Hypersaline Liquid Research Articles

Phase separation and fluid mixing revealed by trace element signatures in pyrite from porphyry systems

Porphyry deposits host various trace elements in economic amounts, but the hydrothermal processes causing their fractionation and enrichment are still not fully understood, but vital to target the most prospective mineralisation. We present the first micro-analytical study on the trace element composition of pyrite from the Koloula Cu-Au porphyry in the young and thin (<25 km) Solomon Islands arc. A statistical evaluation of the trace element data of pyrite indicates that mineral inclusions obscure the chemical signature of the mineralisation processes. The filtered pyrite data, from which the inclusions were excluded, correlate with variations in temperature and salinity, as defined by fluid inclusions from several alteration zones. Trace element ratios in pyrite show systematic variations with fluid temperature and salinity (Co/Ni, Se/Te), phase separation (Co/Ni, Co/As) and mixing of magmatic fluids and meteoric waters (Se/Ge). The mineralisation in the potassic alteration zone was controlled by the formation of a hypersaline liquid (Co/As > 1, Co/Ni > 50) from a magma-derived fluid (Se/Ge ~ 100) at lithostatic pressure conditions and temperatures of up to 700 °C (Se/Te > 50). This was followed by a transition to hydrostatic pressure conditions due to open-fracture continuity towards the paleo-surface, marking the onset of boiling in the chlorite-sericite to sericitic alteration zone (Co/As < 1), where minor proportions of meteoric water were involved (Se/Ge < 100). The shallowest part of the mineralisation is controlled by lower temperature (<300 °C, Se/Te < 50) vapour-rich fluids (Co/As < 1) that condensed into meteoric waters in an epithermal transition zone (Co/Ni < 50, Se/Ge < 100). Trace element systematics in pyrite from progressive alteration zones therefore preserve the time-space evolution of porphyry (-epithermal) systems in young and thin oceanic island arcs.

Temporal and spatial separation mechanisms of the Cu and Mo mineralization in the Dabate porphyry deposit, Western Tianshan, Xinjiang, China

Dabate deposit is a typical porphyry Cu-Mo deposit in the Western Tianshan, Xinjiang, China. Both the Cu and Mo mineralization are mainly associated with intrusion of rhyolite porphyry. Distinguishing from typical porphyry deposits, the Cu mineralization and Mo mineralization are separated from each other on both the temporal and spatial scales. The Cu orebodies are mainly hosted in the contact zone between the rhyolite porphyry and Tuosiku’ertawu Formation and predominantly occur as fluorite-arsenopyrite-Cu-sulfides ± K-feldspar ± quartz veins (Cu-1 stage), whereas the Mo orebodies are mostly hosted in the inner part of the rhyolite porphyry and are typically presented as Mo-2 stage quartz-molybdenite veins (external Cu and internal Mo). Total homogenization temperatures (Th, L-V) for boiling fluid inclusion assemblage of the Mo-2 stage occurred at 302 to 358 °C, with corresponding salinities of 1.4 to 38.1 wt% NaCleqv. H-O isotope data indicate that the Mo mineralization fluids were mainly derived from magmatic water. The non-boiling fluids of the Cu-1 stage originated from magmatic fluids and meteoric water, which were characterized by high temperature (323 to 379 °C) and low salinity (2.6 to 5.9 wt% NaCleqv) as well as Cu, As, and volatile enrichment. These features are different from the initial magmatic fluids of this deposit, indicating that the Cu mineralization may occur before the Mo mineralization (early Cu and late Mo) and the magmatic fluid components of the Cu-1 stage should be derived from the condensation of the low-salinity vapor generated by boiling of the hydrothermal fluids (351 to 405 °C; 1.8 to 40.1 wt% NaCleqv) for the earliest Mo-1 stage barren quartz veins. The positive δ34S values (5.5 to 9.8‰) of sulfides indicate that the sulfur in the ore-forming fluids was derived from magma and country rocks. The subtle change in fluid conditions from the high temperature (peak range 340 to 360 °C), alkaline, and slightly more oxidized of the Cu-1 stage to high temperature (peak range = 320 to 340 °C), more reduced, and acidic of the Mo-2 stage gave rise to the temporal separation of Cu and Mo mineralization. The Cu, As, and volatiles (e.g., CO2, HF), preferentially partitioned into the vapor phase, were highly enriched in Cu ore-forming fluids, whereas Mo mineralization fluids contained the majority of Mo with strong preference for the brine phase. Therefore, the spatial separation of the Cu and Mo mineralization could be attributed to selectively fractionating between the vapor phase and hypersaline liquid of the Cu and Mo metals during the process of fluid boiling.

Formation and evolution of the calcic-magnesian Saheb Fe (Cu) skarn deposit from the Sanandaj-Sirjan Belt, NW Iran: Evidence for multistage boiling in episodes of magnetite saturation

The Saheb Fe (Cu) skarn deposit is located along the northwestern end of the Sanandaj-Sirjan Zone. This deposit occurs over an approximately 2 km distance along the contact zone between the Upper Cretaceous causative granite and the Upper Permian calcareous host rock, with several iron orebodies occurring as high-grade lenticular massive magnetite bodies (with a length of up to 90 m and a width of 25 m).Following the formation of pyroxene hornfels facies, four main stages of skarn formation have been recognized: (I) early prograde stage (type I garnet + clinopyroxene + olivine): fluid inclusions in the type I garnet yielded a high temperature and salinity (average of 506 °C and 57 wt% NaCl equiv.), which may represent the composition of initial magmatic fluids. Higher salinities at this early stage can be associated with orthomagmatic differential fluid exsolution. (II) late prograde stage (type II and III garnets ± clinopyroxene ± disseminated magnetite): the coexistence of vapour-rich and halite-bearing fluid inclusions in type II garnet and their similar homogenization temperatures (420°–480 °C) presumably signify that fluid immiscibility from a supercritical fluid occurred at lithostatic pressures of 300 to 500 bar, corresponding to a depth of 1.5–2.0 km. (III) early retrograde stage (massive magnetite + pyrite + chalcopyrite + epidote + quartz + type I calcite + amphibole + serpentine + talc): hypersaline liquid and low-salinity vapour phases trapped within the epidote, quartz, and type I calcite are coexisting, indicating phase separation of hydrothermal fluids at temperatures of 300°–400 °C and pressures ranging from 310 to >100 bar under hydrostatic conditions, equivalent to a depth of 1.5 to 2.0 km. Hypersaline inclusions in the quartz and type I calcite show Td(NaCl) > Th(L-V), deduced to have been trapped by the over-saturated fluids or under over-pressured conditions before the hydrofracturing (up to 2200 bars). (IV) Late retrograde stage (type II calcite ± quartz ± chlorite), which is characterized by moderate temperature and salinity and non-boiling fluid inclusion assemblage (with average of 172 °C and 17 wt% NaCl equiv.).The first boiling event is documented in the type II garnet of the late prograde stage and provoked the ore-bearing fluids to precipitate the disseminated iron ore. The main deposition of magnetite has plausibly been triggered by the second episode of fluid boiling, recorded in epidote, quartz, and type I calcite during the early retrograde stage. Two boiling events mean producing more fractured and brecciated zones, which can act as conduits for the iron-bearing hydrothermal fluids. This seems to be why there are dozens of isolated magnetite orebodies in the Saheb skarn deposit, which extend over an area of greater than two kilometers (in an E-W direction). Comparably higher salinities even in the type II calcite of the late retrograde stage (25 wt% NaCl equiv.) may reveal that significant mixing of saline magmatic fluids with external, dilute, and cold fluids is almost implausible, despite the presence of brecciated zones. Boiling, therefore, can be pondered as the most salient factor in controlling the ore precipitation at the Saheb Fe (Cu) skarn deposit. However, mixing with meteoric fluids and shifting in pH values could also facilitate the alteration and mineralization.

Evolution of the Magmatic-Hydrothermal System at the Santa Rita Porphyry Cu Deposit, New Mexico, USA: Importance of Intermediate-Density Fluids in Ore Formation

Abstract The Santa Rita porphyry Cu deposit in New Mexico, USA, is characterized by a stockwork of three vein types that differ in morphology, mineralogy, and associated alteration assemblages. Early quartz veins associated with potassic alteration are composed of recrystallized granular quartz grains that host ubiquitous hypersaline liquid and vapor-rich fluid inclusions. The early quartz likely formed at high (≳500°C) temperatures and lithostatic pressures. Hypogene Cu mineralization at Santa Rita is in sulfide veins that reopened or crosscut the early quartz veins. The sulfide veins are surrounded by alteration halos containing chlorite and K-feldspar. Rare quartz crystals are present in some of these chalcopyrite and pyrite veins. The cores of the quartz crystals contain hypersaline liquid and vapor-rich fluid inclusions, whereas the rims mostly contain hypersaline liquid inclusions. The quartz crystals are interpreted to have formed close to the ductile-brittle transition as a result of the pressure drop from lithostatic to hydrostatic conditions. Formation of the quartz crystals was postdated by the deposition of Cu sulfides. Grain boundaries between the quartz and the sulfide minerals are irregular in shape, with sulfide crosscutting growth zones in the quartz. The Cu sulfides are interpreted to have formed from intermediate-density fluids that form secondary fluid inclusion assemblages in all earlier-formed quartz types. Microthermometric investigations showed that these fluid inclusion assemblages homogenize at ~385° to 435°C by critical or near-critical behavior and have salinities of &amp;lt;10 wt % NaCl equiv. The precipitation of Cu sulfides occurred as a result of cooling of these fluids following their escape from the lithostatic into the hydrostatic realm. Retrograde quartz solubility caused the corrosion of earlier-formed quartz during Cu sulfide deposition. The youngest veins at Santa Rita are composed of quartz and pyrite. These veins are associated with intense sericite alteration that overprinted all earlier alteration assemblages. The late quartz hosts primary and secondary liquid-rich fluid inclusions, but no intermediate-density fluid inclusions were identified. This quartz vein type formed at temperatures &amp;lt;360°C and hydrostatic pressures. The paragenetic relationships show that hypogene Cu mineralization at Santa Rita postdated potassic alteration of the host rocks. The Cu mineralization was formed by cooling intermediate-density fluids with critical or near-critical densities as they escaped from lithostatic to hydrostatic conditions.

Understanding the evolution of magmatic-hydrothermal systems based on microtextural relationships, fluid inclusion petrography, and quartz solubility constraints: insights into the formation of the Yulong Cu-Mo porphyry deposit, eastern Tibetan Plateau, China

The evolution of the magmatic-hydrothermal system that formed the Eocene Yulong Cu-Mo porphyry deposit of the eastern Tibetan Plateau, China, is reconstructed based on the study of the sequence of stockwork vein sets showing systematic crosscutting relationships in hand specimen. Early A veins associated with potassic alteration of the porphyritic host are composed of vitreous quartz that is extensively recrystallized and has a dark blue cathodoluminescence. Fluid inclusions contained in the quartz have been affected by post-entrapment modification. Some of the A veins were reopened and contain ribbons of microscopic molybdenite flakes. Formation of the molybdenite was associated with recrystallization of the earlier formed quartz and concomitant with the development of a dark purple to brownish cathodoluminescence signature. Reopening of the early veins also resulted in the formation of AB veins containing euhedral quartz crystals that contain encapsulated molybdenite flakes and are intergrown with coarse laths of molybdenite. These euhedral quartz crystals showing a dark purple to brownish cathodoluminescence host vapor-rich, intermediate-density fluid inclusions as well as hypersaline liquid and vapor-rich fluid inclusions, indicating that fluid immiscibility at hydrostatic pressure conditions occurred during crystal growth. Later, C veins that crosscut and commonly reopen the earlier A and AB veins lack quartz as a gangue mineral and consist entirely of chalcopyrite and pyrite with minor molybdenite. Sulfide formation was accompanied by chlorite or sericite alteration of the wall rocks. Late D veins containing quartz and pyrite with associated sericitic alteration of the porphyritic wall rocks crosscut all earlier vein types. Only minor amounts of molybdenite and chalcopyrite are present. Euhedral quartz crystals in the D veins contain liquid-rich fluid inclusions that have not been affected by post-entrapment modification. The results of this study indicate that Mo and Cu mineralization at Yulong was introduced by single-phase, intermediate-density magmatic-hydrothermal fluids as the porphyry system was transitioning from ductile to brittle conditions. The bulk of the Mo endowment predated Cu mineralization and formed during the change from lithostatic to hydrostatic conditions and associated immiscibility of the magmatic-hydrothermal fluids. Chalcopyrite precipitation followed as the single-phase, intermediate-density magmatic-hydrothermal fluids was escaping into the hydrostatic-pressured regime. Cooling of the magmatic-hydrothermal fluids appears to have been the principal control on metal precipitation.

Fluid inclusion systematics in porphyry copper deposits: The super-giant Grasberg deposit, Indonesia, as a case study

Fluid inclusion data provide a unique insight into the behaviour of magmatic fluids as they expand from source to surface to form porphyry copper deposits. For example, saline, liquid phase inclusions in combination with vapor phase inclusions help to define the environment of mineralization in terms of large scale, two-phase fluid flow within a magmatic vapor plume. However, the pressure at which ore formation occurs within the plume is controversial because inclusion-based estimates are commonly much higher than those based on geological estimates. Uniquely, the Grasberg supergiant porphyry copper deposit occupies the breccia-filled diatreme underlying the crater of a maar volcano and preserved a lacustrine-volcaniclastic sequence that marks the paleo-surface to within a few hundred meters. Interpreting fluid inclusion data with respect to this paleo-surface shows that porphyry mineralization extended from a paleo-depth of about 500 m to over 1500 m depth, as defined by drilling.The Grasberg deposit has three distinct populations of fluid inclusions (low salinity, hypersaline liquid and multi-solid inclusions) that are strongly clustered with respect to salinity and trapping temperature. Similar clusters of co-existing liquid- and vapor-rich inclusions are also common to porphyry copper deposits worldwide. Applying the principles of energy and mass conservation, a simple model of isenthalpic phase separation by condensation may be derived to account for these data clusters and how they are related. Vapor- and liquid-rich hypersaline inclusions may be shown quantitatively to be the consequence of expansion of a continuum low salinity, low density magmatic vapor phase to a two-phase fluid where the liquid fraction is minor (<2 vol%) and is best considered to be an aerosol or fog. The clustering of the inclusion data is the product of the different ranges of pressures that fluids encountered from the initiation of individual stockwork fractures through to their resealing.The application of mass and energy conservation principles also shows that, even though metal partitioning to the liquid phase may be favored, the proportion of total metal fractionated to the small mass of liquid is low relative to that remaining in the vapor phase. Therefore, while partitioning of metals between liquid and vapor phases may be a contributing process for metal deposition in porphyry copper deposits, other vapor-phase processes are required to efficiently deposit these major metal resources.

Hydrothermal evolution and ore precipitation of the No. 2 porphyry Cu–Au deposit in the Xiongcun district, Tibet: Evidence from cathodoluminescence, fluid inclusions, and isotopes

The No. 2 porphyry Cu–Au deposit in the Xiongcun district forms part of the Gangdese porphyry copper belt of Tibet. This study clarifies the fluid evolution and ore precipitation mechanisms of the magmatic-hydrothermal system that formed the deposit by combining the results of fluid inclusion petrography, microthermometry, scanning electron microscope-cathodoluminescence imaging, and stable isotope analyses of multiple quartz-dominated veins. Four distinct sets of quartz-dominated veins and eight generations of quartz (Q1–Q8) within the veins were identified, namely from early to late, early barren quartz veins (V1) comprised of equigranular CL-bright Q1 quartz, quartz–pyrite–chalcopyrite ± magnetite veins (V2) containing early equigranular CL-bright Q1 quartz and later CL-gray or CL-dark Q2–3 (Q2 + Q3) quartz grains intergrown with Cu–Fe sulfides, quartz–molybdenite ± pyrite ± chalcopyrite veins (V3) comprised of quartz grains (Q4–Q6) characterized by subhedral comb-like textures with well-developed oscillatory growth zoning, and late quartz veins (V4) containing CL-gray Q7 quartz with euhedral growth zones and later CL-dark Q8 quartz. Fluid inclusions in these veins can be classified into six types: B40, B40H, B80, B15H, B15H+, and B15. The B40 and B40H inclusions; B80 inclusions; and B15, B15H, and B15H+ inclusions contain vapor bubbles occupying 30–60 vol%, >70 vol%, and 5–25 vol%, respectively; in addition, B15H, B15H+, and B40H inclusions contain transparent daughter minerals (halite, and in some cases, sylvite). Raman spectra showed that CO2 is only present in B40 and B80 inclusions. In the Q1 quartz in V1 and V2 veins, the dominant type of inclusions is B40, which have homogenization temperatures (Th) of 278 °C–389 °C (peaking at 310 °C–330 °C) and salinities of 2.0–12.8 wt% NaCl equiv. In Q2–3 quartz in V2 veins, all inclusion types were observed. These were trapped at temperatures of approximately 325 °C–340 °C and had salinities of 1.8–69.7 wt% NaCl equiv. In V3 veins, only B15H and B15 inclusions were observed, which had Th values of 171 °C–320 °C (peaking at 240 °C–260 °C) and 173 °C–317 °C (peaking at 210 °C–230 °C) and salinities of 28.7–33.9 wt% NaCl equiv and 5.6–23.1 wt% NaCl equiv, respectively. In V4 veins, only B15 inclusions were observed. Primary B15 inclusions in V4 veins yielded Th values of 166 °C–229 °C (peaking at 170 °C–200 °C) and salinities of 5.1–17.1 wt% NaCl equiv. The 3He/4He and 40Ar/36Ar ratios of the fluid inclusions exhibited the ranges of 0.08–0.84 Ra and 451.3–1567.8, respectively, and the δ18Ofluid and δDfluid values varied from −3.2‰ to 5.8‰ and −92.8‰ to −80.3‰, respectively. By integrating all results from the fluid inclusion, cathodoluminescence, and isotopic analyses, we conclude that the initial ore-forming fluids of the No. 2 deposit were low-salinity, CO2-rich single-phase fluids of magmatic origin. Subsequently, fluid immiscibility developed in the initial ore-forming fluids, generating hypersaline liquid and low-salinity vapor phases and leading to the separation of a CO2 phase plus chalcopyrite precipitation from the fluids. As meteoric water was injected into the hydrothermal system, the ore-forming fluids gradually evolved to become meteoric water-dominated, low temperature, low-salinity, and CO2-poor; in addition, fluid-cooling due to the meteoric water input resulted in molybdenite precipitation.

Membrane Processes for the Regeneration of Liquid Desiccant Solution for Air Conditioning

Regeneration of liquid desiccant solutions is critical for the liquid desiccant air conditioning (LDAC) process. In most LDAC systems, the weak desiccant solution is regenerated using the energy-intensive thermal evaporation method which suffers from desiccant carry-over. Recently, membrane processes have gained increasing interest as a promising method for liquid desiccant solution regeneration. This paper provides a comprehensive review on the applications of membrane processes for regeneration of liquid desiccant solutions. Fundamental knowledge, working principles, and the applications of four key membrane processes (e.g., reverse osmosis (RO), forward osmosis (FO), electrodialysis (ED), and membrane distillation (MD)) are discussed to shed light on their feasibility for liquid desiccant solution regeneration and the associated challenges. RO is effective at preventing desiccant carry-over; however, current RO membranes are not compatible with hypersaline liquid desiccant solutions. FO deploys a concentrated draw solution to overcome the high osmotic pressure of liquid desiccant solutions; hence, it is feasible for their regeneration despite the issues with internal/external concentration polarization and reverse salt flux. ED has proven its technical feasibility for liquid desiccant solution regeneration; nevertheless, more research into the process energy efficiency and the recycling of spent solution are recommended. Finally, as a thermally driven process, MD is capable of regenerating liquid desiccant solutions, but it is adversely affected by the polarization effects associated with the hypersalinity of the solutions. Extensive studies are required to realize the applications of membrane processes for the regeneration of liquid desiccant solutions used for LDAC systems.

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

AbstractThe 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 &lt;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 &lt;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.

Heterogeneous melt and hypersaline liquid inclusions in shallow porphyry type mineralization as markers of the magmatic-hydrothermal transition (Cerro de Pasco district, Peru)

Recently identified occurrences of porphyry-style mineralization evidence the link of the world's second largest known epithermal base metal Cerro de Pasco deposit (Peru) to a porphyry system emplaced at depth. They consist of (i) quartz-monzonite dykes and (ii) the south-western part of the large diatreme-dome complex adjacent to the main ore bodies of Cerro de Pasco, and (iii) stockwork of banded quartz-magnetite-chalcopyrite-(pyrite) porphyry-type veinlets crosscutting trachyte porphyritic intrusion cropping out at surface in the central part of the diatreme-dome complex. The latter porphyry-type mineralization observed at the same erosion level as the main epithermal base metal carbonate-replacement ore bodies is the subject of this work. Geological constraints indicate a shallow emplacement level (depth<1km, P<270bar), implying rather unusual low-pressure and high-temperature environment for the formation of porphyry-style mineralization.The banded porphyry-type veinlets record a multiphase history of formation with two successive high-temperature (>600°C) stages, followed by a lower-temperature (<350°C) stage. More than 90% of the quartz in veinlets precipitates during the first two high-temperature stages. Stage 1 is characterized by the entrapment in hydrothermal quartz of inclusions containing variable proportions of both silicate melt and metal-rich hypersaline (>90wt% NaCl eq.) liquid, hereafter referred to as heterogeneous silicate melt inclusions (HSMIs). The latter are rarely described in porphyry-type mineralization. We suggest that during stage 1, the inclusions result from heterogeneous entrapment of an evolved hydrous rhyolitic melt mixed with a hypersaline fluid phase at low pressure (270bar) and high temperature (>600°C). The stage 2 is marked by the entrapment of metal- and sulfur-rich hypersaline liquid inclusions, with salinity around 70wt% NaCl eq., originated from the adiabatic ascent of magmatic hypersaline fluids transferred from deeper parts of the system. The lower-temperature stage 3 is characterized by an important temperature drop from >600°C to <350°C as revealed by microthermometry of aqueous two-phase liquid-vapor (L-V) inclusions. Quartz textures revealed by SEM-CL imaging allow ascribing the sulfide precipitation to the low-temperature mineralization stage 3. In-situ SIMS 18O/16O isotope analyses of quartz across the veinlets are indicative of a magmatic signature of the fluids during the first two stages; while quartz from stage 3 has oxygen isotopic compositions suggestive of minor contribution of meteoric waters to a predominantly magmatic aqueous fluid (~10vol.% of meteoric input), which probably triggered Cu-Fe sulfide precipitation in the stockwork. High metal and sulfur contents of HSMIs and hypersaline liquid inclusions determined by LA-ICP-MS are interpreted to represent the fluid composition prior to the main sulfide precipitation event. The similar Pb-Zn ratio of the bulk ore extracted from the epithermal ore bodies at Cerro de Pasco and the HSMIs and hypersaline liquid inclusions suggest a common source of the fluids associated with the different mineralization styles at Cerro de Pasco.

Magmatic salt melt and vapor: Extreme fluids forming porphyry gold deposits in shallow subvolcanic settings

Research Article| June 01, 2014 Magmatic salt melt and vapor: Extreme fluids forming porphyry gold deposits in shallow subvolcanic settings Peter Koděra; Peter Koděra 1Department of Geology of Mineral Deposits, Faculty of Natural Sciences, Comenius University, Mlynská dolina, 842 15 Bratislava, Slovakia Search for other works by this author on: GSW Google Scholar Christoph A. Heinrich; Christoph A. Heinrich 2Department of Earth Sciences, ETH Zürich, 8092 Zürich, Switzerland Search for other works by this author on: GSW Google Scholar Markus Wälle; Markus Wälle 2Department of Earth Sciences, ETH Zürich, 8092 Zürich, Switzerland Search for other works by this author on: GSW Google Scholar Jaroslav Lexa Jaroslav Lexa 3Geological Institute, Slovak Academy of Sciences, Dúbravská cesta 9, 840 05 Bratislava, Slovakia Search for other works by this author on: GSW Google Scholar Author and Article Information Peter Koděra 1Department of Geology of Mineral Deposits, Faculty of Natural Sciences, Comenius University, Mlynská dolina, 842 15 Bratislava, Slovakia Christoph A. Heinrich 2Department of Earth Sciences, ETH Zürich, 8092 Zürich, Switzerland Markus Wälle 2Department of Earth Sciences, ETH Zürich, 8092 Zürich, Switzerland Jaroslav Lexa 3Geological Institute, Slovak Academy of Sciences, Dúbravská cesta 9, 840 05 Bratislava, Slovakia Publisher: Geological Society of America Received: 06 Nov 2013 Revision Received: 05 Mar 2014 Accepted: 12 Mar 2014 First Online: 09 Mar 2017 Online ISSN: 1943-2682 Print ISSN: 0091-7613 © 2014 Geological Society of America Geology (2014) 42 (6): 495–498. https://doi.org/10.1130/G35270.1 Article history Received: 06 Nov 2013 Revision Received: 05 Mar 2014 Accepted: 12 Mar 2014 First Online: 09 Mar 2017 Cite View This Citation Add to Citation Manager Share Icon Share Facebook Twitter LinkedIn MailTo Tools Icon Tools Get Permissions Search Site Citation Peter Koděra, Christoph A. Heinrich, Markus Wälle, Jaroslav Lexa; Magmatic salt melt and vapor: Extreme fluids forming porphyry gold deposits in shallow subvolcanic settings. Geology 2014;; 42 (6): 495–498. doi: https://doi.org/10.1130/G35270.1 Download citation file: Ris (Zotero) Refmanager EasyBib Bookends Mendeley Papers EndNote RefWorks BibTex toolbar search Search Dropdown Menu toolbar search search input Search input auto suggest filter your search All ContentBy SocietyGeology Search Advanced Search Abstract The recently discovered Biely Vrch deposit in the Western Carpathian magmatic arc is the most extreme example of a porphyry gold deposit, being practically free of copper, molybdenum or any other sulfide minerals. Microanalytical data on fluid inclusions in quartz veinlets, including a characteristic type of banded veinlets, show that this deposit formed from nearly anhydrous Fe-K-Na-Cl salt melts containing ∼10 ppm Au, coexisting with hydrous vapor of very low density. This exceptional fluid evolution required an Fe-rich dioritic source magma that was emplaced at shallow subvolcanic depth (<3.5 km), directly exsolving a hypersaline liquid and magmatic vapor at high temperature (∼850 °C). During ascent to the level of the porphyry intrusion (0.5–1 km), fluid expansion at high temperature but low pressure led to halite precipitation and further water loss to the vapor, generating an increasingly Fe-K-rich salt melt that transported high concentrations of Au but negligible Cu into the fractured porphyry stock. The low sulfur fugacity resulting from fluid expansion suppressed precipitation of sulfide, explaining the gold-only enrichment in this globally recurring but rare type of gold ore. You do not have access to this content, please speak to your institutional administrator if you feel you should have access.

Selective copper diffusion into quartz-hosted vapor inclusions: Evidence from other host minerals, driving forces, and consequences for Cu–Au ore formation

Recent experimental studies have raised concerns that Cu concentrations in quartz-hosted fluid inclusions from magmatic–hydrothermal ore deposits do not represent pristine concentrations in the trapped fluids, but are modified by post-entrapment diffusional exchange through the host quartz. New microanalyses of fluid inclusions hosted in topaz show significantly lower Cu concentrations in vapor inclusions, compared to otherwise identical inclusions hosted by coexisting quartz, whereas coeval brine (hypersaline liquid) inclusions are very similar independent of host mineral in one sample. Sulfur is present as a major component in all vapor inclusions, as in most porphyry-related vapor inclusions, and Cu never exceeds S, but commonly matches the S content at a molar ratio of Cu:S⩽2 in vapor inclusions hosted by quartz.Univalent ions with a radius smaller than ∼1Å are known to diffuse rapidly through the channels of the quartz structure, parallel to its crystallographic c axis. Since only Cu concentrations differ between topaz- and quartz-hosted inclusions, we hypothesize that Cu+ and H+ re-equilibrate by diffusional ion exchange through these channels, while all other element concentrations remain essentially unchanged. A thermodynamic model considering charge-balanced Cu+H+ exchange and diffusive H2 re-equilibration of an initially Cu-poor but S-rich vapor inclusion with a typical rock-buffered fluid environment outside the host crystal demonstrates a strong chemical driving force for Cu+ to migrate from the surrounding rock into the fluid inclusion during cooling of the system. The driving force for Cu diffusion, against the gradient in total Cu concentration, is the abundant H+ liberated inside the inclusion by dissociation of HCl and particularly by the precipitation of CuFeS2 by reaction with the initially trapped H2S and/or SO2. Gold is not only a much larger ion, but is subject to an opposing driving force, suggesting that high concentrations of this larger ion analyzed in vapor inclusions probably represent true gold concentrations in magmatic–hydrothermal vapor.These findings imply that brine–vapor separation in porphyry deposits does not cause selective Cu transfer to the vapor, but is more likely to destabilize Cu complexes and promote copper ore deposition during decompression and unmixing of the two fluid phases. By contrast, Au may be selectively transferred into the vapor phase, allowing its transport through the deeper porphyry copper deposits to form epithermal gold deposits closer to the earth’s surface.

Porphyry Copper Systems

Porphyry Copper Systems

Evolution of Magmatic Vapor to Gold-Rich Epithermal Liquid: The Porphyry to Epithermal Transition at Nevados de Famatina, Northwest Argentina

Fluid inclusions in the subeconomic porphyry Cu-Mo-Au system at Nevados de Famatina and closely associated high-sulfidation epithermal Cu-Au-(Ag-As-Sb-Te) veins at La Mejicana, northwest Argentina, were studied to reconstruct the evolution of hydrothermal fluids from their deep magmatic source to the shallow epithermal environment. Field geology, vein petrography, fluid inclusion microthermometry, and single-inclusion microanalysis by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) were combined to determine the evolution of pressure, temperature, and ore metal concentrations in the fluids. Cathodoluminescence imaging complements transmitted light petrography to constrain the successive stages of quartz formation and the entrapment sequence of the fluid inclusion populations. Aqueous liquid inclusions of ~5 wt percent NaCl equiv salinity trapped in quartz-sericite-pyrite (QSP) veins between 360° and 325°C contain unusually high concentrations of Cu (400–5,000 ppm), As (~200 ppm), Sb and Te (both up to 100 ppm), and Au (several ppm) along with other ore-forming elements. These veins are paragenetically transitional between subeconomic porphyry copper mineralization exposed in the valley floor, and high-sulfidation epithermal veins with high Au grades, which are preserved along a high ridge adjacent to the porphyry stock. Low-density vapor and hypersaline liquid (i.e., brine) inclusions were trapped in early-formed quartz of the porphyry stockwork veins, between 450° and >600°C. The brine contains lower Cu and Au concentrations than coexisting vapor inclusions and texturally even earlier inclusions of intermediate density that are trapped in phenocrysts and some stockwork veins; the latter may be equivalent to a parental fluid. The low- and intermediate-density fluids compositionally overlap in salinity with the aqueous liquids recorded by the later transitional quartz-sericite-pyrite veins. Fluid inclusions and geologic time relations indicate that the transitional quartz-sericite-pyrite veins were the channelways for metal-rich aqueous liquids that generated the high-sulfidation epithermal Cu-Au deposit. These mineralizing liquids are interpreted to have evolved by continuous density increase (“contraction”) from a low-salinity, S-rich magmatic fluid of low to intermediate density. This vaporlike fluid was produced by exsolution from a magma that existed at greater depth during the late stages of cooling of the magmatic-hydrothermal complex, and probably underwent minor brine separation prior to reaching the present level of exposure. Epithermal mineral precipitation occurred upon dilution of the low-salinity magmatic fluid with meteoric water, which entered the hydrothermal system as it was cooled and successively eroded during continued magmatic fluid ascent.

Experimental study of the behavior of copper and zinc in a boiling hydrothermal system

Vapor-liquid partitioning coefficients for Cu and Zn in aqueous fluid were determined under boiling conditions at 500–650 °C and 35–100 MPa in sulfur-bearing and sulfur-free systems. A synthetic fluid inclusion technique was used to sample the experimental system of coexisting vapor-rich and liquid-rich fluid inclusions; the Cu and Zn concentrations in individual fluid inclusions were then analyzed by synchrotron radiation X-ray fluorescence. The vapor-liquid distribution constant of Cu [K D m Cu(vapor) / m Cu(liquid) ], where = m denotes the molality of metal, is found to be strongly dependent on the sulfur content in the experimental solutions. In sulfur-bearing systems, Cu preferentially partitions into the vapor phase, whereas Zn preferentially fractionates into the hypersaline liquid. The K D values for Cu and Zn obtained in this study correspond well with those obtained from natural fluid inclusions in hydrothermal ore deposits. The results suggest that differential volatility of metals is an important factor affecting the enrichment of certain metals in different hydrothermal ore deposits.

Fluid unmixing/immiscibility as an ore-forming process in the giant REE–Nb–Fe deposit, Inner Mongolian, China: Evidence from fluid inclusions

The giant Bayan Obo REE–Nb–Fe deposit consists of replacement bodies hosted in dolomite marble made up of magnetite, REE fluorocarbonates, fluorite, aegirine, amphibole, calcite and barite. Two or three phase CO 2-rich, three phase hypersaline liquid–vapor–solid, and two phase liquid-rich inclusions have been recognized in mineralized fluorite and quartz samples. Microthermometry measurements indicate that the carbonic phase in CO 2-rich inclusions is nearly pure CO 2. Fluids involving in REE–Nb–Fe mineralization at Bayan Obo might be mainly of H 2O–CO 2–NaCl–(F–REE) system. Coexistences of brine inclusions and CO 2-rich inclusions with similar homogenization temperatures give evidence that immiscibility happened during REE mineralization. An unmixing of an original H 2O–CO 2–NaCl fluid probably derived from carbonatitic magma. The presence of REE-carbonates as an abundant solid in fluid inclusions shows that the original ore-forming fluids are very rich in REE, and therefore, have the potential to produce economic REE ores at Bayan Obo.

100th Anniversary Special Paper: Vapor Transport of Metals and the Formation of Magmatic-Hydrothermal Ore Deposits

In most published hydrothermal ore deposit models, the main agent of metal transport is an aqueous liquid. However, there is increasing evidence from volcanic vapors, geothermal systems (continental and submarine), vapor-rich fluid inclusions, and experimental studies that the vapor phase may be an important and even dominant ore fluid in some hydrothermal systems. This paper reviews the evidence for the transport of metals by vapor (which we define as an aqueous fluid of any composition with a density lower than its critical density), clarifies some of the thermodynamic controls that may make such transport possible, and suggests a model for the formation of porphyry and epithermal deposits that involves precipitation of the ores from vapor or a vapor-derived fluid. Analyses of vapor (generally >90% water) released from volcanic fumaroles at temperatures from 500° to over 900°C and near-atmospheric pressure typically yield concentrations of ore metals in the parts per billion to parts per million range. These vapors also commonly deposit appreciable quantities of ore minerals as sublimates. Much higher metal concentrations (from ppm to wt %) are observed in vapor inclusions trapped at pressures of 200 to 1,000 bars in deeper veins at lower temperatures (400°–650°C). Moreover, concentrations of some metals, notably Cu and Au, are commonly higher in vapor inclusions than they are in inclusions of coexisting hypersaline liquid (brine). Experiments designed to determine the concentration of Cu, Sn, Ag, and Au in HCl-bearing water vapor at variable although relatively low pressures (up to 180 bars) partly explain this difference. These experiments show that metal solubility is orders of magnitude higher than predicted by volatility data for water-free systems, and furthermore that it increases sharply with increasing water fugacity and correlates positively with the fugacity of HCl. Thermodynamic analysis shows that metal solubility is greatly enhanced by reaction of the metal with HCl and by hydration, which results in the formation of species such as MeCl m . n H2O. Nonetheless, the concentrations measured by these experiments are considerably lower than those measured in experiments involving aqueous liquids or determined for vapor fluid inclusions. A possible explanation for this and for the apparent preference of metals such as Cu and Au for the vapor over the coexisting brine in some natural settings is suggested by limited experimental studies of metal partitioning between vapor and brine. These studies show that, whereas Cu, Fe, and Zn all partition strongly into the liquid in chloride-bearing sulfur-free systems, Cu partitions preferentially into the vapor in the presence of significant concentrations of sulfur. We therefore infer that high concentrations of Cu and Au in vapor inclusions reflect the strong preference of sulfur for the vapor phase and the formation of sulfur-bearing metallic gas species. Phase stability relationships in the system NaCl-H2O indicate how vapor transport of metals may occur in nature, by showing a range of possible vapor evolution paths for the conditions of porphyry-epithermal systems. At the world-class Bingham Canyon porphyry Cu-Au deposit, evidence from fluid inclusions supports a model in which a single-phase fluid of intermediate to vapor-like density ascends from a magma chamber. On cooling and decompression, this fluid condenses a small fraction of brine by intersecting the two-phase surface on the vapor side of the critical curve, without significantly changing the composition of the expanding vapor. Vapor and brine reach Cu-Fe sulfide saturation as both phases cool below 425°C. Vapor, which is the dominant fluid in terms of the total mass of H2O, Cu, and probably even Cl, is interpreted to be the main agent of metal transport. The evolution of fluids leading to high-grade epithermal gold mineralization is initiated by an H2S-, SO2-, Au-, and variably Cu- and As-rich vapor, which separates from an FeCl2-rich brine in a subjacent porphyry environment. In the early stages of the hydrothermal system, vapor expands rapidly and on reaching the epithermal environment, condenses, producing hypogene advanced argillic alteration and residual vuggy quartz and, in some cases, coeval high-sulfidation precious metal mineralization (e.g., Pascua). More commonly, the introduction of precious metals occurs somewhat later, after the site of magmatic fluid exsolution has receded to greater depth. Because of the relatively high pressure, the vapor separating from brine at this stage cools along a pressure-temperature path above the critical curve of the system, causing it to contract to a liquid capable of transporting several parts per million Au to temperatures as low as 150°C.

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.

Copper deposition by fluid cooling in intrusion-centered systems: New insights from the Bingham porphyry ore deposit, Utah

Quartz veins in porphyry copper deposits record the physiochemical evolution of fluids in subvolcanic magmatic-hydrothermal systems. We have combined cathodoluminescence (CL) petrography with fluid-inclusion microthermometry to unravel the growth history of individual quartz veins and to link this history to copper ore formation at Bingham, Utah. Early barren quartz veins with K-feldspar + biotite (potassic) alteration selvages occur throughout the 2 km vertical exposure of quartz monzonite porphyry stock. At depths of 500 m to at least 1350 m below the orebody, fluid inclusions in these barren veins trapped a single-phase CO 2 -bearing fluid containing ∼2-12 wt% NaCl e q u i v . Within and to depths of 500 m below the orebody, early quartz veins contain abundant hypersaline liquid (38-50 wt% NaCl e q u i v ) and vapor-rich inclusions trapped together at temperatures of 560-350 °C and pressures of 550-140 bar, consistent with fluctuations between lithostatic and hydrostatic pressure at paleodepths of 1.4 to 2.1 km. CL petrography shows that bornite and chalcopyrite were deposited together with a later generation of quartz and K-feldspar in microscopic fractures and dissolution vugs in early barren quartz veins and wall rock. This late quartz contains hypersaline liquid (36-46 wt% NaCl e q u i v ) and vapor-rich inclusions trapped at 380-330 °C and at 160-120 bar hydrostatic pressure. We conclude that a single-phase magmatic-hydrothermal fluid underwent phase separation to hypersaline liquid (or brine) and vapor ∼500 m below the base of the orebody at a paleodepth of ∼2.5 km. Brine and vapor continued to ascend and formed multiple generations of barren quartz veins with potassic selvages. Thermal decline to temperatures below 400 °C was the main driving force for copper-iron sulfide deposition, given the lack of evidence of mixing of brines with low-salinity waters, the lack of correspondence of the ore zone with the initiation of phase separation, and no change in wall-rock alteration style.

Melt inclusions in veins: linking magmas and porphyry Cu deposits.

At a porphyry copper-gold deposit in Bajo de la Alumbrera, Argentina, silicate-melt inclusions coexist with hypersaline liquid- and vapor-rich inclusions in the earliest magmatic-hydrothermal quartz veins. Copper concentrations of the hypersaline liquid and vapor inclusions reached maxima of 10.0 weight % (wt %) and 4.5 wt %, respectively. These unusually copper-rich inclusions are considered to be the most primitive ore fluid found thus far. Their preservation with coexisting melt allows for the direct quantification of important oreforming processes, including determination of bulk partition coefficients of metals from magma into ore-forming magmatic volatile phases.