Sulfur-poor intense acid hydrothermal alteration: A distinctive hydrothermal environment

A fundamentally distinct, sulfide-poor variant of intense acid (advanced argillic) alteration occurs at the highest structural levels in iron oxide-rich hydrothermal systems. Understanding the mineralogy, and geochemical conditions of formation in these sulfide-poor mineral assemblages have both genetic and environmental implications. New field observations and compilation of global occurrences of low-sulfur advanced argillic alteration demonstrates that in common with the sulfide-rich variants of advanced argillic alteration, sulfide-poor examples exhibit nearly complete removal of alkalis, leaving a residuum of aluminum-silicate + quartz. In contrast, the sulfur-poor variants lack the abundant pyrite ± other sulfides, hypogene alunite, Al-leached rocks (residual “vuggy” quartz) as well as the Au-Cu-Ag ± As-rich mineralization of some sulfur-rich occurrences. Associated mineralization is dominated by magnetite and/or hematite with accessory elements such as Cu, Au, REE, and P. These observations presented here indicate there must be distinct geologic processes that result in the formation of low-sulfur advanced argillic styles of alteration.Hydrolysis of magmatic SO₂ to sulfuric acid is the most commonly recognized mechanism for generating hypogene advanced argillic alteration, but is not requisite for its formation. Low sulfur iron-oxide copper-gold systems are known to contain abundant acid-styles of alteration (e.g. sericitic, chloritic), which locally reaches advanced argillic assemblages. A compilation of mapping in four districts in northern Chile and reconnaissance observations elsewhere show systematic zoning from near surface low-sulfide advanced argillic alteration through chlorite-sericite-albite and locally potassic alteration. The latter is commonly associated with specular hematite-chalcopyrite mineralization. Present at deeper structural levels are higher-temperature styles of sodic-calcic (oligoclase/scapolite – actinolite) alteration associated with magnetite ± chalcopyrite mineralization. These patterns are in contrast to the more sulfur-rich examples which generally zone to higher pyrite and locally alunite-bearing alteration.Fluid inclusion evidence from the systems in northern Chile shows that many fluids contain 25 to >50 wt% NaCl_eq with appreciable Ca, Fe, and K contents with trapping temperatures >300 °C. These geological and geochemical observations are consistent with the origin of the low-sulfur advanced argillic assemblages from HCl generated by precipitation of iron oxides from iron chloride complexes from a high-salinity fluid by reactions such as 3FeCl₂ + 4H₂O = Fe₃O₄ + 6HCl + H₂. Such HCl-rich (and relatively HSO₄⁼-poor) fluids can then account for the intense acid, Al-silicate-rich styles of alteration observed at high levels in some iron-oxide-coppe-gold (IOCG) systems. The geochemical differences between the presence of sulfide-rich and sulfur-poor examples of advanced argillic alteration are important to distinguishing between system types and the acid-producing capacity of the system, including in the modern weathering environment. They have fundamental implications for effective mineral exploration in low-sulfur systems and provide yet another vector of exposed alteration in the enigmatic IOCG clan of mineral deposits. Furthermore, understanding the geochemistry and mineralogy of this distinct geologic environment has applications to understanding the acid generating capacity and deleterious heavy metals associated with advanced argillic alteration.     

Fluid evolution,wallrock alteration,and ore mineralization associated with the Rodalquilar epithermal gold-deposit in southeast Spain

At Rodalquilar gold mineralization is found in Late Tertiary volcanic rocks of the Sierra del Cabo de Gata and is related to a caldera collapse. Radial and concentric faults were preferred sites for gold deposition. Hydrothermal activity produced a specific alteration zoning around gold-bearing vein structures, grading from an innermost advanced argillic via an argillic into a more regionally developed propylitic zone. Advanced argillic alteration with silica, pyrophyllite, alunite, and kaolinite extends down to several hundred m indicating a hypogene origin. High-grade gold mineralization in vein structures is confined to the near-surface part of the advanced argillic alteration. Fine-grained gold is associated with hematite, jarosite, limonite, or silica. At a depth of about 120 m, the oxidic ore assemblage grades into sulfide mineralization with pyrite and minor chalcopyrite, covellite, bornite, enargite, and tennantite. Two types of fluids from different sources were involved in the hydrothermal system. Overpressured and hypersaline fluids of presumably magmatic origin initiated the hydrothermal system. Subsequent hydrothermal processes were characterized by the influx of low-salinity solutions of probable marine origin and by interactions between both fluids. Deep-reaching, advanced argillic alteration formed from high-salinity fluids with 20–30 equiv. wt% NaCl at about 225°C. Near-surface gold precipitation and silification are related to fluids with temperatures of about 175°C and 3–4 equiv. wt% NaCl. Gold was transported as Au(HS) ₂ ^– , and precipitation resulted from boiling with a concomitant decrease in temperature, pressure, and pH and an increase in fO₂. All features of the Rodalquilar gold deposit reveal a close relationship to acid-sulfate-type epithermal gold mineralization.     

Geochemistry and evolution of ore-forming fluids of the Yueshan Cu–Au skarn- and vein-type deposits, Anhui Province, South China

The Yueshan mineral belt is geotectonically located at the centre of the Changjiang deep fracture zone or depression of the lower Yangtze platform. Two main types of ore deposits occur in the Yueshan orefield: Cu–Au–(Fe) skarn deposits and Cu–Mo–Au–(Pb–Zn) hydrothermal vein-type deposits. Almost all deposits of economic interest are concentrated within and around the eastern and northern branches of the Yueshan dioritic intrusion. In the vicinity of the Zongpu and Wuhen intrusions, there are many Cu–Pb–Zn–Au–(S) vein-type and a few Cu–Fe–(Au) skarn-type occurrences.Fluid inclusion studies show that the ore-forming fluids are characterised by a Cl⁻(S)–Na⁺–K⁺ chemical association. Hydrothermal activity associated with the above two deposit types was related to the Yueshan intrusion. The fluid salinity was high during the mineralisation processes and the fluid also underwent boiling and mixed with meteoric water. In comparison, the hydrothermal activity related to the Zongpu and Wuhen intrusions was characterised by low salinity fluids. Chlorine and sulphur species played an important role in the transport of ore-forming components.Hydrogen- and oxygen-isotope data also suggest that the ore-forming fluids in the Yueshan mineral belt consisted of magmatic water, mixed in various proportions with meteoric water. The enrichment of ore-forming components in the magmatic waters resulted from fluid–melt partitioning. The ore fluids of magmatic origin formed large Cu–Au deposits, whereas ore fluids of mixed magmatic-meteoric origin formed small- to medium-sized deposits.The sulphur isotopic composition of the skarn- and vein-type deposits varies from − 11.3‰ to + 19.2‰ and from + 4.2‰ to + 10.0‰, respectively. These variations do not appear to have been resulted from changes of physicochemical conditions, rather due to compositional variation of sulphur at the source(s) and by water–rock interaction. Complex water–rock interaction between the ore-bearing magmatic fluids and sedimentary wall rocks was responsible for sulphur mixing. Lead and silicon isotopic compositions of the two deposit types and host rocks provide similar indications for the sources and evolution of the ore-forming fluids.Hydrodynamic calculations show that magmatic ore-forming fluids were channelled upwards into faults, fractures and porous media with velocities of 1.4 m/s, 9.8 × 10^− 1 to 9.8 × 10^− 7 m/s and 3.6 × 10^− 7 to 4.6 × 10^− 7 m/s, respectively. A decrease of fluid migration velocity in porous media or tiny fractures in the contact zones between the intrusive rocks and the Triassic sedimentary rocks led to the deposition of the ore-forming components. The major species responsible for Cu transport are deduced to have been CuCl, CuCl₂⁻, CuCl₃²⁻ and CuClOH, whereas Au was transported as Au₂(HS)₂S²⁻, Au(HS)₂⁻, AuHS and AuH₃SiO₄ complexes. Cooling and a decrease in chloride ion concentration caused by fluid boiling and mixing were the principal causes of Cu deposition. Gold deposition was related to decrease of pH, total sulphur concentration and fO₂, which resulted from fluid boiling and mixing.Geological and geochemical characteristics of the two deposit types in the Yueshan mineral belt suggest that there is a close genetic relationship with the dioritic magmatism. Geochronological data show that the magmatic activity and the mineralisation took place between 130 and 136 Ma and represent a continuous process during the Yanshanian time. The cooling of the intrusions and the mineralisation event might have lasted about 6 Ma. The cooling rate of the magmatic intrusions was 80 to 120 °C my^− 1, which permitted sufficient heat supply by magma to the ore-forming system.     

Porphyry to epithermal transition in the Agua Rica polymetallic deposit, Catamarca, Argentina: An integrated petrologic analysis of ore and alteration parageneses

Agua Rica (27°26′S–66°16′O) is a world class Cu–Au–Mo deposit located in Catamarca, Argentina. In the E–W 6969400 section examined, the Seca Norte and the Trampeadero porphyries that have intruded the metasedimentary rock are cut by interfingered igneous and hydrothermal heterolithic and monolithic breccias, and sandy dikes. Relic biotite and K-feldspar of the early potassic alteration (370° to > 550 °C) with Cu (Mo–Au) mineralization are locally preserved and encapsulated in a widespread, white mica + quartz + rutile or anatase halo (phyllic alteration) with pyrite + covellite that suggests fluids with temperatures ≤ 360 °C and high f(S₂). The Trampeadero porphyry and the surrounding metasedimentary rock with phyllic alteration have molybdenite in stringers and B-type quartz veinlets and the highest Mo grades (> 1000 ppm).Multistage advanced argillic alteration overprinted the earlier stages. Early andalusite ± pyrite ± quartz is preserved in the roots of the argillic halo rimmed by an alumina–silica material and white micas. This alteration assemblage is considered to have been formed at temperatures ≥ 375 °C from condensed magmatic vapor. At higher levels, pyrophyllite replaces muscovite and illite in clasts of hydrothermal breccias in the center and east sector of the study section, suggesting temperatures of 280 to 360 °C. Clasts of vuggy silica in the uppermost levels of the central breccia, indicates that at lower temperatures (< 250 °C), fluids reached very low pH (pH < 2). In this early stage of the advanced argillic alteration, hydrothermal fluids seem to have not precipitated sulfides or sulfosalts.Hydrothermal brecciation was concurrent with fluid exsolution (↑? V), which precipitated intermediate-temperature advanced argillic alunite (svanbergite + woodhouseite) ± diaspore ± zunyite as breccia cement along with abundant covellite + pyrite + enargite ± native sulfur ± kuramite at intermediate depths and in lateral transitional zones to unbrecciated rocks. This mineral assemblage indicates temperatures near 300 °C, oxidized and silica-undersaturated hydrothermal fluids with high sulfur fugacity to prevent gold precipitation. Multiple generations of pyrite, emplectite, colusite, Pb- and Bi-bearing sulfosalts, and native sulfur with Au and Ag, accompanied by alunite introduction in the upper level breccias, probably occurred at lower temperatures, but still high sulfur and oxygen activity. An independent Zn and Pb (as galena) mineralization stage locally coincides with Au–Ag and sulfosalts, and advanced at depth, controlled by fractures and overprinting much of the previous mineralization. A later paragenesis of veinlets of alunite + woodhouseite + svanvergite + pyrite ± enargite that cut the phyllic halo suggests temperatures ~ 250 °C and without woodhouseite + svanvergite, temperatures ~ 200 °C. Kaolinite occurs in the phyllic halo as a late mineral in clots and in veinlets thus, in this zone, the fluid had cooled enough for its formation.     

2: Hydrothermal ore deposits related to post-orogenic extensional magmatism and core complex formation: The Rhodope Massif of Bulgaria and Greece

The Rhodope Massif in southern Bulgaria and northern Greece hosts a range of Pb–Zn–Ag, Cu–Mo and Au–Ag deposits in high-grade metamorphic, continental sedimentary and igneous rocks. Following a protracted thrusting history as part of the Alpine–Himalayan collision, major late orogenic extension led to the formation of metamorphic core complexes, block faulting, sedimentary basin formation, acid to basic magmatism and hydrothermal activity within a relatively short period of time during the Early Tertiary. Large vein and carbonate replacement Pb–Zn deposits hosted by high-grade metamorphic rocks in the Central Rhodopean Dome (e.g., the Madan ore field) are spatially associated with low-angle detachment faults as well as local silicic dyke swarms and/or ignimbrites. Ore formation is essentially synchronous with post-extensional dome uplift and magmatism, which has a dominant crustal magma component according to Pb and Sr isotope data. Intermediate- and high-sulphidation Pb–Zn–Ag–Au deposits and minor porphyry Cu–Mo mineralization in the Eastern Rhodopes are predominantly hosted by veins in shoshonitic to high-K calc-alkaline volcanic rocks of closely similar age. Base-metal-poor, high-grade gold deposits of low sulphidation character occurring in continental sedimentary rocks of synextensional basins (e.g., Ada Tepe) show a close spatial and temporal relation to detachment faulting prior and during metamorphic core complex formation. Their formation predates local magmatism but may involve fluids from deep mantle magmas.The change in geochemical signatures of Palaeogene magmatic rocks, from predominantly silicic types in the Central Rhodopes to strongly fractionated shoshonitic (Bulgaria) to calc-alkaline and high-K calc-alkaline (Greece) magmas in the Eastern Rhodopes, coincides with the enrichment in Cu and Au relative to Pb and Zn of the associated ore deposits. This trend also correlates with a decrease in the radiogenic Pb and Sr isotope components of the magmatic rocks from west to east, reflecting a reduced crustal contamination of mantle magmas, which in turn correlates with a decreasing crustal thickness that can be observed today. Hydrogen and oxygen isotopic compositions of the related hydrothermal systems show a concomitant increase of magmatic relative to meteoric fluids, from the Pb–Zn–Ag deposits of the Central Rhodopes to the magmatic rock-hosted polymetallic gold deposits of the Eastern Rhodopes.     

Comparison between the fluid characteristics of the Rodalquilar and two neighbouring epithermal gold deposits in Spain

The operating Rodalquilar gold deposit and the abandoned Triunfo and Maria Josefa gold mines are located within the Sierra del Cabo de Gata volcanic field some 40 km east of Almeria in SE Spain. While the gold mineralization at Rodalquilar is mainly controlled by caldera-tectonics, vein structures at Triunfo and Maria Josefa are not. Wall-rock alteration at Triunfo and Maria Josefa is characterized by argillic alteration (illite/sericite, kaolinite). The alteration zonation around the gold-mineralized vein structures at Rodalquilar ranges from advanced argillic alteration (porous quartz, alunite, pyrophyllite, dickite) over argillic alteration into a regionally developed propylitization. Fluid inclusion studies from all three mines indicate that gold was deposited from low-salinity fluids (2–5 wt.% NaCl equivalent) between 170° and 250 °C. However, the hydrothermal system at Rodalquilar was fed by a second fluid source. High-salinity, halite and/or sylvite-bearing, liquid-rich, and vapour-dominated, CO₂-bearing fluid inclusions are assumed to be of magmatic origin. High sulfidation ore mineral assemblages at depth (covellite, enargite, tennantite) and part of the advanced argillic alteration can be related to these fluids. Thus, part of those features which attribute the Rodalquilar gold deposit to the acid-sulfate or high sulfidation type of epithermal gold deposits, stem from magmatically derived fluids which are typical for a porphyry environment, whereas gold mineralization at all three localities is associated with low-salinity fluids, probably of marine origin.     

“Cockade” formations in hydrothermally altered rocks of Ebeko central crater (Paramushir Island)

Strongly acidic chloride-sulfide hydrothermal solutions altered ejecta from the Central Ebeko crater. The solutions formed by oxidation of magmatic emanations and produced concentric zones of differential alteration in individual blocks known as “cockade” structure. It is postulated that chloride-rich solutions penetrated the core of blocks while chloride-sulfate solutions affected intermediate portions and sulfate-rich solutions were not active around the periphery of blocks. Chemical and mineralogical analyses indicate that Cl, H₂O and S were added to the blocks while alumina, the alkali and alkaline earth metals were leached. SiO₂ and porosity were relatively increased from the core outward. Alteration products include iron chlorides, hydromicas, zunyite (?), alunite, leucoxene, rutile, sulfur and opal. — R. C. Epis.     

Sulfur isotopic composition of hydrothermal precipitates from the Lau back-arc: implications for magmatic contributions to seafloor hydrothermal systems

The sulfur isotopic composition of sulfides and barite from hydrothermal deposits at the Valu Fa Ridge back-arc spreading center in the southern Lau Basin has been investigated. Sulfide samples from the White Church area at the northern Valu Fa Ridge have δ³⁴S values averaging +3.8‰ (n= 10) for bulk sphalerite-chalcopyrite mineralization and +4.8‰ for pyrite (n= 10). Barite associated with the massive sulfides exhibits an average of +20.7‰ (n= 10). Massive sulfides from the active Vai Lili hydrothermal field at the central Valu Fa Ridge have much higher δ³⁴S ratios averaging +8.0‰ for bulk sphalerite-chalcopyrite mineralization (n= 5), +9.3‰ for pyrite samples (n= 5), and +8.0‰ and +10.9‰ for a chalcopyrite and a sphalerite separate, respectively. The isotopic composition of barite from the Vai Lili field is similar to that of barite from the White Church area and averages +21.0‰ (n= 8). Sulfide and barite samples from the Hine Hina area at the southern Valu Fa Ridge have δ³⁴S values that are considerably lighter than those observed for samples from the other areas and average −4.9‰ for pyrite (n= 9), −4.0 and −5.7‰ for two samples of sphalerite-chalcopyrite intergrowth, and −3.4‰ for a single chalcopyrite separate. The total spread in the isotopic composition of sulfides from Vai Lili and Hine Hina is more than 20‰ over a distance of less than 30 km. The δ³⁴S values of sulfides at Hine Hina are the lowest values so far reported for volcanic-hosted polymetallic massive sulfides from the modern seafloor. Barite from the Hine Hina field also has unusually light sulfur with δ³⁴S values of +16.1 to +16.7‰ (n= 5). Isotopic compositions of the sulfides at Hine Hina indicate a dramatic decrease in δ³⁴S from ordinary magmatic values and, in the absence of biogenic sulfur and/or boiling, imply a unique ³⁴S-depleted source of probable magmatic origin. Sulfide-barite mineralization in the Hine Hina area is associated with a distinctive alteration assemblage consisting of cristobalite, pyrophyllite, kaolinite, opal-CT, talc, pyrite, native sulfur, and alunite. Similar styles of alteration are typically known from high-sulfidation epithermal systems on land. Alunite-bearing, advanced argillic alteration in the Hine Hina field confirms the role of acidic, volatile-rich fluids, and a δ³⁴S value of +10.4‰ for the sulfur in the alunite is consistent with established kinetic isotope effects which accompany the disproportionation of magmatic SO₂ into H₂S and H₂SO₄. The Hine Hina field occurs near the propagating tip of the Valu Fa back-arc spreading center (i.e., dominated by dike injections and seafloor eruptions) and therefore may have experienced the largest contribution of magmatic volatiles of the three fields. The sulfur isotopic ratios of the hydrothermal precipitates and the presence of a distinctive epithermal-like argillic alteration in the Hine Hina field suggest a direct contribution of magmatic vapor to the hydrothermal system and support the concept that magmatic volatiles may be an important component of some volcanogenic massive sulfide-forming hydrothermal systems. Received: 16 January 1997 / Accepted: 28 October 1997     

Zonation of Sulfate and Sulfide Minerals and Isotopic Composition in the Far Southeast Porphyry and Lepanto Epithermal Cu–Au Deposits,Philippines

The world‐class Far Southeast (FSE) porphyry system, Philippines, includes the FSE Cu–Au porphyry deposit, the Lepanto Cu–Au high‐sulfidation deposit and the Victoria–Teresa Au–Ag intermediate‐sulfidation veins, centered on the intrusive complex of dioritic composition. The Lepanto and FSE deposits are genetically related and both share an evolution characterized by early stage 1 alteration (deep FSE potassic, shallow Lepanto advanced argillic‐silicic, both at ~1.4 Ma), followed by stage 2 phyllic alteration (at ~1.3 Ma); the dominant ore mineral deposition within the FSE porphyry and the Lepanto epithermal deposits occurred during stage 2. We determined the chemical and S isotopic composition of sulfate and sulfide minerals from Lepanto, including stage 1 alunite (12 to 28 permil), aluminum–phosphate–sulfate (APS) minerals (14 to 21 permil) and pyrite (?4 to 2 permil), stage 2 sulfides (mainly enargite–luzonite and some pyrite, ?10 to ?1 permil), and late stage 2 sulfates (barite and anhydrite, 21 to 27 permil). The minerals from FSE include stage 2 chalcopyrite (1.6 to 2.6 permil), pyrite (1.1 to 3.4 permil) and anhydrite (13 to 25 permil). The whole‐rock S isotopic composition of weakly altered syn‐mineral intrusions is 2.0 permil. Stage 1 quartz–alunite–pyrite of the Lepanto lithocap, above about 650 m elevation, formed from acidic condensates of magmatic vapor at the same time as hypersaline liquid formed potassic alteration (biotite) near sea level. The S isotopic composition of stage 1 alunite–pyrite record temperatures of approximately 300–400°C for the vapor condensate directly over the porphyry deposit; this cooled to <250°C as the acidic condensate flowed to the NW along the Lepanto fault where it cut the unconformity at the top of the basement. Stage 1 alunite at the base of the advanced argillic lithocap over FSE contains cores of APS minerals with Sr, Ba and Ca; based on back‐scattered electron images and ion microprobe data, these APS minerals show a large degree of chemical and S‐isotopic heterogeneity within and between samples. The variation in S isotopic values in these finely banded stage 1 alunite and APS minerals (16 permil range), as well as that of pyrite (6 permil range) was due largely to changes in temperature, and perhaps variation in redox conditions (average ~ 2:1 H₂S:SO₄). Such fluctuations could have been related to fluid pulses caused by injection of mafic melt into the diorite magma chamber, supported by mafic xenoliths hosted in diorite of an earlier intrusion. The S isotopic values of stage 2 minerals indicate temperatures as high as 400°C near sea level in the porphyry deposit, associated with a relatively reduced fluid (~10:1 H₂S:SO₄) responsible for deposition of chalcopyrite. Stage 2 fluids were relatively oxidized in the Lepanto lithocap, with an H₂S:SO₄ ratio of about 4. The oxidation resulted from cooling, which was caused by boiling during ascent and then dilution with steam‐heated meteoric water in the lithocap. This cooling also resulted in the sulfidation state of minerals increasing from chalcopyrite stability in the porphyry deposit to that of enargite in the lithocap‐hosted high‐sulfidation deposit. The temperature at the base of the lithocap during stage 2 was ≥300°C, cooling to <250°C within the main lithocap, and about 200°C towards the limit of the Lepanto orebody, approximately 2 km NW of the porphyry deposit. Approximate 300°C and 200°C isotherms, estimated from S isotopic and fluid inclusion temperatures during stage 1 and stage 2, shifted towards the core of the FSE porphyry deposit with time. This general retreat in isotherms was more than 500 m laterally within Lepanto and 500 m vertically within FSE as the magmatic–hydrothermal system evolved and collapsed over the magmatic center. During this evolution, there is also evidence recorded by large S isotopic variations in individual crystals for sharp pulses of higher temperature, relatively reduced fluid injected into the porphyry deposit.     

Role of fluid mixing and wallrock sulfidation in gold mineralization at the Semna mine area, central Eastern Desert of Egypt: Evidence from hydrothermal alteration, fluid inclusions and stable isotope data

The Semna gold deposit is one of several vein-type gold occurrences in the central Eastern Desert of Egypt, where gold-bearing quartz veins are confined to shear zones close to the boundaries of small granitoid stocks. The Semna gold deposit is related to a series of sub-parallel quartz veins along steeply dipping WNW-trending shear zones, which cut through tectonized metagabbro and granodiorite rocks. The orebodies exhibit a complex structure of massive and brecciated quartz consistent with a change of the paleostress field from tensional to simple shear regimes along the pre-existing fault segments. Textural, structural and mineralogical evidence, including open space structures, quartz stockwork and alteration assemblages, constrain on vein development during an active fault system. The ore mineral assemblage includes pyrite, chalcopyrite, subordinate arsenopyrite, galena, sphalerite and gold. Hydrothermal chlorite, carbonate, pyrite, chalcopyrite and kaolinite are dominant in the altered metaggabro; whereas, quartz, sericite, pyrite, kaolinite and alunite characterize the granodiorite rocks in the alteration zones. Mixtures of alunite, vuggy silica and disseminated sulfides occupy the interstitial open spaces, common at fracture intersections. Partial recrystallization has rendered the brecciation and open space textures suggesting that the auriferous quartz veins were formed at moderately shallow depths in the transition zone between mesothermal and epithermal veins.Petrographic and microthermometric studies aided recognition of CO₂-rich, H₂O-rich and mixed H₂O–CO₂ fluid inclusions in the gold-bearing quartz veins. The H₂O–CO₂ inclusions are dominant over the other two types and are characterized by variable vapor: liquid ratios. These inclusions are interpreted as products of partial mixing of two immiscible carbonic and aqueous fluids. The generally light δ³⁴S of pyrite and chalcopyrite may suggest a magmatic source of sulfur. Spread in the final homogenization temperatures and bulk inclusion densities are likely due to trapping under pressure fluctuation through repeated fracture opening and sealing. Conditions of gold deposition are estimated on basis of the fluid inclusions and sulfur isotope data as 226–267 °C and 350–1100 bar, under conditions transitional between mesothermal and epithermal systems.The Semna gold deposit can be attributed to interplay of protracted volcanic activity (Dokhan Volcanics?), fluid mixing, wallrock sulfidation and a structural setting favoring gold deposition. Gold was transported as Au-bisulfide complexes under weak acid conditions concomitant with quartz–sericite–pyrite alteration, and precipitated through a decrease in gold solubility due to fluid cooling, mixing with meteoric waters and variations in pH and fO₂.     

Rosia Poieni copper deposit,Apuseni Mountains,Romania: advanced argillic overprint of a porphyry system

The Rosia Poieni deposit is the largest porphyry copper deposit in the Apuseni Mountains, Romania. Hydrothermal alteration and mineralization are related to the Middle Miocene emplacement of a subvolcanic body, the Fundoaia microdiorite. Zonation of the alteration associated with the porphyry copper deposit is recognized from the deep and central part of the porphyritic intrusion towards shallower and outer portions. Four alteration types have been distinguished: potassic, phyllic, advanced argillic, and propylitic. Potassic alteration affects mainly the Fundoaia subvolcanic body. The andesitic host rocks are altered only in the immediate contact zone with the Fundoaia intrusion. Mg-biotite and K-feldspar are the main alteration minerals of the potassic assemblage, accompanied by ubiquitous quartz; chlorite, and anhydrite are also present. Magnetite, pyrite, chalcopyrite and minor bornite, are associated with this alteration. Phyllic alteration has overprinted the margin of the potassic zone, and formed peripheral to it. It is characterized by the replacement of almost all early minerals by abundant quartz, phengite, illite, variable amounts of illite-smectite mixed-layer minerals, minor smectite, and kaolinite. Pyrite is abundant and represents the main sulfide in this alteration zone. Advanced argillic alteration affects the upper part of the volcanic structure. The mineral assemblage comprises alunite, kaolinite, dickite, pyrophyllite, diaspore, aluminium-phosphate-sulphate minerals (woodhouseite-svanbergite series), zunyite, minamyite, pyrite, and enargite (luzonite). Alunite forms well-developed crystals. Veins with enargite (luzonite) and pyrite in a gangue of quartz, pyrophyllite and diaspore, are present within and around the subvolcanic intrusion. This alteration type is partially controlled by fractures. A zonal distribution of alteration minerals is observed from the centre of fractures outwards with: (1) vuggy quartz; (2) quartz + alunite; (3) quartz + kaolinite ± alunite and, in the deeper part of the argillic zone, quartz + pyrophyllite + diaspore; (4) illite + illite-smectite mixed-layer minerals ± kaolinite ± alunite, and e) chlorite + albite + epidote. Propylitic alteration is present distal to all other alteration types and consists of chlorite, epidote, albite, and carbonates. Mineral parageneses, mineral stability fields, and alteration mineral geothermometers indicate that the different alteration assemblages are the result of changes in both fluid composition and temperature of the system. The alteration minerals reflect cooling of the hydrothermal system from >400 °C (biotite), to 300–200 °C (chlorite and illite in veinlets) and to lower temperatures of kaolinite, illite-smectite mixed layers, and smectite crystallization. Hydrothermal alteration started with an extensive potassic zone in the central part of the system that passed laterally to the propylitic zone. It was followed by phyllic overprint of the early-altered rocks. Nearly barren advanced argillic alteration subsequently superimposed the upper levels of the porphyry copper alteration zones. The close spatial association between porphyry mineralization and advanced argillic alteration suggests that they are genetically part of the same magmatic-hydrothermal system that includes a porphyry intrusion at depth and an epithermal environment of the advanced argillic type near the surface.Editorial handling: B. Lehmann     

Formation of the Vysoká–Zlatno Cu–Au skarn–porphyry deposit, Slovakia

The central zone of the Miocene Štiavnica stratovolcano hosts several occurrences of Cu–Au skarn–porphyry mineralisation, related to granodiorite/quartz–diorite porphyry dyke clusters and stocks. Vysoká–Zlatno is the largest deposit (13.4 Mt at 0.52% Cu), with mineralised Mg–Ca exo- and endoskarns, developed at the prevolcanic basement level. The alteration pattern includes an internal K- and Na–Ca silicate zone, surrounded by phyllic and argillic zones, laterally grading into a propylitic zone. Fluid inclusions in quartz veinlets in the internal zone contain mostly saline brines with 31–70 wt.% NaCl eq. and temperatures of liquid–vapour homogenization (Th) of 186–575°C, indicating fluid heterogenisation. Garnet contains inclusions of variable salinity with 1–31 wt.% NaCl eq. and Th of 320–360°C. Quartz–chalcopyrite veinlets host mostly low-salinity fluid inclusions with 0–3 wt.% NaCl eq. and Th of 323–364°C. Data from sphalerite from the margin of the system indicate mixing with dilute and cooler fluids. The isotopic composition of fluids in equilibrium with K-alteration and most skarn minerals (both prograde and retrograde) indicates predominantly a magmatic origin (δ¹⁸O_fluid 2.5–12.3‰) with a minor meteoric component. Corresponding low δD_fluid values are probably related to isotopic fractionation during exsolution of the fluid from crystallising magma in an open system. The data suggest the general pattern of a distant source of magmatic fluids that ascended above a zone of hydraulic fracturing below the temperature of ductile–brittle transition. The magma chamber at ∼5–6 km depth exsolved single-phase fluids, whose properties were controlled by changing PT conditions along their fluid paths. During early stages, ascending fluids display liquid–vapour immiscibility, followed by physical separation of both phases. Low-salinity liquid associated with ore veinlets probably represents a single-phase magmatic fluid/magmatic vapour which contracted into liquid upon its ascent.     

The Daduhe gold field at the eastern margin of the Tibetan Plateau: He, Ar, S, O, and H isotopic data and their metallogenic implications

The Daduhe gold field comprises several shear-zone-controlled Tertiary lode gold deposits distributed at the eastern margin of the Tibetan Plateau. The deposits are hosted in a Precambrian granite–greenstone terrane within the Yangtze Craton. The gold mineralization occurs mainly as auriferous quartz veins with minor sulphide minerals. Fluid inclusions in pyrite have ³He/⁴He ratios of 0.16 to 0.86 R_a, whereas their ⁴⁰Ar/³⁶Ar ratios range from 298 to 3288, indicating a mixing of fluids of mantle and crust origins. The δ³⁴S values of pyrite are of 0.7–4.2‰ (n = 12), suggesting a mantle source or leaching from the mafic country rocks. δ¹⁸O values calculated from hydrothermal quartz are between − 1.5‰ and + 6.0‰ and δD values of the fluids in the fluid inclusions in quartz are − 39‰ and − 108‰. These ranges demonstrate a mixing of magmatic/metamorphic and meteoric fluids. The noble gas isotopic data, along with the stable isotopic data suggest that the ore-forming fluids have a dominantly crustal source with a significant mantle component.     

The behaviour of trace and rare earth elements (REE) during hydrothermal alteration in the Rangan area (Central Iran)

The rhyolitic dome in the Rangan area has been subjected to hydrothermal alterations by two different systems, (1) A fossil magmatic–hydrothermal system with a powerful thermal engine of a deep monzodioritic magma, (2) An active hydrothermal system dominated by meteoric water. Based on mineralogical and geochemical studies, three different alteration facies have been identified (phyllic, advanced argillic and silicic) with notable differences in REE and other trace elements behaviour. In the phyllic alteration zone with assemblage minerals such as sericite, pyrite, quartz, kaolinite, LREE are relatively depleted whereas HREE are enriched. The advanced argillic zone is identified by the presence of alunite–jarosite and pyrophyllite as well as immobility of LREE and depletion in HREE. In the silicic zone, most of LREE are depleted but HREE patterns are unchanged compared to their fresh rock equivalents. All the REE fractionation ratios (La/Yb)_cn, (La/Sm)_cn, (Tb/Yb)_cn, (Ce/Ce¹)_cn and (Eu/Eu¹)_cn are low in the phyllic altered facies. (Eu/Eu¹)_cn in both advanced and silicic facies is low too. In all alteration zones, high field strength elements (HFSE) (e.g. Ti, Zr, Nb) are depleted whereas transition elements (e.g. V, Cr, Co, Ni, Fe) are enriched. Geochemically speaking, trace and rare earth elements behave highly selective in different facies.     

Sulfur isotopic compositions of the Huize super-large Pb–Zn deposit, Yunnan Province, China: Implications for the source of sulfur in the ore-forming fluids

The Huize Pb–Zn deposit of Yunnan Province, China, is located in the center of the Sichuan–Yunnan–Guizhou Pb–Zn–Ag district. Four primary orebodies (orebody No. 1, No. 6, No. 8 and No. 10), with Pb + Zn reserves from 0.5 Mt to 1 Mt, have been found at depth in this deposit. This paper provides new data on the sulfur isotopic compositions of the four orebodies. The data show that the principal sulfide minerals (galena, sphalerite and pyrite) in the four orebodies are enriched in heavy sulfur, the δ³⁴S values between 10.9‰ and 17.7‰ and where δ³⁴S_pyrite > δ³⁴S_sphalerite > δ³⁴S_galena. The δ³⁴S values of sulfide are close to that of the sulfates from the carbonate strata within the region. The similarity in sulfur isotope composition between sulfides and sulfates indicates the sulfur in the ore-forming fluids was likely derived by thermochemical sulfate reduction of sulfates contained within carbonate units.     

Nature of fluids and regional implications for Lesser Himalayan carbonates and associated mineralization

Fluid inclusion data are presented for the successive stages of limestone, dolomite, magnesite and sulphide-bearing quartz veins in Proterozoic carbonate rocks of the Lesser Himalaya. Subsurface fluids were H₂O–NaCl–KCl ± MgCl₂ ± CaCl₂ and showed successive increase in salinity and temperature. The salinity of the pore fluid during limestone diagenesis was in the range of 7.5–15 eq wt.% NaCl and the magnesite-forming fluids had a salinity of about 9 to 19 eq wt.% NaCl. This progressive rise in salinity is attributed to a more saline fluid in the deeper zones. The inverse relation between homogenization temperatures and final melting temperatures suggests mixing of the fluids during diagenesis, and highly depleted δ¹⁸O values rule out participation of magmatic fluid in the mixing. A late stage carbonic fluid is linked with talc formation. The low temperature of sulphide-forming epigenetic solutions, as obtained from fluid inclusions, is also substantiated by the chemical data from these sulphides. δ³⁴S values in galena infer that magmatic sulphur was probably not involved, and the sulphur of the galena is derived from an isotopically heavy source.     

Geologic model of the magmatichydrothermal system of vulcano (Aeolian Islands, Italy)

Summary This paper presents a model of the active magmatic-hydrothermal (high-sulfidation) system of La Fossa volcano, based on mineralogical and geochemical studies of hydrothermal alteration on the surface and in the subsoil (geothermal wells and lithic clasts from explosive eruptions).The main engine of this system is represented by the shallow magmatic feeding system of La Fossa, which produces substantial degassing of volatiles (H₂O, S, Cl). The introduction of magmatic fluids into the conduit system causes high temperature recrystallisation and metasomatism of the volcanic and sub-volcanic rocks. Lateraly to the volcanic conduits, the magmatic fluids undergo a primary neutralization, forming neutral low permeability hydrothermal zones. During their rise to the surface, the magmatic vapours may condense in groundwater, forming acid solutions that react with rocks to form superficial hydrothermal alteration. Silicic, advanced argillic and intermediate argillic alteration facies develop. This reflects the progressive neutralisation of extremely acid fluids. High contents of trace elements, like TI and Bi, supporting evidence for magmatic fluid transport, were found close to the high temperature fumaroles (up to 500°Q in the silicic alteration zone of La Fossa.

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Ein geologisches Modell des magmatisch-hydrothermalen Systems von Vulcano, Aeolische Inseln, Italien

Zusammenfassung Diese Arbeit stellt ein Modell für das aktive magmatisch-hydrothermale (highsulfidation) System des La Fossa Vulkans vor. Dieses beruht auf mineralogischen und geochemischen Studien der hydrothermalen Umwandlung an der Oberfläche und im Untergrund (geothermale Bohrungen und lithische Klasten von explosiven Eruptionen). Als Energiequelle fungiert das seichte magmatische Zufuhrsystem von La Fossa, das signifikante Entgasung volatiler Phasen (H₂O, S, HCl) mit sich bringt. Das Eindringen magmatischer Fluide in die Zufuhrkanäle verursacht Rekristallisation und Metasomatose der vulkanischen und subvulkanischen Gesteine bei hohen Temperaturen. In lateralen Bereichen der vulkanischen Zufuhrkanäle erfahren die magmatischen Fluide eine primäre Neutralisation, wobei neutrale hydrothermale Zonen niedriger Permeabilität entstehen. Während des Aufstiegs an die Oberfläche können die magmatischen Fluide im Grundwasser kondensiert werden, wobei sie saure Lösungen bilden, die wiederum mit den Gesteinen reagieren und zu Hydrothermalalteration führen. Dabei entstehen silizische, fortgeschrittene argillische und intermediäre agillische Umwandlungsfazies. Dies entspricht der zunehmenden Neutralisation extrem saurer Fluide. Hohe Gehalte an Spurenelementen, wie TI und Bi können als zusätzliche Hinweise für magmatischen Fluidtransport gesehen werden, sie treten in der Nähe der HochTemperatur-Fumarolen (bis 500'C) in der silizischen Alterationszone von La Fossa auf.

     

The physical and chemical evolution of low-salinity magmatic fluids at the porphyry to epithermal transition: a thermodynamic study

Fluid-phase relationships and thermodynamic reaction modelling based on published mineral solubility data are used to re-assess the Cu–Au-mineralising fluid processes related to calc-alkaline magmatism. Fluid inclusion microanalyses of porphyry ore samples have shown that vapour-like fluids of low to intermediate salinity and density (~2–10 wt% NaCl eq.; ~0.1–0.3 g cm^–3) can carry percentage-level concentrations of copper and several ppm gold at high temperature and pressure. In epithermal deposits, aqueous fluids of similar low to intermediate salinity but liquid-like density are ubiquitous and commonly show a magmatic isotope signature. This paper explores the physical evolution of low-salinity to medium-salinity magmatic fluids of variable density, en route from their magmatic source through the porphyry regime to the near-surface epithermal environment, and investigates the chemical conditions required for effective transport of gold and other components from the magmatic to the epithermal domain. Multicomponent reaction modelling guided by observations of alteration zonation and vein overprinting relationships predicts that epithermal gold deposits are formed most efficiently by a specific succession of processes during the evolution of a gradually cooling magmatic–hydrothermal system. (1) The low-salinity to medium-salinity fluid, after separating from the magma and possibly condensing out some hypersaline liquid in the high-temperature porphyry environment, must physically separate from the denser and more viscous liquid, and then cool within the single-phase fluid stability field. By cooling under adequate confining pressure, such a vapour will evolve above the critical curve and contract, without any heterogeneous phase change, to an aqueous liquid of the same salinity. (2) High concentrations of gold, transported as stable Au bisulphide complexes supporting >1 ppm Au even at 200°C, can be maintained throughout cooling, provided that the fluid initially carries an excess of H₂S over Cu+Fe on a molal scale. This condition is favoured by an initially high sulphide content in a particularly low-salinity magmatic fluid, or by preferential partitioning of sulphur into a low-salinity vapour and partial removal of Fe into a hypersaline liquid at high temperature. (3) Acid neutralisation further optimises gold transport by maximising the concentration of the HS^– ligand. This may occur by feldspar destructive alteration along pyrite±chalcopyrite±sulphate veins, in the transition zone between the porphyry and epithermal environments. An alternative acid/base control is the dissolution of calcite in sediments, which may enable long-distance gold transport to Carlin-type deposits, because of the positive feedback between acid neutralisation and permeability generation. The three physical and chemical transport requirements for high-grade epithermal gold mineralisation are suggested to be the common link of epithermal gold deposits to underlying magmatic–hydrothermal systems, including porphyry-Cu–Au deposits. Both mineralisation types are the result of gradual retraction of isotherms around cooling hydrous plutons in similar tectonic and hydrologic environments. As magmatic fluid is generated at increasing depths below the surface the importance of vapour contraction increases, leading to the typical overprinting of potassic, phyllic and advanced argillic alteration and their related ore styles.Editorial handling: B. Lehmann     

The Shanggong gold deposit, Eastern Qinling Orogen, China: Isotope geochemistry and implications for ore genesis

The Shanggong Au deposit in the Xiong’er Terrane, East Qinling, China, has resources of about 30 ton Au, making it one of the largest orogenic-mesothermal Au deposits hosted in volcanic rocks of the Mesoproterozoic Xiong’er Group. Three stages of hydrothermal activity are recognized (early, middle and late), of which two (early and middle) were ore producing and characterized by quartz–pyrite and polymetallic sulfides, respectively. The third and late stage is represented by a carbonate–quartz assemblage. Hydrogen, oxygen and carbon isotope systematics of the Shanggong deposit from a previous work suggest that the early stage fluids were derived from magmatic and/or metamorphic devolatilization of sedimentary rocks at depth. This is supported by new C, S and published Sr and Pb isotopic data, presented in this paper. These new data, δ¹³C values ranging from 1.5 ‰ for early stage ankerite to −2.2 ‰ for late stage ankerite, negative δ³⁴S values for sulfides from the middle stage (–19.2 to –6.3 ‰), suggest a contribution from organic matter and that the ore fluid evolved from deeply sourced to shallowly sourced, with those of the middle stage representing a mixture of these two fluid systems. The comparison of the hydrogen–oxygen–carbon–sulfur–lead–strontium isotope systematics between the Shanggong deposit and the main lithologies in the Xiong’er Terrane, shows that neither these nor the underlying lower crust and mantle, or combinations thereof, could be considered as the source of ore fluids for the Shanggong Au deposit. A likely source was a carbonaceous carbonate, sandstone, shale, chert sequence in the underthrusted Guandaokou and Luanchuan Groups, exposed south of the Xiong’er Terrane.Ar–Ar and Rb–Sr isochron ages for mineral phases of the early, middle and late stages, together with geological field data, constrain the timing of the hydrothermal activity and Au metallogenesis at 242 ± 10, 167 ± 7 and 112 ± 7 Ma, respectively. This metallogenesis and associated granitic magmatism, can be related to the continental collision between the Yangtze and North China Cratons that resulted in the formation of the Qinling Orogen, led to the different hydrothermal systems that were responsible for the three stages that formed the Shanggong Au deposit, over a period of about 130 Myrs.     

Geochronological and geochemical study of mafic dykes from the northwest Chinese Altai: Implications for petrogenesis and tectonic evolution

Fifteen zircons separated from a mafic dyke in the Chinese Altai give a concordant age population with a weighted mean ²⁰⁶Pb/²³⁸U age of 375.5 ± 4.8 Ma, suggesting a Devonian emplacement. On the basis of their mineralogical compositions and textures, the coeval dykes can be divided into gabbroic and doleritic types. They are both sub-alkaline, tholeiitic, characterized by similarly low SiO₂ contents (45.2–52.7 wt.%) and total alkaline (K₂O + Na₂O = 0.99–4.93 wt.%). Rare earth element patterns of the gabbroic dykes are similar to N-MORB (La/Yb_N = 0.86–1.1), together with their high ε_Nd(t) values (+ 7.6 to + 8.1), indicating that their precursor magma was mainly derived from a N-MORB-type depleted asthenospheric mantle. While the REE patterns of the doleritic dykes resemble that of E-MORB (La/Yb_N = 1.12–2.28), enriched in LILEs and strongly depleted in HFSEs, with relative low ε_Nd(t) values (+ 3.4 to + 5.4) and high initial ⁸⁷Sr/⁸⁶Sr ratios (0.7057–0.7060). The zircon Hf isotopic analysis of the doleritic dykes give ε_Hf(t) values from + 10.7 to + 13.8. These signatures suggest that a depleted mantle wedge metasomatized by slab-derived fluids and/or melts was possibly involved in the generation of the doleritic magma. The refractory peridotite may have been melted with variable degrees caused by upwelling of the hot asthenosphere. The petrogenesis of the mafic dykes suggest a high heat flux as a result of upwelling of the hot asthenosphere and the contrast geochemical signatures can be interpreted by a ridge subduction, which could be an important tectonic control in the accretionary process of the Chinese Altai.