Antonin Richard

Porphyry deposits are the dominant sources of copper and major sources of several base and precious metals. They are commonly formed via the repeated emplacement of hydrous magmas and associated fluid exsolution. As a result, mineralized hydrothermal veins may undergo multiple deposition and reopening processes that are not fully accounted for by existing fluid models. The Tongchang porphyry Cu deposit is a rare example of being related to a single intrusion. The simplicity in intrusive history provides an ideal starting point for studying fluid processes in more complex multi-intrusion porphyry systems. Detailed scanning electron microscope (SEM) cathodoluminescence imaging (CL) revealed rich microtextures in quartz and anhydrite that point to a fluid timeline encompassing early quartz deposition followed by fluid-aided dynamic recrystallization, which was succeeded by an intermediate stage of quartz dissolution and subsequent deposition, and ended with a late stage of continuous quartz deposition, brecciation, and fracturing. Vein reopening is more common than expected. Fifteen out of seventeen examined vein samples contained quartz and/or anhydrite that was older or younger than the vein age defined by vein sequences. Thermobarometry and solubility analysis suggests that the fluid events occurred in a general cooling path (from 650 °C to 250 °C), interspersed with two episodes of fluid pressurization. The first episode occurred at high-T (>500 °C), under lithostatic conditions alongside dynamic recrystallization, whereas the second one took place at a lower temperature (~400 °C), under lithostatic to hydrostatic transition conditions. The main episode of chalcopyrite veining took place subsequent to the second overpressure episode at temperatures of 380–300 °C. The results of this study reaffirm that thermal and hydraulic conditions are the main causative factors for vein reopening and growth in porphyry deposits.

The Ranger deposit (Northern Territory, Australia) is one of the largest uranium deposits in the world. Uranium mineralisation occurs in crystalline basement rocks and is thought to belong to the unconformity-related category. In order to address the sources of magnesium and boron, and the temperature of the fluids related to boron and magnesium metasomatism that occurred shortly before and during the main uranium stage, in situ analyses of chlorite and tourmaline were carried out. The chemical composition of tourmaline shows an elevated X-site vacancy and a low Fe_tot/(Fe_tot + Mg) ratio typical of Mg-foitite. Uranium-related chlorite has relatively low Fe content (0.28–0.83 apfu) and high Mg content (3.08–3.84 apfu), with Si/Al = 1.08−1.22 and Mg/(Mg + Fe_tot) = 0.80−0.93 indicating a composition lying between the clinochlore and Mg-amesite fields. Chlorite composition indicates crystallisation temperature of 101–163 °C. The boron isotopic composition of tourmaline shows a range of δ¹¹B values of ~1–9‰. A model is proposed involving two boron sources that contribute to a mixed isotopic signature: (i) evaporated seawater, which is typically enriched in magnesium and boron (δ¹¹B ~ 40‰), and (ii) boron from the crystalline basement (δ¹¹B ~ −30 to +10‰), which appears to be the dominant source. Collectively, the data indicate similar tourmaline chemistry but significant differences of tourmaline boron isotopic composition and chlorite chemistry between the Ranger deposit and some of the Canadian unconformity-related uranium deposits. However, lithogeochemical exploration approaches based on identification of boron- and magnesium-enriched zones may be usefully applied to uranium exploration in the Northern Territory.

The formation of most fluorite deposits in northern Coahuila (NE Mexico) is explained by MVT models, and is a part of the metallogenic province of northeastern Mexico. However, fluorite skarn deposits also occur in the same region, and there is evidence for late hydrothermal manifestations with no clear origin and evolution. The latter are the main focus of this study; in particular, F–Be–U–Mo–V–P stringers in the Aguachile-Cuatro Palmas area that overprint preexisting fluorite mantos. The region experienced the emplacement of several intrusives during the Eocene and the Oligocene that are collectively grouped into the East Mexico Alkaline Province (EMAP) and postdate MVT-like deposits. Some of these intrusives have associated skarn deposits; most of them are polymetallic, but the unusual El Pilote deposit contains fluorite mineralisation that was remobilised from MVT-like deposits. The formation of the Aguachile deposit (and, collectively, part of the Cuatro Palmas deposit) has been attributed to a shallow retrograde skarn model. The Cuatro Palmas and Las Alicias fluorite deposits consist of MVT-like deposits overprinted by late hydrothermal fluorite mineralisation rich in Be–U–Mo–V–P, and the Aguachile deposit consists entirely of the latter type. The systematic fluid inclusion study of MVT-like, skarn, and late hydrothermal fluorite deposits reveals a very different distribution of temperature and salinity data that allows the discrimination of mineralising fluids for the type of deposit. MVT-like deposits were formed by fluids with temperatures of homogenisation that range between 50 °C and 152 °C and salinities between 5 and 15.5 wt.% NaCl equivalent. The El Pilote fluorite skarn was formed by fluids with temperatures of homogenisation that range between 78 °C and 394 °C and salinities between 5 and 34 wt.% NaCl equivalent, and include CaCl₂-rich brines with salinities that range between 24.5 and 29.1 wt.% CaCl₂. Late shallow fluorite–Be–U–Mo–V–P hydrothermal deposits were formed by fluids with temperatures of homogenisation that range between 70 °C and 180 °C and salinities between 0.9 and 3.4 wt.% NaCl equivalent; the sole exception to the above is the La Fácil deposit, with salinities that range between 7.9 and 8.8 wt.% NaCl equivalent. While temperatures of homogenisation are similar between MVT-like and late hydrothermal deposits, and both even have hydrocarbon-rich fluid inclusion associations, the salinity of late deposits is similar to that of retrograde skarn fluids, although further diluted. However, homogenisation temperatures tend to be higher in late hydrothermal than in MVT-like deposits, thus making them more similar to retrograde skarn fluids. Although this characteristic cannot solely establish a genetic link between a retrograde skarn model and late hydrothermal deposits in the study area, the characteristics of fluids associated with the latter separate these deposits from those ascribed to an MVT-like model. Assuming that mineralising fluids for late fluorite–Be–U–Mo–V–P hydrothermal deposits may correspond to a retrograde skarn (or “epithermal”) deposit, the source for fluorine may be either from (A) the dissolution of earlier formed MVT-like deposits, (B) the entrainment of remaining F-rich basinal brines, or (C) hydrothermal fluids exsolved from highly evolved magmas. Possibilities A and B are feasible due to a hypothetical situation similar to the El Pilote skarn, and due to the occurrence of hydrocarbon-rich fluid inclusions at the La Fácil deposit. Possibility C is feasible because intrusive bodies related to highly evolved magmas would have provided other highly lithophile elements like Be, U and Mo upon the exsolution of their hydrothermal fluids. Such intrusive bodies occur in both study areas, and are particularly conspicuous at the Aguachile collapse structure.

Spectacular alteration of monazite by diagenetic/hydrothermal brines is well documented in some Proterozoic sedimentary basins in close relationship with high-grade uranium (U) deposits. Hence, monazite has been proposed as a viable source for some U deposits. However, monazite alteration remains enigmatic with regard to its high stability in relatively low temperature hydrothermal conditions. Here, the results of batch experiments in which 10 mg of natural monazite grains were reacted with 15 mL of Na-Ca-Cl (6 molal Cl) solutions as well as in pure water at 150 ºC and saturated vapor pressure (psat) for one and six months are reported. The influence of pH (pH = 1, 3, 7) and relative molar proportions of Na and Ca (Na/(Na + Ca) = 0, 0.5, 1), were tested. Discrete alteration features (etch pits and roughened surfaces) appear in a minority of the one month experiments and are more developed in the six months experiments, especially at pH = 1 and 3. Although spectacular alteration of monazite, as seen around U deposits, could not be reproduced here, this study shows that monazite is unstable in the presence of fluids analogous to acidic deep basinal brines.