Artur Deditius

Iron oxide-apatite (IOA) deposits, also known as magnetite-apatite or Kiruna-type deposits, are a major source of iron and potentially of rare earth elements and phosphorus. To date, the youngest representative of this group is the Pleistocene (~2 Ma) El Laco deposit, located in the Andean Cordillera of northern Chile. El Laco is considered a unique type of IOA deposit because of its young age and its volcanic-like features. Here we report the occurrence of similarly young IOA-type mineralization hosted within the Laguna del Maule Volcanic Complex, an unusually large and recent silicic volcanic system in the south-central Andes. We combined field observations and aerial drone images with detailed petrographic observations, electron microprobe analysis (EMPA), and 40Ar/39Ar dating to characterize the magnetite mineralization—named here “Vetas del Maule”—hosted within andesites of the now extinct La Zorra volcano (40Ar/39Ar plateau age of 1.013 ± 0.028 Ma). Five different styles of magnetite mineralization were identified: (1) massive magnetite, (2) pyroxene-actinolite-magnetite veins, (3) magnetite hydrothermal breccias, (4) disseminated magnetite, and (5) pyroxene-actinolite veins with minor magnetite. Field observations and aerial drone imaging, coupled with microtextural and microanalytical data, suggest a predominantly hydrothermal origin for the different types of mineralization. 40Ar/39Ar incremental heating of phlogopite associated with the magnetite mineralization yielded a plateau age of 873.6 ± 30.3 ka, confirming that the emplacement of Vetas del Maule postdated that of the host andesite rocks. Our data support the hypothesis that the magnetite mineralization formed in a volcanic setting from Fe-rich fluids exsolved from a magma at depth. Ultimately, Vetas del Maule provides evidence that volcanic-related IOA mineralization may be more common than previously thought, opening new opportunities of research and exploration for this ore deposit type in active volcanic arcs.

The rare-earth elements (REEs, La–Lu, Y) are essential for the development of renewable technologies. Bastnäsite (REECO3F) is a common REE ore mineral that is often subject to hydrothermal alteration at all crustal levels. Mechanisms of hydrothermal bastnäsite alteration therefore govern the evolution of REE deposits, though these mechanisms remain poorly understood. This experimental work investigates the hydrothermal replacement of bastnäsite by rhabdophane (REEPO4∙xH2O, x = 0–1) and monazite (REEPO4) in phosphatic fluids. Two temperature-dependent alteration pathways were identified; both follow the coupled dissolution-reprecipitation (CDR) mechanism. At 90 °C, bastnäsite was replaced by highly-porous metastable rhabdophane which was then replaced by monazite, forming an inner layer of rhabdophane and an outer layer of monazite. At 220 °C, bastnäsite was replaced directly by monazite. Although replacement initiated more quickly at 220 °C, greater overall replacement occurred at 90 °C (~ 61 wt.% after 500 h, compared to ~ 13 wt.% at 220 °C) due to surface passivation by monazite at 220 °C. Geochemical analyses showed REE fractionation during bastnäsite alteration. At 90 °C, rhabdophane was enriched in heavy REEs (Eu–Lu, Y), likely due to the evolving fluid chemistry, while at 220 °C secondary monazite was enriched in Sm and Ho compared to bastnäsite. These results indicate that: 1) the hydrothermal alteration of bastnäsite by rhabdophane and monazite in ore deposits leads to REE immobilisation, with little net loss of REEs to solution; 2) rhabdophane is metastable relative to monazite at 90 °C, and; 3) variable temperatures can cause different mineral textures and REE fractionation trends during hydrothermal alteration and mineral replacement.

The authors have retracted this article because an error in the application of the actinolite geothermometer, used to estimate formation temperature in the Candelaria iron oxide-copper-gold deposit, undermines our conclusion that actinolite can be used as a geothermometer in iron oxide-copper-gold deposits.

The geothermometer is based on the iron content of actinolite coexisting with quartz, two pyroxenes and vapour; however, quartz and pyroxenes are rare or absent in the Candelaria deposit. This means that the geothermometer cannot be used for temperature estimation because the rocks in question did not contain the requisite equilibrium assemblage for which the actinolite geothermometer had been developed.

Our conclusion that the Candelaria iron oxide-copper-gold deposit formed during at least two distinct mineralization stages, where both stages include actinolite with distinct chemical compositions that probably crystallized over different ranges of temperature, remains supported. However, we acknowledge that actinolite compositions are not a proxy for temperature of formation in this case. Given that without this element, the study does not demonstrate the applicability of actinolite as a geothermometer in iron oxide-copper-gold deposits, the Communications Earth & Environment editors asked for a Retraction, which we accept. A revised paper, without the temperature estimations from the actinolite geothermometer, will be submitted to another journal with details added to this note if and when it is published.

The editors and authors acknowledge Mathew Steele-MacInnis, Fernando Tornos and John Hanchar for bringing the issue to their attention.

All authors agree to this retraction.

Iron oxide-copper-gold (IOCG) deposits are a globally important source of copper, gold and critical commodities. Despite their relevance, IOCG deposits remain an ill-defined clan, with a range of characteristics that has complicated development of the general genetic model. Here we focus on the Candelaria IOCG deposit in Chile and reveal that by using micro-textural and compositional variations in actinolite, a common alteration mineral found in many IOCG deposits, we can constrain the evolution of these systems. We demonstrate that Candelaria formed by the superposition of at least two pulses of mineralization with a late Cu-rich event overprinting and superimposed over an early, and probably higher temperature, iron oxide-apatite (IOA) mineralization event. These distinct pulses were likely caused by episodic injections of magmatic-hydrothermal fluids from crystallizing magmas at depth. Our data provide empirical evidence of grain-to-deposit scale compositional and potentially temperature changes in an IOCG system. The results support the use of actinolite chemistry as a novel approach to understand the formation of IOCG deposits and a potential tool for vectoring in exploration.

This study focuses on enhancing sustainability through energy-efficient methods in producing hierarchically structured porous carbons. A novel approach, utilizing an ultrasonic spray nozzle-quartz tube reactor (USN-QTR), is introduced for fabricating carbon beads with customizable ultra-, super-, and mesopores. This study showcases noteworthy results from subjecting spherical char particles to activation processes involving carbon dioxide, a mixture of carbon dioxide and micron-sized water droplets, and highly concentrated supercritical steam at a temperature of 1173 K for durations of 3 and 5 h. Through pulse-field gradient nuclear magnetic resonance measurements, it was noted that carbon beads produced using USN-generated highly concentrated supercritical steam displayed remarkably elevated intrabead self-diffusivity of n-hexane. Inductively coupled plasma-optical emission spectroscopy demonstrates superior gold recovery kinetics from cyanide solutions compared to that from an industrial benchmark. The energy expenditure for USN-generated steam, producing carbon beads with an apparent surface area of 2691 m2/g, is estimated at 97 J per 1 m2 of carbon. This contrasts with the traditional steam generation method requiring approximately the energy of 190 J/m2 for activated carbon with an SBET of 2130 m2/g, making the USN-assisted activation method a more environmentally friendly and sustainable option with nearly half the energy consumption.

The El Laco iron oxide mineral deposit in the Central Andes of Chile has attracted significant attention because of its uniquely preserved massive magnetite orebodies, which bear a remarkable similarity to volcanic products. To date, the outcropping highly vesicular and porous massive magnetite orebodies have received little attention from a microtextural point of view, limiting our understanding about the role of volcanogenic processes on iron mineralization. Here, we report the chemical composition of vesicular magnetite at El Laco using EPMA and LA-ICP-MS methods and provide detailed 2D and 3D imaging of the internal structure of these texturally complex magnetite ores by combining SEM observations, synchrotron radiation micro-X-ray fluorescence chemical mapping, and high-resolution X-ray computed microtomography. Our observations reveal the presence of abundant magnetite microspheres with diameters ranging from ∼100 to ∼900 μm, as well as dendritic microstructures forming interconnected networks up to a few millimeters in size. Two-dimensional microtextural and geochemical imaging of the microspheres show that these features are formed by multiple euhedral magnetite crystals growing in all directions and occur immersed within a porous matrix conformed by smaller-sized (∼2–20 μm) and irregularly shaped magnetite microparticles. These types of morphologies have been reported in hydrothermal vents associated with hydrovolcanic processes and commonly described in hydrothermal synthesis experiments of magnetite microspheres, suggesting precipitation from iron-rich fluids. A hydrothermal origin for the magnetite microparticles reported here is further supported by their geochemical signature, which shows a strong depletion in most minor and trace elements typical from magnetite precipitated from hydrothermal fluids in ore-forming environments. We propose that decompression, cooling, and boiling of fluids triggered massive iron supersaturation, resulting in the nucleation of magnetite microparticles or colloids, followed by self-assembly into larger and more complex microstructures. Our data from El Laco deposit agree with models invoking magmatic-hydrothermal fluids to explain the origin of the deposit and provide new insights on the potential role of iron colloids as agents of mineralization in volcanic systems.

To accelerate the design and production of porous carbons targeting desired performance characteristics, we propose to incorporate machine learning (ML) regression into pore size distribution (PSD) analysis. Here, we implemented a ML algorithm for predicting paracetamol adsorption capacity of porous carbons from two pore structure parameters: total surface area and surface area of supermicropores-mesopores. These structural parameters of porous carbons are accessible from the software provided with automatic volumetric gas adsorption analyzers. It was shown that theoretical paracetamol capacities of porous carbons predicted using the ML algorithm lies within the range of experimental uncertainty. Nanoporous carbon beads with a high surface area of supermicropores (997 m2/g) and mesopores (628 m2/g) had the highest adsorption capacity of paracetamol (experiment: 480 ± 24 mg/g, ML predicted: 498 mg/g). The novel strategy for designing of porous carbon adsorbents using ML-PSD approach has a great potential to facilitate production of novel carbon adsorbents optimized for purification of aqueous solutions from non-electrolyte contaminates.

The Plio-Pleistocene El Laco magnetite ore bodies in the Chilean Altiplano represent an unusual subvolcanic/aerial type of an iron oxide-apatite (IOA) deposit. The textures of these magnetite ore bodies have sustained a long-standing geological controversy on the origin of iron oxide deposits with models spanning the spectrum from purely igneous to magmatic-hydrothermal processes. In particular, the link between the geochemical processes taking place in the source magma and the subsequent evolution of the overlying magmatic-hydrothermal system are still not well understood. Here we address this problem by focusing on microtextural and geochemical features of iron ore and silicate gangue minerals retrieved from drill core samples from El Laco ore bodies, as well as from the andesite volcanic host rocks. We report a comprehensive geochemical dataset of magnetite assemblages at El Laco obtained using a combination of EPMA, LA-ICP-MS, and synchrotron radiation µ-XRF methods. Microtextural and geochemical data of magnetite reveal consistent variations with depth. Magnetite in the andesitic host rocks and from deep/intermediate levels of the ore bodies have a high concentration of trace elements including Ti, V, Ni, Mn, Zn, Cr, Al, Ga, Cu and Co in comparison with magnetite from the upper sections of the ore bodies. Clinopyroxene is present in the andesite host rocks as well as the ore bodies, showing chemical differences between both types, with Mn and Fe contents that are higher in the former, and Na and Ca concentrations enriched in the latter. We interpret the enriched-to-depleted compositional trends in magnetite and clinopyroxene as resulting from a transition from purely igneous conditions to a fluid-dominated, cooling magmatic-hydrothermal system. Detailed microtextural analysis of magnetite and clinopyroxene from the ore bodies support this notion, revealing multiple growth stages punctuated by dissolution-reprecipitation processes. Our data further supports a genetic model that explains the formation of the El Laco iron oxide deposit through the injection, upward migration and venting of magmatically-derived Fe-rich fluids.

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.