Coupled Dissolution Reprecipitation Reactions Research Articles

HRTEM Study of Desulfurization of Pt- and Pd-Rich Sulfides from New Caledonia Ophiolite

Oxygen-bearing platinum group minerals (O-bearing PGMs) are intergrown with base metal sulfides (BMS, e.g., pentlandite–[NiFe]9S8) within fractures in chromite grains from chromitite bodies on Ouen Island, New Caledonia. These PGMs are hosted in chlorite and serpentine, which formed during serpentinization of olivine and pyroxene. The O-bearing PGM grains are polygonal, show microfracturing (indicating volume loss), and contain Pt-Pd-rich sulfide remnants, suggesting pseudomorphic replacement of primary (magmatic) sulfides. They display chemical zonation, with Pt(-Pd-Ni-Fe) relict sulfide cores replaced by Pt-Fe-Ni oxidized alloy mantles and Pt-Cu-Fe(-Pd) alloy rims (tulameenite), indicating desulfurization. The core and mantle show a nanoporous structure, interpreted as the result of coupled dissolution–reprecipitation reactions between magmatic sulfides and low fO2–fS2 serpentinite-related fluids, probably formed during olivine transformation to serpentine + magnetite (early stages of serpentinization). This fluid infiltrated magmatic sulfides (PGE-rich and BMS), degrading them to secondary products and releasing S and metals that were accommodated in the mantle and rim of O-bearing PGMs. Upon olivine exhaustion, an increase in fO2 might have stabilized Pt-Fe-O compounds (likely Pt0/Pt-Fe + Fe oxyhydroxides) alongside Ni-Fe alloys. Our results show that post-magmatic desulfurization of primary sulfides produces complex nano-scale intergrowths, mainly driven by changes in the fluid’s physicochemical properties during serpentinization.

Implications for metallogenic evolution of the Balong gold deposit, East Kunlun metallogenic belt: Insights from in-situ trace elements and S isotopes of sulfides

The Balong gold deposit is one of numerous lode gold deposits in the East Kunlun metallogenic belt. Gold mineralization is hosted in Triassic granitoids, typified by auriferous quartz veins. Hydrothermal alteration includes sericite, quartz, sulfide, chlorite, and calcite. Pyrite, as the most abundant sulfide in the ore, is sometimes seen in the company of arsenopyrite. Three types of pyrite have been identified. The porous Py1 exhibits low Co and Ni contents, with an absence of gold. Subhedral Py2-1 shows higher Co (median 80 ppm) and Ni (median 10.5 ppm) contents and contains various Cu-Pb-Zn-Ag mineral inclusions. Py2-2 shows an increase in As (median 17, 073 ppm) and Au (median 3.79 ppm), exhibiting obvious distinctions between Py2-1 and Py2-2.Gold in the Balong deposit consists of both visible and invisible gold. Gold occurs within micro-fractures of pyrite and arsenopyrite, appearing as irregular inclusions or as infillings. Apart from visible gold grains, the majority of invisible gold hosted in Py2-2 occurs as solid solutions (Au+). Coupled dissolution-reprecipitation reactions of early pyrite are a key factor for visible gold precipitation and later invisible gold enrichment. Pyrite records a narrow range of δ34S values from −1.6 to 5.4 ‰, reflecting sulfur from a deep magmatic source. These findings indicate a connection between the ore-forming materials and the evolved magmatic-hydrothermal fluids.

Genesis of high-grade lode gold shoot dominated by ore fluid overprinting during a ductile-brittle shear event

Lode gold deposits hosted by ductile-brittle shear zones account for more than one-third of the world’s gold production. High-grade ore shoots from this type of deposit are the most critical exploration targets. The ore shoots can form through the post-depositional deformation of auriferous sulfides or overprinting of ore fluids accompanied by coupled dissolution-reprecipitation (CDR) reactions. However, the mechanism that dominates ore shoot genesis remains unknown, primarily due to the controversial single progressive or polyphase nature of ore-bearing shear zones. Here, we report on geological and geochemical analyses we conducted at the large Hetai goldfield, South China, to construct an accurate gold upgrading model for the formation of ore shoots. Stages 1−3 of mineralization at Hetai show features typical of ductile shearing, while Stage 4 is characterized by quartz-sulfide veinlets in brittle fractures. 40Ar/39Ar ages of ca. 184 Ma and 157 Ma for the mineralization of stages 1 and 4 overlap with the regionally dextral ductile-brittle shear that occurred during ca. 210−162 Ma. Thus, the gold event at Hetai should have been controlled by a single progressive ductile-brittle shear episode, rather than polyphase structural events. The auriferous fluids at Hetai precipitated minor invisible gold in pyrites (mean 0.173 ppm) produced during stages 1−4 through fluid-rock interaction. The systematic increase of elements Au, As, Sb, Bi, Ag, and Cu and δ34S values in ductile-deformed pyrites from stages 1−3 indicate that early invisible gold upgrading should be the result of the post-depositional remobilization of auriferous sulfides during the long-lived ductile-brittle transition. Cataclastic pyrites hosting invisible gold from Stage 4 have zoned and porous mantles with elevated invisible gold (mean 0.503 ppm) and Sb, Bi, Pb, Co, Ni, and Ti contents. These pyrites are further replaced by chalcopyrite and pyrrhotite with increasing invisible gold, Co, and Ni contents. In addition, numerous visible native gold grains in Stage 4 are included in sulfides formed by replacement and develop along the microfractures and grain boundaries of these sulfides. We suggest the late invisible and visible gold upgrading events in Stage 4 can be attributed to the auriferous fluid superposition and subsequent replacement of pyrite via CDR reactions in a brittle regime. Therefore, the gold upgrading process at Hetai is jointly caused by the early remobilization induced by ductile-brittle deformation and the late ore fluid superposition with accompanying CDR reactions within a brittle domain. As the ore fluid superposition and CDR reactions in Stage 4 produce a significant amount of visible gold, they exert a first-order control on the genesis of ore shoots at Hetai. The refined model may be widely applicable to lode gold deposits elsewhere and can be used to identify regions with promising exploration targets.

Experimental metasomatic alteration of titanite in a series of metamorphic fluids at 700 °C and 200 MPa

Seven experiments exploring the reaction of titanite with various hydrothermal solutions have been carried out at 700 °C and 200 MPa for a run duration of 16 days. In experiments involving fluids consisting of NaCl+H2O, KCl+H2O, CaCl2+H2O, 2M NaOH, or 2M KOH, no reaction of the titanite with the fluid was observed other than a slight dissolution of the titanite. Experiments involving NaF+H2O and Ca(OH)2+H2O resulted in visible alteration of the titanite in texture and composition, coupled with the formation of perovskite. In the NaF+H2O experiment, perovskite, enriched with rare earth elements (REE), formed as euhedral to subhedral crystals on the surface of the recrystallized titanite. In the Ca(OH)2+H2O experiment perovskite took in minor amounts of REE, and formed as a reaction rim partially replacing the titanite via a coupled dissolution-reprecipitation reaction. Wollastonite, along with minor calcite, and grossular garnet, formed as an outer rim on the perovskite. In the NaF+H2O experiment major and trace elements were leached from the titanite, whereas in the Ca(OH)2+H2O experiment no leaching of major or trace elements was observed. Nb/Ta, Th/U, and Y/Ho were investigated as potential indicators of hydrothermal processes. While the Nb/Ta ratio was altered in the experimentally metasomatised titanite, the degree of alteration was the same for both fluids. In contrast, only small changes in the Th/U and Y/Ho ratios between the altered and original titanite were seen for either experiment. The formation of perovskite at the expense of titanite in NaF+H2O or Ca(OH)2+H2O fluids demonstrates how titanite reacts with these fluids in simple, low silica activity systems under mid to upper crustal P-T conditions.

Experimental incorporation of U into xenotime at mid to lower crustal pressures and temperatures utilizing alkali-bearing fluids under reducing and oxidizing conditions

A natural gem quality, inclusion-free, U-poor xenotime has been metasomatically altered at 900 °C and 500–1000 MPa in a series of alkali-bearing fluids including 2 N KOH, 2 N NaOH, Na2Si2O5 + H2O, and NaF + H2O to which UO2 and SiO2 have been added. All experiments were buffered to CO2-CO-graphite with the exception of the NaF + H2O experiment at 900 °C and 500 MPa, which was buffered to magnetite-hematite. With the exception of the Na2Si2O5 + H2O experiment, the xenotime reacted with the fluid tried in all of the remaining experiments to varying degrees. The xenotime showed the greatest degree of reactivity in the two NaF + H2O experiments tried. This reactivity takes the form of a coupled dissolution-reprecipitation reaction, which involves enriching reacted areas of the xenotime in U + Si as well as remobilizing the HREE in these areas inherent to the original xenotime. One result was the formation of alternating bands of Y-rich and HREE- + U-rich bands in the NaF + H2O experiment when the system was oxidized, which are presumed to have formed due a combination of simple chemical zoning coupled with diffusion and coupled dissolution-reprecipitation in the altered areas of the xenotime. A total lack of fluid and mineral inclusions on the nano-scale, as well as no disturbances in the crystal lattice in the reacted areas of the xenotime under HRTEM imaging, indicated that total recrystallization of the reacted areas took place during the course of the NaF + H2O experiment. The results of these experiments has important implications for the metasomatic resetting of the xenotime geochromometer in the presence of alkali-bearing fluids, which would potentially allow metasomatised xenotime to time and record metasomatic events affecting the rock.

Release and re-enrichment of invisible gold in arsenian pyrite promoted by coupled dissolution-reprecipitation reactions

The mechanisms responsible for invisible gold enrichment driven by coupled dissolution-reprecipitation reaction (CDR) are debated. Here we report the micro- to nano-scale textures of arsenian pyrite in a high-grade (>10 g/t) gold ore from the Chang’an deposit to trace the gold enrichment process. Our study records a CDR-driven evolution of mineral growth from an As-rich, Au-poor pyrite core, with numerous fine arsenopyrite inclusions, to an inclusion-free, As-Au-rich oscillatory pyrite rim. The reaction occurred at ~260 °C under 4.7 to 5.8 pH and –36.6 to –32.9 logfO2 conditions. The elevated As but depleted S contents in the pyrite core indicate a combined elevation of S fugacity and solubility of Au. The coprecipitation of arsenopyrite inclusions in the core caused a depletion of S fugacity to –13.8 ~ –11.7, triggering Au enrichment in the rim. This non-unique process has the potential to explain the upgrade of invisible Au in arsenian sulfides, worldwide.

Coupled Microstructural EBSD and LA-ICP-MS Trace Element Mapping of Pyrite Constrains the Deformation History of Breccia-Hosted IOCG Ore Systems

Electron backscatter diffraction (EBSD) methods are used to investigate the presence of microstructures in pyrite from the giant breccia-hosted Olympic Dam iron–oxide copper gold (IOCG) deposit, South Australia. Results include the first evidence for ductile deformation in pyrite from a brecciated deposit. Two stages of ductile behavior are observed, although extensive replacement and recrystallization driven by coupled dissolution–reprecipitation reaction have prevented widespread preservation of the earlier event. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) element maps of pyrite confirm that many pyrite grains display compositional zoning with respect to As, Co, and Ni, but that the zoning is often irregular, patchy, or otherwise disrupted and are readily correlated with observed microstructures. The formation of ductile microstructures in pyrite requires temperatures above ~260 °C, which could potentially be related to heat from radioactive decay and fault displacements during tectonothermal events. Coupling EBSD methods with LA-ICP-MS element mapping allows a comprehensive characterization of pyrite textures and microstructures that are otherwise invisible to conventional reflected light or BSE imaging. Beyond providing new insights into ore genesis and superimposed events, the two techniques enable a detailed understanding of the grain-scale distribution of minor elements. Such information is pivotal for efforts intended to develop new ways to recover value components (precious and critical metals), as well as remove deleterious components of the ore using low-energy, low-waste ore processing methods.

Pb-bearing Cu-(Fe)-sulfides: Evidence for continuous hydrothermal activity in the northern Olympic Cu-Au Province, South Australia

Lead-isotope data were obtained for a population of Pb-chalcogenides (galena, clausthalite and altaite) and Cu-(Fe)-sulfides in Cu-(Fe)-sulfide mineral separates from the Prominent Hill iron-oxide copper gold deposit, Mt Woods Inlier, South Australia. Each mineral displays wide variability in 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb ratios, ranging from moderately radiogenic Pb signatures to strongly radiogenic. Any contribution from non-radiogenic (common) lead at the time of initial deposit formation (1600–1585 Ma) is minor. Lead is overwhelmingly derived from the decay of U, with a minor contribution from the decay of Th also present within the ores. The heterogenous nature of the recorded Pb isotope values suggests a mixing of isotope signatures during repeated cycles of fluid-assisted dissolution, remobilisation and reprecipitation of U- and Pb-bearing phases. Hydrothermal experiments showed that the incorporation of Pb-chalcogenide (galena) occurs rapidly (days) at relatively mild conditions (≤150 °C), via precipitation in reaction-induced porosity formed during coupled dissolution reprecipitation reactions of the host Cu-(Fe)-sulfides. Hence, even minor hydrothermal activity may result in some trapping of radiogenic Pb by pre-existing Cu-(Fe)-sulfides. Construction of Pb-Pb pseudo-isochrons from the data supports these assessments, returning a range of possible (theoretical) ages (0–0.535 Ga) for Pb-chalcogenide formation. An additional (two-stage) Pb evolution model is preserved by the data with separation of each reservoir from the bulk silicate earth at ∼ 830 Ma and mixing of the two reservoirs at ∼ 500 Ma. Although the Pb-isotope data can be interpreted as resulting from a number of discrete events that generated regional-scale fluid flow, near-continuous Pb (re)-mobilisation at the nm- to deposit-scales is an equally valid interpretation, and is also consistent with observations of modern radionuclide mobility in the ores. The observations made within this study should be considered when discussing the mobility of elements within and between mineral phases in ore-forming systems. They show that many mineral phases, particularly the sulphide mineral phases discussed here, should not be considered as closed systems, but potentially, as systems in which chemistry and mineral stoichiometry evolve continuously over geological time.

Pyrite oxidation under a carbonate buffer and its environmental implications: a case study from the Shangmanggang gold deposit, SW China

Understanding the process and influencing factors of the oxidation of pyrite is beneficial for the management of environmental problems in mining areas. In this study, we investigated the morphology and geochemistry of the pyrite and related goethite from the weathering crust of the Shangmanggang (SMG) gold deposit, SW China, via petrographic work, electron microprobe analysis, X-ray diffraction analysis, and PHREEQC geochemical modelling. The weathering profile of the SMG is composed of the unweathered Carlin-type zone, the semi-weathered zone, and the highly weathered red-clay zone, and different types of pyrite, framboidal pyrite (Py1), cube pyrite (Py2) and zoned pyrite (Py3), were differentially oxidized and transferred into corresponding pyrite–pseudomorphic goethite commonly comprised of the early and late phase. Furthermore, the stronger oxidation is related to more late goethite with more Al and Si content. The ubiquitous dolomite buffer kept the pH of the pore fluid neutral, resulting in the precipitation and accumulation of a goethite coating around the pyrite, which further reduced the oxidation rate and formed pyrite–pseudomorphic goethite ultimately via coupled dissolution–reprecipitation reactions. In addition, the different mineralogical properties resulted in the differential oxidation of pyrite such that the smaller grains oxidized faster, and As within the pyrite accelerated the oxidation. Moreover, the rate-limited oxidation of pyrite under a carbonate buffer prevents acid mine drainage from forming and limits As release from arsenian pyrite into the external environment. Supplementary material: Supplement 1, the EMPA data of goethite and pyrite from the SMG; Supplement 2, the size of pyrite and goethite from the SMG and Supplement 3, PHREEQC code of pyrite oxidation in the SMG are available at https://doi.org/10.6084/m9.figshare.c.6267700

Micro-textural and chemical fingerprints of hydrothermal cobalt enrichment in the Jingchong Co-Cu polymetallic deposit, South China

The Jiangnan Orogen, located at the margin of the southeastern Yangtze Block, has Co reserve more than 20,000 t, in which Co occurs mainly along with Cu deposits, with minor as independent Co deposits. As for Co enrichment in the Jiangnan Orogen, it remains unclear whether Co was enriched by the same mineralizing episodes as that precipitating Cu ores or from other processes. The Jingchong Co-Cu polymetallic deposit as a representative was chose to illuminate this issue, based on the integrated TIMA, EBSD, EPMA, LA-ICPMS and LA-MC-ICPMS analyses. The results show that cobaltiferous sulfides have complex textural and compositional zoning patterns. Four generations of pyrite (i.e., PyI, PyII, PyIII and PyIV) corresponding to four different ore stages (i.e., barren stage I, Cu-rich stage II, Co-rich stage III, and Pb-Zn-rich stage IV) were identified. The PyIII which consists of PyIII-1 (0.02–0.79 wt% Co and 0.16–3.08 wt% As) rimmed by PyIII-2 (0.19–13.66 wt% Co and 0.20–7.42 wt% As), arsenopyrite consisting of Apy-1 (up to 0.90 wt% Co and 39.70–42.06 wt% As) and Apy-1 (up to 0.60 wt% Co and 42.42–45.61 wt% As), and cobaltite-alloclasite (18.84–34.98 wt% Co) of stage III dominate the Co occurrence. These inhomogeneous features were explained by the fluid-mediated coupled dissolution-reprecipitation reactions (CDR), and the super-enrichment of the Co metal budget at the interface of PyIII-2 with PyIII-1 was caused by the non-equilibrium process at the advancing reaction front. In combination with the high Co and As contents and Co/Ni ratios (>1) at stage III, as well as the δ34S ranges (−4.47‰ to 3.57‰) similar to that of magmatic sulfur, Co enrichment in the Jingchong deposit could be ascribed to the interaction of a Co– and As-rich magmatic-hydrothermal fluid pulse with wall rock (including the early ores), later than Cu mineralization. The decreasing temperature together with increasing sulfur and oxygen fugacity serve as the critical factors controlling Co precipitation from solutions. This study provides a detailed mineralogical insight into Co enriching process in magmatic-hydrothermal Cu deposits. Finally, a significant mineral indicator (i.e., the coexistence of fine-grained pyrite and arsenopyrite) for Co ore exploration and one more suggestion (i.e., crushing sulfides ores into fine pieces, smaller than 15–20 μm) for efficient cobalt recovery were proposed.

In situ trace elements and sulfur isotopes of sulfides in the Dabaiyang Te-Au deposit, Hebei Province, China: Implications for Au remobilization from pyrite

Coupled dissolution–reprecipitation (CDR) reactions and low-melting point chalcophile elements (LMCE) melt scavenging are effective mechanisms for gold remobilization and are important for the formation of Te-Au deposits. The Dabaiyang deposit is a typical Te-Au deposit in the Zhangjiakou district and contains tellurides, including altaite, hessite, petzite, tetradymite and tellurobismuthite. Two generations of pyrite have been recognized in the deposit: early pyrite without fractures or alteration (Py1) and later pyrite with more porosity, inclusions and fractures (Py2), and Py2 could be separated into Py2a that containing many fractures without mineral inclusions and Py2b that containing microfractures, micropores and mineral inclusions. Pyrite containing large amounts of mineral inclusions and free of microfractures (Py-MI) has also been recognized, but timing relationships between Py-MI and Py1 (or Py2) is hard to establish. The Pyrite textures indicate that Py2a underwent brittle deformation and that Py2b underwent CDR reactions and Te-melt scavenging. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analyses show that Py2a contains trace elements similar to Py1, while Py2b contains higher Au, Ag, Te and other trace elements, indicating that brittle fracturing has no effect on element mobilization and reprecipitation, and porous pyrite has Au-Ag-Te concentrations. High Co/Ni ratios and Te contents and low Se contents show that the Dabaiyang deposit has a genetic relationship with magmatic activity. In situ δ34S values of sulfides range from −15.77‰ to −6.09‰ (mostly from −13.89 to −10.06‰), which is consistent with bulk sulfide δ34S values. The negative δ34S values more likely resulted from sulfur isotope fractionation in high fO2 hydrothermal fluids. CDR reactions liberated Au, Te, Ag and other trace elements from pyrite and formed porous textures. Then, Te-rich melts scavenged Au from fluid and wallrocks during migration. Finally, the melt precipitated as mineral inclusions in pores or fractures in pyrite. CDR reactions and LMCE melt scavenging played an important role in upgrading the ores and the occurrence of visible native gold in the Dabaiyang gold deposit, as well as other Te-Au deposits in the Zhangjiakou district.

A new mode of mineral replacement reactions involving the synergy between fluid-induced solid-state diffusion and dissolution-reprecipitation: A case study of the replacement of bornite by copper sulfides

Mineral replacement reactions are one of the most important phenomena controlling the geochemical cycle of elements on Earth. In the early years, solid-state diffusion was proposed as the main mechanism for mineral replacement reactions, but over the past 20 years the importance of the coupled dissolution-reprecipitation (CDR) mechanism has been recognized. In the presence of a fluid phase and at low temperatures (e.g., <300 °C), CDR is the predominant mineral replacement process compared to relatively slow solid-state diffusion. However, in the present case study, we show that the rate of solid-state diffusion is comparable to the rate of CDR processes during the replacement of bornite (Cu5FeS4) by copper sulfides at 160–200 °C. The experiments initially produced chalcopyrite lamellae homogeneously distributed in the entire bornite grain, and each lamella was enveloped by digenite. The lamellae were formed by removing Fe3+ from bornite via solid-state diffusion, since there was no evidence for fluid entering the bornite grains during lamellae formation. An interesting discovery is that solid-state exsolution of chalcopyrite lamellae was induced by the bulk hydrothermal fluids surrounding the mineral grains, because in the absence of fluids under otherwise identical conditions, no exsolution occurred, and because the exsolution rate and lamellae size were sensitive to the composition of hydrothermal fluids. We hypothesize that this fluid-induced solid-state diffusion (FI-SSD) mechanism is made possible by the similar topology of the crystal structure of these phases. The solid-state diffusion of Fe3+ within bornite and across the resultant chalcopyrite and digenite phase boundaries is facilitated by the near-identical S framework. Parallel to and after lamellae exsolution, CDR reactions proceeded from the surface to the interior of the grains or along fractures, replacing chalcopyrite by digenite, and digenite by covellite and/or chalcocite, depending on experimental conditions. The synergy between FI-SSD and CDR resulted in complex reaction pathways for reactions in five acidic hydrothermal fluids with or without added Cu2+, Cu+, Cl−, SO42−, and SO32−. The outcomes of these experiments imply that (1) under conditions where cation diffusion rates are of the same order of magnitude as dissolution and precipitation rates, hydrothermal fluids can induce and control solid-state diffusion processes, e.g., exsolution; (2) mineral replacement can be a result of the synergy between FI-SSD and CDR mechanisms; this happens at low temperatures (≤200 °C) in chalcogenide systems, but could affect silicate and oxide systems at amphibolite to granulite to eclogitic metamorphic grade; and (3) the synergy between FI-SSD and CDR mechanisms can lead to complex reaction pathways that cannot be easily predicted empirically.

Interpretation of hydrothermal evolution in the Qolqoleh gold deposit, southwest of Saqqez, Iran: Analysis of pyrite by LA-ICP-MS and sulfur isotopes

The Qolqoleh gold deposit is located in the northern part of the Sanandaj-Sirjan Zone (SaSZ), northwest Iran. The main host rocks include mylonitic granite and chlorite schist. Four generations of Au-bearing sulfides have been identified and are referred to as Py1 to Py4. LA-ICP-MS elemental maps and spot analyses of gold and other trace elements in Py1 to Py4 were performed to provide robust information about the ore-forming fluid and conditions of saturation. Element compositions in all generations of pyrite show heterogeneity in fluid compositions and reflect the role of a multistage hydrothermal system in their formation. The earliest hydrothermal event is related to magmatic fluids synchronous with magmatic fluids from a granitic pluton emplacement in Carboniferous time. Multistage magmatism and related heating caused reaction, replacement, and recrystallization (RRR) of original Py1, generating overgrowths of Py2 to Py4. The variation in the Au-As rim compositions shows that fluctuating temperatures occurred during overgrowths of pyrite. The ratios of Co/Ni for most Py1 to Py4 are higher than 1. This along with the high Te contents infer that the ore-forming fluids came from mainly a magmatic source with low redox conditions. The increase in Au and other elements in Py2 and Py4 shows enrichment through the coupled dissolution-reprecipitation reaction (CDRR) mechanism in response to greater non-metamorphic fluids. The bulk δ34S values range from 3.1 to 6.9‰. Two samples range from 13.8 to 14.3‰, which are compatible with a main magmatic source and to a minor metamorphic source for the ore-forming fluids. Subsequently, dextral movements caused brittle-ductile deformation and dislocation of mineralization and mylonitization. However, this study determines that the Qolqoleh deposit is a magmatic-related gold deposit.

Three-Dimensional and Microstructural Fingerprinting of Gold Nanoparticles at Fluid-Mineral Interfaces

Abstract Recent studies have identified gold nanoparticles in ores in a range of deposit types, but little is known about their formation processes. In this contribution, gold-bearing magnetite from the well-documented, world-class Beiya Au deposit, China, was investigated in terms of microstructure and crystallography at the nanoscale. We present the first three-dimensional (3D) focused ion beam/scanning electron microscopy (FIB/SEM) tomography of the distribution of gold nanoparticles in nanopores in the low-Si magnetite. The porous low-Si magnetite, which overprints an earlier generation of silician magnetite, was formed by a coupled dissolution-reprecipitation reaction (CDRR). The extrinsic changes in thermodynamic conditions (e.g., S content and temperature) of the hydrothermal fluids resulted in the CDRR in magnetite and the disequilibrium of Au-Bi melts. The gold nanoparticles crystallized from Au-supersaturated fluids originating from the disequilibrium of Au-Bi melts and grew in two ways depending on the intrinsic crystal structure and pore textures: (1) heteroepitaxial growth utilizing the (111) lattice planes of magnetite, and (2) randomly oriented nucleation and growth. Therefore, this study unravels how intrinsic and extrinsic factors drove the formation of gold nanoparticles at fluid-mineral interfaces.

Trace-element remobilisation from W–Sn–U–Pb zoned hematite: Nanoscale insights into a mineral geochronometer behaviour during interaction with fluids

AbstractPreferential removal of W relative to other trace elements from zoned, W–Sn–U–Pb-bearing hematite coupled with disturbance of U–Pb isotope systematics is attributed to pseudomorphic replacement via coupled dissolution reprecipitation reaction (CDRR). This hematite has been studied down to the nanoscale to understand the mechanisms leading to compositional and U/Pb isotope heterogeneity at the grain scale. High-Angle Annular Dark Field Scanning Transmission Electron Microscopy (HAADF STEM) imaging of foils extracted in situ from three locations across the W-rich to W-depleted domains show lattice-scale defects and crystal structure modifications adjacent to twin planes. Secondary sets of twins and associated splays are common, but wider (up to ~100 nm) inclusion trails occur only at the boundary between the W-rich and W-depleted domains. STEM energy-dispersive X-ray mapping reveals W- and Pb-enrichment along 2–3 nm-wide features defining the twin planes; W-bearing nanoparticles occur along the splays. Tungsten and Pb are both present, albeit at low concentrations, within Na–K–Cl-bearing inclusions along the trails. HAADF STEM imaging of hematite reveals modifications relative to ideal crystal structure. A two-fold hematite superstructure (a = b = c = 10.85 Å; α = β = γ = 55.28°) involving oxygen vacancies was constructed and assessed by STEM simulations with a good match to data. This model can account for significant W release during interaction with fluids percolating through twin planes and secondary structures as CDRR progresses from the zoned domain, otherwise apparently undisturbed at the micrometre scale. Lead remobilisation is confirmed here at the nanoscale and is responsible for a disturbance of U/Pb ratios in hematite affected by CDRR. Twin planes can provide pathways for fluid percolation and metal entrapment during post-crystallisation overprinting. The presence of complex twinning can therefore predict potential disturbances of isotope systems in hematite that will affect its performance as a robust geochronometer.

Gold Remobilization: Insights from Gold Deposits in the Archean Swayze Greenstone Belt, Abitibi Subprovince, Canada

Abstract Recognizing if and how Au is remobilized, in solid, melt, or fluid state, is critical for understanding the origin of high-grade ore zones in Au deposits. When evidence for Au remobilization can be demonstrated, then primary versus secondary processes can be distinguished, resulting in a more complete understanding of Au deposit formation. To address this, samples from two Au deposits, Jerome and Kenty, in the Archean Swayze greenstone belt of northern Ontario, Canada, together with archived samples from 39 high-grade Au deposits from the Abitibi greenstone belt across Ontario and Quebec, were geochemically characterized using integrated scanning electron microscopy-energy dispersive spectroscopy and electron microprobe imaging and analyses in addition to laser ablation-inductively coupled plasma-mass spectrometry elemental mapping. These data provided the basis to develop a model for Au remobilization and upgrading of Au that is widely applicable to orogenic gold settings. Data for the Jerome deposit indicate that Au uptake into early pyrite was not due to pulsing of different fluids, but instead was predominantly controlled by S availability, whereby the oscillatory/sector zoning in pyrite resulted from the substitution of As into S sites during rapid growth due to local chemical disequilibrium. In addition, Au-bearing pyrite from both the Jerome and Kenty deposits records textures, such as porosity development coincident with the presence of native gold and accessory sulfide phases, that are strongly suggestive of coupled dissolution-reprecipitation (CDR) reactions that liberated Au and associated elements from earlier auriferous (100–5,000 ppm Au) pyrite. During the remobilization process, Au and Ag were decoupled, which resulted in (1) a change in Au/Ag ratios of 0.5 to 5 in early pyrite to ≈9 in the new native gold (900 Au fineness) and (2) incorporation of Ag into cogenetic secondary mineral phases (e.g., chalcopyrite, tetrahedrite, and galena). Evidence for an association of low-melting point chalcophile elements (LMCE; Hg, Te, Sb, and Bi) with Au at the Jerome, Kenty, and many (&amp;gt;50%) of the 39 historic deposits sampled, along with native gold filling structurally favorable sites in vein quartz in all samples, indicates a fluid might not have been the only factor contributing to remobilization. This systematic Au-LMCE association strongly supports a model whereby Au is released by CDR reactions and is then remobilized by fluid-mediated, LMCE-rich melts that began to form at 335°C and/or by local, nanoparticle (nanomelt?) transport during deformation and metamorphism. Conclusions drawn from this study have implications for Au deposits globally and can account for the common presence of coarse-grained, commonly crystalline, native gold filling fractures in quartz and the paragenetically late-stage origin of gold in veins. They can also better explain the inability of Au in solution remobilization models to account for locally high gold grades, given the relatively low solubility of Au in hydrothermal fluids.

Pseudomorphic Rhythmically Banded and Oscillatory Tetrahedrite–Tennantite Aggregates in the Darasun Gold Deposit (Eastern Transbaikalia, Russia): A Result of Coupled Dissolution–Reprecipitation Reactions

The rhythmically banded aggregates of Fe–tennantite with oscillatory zoning resulting from simultaneous variations in the concentrations of Sb and As and Zn and Fe were registered in the Darasun gold deposit (Eastern Transbaikalia). These aggregates were formed upon pseudomorphic replacement of early Zn–tetrahedrite. This process was initiated by the dissolution of Zn–tetrahedrite with the formation of an aggregate of galena, bournonite, and late tetrahedrite–tennantite. It is shown that rhythmically banded aggregates with an oscillatory zoning were formed as a result of coupled dissolution–reprecipitation reactions under the conditions that are far from the mineral–fluid chemical equilibrium and variations in the fluid composition controlled by kinetic factors.

Feldspar mineralogy and rare-earth element (re)mobilization in iron-oxide copper gold systems from South Australia: a nanoscale study

ABSTRACTNanoscale characterization (TEM on FIB-SEM-prepared foils) was undertaken on feldspars undergoing transformation from early post-magmatic (deuteric) to hydrothermal stages in granites hosting the Olympic Dam Cu-U-Au-Ag deposit, and from the Cu-Au skarn at Hillside within the same iron-oxide copper-gold (IOCG) province, South Australia. These include complex perthitic textures, anomalously Ba-, Fe-, or REE-rich compositions, and REE-flourocarbonate + molybdenite assemblages which pseudomorph pre-existing feldspars. Epitaxial orientations between cryptoperthite (magmatic), patch perthite (dueteric) and replacive albite (hydrothermal) within vein perthite support interface-mediated reactions between pre-existing alkali-feldspars and pervading fluid, irrespective of micro-scale crystal morphology. Such observations are consistent with a coupled dissolution-reprecipitation reaction mechanism, which assists in grain-scale element remobilization via the generation of transient interconnected microporosity. Micro-scale aggregates of hydrothermal hyalophane (Ba-rich K-feldspar), crystallizing within previously albitized areas of andesine, reveal a complex assemblage of calc-silicate, As-bearing fluorapatite and Fe oxides along reaction boundaries in the enclosing albite-sericite assemblage typical of deuteric alteration. Such inclusions are good REE repositories and their presence supports REE remobilization at the grain-scale during early hydrothermal alteration. Iron-metasomatism is recognized by nanoscale maghemite inclusions within ‘red-stained’ orthoclase, as well as by hematite in REE-fluorocarbonates, which reflect broader-scale zonation patterns typical for IOCG systems. Potassium-feldspar from the contact between alkali-granite and skarn at Hillside is characterized by 100–1000 ppm REE, attributable to pervasive nanoscale inclusions of calc-silicates, concentrated along microfractures, or pore-attached. Feldspar replacement by REE-fluorcarbonates at Olympic Dam and nanoscale calc-silicate inclusions in feldspar at Hillside are both strong evidence for the role of feldspars in concentrating REE during intense metasomatism. Differences in mineralogical expression are due to the availability of associated elements. Lattice-scale intergrowths of assemblages indicative of Fe-metasomatism, REE-enrichment and sulfide deposition at Olympic Dam are evidence for a spatial and temporal relationship between these processes.

Chemical and textural equilibration of garnet during amphibolite facies metamorphism: The influence of coupled dissolution–reprecipitation

AbstractMetamorphic equilibration requires chemical communication between minerals and may be inhibited through sluggish volume diffusion and or slow rates of dissolution in a fluid phase. Relatively slow diffusion and the perceived robust nature of chemical growth zoning may preclude garnet porphyroblasts from readily participating in low‐temperature amphibolite facies metamorphic reactions. Garnet is widely assumed to be a reactant in staurolite‐isograd reactions, and the evidence for this has been assessed in the Late Proterozoic Dalradian pelitic schists of the Scottish Highlands. The 3D imaging of garnet porphyroblasts in staurolite‐bearing schists reveals a good crystal shape and little evidence of marginal dissolution; however, there is also lack of evidence for the involvement of either chlorite or chloritoid in the reaction. Staurolite forms directly adjacent to the garnet, and its nucleation is strongly associated with deformation of the muscovite‐rich fabrics around the porphyroblasts. “Cloudy” fluid inclusion‐rich garnet forms in both marginal and internal parts of the garnet porphyroblast and is linked both to the production of staurolite and to the introduction of abundant quartz inclusions within the garnet. Such cloudy garnet typically has a Mg‐rich, Mn‐poor composition and is interpreted to have formed during a coupled dissolution–reprecipitation process, triggered by a local influx of fluid. All garnet in the muscovite‐bearing schists present in this area is potentially reactive, irrespective of the garnet composition, but very few of the schists contain staurolite. The staurolite‐producing reaction appears to be substantially overstepped during the relatively high‐pressure Barrovian regional metamorphism reflecting the limited permeability of the schists in peak metamorphic conditions. Fluid influx and hence reaction progress appear to be strongly controlled by subtle differences in deformation history. The remaining garnet fails to achieve chemical equilibrium during the reaction creating distinctive patchy compositional zoning. Such zoning in metamorphic garnet created during coupled dissolution–reprecipitation reactions may be difficult to recognize in higher grade pelites due to subsequent diffusive re‐equilibration. Fundamental assumptions about metamorphic processes are questioned by the lack of chemical equilibrium during this reaction and the restricted permeability of the regional metamorphic pelitic schists. In addition, the partial loss of prograde chemical and textural information from the garnet porphyroblasts cautions against their routine use as a reliable monitor of metamorphic history. However, the partial re‐equilibration of the porphyroblasts during coupled dissolution–reprecipitation opens possibilities of mapping reaction progress in garnet as a means of assessing fluid access during peak metamorphic conditions.

Replacement of Uraninite By BorniteViaCoupled Dissolution-Reprecipitation: Evidence From Texture and Microstructure

Abstract The occurrence and nature of rhythmically intergrown crystals of uraninite and bornite from the Olympic Dam iron oxide-copper-gold (IOCG)-U-Ag deposit, South Australia, is reported. Distinct zones within primary, euhedral uraninite crystals have been replaced by bornite and minor fluorite leaving a skeleton of uraninite, infilled with these minerals. The partially replaced uraninite crystals are always closely associated with locally abundant bornite and fluorite. The textural features of the intergrowth are consistent with partial replacement of uraninite by bornite via a coupled dissolution-reprecipitation reaction driven by a F-rich and Cu-Fe-sulfide-bearing hydrothermal fluid rather than a form of oscillatory growth or exsolution from a U–Cu–Fe–S solid solution. The crystallographic relationship between the parent uraninite and the daughter bornite and fluorite were explored by electron backscattered diffraction, as all three minerals share common crystal structural features, despite their chemical diversity. Generally speaking, the crystallographic orientation of the uraninite parent is initially inherited by the replacing bornite, but later the orientation of the bornite changes.