Trace element zoning of sulfides and quartz at Sheba and Fairview gold mines: Clues to Mesoarchean mineralisation in the Barberton Greenstone Belt,South Africa

The Fairview and Sheba mines are two of the major gold mines in the Paleoarchean Barberton Greenstone Belt of Southern Africa. At these mines, gold is associated with quartz–carbonate ± rutile veins and occurs both as “invisible” gold finely dispersed in sulfides (primarily pyrite and arsenopyrite), and as visible electrum grains hosted in pyrite. Up to approximately 1000 ppm Au are contained in pyrite, and up to approximately 1700 ppm in arsenopyrite. Mapping of trace element distribution in sulfide minerals using electron microprobe and proton probe techniques revealed multiple events of ore formation and Au mineralisation. At Fairview mine, three stages of pyrite formation were identified, the last of which is associated with arsenopyrite, electrum and other sulfide minerals (sphalerite, chalcopyrite, galena, gersdorffite, and Sb-sulfides). At Sheba mine, pyrite was deposited in two stages, and electrum is associated with the second stage. At both mines, the last stage of sulfide formation is the main stage of Au deposition, and is associated with mobilisation of Au, As, Sb, Cu, Zn, and Ni. The host rock composition seems to have affected the composition of pyrite, since higher Ni and Co concentrations (up to 1.4 and 1.6 wt.%, respectively) have been measured in meta-(ultra)mafic host rocks in comparison with chert and metagreywacke. Arsenopyrite is chemically zoned, and has Sb- and S-rich cores and As- and Ni-rich rims. This zoning indicates variations in fluid compositions (decreasing Sb and increasing Ni), and crystallisation conditions (increasing As content for increasing temperature). Geothermometric estimates based on the As content of arsenopyrite (As ≤ 32 at.%) indicate temperatures up to ~ 420 °C for the crystal rims. Petrographic and cathodoluminescence observations of quartz associated with gold mineralisation show only local brittle deformation, and no plastic deformation. This supports the notion that the ore-transporting veins were emplaced late in the deformation history. Variations of cathodoluminescence of quartz are correlated with changing Al contents (Al ≤ 0.16 wt.%), and can be related to fluctuations in the pH of the mineralising fluids.     

Listvenite–lode association at the Barramiya gold mine,Eastern Desert,Egypt

Several occurrences of gold-bearing quartz veins are situated along the east–northeast-trending Barramiya–Um Salatit ophiolitic belt in the central Eastern Desert of Egypt. In the Barramiya mine, gold mineralization within carbonaceous, listvenized serpentinite and adjacent to post-tectonic granite stocks points toward a significant role of listvenitization in the ore genesis. The mineralization is related to quartz and quartz–carbonate lodes in silicified/carbonatized wallrocks. Ore minerals, disseminated in the quartz veins and adjacent wallrocks are mainly arsenopyrite, pyrite and trace amounts of chalcopyrite, sphalerite, tetrahedrite, pyrrhotite, galena, gersdorffite and gold. Partial to complete replacement of arsenopyrite by pyrite and/or marcasite is common. Other secondary phases include covellite and goethite. Native gold and gold–silver alloy occur as tiny grains along micro-fractures in the quartz veins. However, the bulk mineralization can be attributed to auriferous arsenopyrite and arsenic-bearing pyrite (with hundreds of ppms of refractory Au), as evident by electron microprobe and LA-ICP-MS analyses.The mineralized quartz veins are characterized by abundant carbonic (CO₂ ± CH₄ ± H₂O) and aqueous-carbonic (H₂O–NaCl–CO₂ ± CH₄) inclusions along intragranular trails, whereas aqueous inclusions (H₂O–NaCl ± CO₂) are common in secondary sites. Based on the fluid inclusions data combined with thermometry of the auriferous arsenopyrite, the pressure–temperature conditions of the Barramiya gold mineralization range from 1.3 to 2.4 kbar at 325–370 °C, consistent with mesothermal conditions. Based on the measured δ³⁴S values of pyrite and arsenopyrite intimately associated with gold, the calculated δ³⁴S_Σs values suggest that circulating magmatic, dilute aqueous-carbonic fluids leached gold and isotopically light sulfur from the ophiolitic sequence. As the ore fluids infiltrated into the sheared listvenite rocks, a sharp decrease in the fluid fO₂ via interaction with the carbonaceous wallrocks triggered gold deposition in structurally favorable sites.     

Copper–Gold Skarn Mineralization at the Karavansalija Ore Zone,Rogozna Mountain,Southwestern Serbia

Karavansalija ore zone is situated in the Serbian part of the Serbo‐Macedonian magmatic and metallogenic belt. The Cu–Au mineralization is hosted mainly by garnet–pyroxene–epidote skarns and shifts to lesser presence towards the nearby quartz–epidotized rocks and the overlying volcanic tuffs. Within the epidosites the sulfide mineralogy is represented by disseminated cobalt‐nickel sulfides from the gersdorfite‐krutovite mineral series and cobaltite, and pyrite–marcasite–chalcopyrite–base metal aggregates. The skarn sulfide mineralization is characterized by chalcopyrite, pyrite, pyrrhotite, bismuth‐phases (bismuthinite and cosalite), arsenopyrite, gersdorffite, and sphalerite. The sulfides can be observed in several types of massive aggregates, depending on the predominant sulfide phases: pyrrhotite‐chalcopyrite aggregates with lesser amount of arsenopyrite and traces of sphalerite, arsenopyrite–bismuthinite–cosalite aggregates with subordinate sphalerite and sphalerite veins with bismuthinite, pyrite and arsenopyrite. In the overlying volcanoclastics, the studied sulfide mineralization is represented mainly by arsenopyrite aggregates with subordinate amounts of pyrite and chalcopyrite. Gold is present rarely as visible aggregate of native gold and also as invisible element included in arsenopyrite. The fluid inclusion microthermometry data suggest homogenization temperature in the range of roughly 150–400°C. Salinities vary in the ranges of 0.5–8.5 wt% NaCl eq for two‐phase low density fluid inclusions and 15–41 wt% NaCl eq for two‐phase high‐salinity and three‐phase high‐salinity fluid inclusions. The broad range of salinity values and the different types of fluid inclusions co‐existing in the same crystals suggest that at least two fluids with different salinities contributed to the formation of the Cu–Au mineralization. Geothermometry, based on EPMA data of arsenopyrite co‐existing with pyrite and pyrrhotite, suggests a temperature range of 240–360°C for the formation of the arsenopyrite, which overlaps well with the data for the formation temperature obtained through fluid inclusion microthermometry. The sulfur isotope data on arsenopyrite, chalcopyrite, pyrite and marcasite from the different sulfide assemblages (ranging from 0.4‰ to +3.9‰ δ³⁴S_CDT with average of 2.29 δ³⁴S_CDT and standard deviation of 1.34 δ³⁴S_CDT) indicates a magmatic source of sulfur for all of the investigated phases. The narrow range of the data points to a common source for all of the investigated sulfides, regardless of the host rock and the paragenesis. The sulfur isotope data shows good overlap with that from nearby base‐metal deposits; therefore the Cu–Au mineralization and the emblematic base‐metal sulfide mineralization from this metallogenic belt likely share same fluid source.     

Ore petrology,hydrothermal alteration,fluid inclusions,and sulfur stable isotopes of the Milin Kamak intermediate sulfidation epithermal Au-Ag deposit in Western Srednogorie,Bulgaria

The Milin Kamak gold-silver deposit is located in Western Srednogorie zone, 50 km west of Sofia, Bulgaria. This zone belongs to the Late Cretaceous Apuseni-Banat-Timok-Srednogorie magmatic and metallogenic belt. The deposit is hosted by altered trachybasalt to andesitic trachybasalt volcanic and volcanoclastic rocks with Upper Cretaceous age, which are considered to be products of the Breznik paleovolcano. Milin Kamak is the first gold-silver intermediate sulfidation type epithermal deposit recognized in Srednogorie zone in Bulgaria. It consists of eight ore zones with lengths ranging from 400 to 1000 m, widths from several cm to 3–4 m, rarely to 10–15 m, an average of 80–90 m depth (a maximum of 200 m) and dip steeply to the south. The average content of gold is 5.04 g/t and silver – 13.01 g/t. The styles of alteration are propylitic, sericite, argillic, and advanced argillic. Ore mineralization consists of three stages. Quartz-pyrite stage I is dominated by quartz, euhedral to subhedral pyrite, trace pyrrhotite and hematite in the upper levels of the deposit. Quartz-polymetallic stage II is represented by major anhedral pyrite, galena, Fe-poor sphalerite; minor chalcopyrite, tennantite, bournonite, tellurides and electrum; and trace pyrrhotite, arsenopyrite, marcasite. Gangue minerals are quartz and carbonates. The carbonate-gold stage III is defined by deposition of carbonate minerals and barite with native gold and stibnite.Fluid inclusions in quartz are liquid H₂O-rich with homogenization temperature (T_h) ranging from 238 to 345 °C as the majority of the measurements are in the range 238–273 °C. Ice-melting temperatures (T_m) range from −2.2 to −4.1 °C, salinity – from 3.7 to 6.6 wt.% NaCl equiv. These measurements imply an epithermal environment and low- to moderate salinity of the ore-forming fluids.δ³⁴S values of pyrite range from −0.49 to +2.44‰. The average calculated δ³⁴S values are 1.35‰. The total range of δ³⁴S values for pyrite are close to zero suggesting a magmatic source for the sulfur.     

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.     

First-principles calculations of the thermodynamic mixing properties of arsenic incorporation into pyrite and marcasite

The thermodynamic mixing properties of As into pyrite and marcasite have been investigated using first-principles and Monte Carlo calculations in order to understand the incorporation of this important metalloid into solid solution. Using quantum-mechanical methods to account for spin and electron transfer processes typical of sulfide minerals, the total energies of different As–S configurations were calculated at the atomic scale, and the resulting As–S interactions were incorporated into Monte Carlo simulations. Enthalpies, configurational entropies and Gibbs free energies of mixing show that two-phase mixtures of FeS₂ (pyrite or marcasite) and FeAsS (arsenopyrite) are energetically more favorable than the solid solution Fe(S,As)₂ (arsenian pyrite or marcasite) for a wide range of geologically relevant temperatures. Although miscibility gaps dominate both solid solution series, the solubility of As is favored for X_As < 0.05 in iron disulfides. Consequently, pyrite and marcasite can host up to ∼6 wt.% of As in solid solution before unmixing into (pyrite or marcasite) + arsenopyrite. This finding is in agreement with previously published HRTEM observations of As-rich pyrites (> 6 wt.% As) that document the presence of randomly distributed domains of pyrite + arsenopyrite at the nanoscale. According to the calculations, stable and metastable varieties of arsenian pyrite and marcasite are predicted to occur at low (X_As < 0.05) and high (X_As > 0.05) As bulk compositions, respectively.     

The genesis of metal zonation in the Weilasituo and Bairendaba Ag–Zn–Pb–Cu–(Sn–W) deposits in the shallow part of a porphyry Sn–W–Rb system,Inner Mongolia,China

The Weilasituo and Bairendaba Zn–Pb–Ag–Cu–(Sn–W) sulphide deposits are located in the southern part of Great Xing'an Range of Inner Mongolia in China. The deposits are located at shallow depths in the newly discovered Weilasituo porphyry hosting Sn–W–Rb mineralization. The mineralization at Weilasituo and Bairendaba consist of zoned massive sulphide veins within fractures cutting the Xilinhot Metamorphic Complex and quartz diorite. The Weilasituo deposit gradually zones from the Cu-rich Zn–Cu sulphide mineralization in the west to Zn-rich Zn–Cu sulphide mineralization in the east. The Bairendaba deposit has a Cu-bearing and Zn-rich core through a transitional zone devoid of copper to an outer zone of Zn–Pb–Ag mineralization. Three main veins contain more than 50 wt.% of the contained metal in the two deposits with their metal ratios displaying a systematic and gradual increase in Zn/Cu, Pb/Zn and Ag/Zn ratios from the western part of Weilasituo to the eastern part of Bairendaba.Three stages of vein-type mineralization are recognized. Early, sub-economic mineralization consists of a variable proportion of euhedral arsenopyrite, pyrite, quartz, and rare wolframite, scheelite, cassiterite, magnetite and cobaltite. This was succeeded by main stage mineralization with economic concentration of zoned Cu, Zn, Pb and Ag sulphide minerals along strike within the veins. The zones consist of the assemblages: (1) pyrrhotite–Fe-rich sphalerite–chalcopyrite(–quartz–fluorite) at west Weilasituo; (2) pyrrhotite–Fe-rich sphalerite–chalcopyrite(–galena–tetrahedrite–quartz–fluorite) at east Weilasituo; (3) pyrrhotite–Fe-rich sphalerite–chalcopyrite(–galena–tetrahedrite–quartz–fluorite) in the centre of Bairendaba; (4) pyrrhotite–Fe-rich sphalerite–galena(–chalcopyrite–tetrahedrite–quartz–fluorite) in the transition zone of Bairendaba; and (5) pyrrhotite–Fe-rich sphalerite–galena–tetrahedrite(–chalcopyrite–falkmanite–argentite–pyrargyrite–quartz–fluorite) in the outer zone at Bairendaba. Post-main ore stage is devoid of sulphides and characterized overprinting of fluorite, sericite, chlorite, illite, kaolinite and calcite.Zircon SHRIMP U–Pb dating, Zircon LA–ICP–MS U–Pb dating, molybdenite Re–Os isochron dating, and muscovite Ar–Ar dating indicate the Beidashan granitic batholith was intruded at 140 ± 3 Ma (MSWD = 3.3), the porphyritic monzogranite from marginal facies of the Beidashan batholith was intruded at 139 ± 2 Ma (MSWD = 0.75), the mineralized quartz porphyry was intruded at 135 ± 2 Ma (MSWD = 0.91), the greisen mineralization occurred at 135 ± 11 Ma (MSWD = 7.2), and the post-main ore stage muscovite deposited at 129.5 ± 0.9 Ma. The new geochronology data show the porphyry Sn–W–Rb and vein-type sulphide mineralization are contemporaneous with granitic magmatism in the region.The metal zonation at the Weilasituo and Bairendaba deposits is a result of progressive metal deposition. This was during the evolution of a metal-bearing fluid along the strike of the veins and during the main stage of ore formation at the upper part of the deep-seated porphyry Sn–W–Rb system. This progressive zonation indicates that the deposits represent end-numbers formed from one ore-forming fluid, which moved from west to east from the porphyry. The metal zonation patterns of the major veins are consistent with metal-bearing fluid entering the system with the precipitation of chalcopyrite proximally and sphalerite, galena and Ag-bearing minerals more distally. We show that the mechanism of metal deposition is therefore controlled by thermodynamic conditions resulting in the progressive separation of sulphides from the metal-bearing fluid. The temperature gradient between the inflow zone and the outflow zone appears to be one of the key parameters controlling the formation of the metal zonation pattern. The sulphide precipitation sequence is consistent with a low fS₂ and low fO₂ state of the acidic metal-bearing fluid. The metal zonation pattern provides helpful clues from which it is possible to establish the nature of fluid migration and metal deposition models to locate a possible porphyry mineralization at depth in the Great Xing'an Range, which is consistent with the geology of the newly discovered porphyry Sn–W–Rb system.     

Massive sulfides of Mount Jourdanne along the super-slow spreading Southwest Indian Ridge and their genesis

Modern massive sulfide deposits are known to occur in diverse tectonic settings and it is generally expected that hydrothermal deposits of similar geological settings shall have more or less similar mineralogical and geochemical signatures. However, the Mount Jourdanne sulfide deposits along the super-slow spreading Southwest Indian Ridge deviate from this common concept. These sulfide precipitates are Zn-rich (up to 35 wt.%) and are characterized by high concentrations of Pb (≤ 3.5 wt.%), As (≤ 1.1 wt.%), Ag (≤ 0.12 wt.%), Au (≤ 11 ppm), Sb (≤ 967 ppm), and Cd (≤ 0.2 wt.%) which are unusual for a modern sediment-free mid-oceanic ridge system. Therefore, we have reinvestigated the sulfide samples collected during the INDOYO cruise in 1998, in order to explain their unusual mineralogy and geochemical composition. The sulfide samples are polymetallic and are classified as: a) chimneys, b) mounds, and c) hydrothermal breccias. The chimneys are small tube-like symmetrical bodies (30–40 cm high; ~ 10 cm diameter) and consist mainly of sphalerite and less chalcopyrite, set in a matrix of late amorphous silica. The inner wall shows a late-stage colloform sphalerite containing co-precipitates of galena and/or Pb–As sulfosalts. In contrast, the mound samples are dominated either by Fe-sulfides (pyrite) or by a mixture of pyrite and chalcopyrite with less sphalerite, pyrrhotite, amorphous silica and barite. Both, the chimney and mound samples, are characterized by layering and mineral zonation. The hydrothermal breccias are highly altered and mineralogically heterogeneous. They consist of silicified basaltic material that are impregnated with sulfides and contain cm-sized chimney fragments within a matrix of low-temperature minerals such as sphalerite and pyrite. The latter fragments mainly consist of chalcopyrite with isocubanite lamellae. In addition, these breccias contain late-stage realgar, boulangerite, galena, Pb–As sulfosalts and barite that are mostly confined to vugs or fractures. At least five mineralogical associations are distinguished that indicate different thermal episodes ranging from black smoker mineralization conditions to cessation of the hydrothermal activity. Based on the mineralogical associations and established literature in this regard, it is inferred that the mineralization at Mt. Jourdanne occurred mainly in three temperature domains. Above 300 °C, the chalcopyrite (with isocubanite)–pyrrhotite association formed whereas the sphalerite dominated assemblage with much less chalcopyrite and pyrite formed around and below 300 °C. The late-stage mineralization (below 200 °C) contains colloform sphalerite, galena, Pb–As sulfosalts, realgar and barite. The unusual mineralogy and trace element chemistry for this modern VHMS deposit could be explained assuming hydrothermal leaching of some felsic differentiates underneath the basaltic cover and subsequent zone refining processes.     

Geochemical and geochronological constraints on the formation of shear-zone hosted Cu–Au–Bi–Te mineralization in the Stanos area,Chalkidiki, northern Greece

Copper–gold–bismuth–tellurium mineralization in the Stanos area, Chalkidiki Peninsula, Greece, occurs in the Proterozoic- to Silurian-aged Serbomacedonian Massif, which tectonically borders the Mesozoic Circum-Rhodope metamorphic belt to the west and crystalline rocks of the Rhodope Massif to the east. This area contains the Paliomylos, Chalkoma, and Karambogia prospects, which are spatially related to regional NW–SE trending shear zones and hosted by marble, amphibolite gneiss, metagabbro, and various muscovite–biotite–chlorite–actinolite–feldspar–quartz schists of the Silurian Vertiskos Unit. Metallic minerals occur as disseminated to massive aggregates along foliation planes and in boudinaged quartz veins. Iron-bearing sulfides (pyrite, arsenopyrite, and pyrrhotite) formed prior to a copper-bearing stage that contains chalcopyrite along with galena, sphalerite, molybdenite, and various minerals in the system Bi–Cu–Pb–Au–Ag–Te. Fluid inclusion homogenization temperatures of primary aqueous liquid–vapor inclusions in stage I quartz veins range from 170.1 °C to 349.6 °C (peak at ~ 230 °C), with salinities of 4.5 to 13.1 wt.% NaCl equiv. Calculated isochores intersect P–T conditions associated with the upper greenschist facies caused by local overpressures during late-stage tectonic movement along the shear zone in the Eocene, which produced stretching and unroofing of rocks in the region. Values of δ³⁴S for sulfides in the Stanos shear zone range from 2.42 to 10.19‰ and suggest a magmatic sulfur source with a partially reduced seawater contribution. For fluids in equilibrium with quartz, δ¹⁸O at 480 °C varies from 5.76 to 9.21‰ but does not allow for a distinction between a metamorphic and a magmatic fluid.A ¹⁸⁷Re–¹⁸⁷Os isochron of 19.2 ± 2.1 Ma for pyrite in the Paliomylos prospect overlaps ages obtained previously from intrusive rocks spatially-related to the Skouries porphyry Cu–Au, the Asimotrypes Au, and the intrusion-related Palea Kavala Bi–Te–Pb–Sb ± Au deposits in northern Greece, as well as alteration minerals in the carbonate-replacement Madem Lakkos Pb–Zn deposit. Ore-forming components of deposits in the Stanos area were likely derived from magmatic rocks at shallow depth that intruded an extensional shear environment at ~ 19 Ma.     

The Bepkong gold deposit,Northwestern Ghana

The Bepkong gold deposit is located in the Wa–Lawra belt of the Paleoproterozoic Baoulé-Mossi domain of the West African Craton, in NW Ghana. It occurs in pelitic and volcano-sedimentary rocks, metamorphosed to greenschist facies, in genetic association with zones of shear interpreted to form during the regional D₃ deformational event, denominated D_B1 at the deposit scale. The ore zone forms a corridor-like body composed of multiple quartz ± carbonate veins surrounded by an alteration envelope, characterized by the presence of chlorite, calcite, sericite, quartz and disseminated pyrite, arsenopyrite plus subordinate pyrrhotite and chalcopyrite. The veins contain only small proportions of pyrite, whereas most of the sulphides, particularly arsenopyrite, occur in the altered host rock, next to the veins. Pyrite is also common outside of the ore zone. Gold is found in arsenopyrite, where it occurs as invisible gold and as visible – albeit micron-size – grains in its rims, and as free gold within fractures cross-cutting this sulphide. More rarely, free gold also occurs in the veins, in fractured quartz. In the ore zone, pyrite forms euhedral crystals surrounding arsenopyrite, but does not contain gold, suggesting that it formed at a late stage, from a gold-free hydrothermal fluid.     

La Josefina Au–Ag deposit (Patagonia,Argentina): A Jurassic epithermal deposit formed in a hot spring environment

The La Josefina Jurassic epithermal Au–Ag deposit located in Patagonia, Argentina, developed in an extensional setting of a back-arc environment, associated with a widespread Middle–Late Jurassic calc-alkaline volcanism. Block faulting has juxtaposed shallow level features evidenced by hot spring manifestations, hydrothermal eruption breccias and Au-rich veins, which suggest that mineralization in these veins, could extend far below the depths already tested by core drilling. Veins are filled by quartz, chalcedony, opal and minor adularia and barite with massive, comb, cockade, colloform–crustiform bandings and lattice-bladed textures. Ore minerals include electrum, Ag-rich sulfosalts (freibergite), pyrite, galena, sphalerite, chalcopyrite and specular hematite with minor arsenopyrite, marcasite, tetrahedrite and bornite. Four mineralizing stages have been identified, the first two (S1 and S2) are Au and Ag-rich, with temperatures ranging from 225 to 290° and salinities from up to 15 wt.% in S1 decreasing to ~ 1 wt.% NaCl in S2. The third stage (S3) displays higher base metal contents at lower temperatures (~ 200 °C). Finally, the last stage (S4) is barren with temperatures lower than 100 °C. Veins are surrounded by a proximal alteration halo of quartz + pyrite ± adularia ± illite followed outwards by illite/smectite interstratified clays and smectites (with less chlorite) to a propylitic zone. Stable isotope values calculated for the fluids show a mostly meteoric origin for mineralization fluids. Such distinct features place the La Josefina deposits in a hot spring environment with evidences of being formed at a proximal position of the Jurassic paleosurface and paleowater level.     

The Blagodatnoe gold-sulfide deposit (Yenisei Ridge,Russia): the nature of geophysical anomalies and the succession and causes of formation of petrophysical zoning

Data on geophysical fields and petrophysical heterogeneity, parageneses and the thermodynamic conditions and age of their formation, and fluid inclusions were used for the genetic reconstruction of petrophysical zoning at the Blagodatnoe gold-sulfide deposit. Petrophysical associations of the preore and ore stages of the deposit formation are clearly reflected in anomalies of the magnetic and natural electric fields and the aureoles of radioactive elements. At the early preore stage (752 Ma), reduced solutions with high activity of K, enriched in U, Th, and, probably, Au, were supplied to intensely foliated tectonic zones. Their interaction with initial metasedimentary rocks gave rise to contiguous zones of quartz–muscovite and chlorite metasomatic rocks. Accompanying graphitization led to a high electrochemical activity of the metasomatic rocks, which generated anomalies of up to –300 mV in the natural electric field; the most intensely carbonized zones became enriched with U (up to 6.5 × 10^–4%) and, probably, Au. The quartz–muscovite metasomatic rocks accumulated Th and K (up to 29 × 10^–4% and 4%, respectively), whereas the chlorite metasomatic rocks accumulated rock-forming elements (particularly Fe), which led to the compaction of these rocks and the acceleration due to gravity in local positive anomalies. The nonmagnetic character of the fresh pre-ore metasomatic rocks suggests the predominantly pyritic composition of early sulfides. At the ore stage (698 Ma), the minerals were deposited from H₂O–CO₂–As–S solutions at 560 to 315 °C. The activity of these solutions caused a redistribution of radioactive elements and a high petrophysical differentiation of the ore-bearing structure. The amplitudes of the anomalies above this structure vary from 500 to 80 nT in the magnetic field and from –130 to + 10 mV in the natural electric field. It has been found that the hydrothermal fluid hardly affected the polarization properties of graphitized rocks at the maximum temperatures but caused an intense removal of U and the development of magnetic pyrrhotite after pyrite. The temperature decrease in the mineral-forming system was favorable for the formation of siderite. Carbonaceous schists which experienced carbonatization lost their electrochemical activity. The binding of carbon dioxide in the solid phase influenced the migration capability of trace elements and their zonal distribution. With this evolution of the solution, Th accumulated at the lower levels of the mineralized zone, whereas the upper levels of the deposit became enriched with U. Productive gold–arsenopyrite–pyrite–pyrrhotite paragenesis with anomalous magnetic susceptibility evolved at the ore stage. The late galena–sphalerite–chalcopyrite paragenesis (365 Ma) was of strictly local occurrence and reduced the magnetic susceptibility of ores.     

Metamorphosed Pb–Zn–(Ag) ores of the Keketale VMS deposit,NW China: Evidence from ore textures,fluid inclusions,geochronology and pyrite compositions

The Keketale Pb–Zn deposit is located in the Devonian volcanic-sedimentary Maizi basin of the Altay orogenic belt. The mineralization at Keketale is hosted in marbles and deformed volcanic tuffs and biotite–garnet–chlorite schists, folded into a series of overturned synclines formed in multiple deformation events. Keketale contains economic amounts of Pb (0.89 Mt @ 1.51 wt.%), Zn (1.94 Mt @ 3.16 wt.%) and Ag (650 t @ 40 g/t).Detailed petrographic studies have defined two main generations of sulfide development. The banded pyrite of the early Stage A is commonly stratiform, with minor galena, sphalerite and chalcopyrite. Stage B is characterized by a large amount of polymetallic sulfides including pyrrhotite, chalcopyrite, sphalerite and galena, with minor pyrite hosted in quartz veins.Three types of fluid inclusions (FIs), including mixed carbonic-aqueous (C-type), pure carbonic (PC-type) and aqueous (W-type), have been recognized in quartz of stage B. The C-type FIs have homogenization temperatures of 150–326 °C and salinities of 0.2–16.6 wt.% NaCl equivalent. The PC-type FIs are dominated by CO₂ with minor CH₄ and N₂ and have initial ice-melting temperatures of − 57.5 to − 56.7 °C, CO₂ homogenization temperatures of 11–14.1 °C. The W-type primary FIs were completely homogenized at temperatures of 124–359 °C with salinities of 5.0–14.6 wt.% NaCl equivalent. Such CO₂-rich fluid inclusions are consistent with those discovered in orogenic-type deposits in the Altay area and elsewhere.Muscovite separates from the polymetallic quartz veinlets of stage B yield a well-defined ⁴⁰Ar/³⁹Ar isotopic plateau age of 259.33 ± 2.56 Ma, with an isochron age of 259.62 ± 2.65 Ma. This age is coeval with the closure of the Paleo-Asia Ocean and reactivation of the Ertix Fault system.LA-ICP-MS analyses of two generations of pyrite indicate that the banded pyrite of stage A is relatively depleted in metallic elements and contains low contents of Cu (0.39 ppm), Ag (0.20 ppm), Au (below the detection limits), Pb (17.43 ppm) and Zn (14.38 ppm); whereas the pyrite in quartz–polymetallic sulfide veinlets of the stage B is relatively rich in metallic elements, e.g., Cu (2.56 ppm), Ag (3.07 ppm), Au (0.01 ppm), Pb (1047 ppm) and Zn (1136 ppm). The trace amounts of Cu, Pb, Zn, Au and Ag are interpreted to have been initially locked in the lattice of type-A pyrite, and then liberated and precipitated as micromineral inclusions with type-B pyrite during subsequent metamorphism and deformation.Two key factors are considered vital to the formation of economic ores of the Keketale Pb–Zn deposit, namely the original Devonian banded pyrite formed in a VMS system and subsequent Permian deformation and metamorphic processes that liberated Cu, Pb, Zn, Au and Ag from the lattice of type-A pyrite to form galena, sphalerite and chalcopyrite with minor muscovite in quartz veinlets. The model provides a new interpretation of VMS Pb–Zn deposit occurring in back-arc basin environments followed by collision, and new insights into the unique regional Fe–Cu–Pb–Zn–Au mineralization in the Altay orogenic belt.     

Using cocrystallization coefficients of isomorphous admixtures for determination of element concentrations in ore-forming solutions (by the example of Mn/Fe ratio in magnetite)

The cocrystallization coefficient of Mn and Fe (D_Mn/Fe) in magnetite crystals is determined in hydrothermal-growth experiments with internal sampling at 450 and 500 °C and 100 MPa (1 kbar). It is weakly dependent on temperature in the studied PT-region and is constant over a wide range of Mn/Fe values. This permits using the magnetite composition as an indicator of Mn/Fe in the fluid under equilibrium: (Mn/Fe)_aq ≈ 100 (Mn/Fe)_mt. Since Mn is often a macrocomponent of the fluid and a microcomponent of magnetite, local analysis of fluid inclusions for Mn might help to determine Fe even in iron minerals. This will permit evaluation of the contents of other ore metals if the D_Me/Fe values are known. For fine crystals (< 0.1–0.2 mm) with low contents of Mn (< 0.01–0.02%), it is necessary to take into account the fractionation of Mn into the surficial nonautonomous phase, in which its content can reach several percent. Comparison of these data with earlier data on the distribution of Mn in the system magnetite–pyrite–pyrrhotite–greenockite–hydrothermal solution shows that D_Mn/Fe remains constant in the presence of sulfur and sulfides. Precipitation of magnetite, in which Mn is a compatible admixture, cannot affect radically Mn/Fe in the solution because of the low D_Mn/Fe value. This effect is still more unlikely for pyrrhotite and pyrite, in which Mn is an incompatible admixture. The most probable mechanism of Mn fractionation into the solid phase is crystallization of FeOOH at lower temperatures. This is indirectly supported by the strong fractionation of Mn into the nonautonomous oxyhydroxide phase on the surface of magnetite crystals. The necessity of a more rigorous validation of “the new Fe/Mn geothermometer for hydrothermal systems” is substantiated.     

Geochronology and fluid inclusion study of the Yinjiagou porphyry–skarn Mo–Cu–pyrite deposit in the East Qinling orogenic belt,China

The Yinjiagou Mo–Cu–pyrite deposit of Henan Province is located in the Huaxiong block on the southern margin of the North China craton. It differs from other Mo deposits in the East Qingling area because of its large pyrite resource and complex associated elements. The deposit’s mineralization process can be divided into skarn, sulfide, and supergene episodes with five stages, marking formation of magnetite in the skarn episode, quartz–molybdenite, quartz–calcite–pyrite–chalcopyrite–bornite–sphalerite, and calcite–galena–sphalerite in the sulfide episode, and chalcedony–limonite in the supergene episode. Re–Os and ⁴⁰Ar–³⁹Ar dating indicates that both the skarn-type and porphyry-type orebodies of the Yinjiagou deposit formed approximately 143 Ma ago during the Early Cretaceous. Four types of fluid inclusions (FIs) have been distinguished in quartz phenocryst, various quartz veins, and calcite vein. Based on petrographic observations and microthermometric criteria the FIs include liquid-rich, gas-rich, H₂O–CO₂, and daughter mineral-bearing inclusions. The homogenization temperature of FIs in quartz phenocrysts of K-feldspar granite porphyry ranges from 341 °C to >550 °C, and the salinity is 0.4–44.0 wt% NaCl eqv. The homogenization temperature of FIs in quartz–molybdenite veins is 382–416 °C, and the salinity is 3.6–40.8 wt% NaCl eqv. The homogenization temperature of FIs in quartz–calcite–pyrite–chalcopyrite–bornite–sphalerite ranges from 318 °C to 436 °C, and the salinity is 5.6–42.4 wt% NaCl eqv. The homogenization temperature of FIs in quartz–molybdenite stockworks is in a range of 321–411 °C, and the salinity is 6.3–16.4 wt% NaCl eqv. The homogenization temperature of FIs in quartz–sericite–pyrite is in a range of 326–419 °C, and the salinity is 4.7–49.4 wt% NaCl eqv. The ore-forming fluids of the Yinjiagou deposit are mainly high-temperature, high-salinity fluids, generally with affinities to an H₂O–NaCl–KCl ± CO₂ system. The δ¹⁸O_H2O values of ore-forming hydrothermal fluids are 4.0–8.6‰, and the δD_V-SMOW values are between −64‰ and −52‰, indicating that the ore-forming fluids were primarily magmatic. The δ³⁴S_V-CDT values of sulfides range between −0.2‰ and 6.3‰ with a mean of 1.6‰, sharing similar features with deeply sourced sulfur, implying that the sulfur mainly came from the lower crust composed of poorly differentiated igneous materials, but part of the heavy sulfur came from the Guandaokou Group dolostone. The ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb, and ²⁰⁸Pb/²⁰⁴Pb values of sulfides are in the range of 17.331–18.043, 15.444–15.575, and 37.783–38.236, respectively, which is generally consistent with the Pb isotopic signature of the Yinjiagou intrusion, suggesting that the Pb chiefly originated from the felsic–intermediate intrusive rocks in the mine area, with a small amount of lead from strata. The Yinjiagou deposit is a porphyry–skarn deposit formed during the Mesozoic transition of a tectonic regime that is EW-trending to NNE-trending, and the multiepisode boiling of ore-forming fluids was the primary mechanism for mineral deposition.     

Silver-base metal epithermal vein and listwanite hosted deposit Crnac,Rogozna Mts., Kosovo,part II: A link between magmatic rocks and epithermal mineralization

Crnac is an intermediate sulfidation Pb–Zn–Ag epithermal deposit located within the Vardar suture zone of the Central Balkan Peninsula. The epithermal Pb–Zn–Ag mineralization consists of (i) a series of steeply-dipping veins hosted within the Jurassic amphibolites, and (ii) overlying hydrothermal-explosive breccia with angular (level IV) or rounded fragments of listwanite (surface) cemented by epithermal mineralization. The mineralization is related to the Oligocene quartz latite dykes that crosscut the Crnac antiform. Quartz latite rocks predominantly display a shoshonitic character. The obtained ⁴⁰Ar/³⁹Ar age of fresh quartz latite is 28.9 ± 0.3 Ma. Fine-grained sericite from altered quartz latite is dated at 28.6 ± 0.5 Ma. Early, alteration related fluid inclusions within quartz latite show coexistence of high-density brine and a low-density vapor-saturated phase that homogenized at 280–405 °C. Phase separation occurs at a paleodepth of 0.6 to 0.9 km.Epithermal mineralization developed in three stages: (i) early pyrite–arsenopyrite–pyrrhotite–quartz–kaolinite; (ii) main sphalerite–galena–tetrahedrite–chalcopyrite and (iii) late carbonate–pyrite–arsenopyrite assemblage. The onset of mineral deposition within epithermal veins was initiated by boiling of Na–Cl ± K ± Ca ± Mg fluid at a paleodepth of 0.6 to 0.9 km. Coexisting vapor and liquid-rich inclusions display salinities and trapping temperatures of 4 wt.% NaCl equiv., 280–370 °C and 2–27 wt.% NaCl equiv., 230–375 °C, respectively. Boiling continued throughout the deposition of the sphalerite-galena-tetrahedrite-chalcopyrite assemblage. Late stage carbonate was deposited from diluted, non-boiling, low-temperature Na–Ca–Mg–Cl ± CO₂ fluid (0.2 to 4.8 wt.% NaCl equiv., 115–280 °C).About 100–150 m higher in the system, precipitation of listwanite breccia cement began as a result of boiling Na–Cl ± Ca ± Mg ± K fluid of medium salinities (2.6 to 12.1 wt.% NaCl equiv.) at temperatures of 245–370 °C. Boiling and dilution of fluids continue throughout the precipitation of the main sphalerite-galena-tetrahedrite and late, mainly carbonate assemblage. Surface listwanite breccia contain quartz phenocrysts deposited from a homogeneous fluid with a medium salinity (8–10 wt.% NaCl equiv.) and high temperatures (T_h = 295–315 °C), whereas the early and main stage of a surface listwanite breccia cement precipitated from a boiling fluid of decreasing salinity and temperature. Aqueous ± CO₂, high salinity (16 to 18 wt.% NaCl equiv.), low temperature (120 °C), homogeneously trapped fluid that precipitated late stage carbonates, is most likely a remnant of boiled off fluid. The epithermal assemblage of the surface listwanites precipitated at a paleodepth of 0.4 to 0.6 km.The δ¹³C values of the late stage ankerite range from − 4.2 to 4.1‰, whereas δ¹⁸O range from 9.6 to 17.5‰. The calculated δ¹⁸O of fluid that precipitated carbonates within epithermal veins, and listwanite breccia cement range from 6.3 to 11.3‰, indicating a contribution of magmatic water.Deposition of all mineralization types was initiated by neutralization of primary acidic magmatic fluid by water-rock reactions that caused widespread propylitization and sericitization. Extensive and long-lasting boiling combined with dilution by meteoric water increased the pH towards the final stage of hydrothermal activity.     

Geochronological and mineralogical constraints on mineralization of the Hetai goldfield in Guangdong Province,South China

The Hetai goldfield, located in the southern segment of the Qinzhou Bay-Hangzhou Bay Juncture Orogenic Belt (QHJB), is the largest concentration of gold deposits in Guangdong Province, South China. The gold mineralization is hosted within the late Neoproterozoic to early Paleozoic Yunkai Group and strictly confined to mylonite (ductile shear) zones. The nature of the structural control of mineralization, in particular the role of ductile versus brittle deformation and their ages, which remain unclear despite numerous previous studies, are examined in this paper through an integrated study of geochronology and mineralogy.Lamellar and filament structures shown by pyrite and pyrrhotite in the ores suggest that sulfidation took place during ductile deformation and syntectonic metamorphism, but the majority of the ores are associated with brittle deformation features. In combination with macroscopic and microscopy observations on shear fabrics, LA-ICP-MS U-Pb dating on zircons of hydrothermal origin from mylonites suggests that the Hetai goldfield was subjected to two shearing events: an early sinistral ductile shearing at ca. 240 Ma, and a late dextral ductile-brittle shearing at ca. 204 Ma (Indosinian). These ages are ca. 90–30 Ma older than the previously published gold mineralizing ages of ca. 175–152 Ma (Yanshanian), suggesting that the main gold mineralization and related brittle deformation significantly postdate the ductile deformation. This inference is supported by the mineralization temperatures estimated from geothermometers of arsenopyrite (ca. 350–290 °C), chlorite (ca. 260–230 °C), and sphalerite (ca. 230–170 °C) intergrown with native gold, which are considerably lower than that for the ductile deformation (500–300 °C or higher). Based on these data, we propose that the gold mineralization in the Hetai goldfield predominantly occurred during the Yanshanian event, and only minor gold mineralization and associated sulfidation took place during the earlier Indosinian ductile deformation.     

安徽铜陵冬瓜山铜矿床的叠加改造成矿机制：来自矿石结构的证据

长江中、下游地区块状硫化物矿床普遍受到燕山期岩浆及其热液的改造与叠加.本文以铜陵冬瓜山矿床为例,探讨这类矿床的成矿机制.该矿床主要由层状硫化物矿体组成,伴有矽卡岩型和斑岩型矿体.野外地质观察及室内矿相学的研究表明,冬瓜山层状矿体中矿石遭受了强烈的热变质作用及热液交代作用.进变质过程中形成的结构主要为黄铁矿受燕山期岩浆侵...     

Geology,geochemistry and fluid inclusions of the Bianjiadayuan Pb–Zn–Ag deposit,Inner Mongolia,NE China: Implications for tectonic setting and metallogeny

The Bianjiadayuan Pb–Zn–Ag deposit in the Southern Great Xing'an Range consists of quartz-sulfide vein-type and breccia-type mineralization related to granite. Vein orebodies are localized in NW-trending extensional faults. Hydrothermal alteration is well developed and includes silicification, potassic alteration, chloritization and sericitization. Three stages of mineralization are recognized based on field evidence and petrographic observation and are marked by assemblages of quartz–arsenopyrite–pyrite (stage I), quartz–pyrrhotite–chalcopyrite–sphalerite (stage II) and quartz–galena–silver minerals (stage III). The granite, with a zircon age of 143.2 ± 1.5 Ma (n = 14, MSWD = 0.93), is subalkaline, peraluminous and is classified as A2-type granite originating in a post-orogenic extensional setting during the opening of suture zone between the North China Craton and the Siberia Craton from the Late Jurassic to the Early Cretaceous. The δ³⁴S_CDT values of sulfides, ranging from 3.19 to 10.65‰, are not consistent with the majority of magmatic hydrothermal deposits in the SGXR, possibly implying accessory source in addition to magmatic source. Microthermometric measurements show that ore minerals were deposited at intermediate temperatures (347.8–136.4 °C) with moderate salinities (2.9–14.4 wt.% NaCl). Ore-forming fluids were derived largely from magmatic hydrothermal processes, with the addition of meteoric water in late stage. Successive precipitation of Pb, Zn and Ag occurred with changes of physicochemical conditions. Overall considering mineralization features, ore-forming fluids and materials and tectonic setting and comparing with adjacent deposits, the Bianjiadayuan deposit is a mesothermal magmatic hydrothermal vein-type Pb–Zn–Ag deposit controlled by fractures and related to A2-type granite in response to the tectonic/magmatic/hydrothermal activity in late Jurassic. Besides, the explosive breccias in the west area require more attention in future exploration.     

Alteration and mineralization at the Zhibula Cu skarn deposit,Gangdese belt,Tibet

The Zhibula Cu skarn deposit contains 0.32 Mt. Cu metal with an average grade of 1.64% and is located in the Gangdese porphyry copper belt in southern Tibet. The deposit is a typical metasomatic skarn that is related to the interaction of magmatic–hydrothermal fluids and calcareous host rock. Stratiform skarn orebodies occur at the contact between tuff and marble in the Lower Jurassic Yeba Formation. Alteration zones generally grade from a fresh tuff to a garnet-bearing tuff, a garnet pyroxene skarn, and finally to a wollastonite marble. Minor endoskarn alteration zonations are also observed in the causative intrusion, which grade from a fresh granodiorite to a weakly chlorite-altered granodiorite, a green diopside-bearing granodiorite, and to a dark red-brown garnet-bearing granodiorite. Prograde minerals, which were identified by electron probe microanalysis include andradite–grossularite of various colors (e.g., red, green, and yellow) and green diopside. Retrograde metamorphic minerals overprint the prograde skarn, and are mainly composed of epidote, quartz, and chlorite. The ore minerals consist of chalcopyrite and bornite, followed by magnetite, molybdenite, pyrite, pyrrhotite, galena, and sphalerite. Three types of fluid inclusions are recognized in the Zhibula deposit, including liquid-rich two-phase inclusions (type L), vapor-rich two-phase inclusions (type V), and daughter mineral-bearing three-phase inclusions (type S). As the skarn formation evolved from prograde (stage I) to early retrograde (stage II) and later retrograde (stage III), the ore-forming fluids correspondingly evolved from high temperature (405–667 °C), high salinity (up to 44.0 wt.% NaCl equiv.), and high pressure (500–600 bar) to low-moderate temperature (194–420 °C), moderate-high salinity (10.1–18.3 and 30.0–44.2 wt.% NaCl equiv.), and low-moderate pressure (250–350 bar). Isotopic data of δ³⁴S (− 0.1‰ to − 6.8‰, estimated δ³⁴S_fluids = − 0.7‰), δD_H2O (− 91‰ to − 159‰), and δ¹⁸O_H2O (1.5‰ to 9.2‰) suggest that the ore-forming fluid and material came from magmatic–hydrothermal fluids that were associated with Miocene Zhibula intrusions. Fluid immiscibility likely occurred at the stage I and stage II during the formation of the skarn and mineralization. Fluid boiling occurred during the stage III, which is the most important Cu deposition mechanism for the Zhibula deposit.