively. The hydrothermal fluids were derived initially from magmatic water (stage I), but more mixture of magmatic and meteoric water or heated meteoric water was added to the system (stages II and III), and significant water-rock exchange with the Sanggan metamorphic rock happened during evolution. Calculated physicochemical conditions of ore mineral formation shows that pH decreased, logfO2 and logfS2 did not change significantly from the early to the late stage; logfTe2 and logαAu+(aq)/αAg+(aq) values of stage III are −10.7 to −9.8 and −6.8, respectively. Ore-forming fluid did not suffer boiling during evolution, but mixing with low-temperature meteoric water and water-rock reaction were the dominant mechanisms that led to the precipitation of sulfides, tellurides and Au–Ag minerals in the deposit. The Dabaiyang Te-Au deposit is an epithermal gold deposit and its various hydrothermal fluid sources compared with intrusion hosted Te-Au deposits led to their differences in Te and Au contents, hydrothermal systems and mineral deposition mechanisms.