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Porphyry-type Mo deposits have supplied most of the Mo to the world. However, the source of the Mo and the controls on its enrichment in such deposits is still a matter of great debate. In this study, we present in situ trace element and isotopic data for a giant porphyry Mo deposit (the Chalukou Mo deposit in NE China) and use these data to address these issues. Three primary paragenetic stages of mineralization were recognized at Chalukou: (Stage I) K-feldspar + quartz + minor pyrite (Py-I) + minor molybdenite (Mol-I); (Stage II) quartz + sericite + molybdenite (Mol-II) + pyrite (Py-II); (Stage III) quartz + chlorite + epidote + fluorite + pyrite (Py-III) + galena + sphalerite + minor chalcopyrite. The bulk of the molybdenite was deposited in Stage II. In situ S isotope analyses of the sulfide ores show that the δ34S values vary from –5.2 to +7.8‰ (mean = +2.9‰) and correspond to δ34SH2S values from –2.4 to +3.3‰ (mean = +1.1‰). These values are consistent with a magmatic source for the sulfur. In situ Pb isotope compositions of the sulfide ores are almost identical to those of the local Mesozoic granites and other magmatic-hydrothermal ore deposits in this region, suggesting a close genetic association between the Mo mineralization and felsic magmatism. Pyrite from the three stages of mineralization differs significantly in its trace element composition. The first generation, Py-I, has a high Cu content (8.7 ± 49.6 ppm; where the first value is the median and the second is the standard deviation) and Mo content (6.9 ± 3.8 ppm). Pyrite-II has the lowest Cu concentration (1.3 ± 2.1 ppm) and a relatively high Mo concentration (5 ± 128 ppm), and Py-III has a high Cu content (8.7 ± 37.1 ppm) but the lowest Mo content (0.05 ± 5.7 ppm). From this, we infer that pyrite recorded the chemical evolution in the Mo/Cu ratio of the ore fluid and that this ratio reached a maximum in Stage II, coinciding with the widespread saturation of the fluid in molybdenite. The evolution of the Mo/Cu ratio in pyrite implies that the fluid was undersaturated in chalcopyrite at the high temperature of Stage I, despite the Cu concentration of the fluid apparently being at its high level, and chalcopyrite only saturated later, at a lower temperature. Molybdenite, however, because of its lower solubility, saturated early (Stage I) and in the subsequent stage (Stage II) was supersaturated in the fluid. There is a significant enrichment of Mo in the syn-ore intrusions at Chalukou compared to the pre-ore monzogranite. The very low Sr/Y ratios for the Chalukou syn-ore intrusions, which are in sharp contrast to the high Sr/Y ratios of the pre-ore monzogranite and those of porphyries related to Cu deposits, suggest that fractional crystallization of plagioclase may have been a key factor in generating the syn-ore magmas. Molybdenum is a highly incompatible metal and will concentrate in the crust, and assimilation of old continental crust, therefore, may explain the Mo enrichment of the syn-ore intrusions and ultimately the formation of the giant Chalukou deposit.

Rare earth elements (REEs) mobilize, fractionate, and are re-distributed during supergene processes, and thus provide a powerful tool with which to quantitatively reconstruct the effects of chemical weathering. Moreover, under certain conditions, the REEs can concentrate to levels in the regolith sufficient to form giant regolith-hosted REE deposits, that are now responsible for much of the World’s production of heavy REEs (HREEs). Understanding the supergene behavior of the REEs is an important first step towards applying the REEs as a geochemical tool and meeting the growing global demand of the REEs. Thermodynamic calculations predict that dissolution of the main REE minerals in REE-rich protoliths, namely synchysite-(Y), gadolinite-(Y), hingganite-(Y), yttrialite-(Y), allanite-(Ce), eudialyte, chevkinite-(Ce), britholite, euxenite and loparite-(Ce), should occur spontaneously during weathering. It therefore follows that a high abundance of these minerals in the protolith implies high mobility of the REEs during weathering and consequently a high potential for the discovery of economic REE resources. Dissolution of apatite is promoted by metamictization or structural distortion and could be also important at low pH. In contrast, some LREE-fluorocarbonate minerals, notably bastnasite-(Ce) and parisite-(Ce), and monazite-(Ce) are likely thermodynamically stable in acidic environments. Thus, they would be preserved in the regolith. Zircon, titanite, aeschynite, fergusonite, and xenotime-(Y) are resistant to acidic dissolution, consistent with their common occurrence as residual minerals. In the cases of the world-class regolith-hosted REE deposits in South China, the groundwater is mildly acidic to circumneutral and carbonate-rich. The REEs are consequently transported dominantly as hydrated cations and carbonate complexes, depending on the pH. The general inheritance of the REE pattern of the regolith groundwater in the clay-sorbed fraction in the regolith indicates that the REEs in regolith are scavenged from the regolith groundwater. Elemental anomalies of specific REEs in the clay-sorbed fraction are very likely caused by an anomalously high REECO3+ fraction in the corresponding regolith groundwater, suggesting a preferential uptake of the REECO3+ complexes by the clay minerals, feasibly by halloysite through intercalation as interlayer complexes. This reaction is expected to be particularly important for the sorption and enrichment of the HREEs in the regolith. Depending on the pH and carbonate concentration of the water, surface complexation on clay minerals or interlayer intercalation particularly in halloysite control the pattern of REE enrichment. Mixing of the regolith groundwater with the alkaline and carbonate-rich aquifer groundwater increases the pH and carbonate concentration and, in turn, affects the ability of the mixed water to transport the HREEs. Interplay of aqueous complexation with the regolith mineralogy significantly affects the REE fractionation and re-distribution during groundwater-regolith interaction.

Thorium mineralization is frequently hosted in carbonate-bearing rocks, and thorium commonly substitutes into the structures of carbonate-bearing minerals that have precipitated from or been modified by hydrothermal fluids. Given this common association, it is reasonable to consider the hypothesis that the presence of carbonate ligands in hydrothermal solutions promotes the transport of Th through the formation of stable aqueous complexes. Our ability to evaluate this hypothesis, however, is hindered by the lack of experimental data for Th-carbonate species at conditions beyond ambient. The low-temperature data indicate that carbonate is a strong complexing agent for Th. In this contribution, we investigate the solubility of Th in carbonate-bearing fluids relevant to natural systems (0.05–0.5 m NaHCO3/Na2CO3; pHT ~ 7.8–9.8) at elevated temperature (175–250 °C). We demonstrate that, in contrast to the behavior of Th at low temperature, the stability of Th-carbonate complexes is not sufficient for them to predominate at these conditions. Instead, the solubility of Th is governed by hydrolysis reactions. Under the experimental conditions investigated, the predominant hydroxyl complexes are Th(OH)40 and Th(OH)5−. Thermodynamic formation constants were derived for these species at the temperatures considered in our experiments (log β4 = 43.34 and 44.31 at 175 and 200 °C, respectively, and log β5 = 46.15 and 47.9 at 225 and 250 °C, respectively) to permit forward modeling of Th mobility in natural systems. Our study indicates that carbonate ions are unlikely to play a role in transporting Th in hydrothermal fluids. Summarizing the results of this study and our previous studies of the solubility of Th in hydrothermal fluids, we conclude that SO42− is the primary ligand responsible for the hydrothermal transport of Th.

Most tungsten (W) and tin (Sn) deposits are associated with highly evolved granites derived from the anatexis of metasedimentary rocks. They are commonly separated in both space and time, and in the rare cases where the W and Sn mineralization are part of a single deposit, the two metals are temporally separate. The factors controlling this behavior, however, are not well understood. Our compilation of whole-rock geochemical data for W- and Sn-related granites in major W-Sn metallogenic belts shows that the Sn-related granites are generally the products of higher-temperature partial melting (~800 °C) than the W-related granites (~750 °C). Thermodynamic modeling of partial melting and metal partitioning shows that W is incorporated into the magma formed during low-temperature muscovite-dehydration melting, whereas most of the Sn is released into the magma at a higher temperature during biotite-dehydration melting; the Sn of the magma may be increased significantly if melt is extracted prior to biotite melting. At the same degree of partial melting, the concentrations of the two metals in the partial melt are controlled by their concentration in the protolith. Thus, the nature of the protolith and the melting temperature and subsequent evolution of the magma all influence the metallogenic potential of a magma and, in combination, helped control the spatial and temporal segregation of W and Sn deposits in all major W-Sn metallogenic belts.

Ore formation in porphyry Cu-Au-(Mo) systems involves the exsolution of metal-bearing fluids from magmas and the transport of the metals in magmatic-hydrothermal plumes that are subject to pressure fluctuations. Deposition of ore minerals occurs as a result of cooling and decompression of the hydrothermal fluids in partly overlapping ore shells. In this study, we address the role of vapor-like fluids in porphyry ore formation through numerical simulations of metal transport using the Gibbs energy minimization software, GEM-Selektor. The thermodynamic properties of the hydrated gaseous metallic species necessary for modeling metal solubility in fluids of moderate density (100–300 kg/m3) were derived from the results of experiments that investigated the solubility of metals in aqueous HCl- and H2S-bearing vapors. Metal transport and precipitation were simulated numerically as a function of temperature, pressure, and fluid composition (S, Cl, and redox). The simulated metal concentrations and ratios are compared to those observed in vapor-like and intermediate-density fluid inclusions from porphyry ore deposits, as well as gas condensates from active volcanoes. The thermodynamically predicted solubility of Cu, Au, Ag, and Mo decreases during isothermal decompression. At elevated pressure, the simulated metal solubility is similar to the metal content measured in vapor-like and intermediate-density fluid inclusions from porphyry deposits (at ~200–1,800 bar). At ambient pressure, the metal solubility approaches the metal content measured in gas condensates from active volcanoes (at ~1 bar), which is several orders of magnitude lower than that in the high-pressure environment. During isochoric cooling, the simulated solubility of Cu, Ag, and Mo decreases, whereas that of Au reaches a maximum between 35 ppb and 2.6 ppm depending on fluid density and composition. Similar observations are made from a compilation of vapor-like and intermediate-density fluid inclusion data showing that Cu, Ag, and Mo contents decrease with decreasing pressure and temperature. Increasing the Cl concentration of the simulated fluid promotes the solubility of Cu, Ag, and Au chloride species. Molybdenum solubility is highest under oxidizing conditions and low S content, and gold solubility is elevated at intermediate redox conditions and elevated S content. The S content of the vapor-like fluid strongly affects metal ratios. Thus, there is a decrease in the Cu/Au ratio as the S content increases from 0.1 to 1 wt %, whereas the opposite is the case for the Mo/Ag ratio; at S contents of >1 wt %, the Mo/Ag ratio also decreases. In summary, thermodynamic calculations based on experiments involving gaseous metallic species predict that vapor-like fluids may transport and efficiently precipitate metals in concentrations sufficient to form porphyry ore deposits. Finally, the fluid composition and pressure-temperature evolution paths of vapor-like and intermediate-density fluids have a strong effect on metal solubility in porphyry systems and potentially exert an important control on their metal ratios and zoning.

Most of the World’s large tungsten deposits are genetically related to fluorine-rich granitic magmas, their ores contain fluorine minerals, such as fluorite and topaz, and their host rocks have commonly undergone fluorine metasomatism to form greisens. In view of this evidence that tungsten ore fluids are enriched in fluorine, and the potential for fluoride to form stable complexes with hard acids (e.g., W6+), we investigated the solubility and speciation of tungsten in fluoride-bearing fluids at hydrothermal conditions. Experiments were conducted to measure the solubility of tungsten trioxide solid in fluoride-bearing aqueous fluids at temperatures between 100 and 250 °C and vapour-saturated water pressure. Based on the results of these experiments, tungsten is dissolved predominantly as H3WO4F2− in solutions containing 0.05–0.30 m HF at pH(T) values between 1.5 and 3.4. Significantly, the concentration of H3WO4F2− was up to two orders of magnitude higher than that of tungstate species in these experimental solutions. This species formed via the reaction WO3cryst + H2O + 2HF = H3WO4F2− + H+, logarithms of the equilibrium constants for which, vary from −4.39 ± 0.18 at 100 °C to −5.10 ± 0.17 at 250 °C. In solutions containing

Subtropical weathering of granitic catchments in South China has led to the formation of numerous giant regolith-hosted rare earth element (REE) deposits that currently account for more than 15% of global REE production and more than 95% of global heavy REE (HREE) production. Understanding the controls on mobilization and redistribution of the REEs during subtropical weathering in these granitic catchments is crucial for efficient exploration for this type of deposit in the world. As exemplified by the Bankeng light REE (LREE) deposit in South China, the key factors controlling the mobilization and redistribution of the REEs, especially the easily exchangeable REEs, are soil pH and primary REE mineralogy. The nature of the primary REE minerals, apatite, monazite-(Ce), and subordinate bastnäsite-(Ce), parisite-(Ce), and xenotime-(Y) places an important control on the behavior of the REEs during incipient weathering. Dissolution of these minerals is slow during incipient weathering, and, therefore, enrichment in REEs in this stage results largely from the removal of major elements during the decomposition of albite, K-feldspar, and biotite. Dissolution of the primary REE minerals higher in the profile liberates the REEs, which are then transported to locations where the soil pH abruptly increases due to water-regolith interaction, such as the pedolith-saprolite interface, and adsorption on kaolinite-group minerals efficiently fixes the REEs in regolith. Geomorphologically, the Bankeng deposit, like most of the other regolith-hosted REE deposits in South China, is located on concave-convex hillslopes, where erosion is prevalent at the ridgetop and decreases in intensity downslope. Results of this study show that strong erosion, coupled with intense chemical weathering at the ridgetop, is responsible for the enrichment in REEs by releasing the REEs, especially the LREEs, from their primary sources and supplying kaolinite and halloysite needed for the REE adsorption by decomposing albite, K-feldspar, and biotite. Decomposition of these major rock-forming minerals also leads to an enrichment of the REEs through the removal of components. The HREEs are lost preferentially to the groundwater and transported downslope, resulting in the enrichment of these elements in the lower part of the weathering crust at the footslope. Significant lateral Ce transport is also probable. A series of oxic fronts were developed at the footslope, with the most persistent one along the saprolite-saprock interface, due to seasonal fluctuations of the groundwater table. Cerium was immobilized there, predominantly through adsorption on Fe-Mn oxyhydroxides, causing enormous accumulation. Therefore, hillslope processes and groundwater flow could redistribute the REEs across the entire catchment, preferentially enriching the LREEs at the ridgetop and the HREEs at the footslope. Also, intense erosion facilitates chemical weathering and the accumulation of REEs, but the development of a thick weathering crust is favored by weak erosion. Repeated periods of high and low erosion rates in South China have enabled the gradual development of thick weathering crusts at the ridgetops that are sufficiently enriched in REEs to now constitute a major resource of these economically important elements.

The Kallianos Au-Ag-Te deposit in Evia Island (Greece) comprises sixteen syntaxial veins that intersect the schists and marbles of the Cycladic Blueschist Unit. The veins are filled with quartz-I and quartz-II, contain two hypogene ore stages (stages I and II), and are surrounded by infrequent muscovite-chlorite alteration zones. A magmatic origin is deduced for the Kallianos Au-Ag-Te mineralization, based on stable (S, C, Si, O, and H) and radiogenic (Pb, Sr, and Rb) isotopes, and fluid chemistry. The veins were deposited under pressures of ~ 220 to ~ 145 bars and temperatures of ~ 260 to 120 °C, from almost neutral H2Te-bearing hydrothermal fluids with a salinity of 2.2 to 15.8 wt.% NaCl equivalent. The telluride mineralization related to stage II was deposited at ~ 180 °C and evolved from Au- through Bi- to Ag-bearing tellurides. The vein minerals precipitated by simple cooling of almost non-reactive fluids that retained their initial magmatic signature. Taking into account the magmatic origin of the Kallianos deposit, we examine two proximal areas with granodioritic and leucogranitic intrusions similar to those associated with base and precious metal mineralization at Lavrion (~ 8.3 to ~ 7.1 Ma) and Tinos Island (~ 15 to ~ 13 Ma), as potential sources for the Kallianos fluids. Rb-Sr geochronology dating of the distal Kallianos Au-Ag-Te veins gave an age range of 8.1 to 7.6 Ma, implying that an overlapping and channelized hydrothermal system was active at the northern part of the Attico-Cycladic Metallogenetic Massif, utilizing the CBU detachment zones as fluid pathways.

Permian-Triassic granites and associated tin deposits are widespread in the Eastern and Western belts of Peninsular Malaysia. The ages and key controlling factors of tin mineralization, however, are poorly constrained. Cassiterite separates from the Sintok and Rahman tin deposits in the Western belt, and Bandi, Setahum, Lembing, and Cherul tin deposits in the Eastern belt have U-Pb ages of 218.9 ± 3.4 and 226.8 ± 7.6 Ma, and 213.1 ± 3.9, 270.6 ± 4.6, 282.7 ± 4.6, and 281.3 ± 3.5 Ma, respectively. These ages directly constrain the tin mineralization in Peninsular Malaysia to two separate periods: 290 to 270 Ma and 230 to 210 Ma. Zircon crystals from tin-bearing granites in the Cherul and Sintok deposits have U-Pb ages of 276.0 ± 1.9 and 221.9 ± 0.6 Ma, respectively, consistent with the cassiterite U-Pb ages within uncertainties. Zircon crystals from barren granites of the Kuantan pluton in the Eastern belt have a U-Pb age of 260.5 ± 0.7 Ma, which is between the two tin mineralization periods. Zircon from these barren granites have εHf(t) values from −5.4 to 3.6, two-stage Hf model ages (TDM2) from 1.4 to 1.0 Ga, and Ce4+/Ce3+ ratios from 40 to 120. By comparison, zircon crystals from the tin-bearing granites have low εHf(t) values (−9.7 to −3.2) and Ce4+/Ce3+ ratios (4–67) and high TDM2 (1.8–1.4 Ga). Zircon ages, Hf isotopes, and trace elements indicate that the tin-bearing granitic magmas in Peninsular Malaysia had relatively low oxygen fugacity and were derived from reworking of Paleo- to Mesoproterozoic sedimentary rock-dominated crust in response to the Paleo-Tethyan subduction and continental collision. This study confirms that the nature of magma sources and redox states of magmas were key in the formation of the tin-rich granites and associated tin deposits and that the granite-related tin mineralization in Peninsular Malaysia was closely related to the evolution of the eastern Paleo-Tethys.

The solubility of molybdenum trioxide (MoO3(s)) in aqueous solutions has been investigated experimentally at 250°, 300°, and 350°C and saturated water vapor pressure, and total Na concentrations ranging from 0 to 3 molal (m). Results of these experiments show that the solubility of MoO3(s) increases with increasing temperature and at 350°C can reach several thousand parts per million at high salinity (>1 m NaCl). At low Na+ activity, MoO3(s) dissolves dominantly as HMoO4,− whereas at high Na+ activity, the dominant species is NaHMoO40. The two dissolution reactions are MoO3(s)+H2O=HMoO4−+H+(1) and MoO3(s)+H2O+Na+=NaHMoO40+H+.(2) The values of the logarithms of the equilibrium constants for reaction (1) are –5.20 ± 0.12, –5.31 ± 0.17, and –5.50 ± 0.09 at 250°, 300°, and 350°C, respectively, and for reaction (2) the values are –3.40 ± 0.11, –3.25 ± 0.19, and –2.97 ± 0.09 for the same temperatures. In combination, these equilibrium constants yield equilibrium constants for the reaction relating the two aqueous species: Na++HMoO4−=NaHMoO40.(3) The values of the logarithms of the equilibrium constants for reaction (3) are 1.80 ± 0.16, 2.06 ± 0.25, and 2.53 ± 0.13 at 250°, 300°, and 350°C, respectively. Calculations, based on the results of this study and thermodynamic data available for other species, suggest strongly that in ore-forming hydrothermal systems, molybdenum is transported mainly as NaHMoO40 and deposits as molybdenite in response to cooling and possibly a reduction in fO2.

The newly discovered Shuangjianzishan Ag-Pb-Zn deposit, with 145 Mt of ore grading 128.5 g/t Ag (locally up to 32,000 g/t) and 2.2 wt % Pb + Zn, is located in the Great Hinggan Range metallogenic belt, northeastern China, and is currently the largest Ag deposit in Asia. The Ag-Pb-Zn orebodies occur as veins and are hosted primarily by a Permian slate. Recent drilling and core logging have identified a partially Mo mineralized granite porphyry intrusion adjacent to the Ag-Pb-Zn mineralized veins. This well-preserved magmatic-hydrothermal system therefore offers an excellent opportunity to evaluate the possible temporal and genetic relationship between Mo-mineralized porphyry intrusions and Ag-Pb-Zn veins. Three primary paragenetic stages of veining have been recognized: (I) early pyrite + quartz ± K-feldspar, (II) main ore sulfide + sulfosalt + quartz + calcite + sericite + chlorite ± epidote, and (III) post-ore quartz. The silver mineralization occurs mainly in the late paragenetic part of Stage II, in which canfieldite (Ag8SnS6), argentite (Ag2S) and freibergite [(Ag, Cu)12Sb4S13] are the dominant Ag-bearing ore minerals. A combination of ore mineral chemical and sulfur isotope geothermometers and physicochemical calculations suggest that the Ag-Pb-Zn mineralization took place at a temperature of 250° to 200°C, a pH of 6.7 to 5.6, and a Δlogfo2 (HM) of –2.4 to –8.7. A conspicuous enrichment of Sn and Se in the ore, which is represented by minerals containing the metal suite Ag-Pb-Zn-(Cu-Sn-Se-Sb), likely reflects a close genetic association between the base metal mineralization and a magma. In situ analyses show that the δ34S values of the sulfides and Ag-bearing sulfosalts from the Ag-Pb-Zn mineralized veins vary from –4.67 to +2.44‰; the mean value is –2.11 ± 1.49‰ (n = 77). The calculated mean δ34SH2S value of the ore-forming fluid is –1.65 ± 0.83‰, which is indicative of a magmatic sulfur source. In situ Pb isotope analyses of the ore minerals yielded a narrow range of values (206Pb/204Pb of 18.243–18.310, 207Pb/204Pb of 15.503–15.563 and 208Pb/204Pb of 38.053–38.203, n = 59). Comparisons to corresponding isotopic data for the various rock units in the area and sulfides from nearby ore deposits indicate that there were substantial contributions of Pb and other metals (e.g., Ag and Zn) to the Shuangjianzishan deposit from a Mesozoic granitic source. Diorite-granodiorite dikes and dacite are crosscut by the Ag-Pb-Zn veins, and therefore, predate ore formation. These rock units have zircon U-Pb ages of 250.2 ± 2.0 and 133.9 ± 1.4 Ma, respectively. A concealed, weakly Mo mineralized granite porphyry intrusion proximal to the Ag-Pb-Zn mineralized vein system yielded zircon U-Pb ages of 134.4 ± 1.0 (MSWD = 0.1) and 134.4 ± 1.0 Ma (MSWD = 0.2), for coarse- and fine-grained facies, respectively. These ages are indistinguishable within the uncertainty from the zircon ages for the dacite and a granite intrusion ~2 km north of the mineralized veins, which has a weighted mean zircon U-Pb age of 135.2 ± 1.4 Ma (MSWD = 0.78). Molybdenite from three quartz vein/veinlet samples hosted by slate immediately above the porphyry intrusion yielded Re-Os model ages from 136.3 ± 0.9 to 133.7 ± 1.2 Ma and a weighted mean Re-Os age of 134.9 ± 3.4 Ma. Finally, three pyrite samples separated from the Ag-Pb-Zn mineralized veins have a weighted mean Re-Os model age of 135.0 ± 0.6 Ma. The very similar zircon U-Pb ages for the Mo-mineralized granite porphyry and dacite, and Re-Os ages for molybdenite and pyrite in the Shuangjianzishan ore district indicate that the Mesozoic magmatic-hydrothermal activity was restricted to a relatively short time interval (~136–133 Ma). They also suggest that the weakly Mo mineralized granite porphyry was likely the source of the fluids and metals that produced the Ag-Pb-Zn mineralization. Based on our geological observations and an extensive analytical database, a model is proposed for the genesis of the giant Shuangjianzishan Ag-Pb-Zn deposit in which the ore-forming fluid and its metals (i.e., Ag, Pb, and Zn) were exsolved during crystallization of the final phase of a composite granite porphyry intrusion. This fluid transported metals to the distal parts of the system, where they were deposited in preexisting faults or fractures created by the withdrawal of magma during the waning stages of the magmatic-hydrothermal event. The present study of the Shuangjianzishan Ag-Pb-Zn deposit and those of other magmatic-hydrothermal ore deposits in the region provide compelling evidence that the widespread Mesozoic felsic magmatism and Ag-Pb-Zn mineralization in the southern Great Hinggan Range took place in an intracontinental extensional tectonic setting, which was synchronous with, and spatially associated to, Paleo-Pacific slab rollback and lithospheric delamination and thinning.

The solubility of tungsten trioxide solid and the speciation of tungsten in NaCl-bearing solutions have been investigated through experiments conducted at 250, 300, and 350 °C under vapour-saturated water pressure. Based on the results of these experiments, the solubility of tungsten trioxide was controlled by temperature and pH, whereas the NaCl concentration did not affect the solubility except through its influence on the ionic strength of the solution. Two tungsten species were found to be present in the solutions, namely H2WO40 at low pH and HWO4− at higher pH. These two species formed via the reactions WO3 + H2O = H2WO40 and WO3 + H2O = HWO4− + H+, respectively. The logarithms of the equilibrium constants for these reactions are −5.18 ± 0.26, −4.97 ± 0.25, −4.69 ± 0.10, and −7.91 ± 0.30, −7.67 ± 0.29, −7.52 ± 0.18 for 250, 300, and 350 °C, respectively. In addition, the logarithms of the first and second association constants of H2WO40 were determined to be 2.72, 2.71, 2.83, and 5.59, 6.49, 8.07 for 250, 300, and 350 °C, respectively. These values indicate that H2WO40 is only important at low pH values (

Although the ore fluid for Mississippi Valley Type (MVT) deposits is universally considered to be a basinal brine, the common occurrence of liquid hydrocarbons as inclusions in one of the ore minerals (sphalerite) raises the question of whether liquid hydrocarbons could play a role in metal transport. Here we explore the potential of liquid hydrocarbons to act as an ore fluid by determining the steady-state concentration of zinc in crude oil and evaluating the factors that promote its dissolution. To this end, zinc wires were reacted with a series of oils (labelled oils A, B and C) at 150, 200 and 250 °C, and the steady-state concentration of Zn was determined. Zinc concentrations were observed to increase with temperature and with the Total Acid Number (TAN) of the oils, the latter of which is strongly correlated to the carboxylic acid content of crude oil. Crude oil B, the highest TAN oil, dissolved 1700 ± 0.8 ppm at 250 °C, which is comparable to the highest Zn concentration inferred to have been dissolved in brines interpreted to represent MVT ore fluids. X-ray Photoelectron Spectroscopic (XPS) analyses performed on the residual oil coating the zinc wires after the reaction supported the conclusion that Zn has a strong chemical affinity for carboxylic acids in crude oil. Finally, an experiment designed to precipitate sphalerite crystals from a Zn-rich synthetic oil at room temperature showed that sphalerite precipitation from liquid hydrocarbons proceeds efficiently in a carbonate-buffered, H2S -rich environment.

In principle, potentially economic (fertile) granites can be distinguished from uneconomic (barren) granites based on the composition of their magmas. Ideally, this composition would be evaluated by analysing melt inclusions, but such inclusions are rarely preserved and difficult to analyse. Information on the composition of magmas can also be obtained from the composition of the minerals crystallising from these magmas, if the mineral-melt partition coefficients are known. In some cases, where these partition coefficients are not known, they have been calculated from lattice strain theory. Here we report arfvedsonite-melt partition coefficients for the rare earth elements (REE) calculated from the results of analyses of arfvedsonite, bulk rock and melt inclusions in granites and pegmatites in the Strange Lake peralkaline rare metal pluton. These coefficients were fitted to the lattice strain model from which values of the ideal partition coefficient (D0), the ideal radius (r0) and the elastic response (EM) were determined. The light REE were shown to partition preferentially into the M4 site and the heavy REE into the M2 site, requiring that partition coefficients be calculated for each site. The partition coefficients for both sites were shown to decrease systematically with increasing evolution of the magma, i.e., from the early hypersolvus granite to the late pegmatites. In the case of the M4 site, D0, r0 and EM vary linearly with the Ca content of the arfvedsonite. By contrast, these parameters for the M2 site vary linearly with temperature. The two relationships form the basis of a predictive model, in which the arfvedsonite-melt REE partition coefficients for other peralkaline granites can be estimated, provided that the Ca content of the amphibole and its crystallisation temperature are known. This model was applied to a peralkaline granitic pegmatite from the Amis complex (Namibia) for which data on the composition of the amphibole and corresponding magma (melt inclusions) have been reported. The model successfully predicts the concentrations of the various REE in this magma, thereby providing confidence that it can be used to discriminate between granites that are potentially fertile and those that are barren in respect to the REE.

The Proterozoic Athabasca Basin is well known for its unusually large-tonnage and high-grade ‘unconformity-related’ uranium (U) deposits, however, explanations for the basin-wide U endowment have not been clearly identified. Previous studies indicate that U-rich brines with up to ~600 ppm U and variable Na/Ca ratios (from Na-dominated to Ca-dominated) were present at the sites of U mineralization, but it is unknown whether such fluids were developed solely in the vicinity of the U deposits or at a basinal scale. Our microthermometric and LA-ICP-MS analyses of fluid inclusions in quartz overgrowths from the barren part of the basin indicate that U-rich brines (0.6 to 26.8 ppm U), including Na-dominated and Ca-dominated varieties, were widely developed in the basin. These U concentrations, although not as high as the highest found in the U deposits, are more than two orders of magnitude higher than most naturally occurring geologic fluids. The basin-scale development of U-rich diagenetic fluids is interpreted to be related to several geologic factors, including availability of basinal brines and U-rich lithologies, and a hydrogeologic framework that facilitated fluid circulation and U leaching. The combination of these favorable conditions is responsible for the U fertility of the Athabasca Basin.

Titanium (Ti) is typically hosted in detrital minerals in marine sediments and has long been considered to be immobile during diagenesis. In this study, the authigenic titania minerals, brookite and anatase, are observed in early Cambrian carbonaceous shales from the Meishucun and Zhajin sections of South China, respectively. Black shales in the Meishucun section have total organic carbon (TOC) contents from 1.6 to 3.9 wt% and HI (hydrogen index) values from 3.8 to 20 mg HC/g TOC, whereas black shales in the Zhajin section have much higher TOC (7.1–15.6 wt%) but lower HI (

Large peralkaline complexes are ‘factories’ that have produced a variety of ‘exotic’ minerals including high field strength element minerals. In most cases, these minerals are secondary and crystallise in a hydrothermal paragenesis that is extremely difficult to decipher due to the complexity of the textural relationships. The Strange Lake pluton is one of these complexes, and contains 37 exotic minerals, most of which are secondary. Adding to the difficulty in establishing a comprehensive paragenesis for these minerals and an alteration/precipitation path for the pluton is the fact that there were several stages of crystallisation of the same exotic and common secondary minerals, e.g., bastnasite, fluocerite, gadolinite, aegirine, fluorite, and zircon. In this paper, we present a model, which describes a detailed path for the alteration and precipitation of minerals in the closed hydrothermal system of a peralkaline granitic pegmatite, based on direct measurements of the evolving composition of the aqueous fluid that exsolved from the late-stage magma crystallising rare-metal pegmatites in the Strange Lake pluton. The driving force for this evolution was cooling-induced oxidation that ultimately transformed the CH4-H2 gas in this fluid to CO2. This led to a large drop in the pH, which was a major control on the composition of the fluid and the crystallisation of secondary minerals. Although large numbers of minerals formed and were replaced during the different stages of fluid evolution, the changing chemistry of the fluid was largely a response to the alteration of four minerals, namely arfvedsonite, elpidite, narsarsukite and fluorite. The earliest stage of alteration, which took place at ~360 °C, was marked by the replacement of arfvedsonite by aegirine. This alteration decreased salinity and released K, Li, and Rb to the fluid, causing K-metasomatism. At ~300 °C, CH4 and higher hydrocarbons reacted to produce CO2. This caused a massive drop in pH from a value > 10 to a value of ~3 and intense alteration, which included the dissolution of fluorite, the breakdown of elpidite to zircon and quartz and the replacement of narsarsukite by titanite. With ongoing dissolution of fluorite, Ca activity reached a level sufficient to promote the alteration of elpidite to armstrongite or gittinsite. This was accompanied by alteration of arfvedsonite to ferroceladonite and microcline to Al-phyllosilicates, enriching the fluid in Na, Fe and F. Soon after, there was a near total loss of CO2 (at ~230 °C). This loss was catastrophic and was focused along conical fractures (these developed as a result of the collapse of the roof of the pluton), with resultant fragmentation of the rocks along the fluid path. Alteration to phyllosilicates continued after the loss of CO2, as the system cooled to ~190 °C. This marked the beginning of the final stage of alteration, which involved the replacement of arfvedsonite by aegirine and hematite. It also coincided with large scale hematisation within the pluton. Finally, it led to the cementation of the fragments along the fluid path to form the fluorite-hematite ring breccia that is now evident at the margins of the pluton. The model of fluid evolution presented here is potentially applicable to many other peralkaline complexes. The only requirements are that the system was closed until a relatively late stage and that the exsolved fluid was saline and contained a reduced carbonic component. This is a feature of many peralkaline complexes, most notably, the Khibiny and Lovozero complexes in Russia, and Ilimaussaq in Greenland.

This contribution presents a thermodynamic model revealing the mechanisms responsible for separation of Heavy and Light Rare Earth (HREE and LREE) phosphates in natural hydrothermal systems at temperatures of 250–350 °C. Our calculations were performed for an isothermal column of rock containing 0.5 wt% of apatite (Ca phosphate), which served as an immobilizing agent for REE dissolved in the solution. REE were transported by 10 wt% NaCl acidic solution. The model accounted for formation of REE phosphate solid solutions through a regular mixing model. It demonstrates that hydrothermal flushing can efficiently separate REE forming xenotime (HREE phosphate solid solutions) at the beginning of the column, and re-transportation of monazite (LREE rich) to the end of the column. This separation is primarily due to the fact that at elevated temperatures stability LREE chloride complexes is significantly higher than that for HREE. The model also evaluates behavior of U and Th, which accompany REE in vast majority of natural locations. It was found that U strongly fractionates to xenotime, whereas Th fractionates to monazite. This phenomenon can be explained by the differences in crystal-chemical characteristics between monazite and xenotime, and the mobility of Th in aqueous solutions at elevated temperatures.

Significance Hydrothermal veins supply much of the Earth’s gold. Their propensity to contain “bonanza” occurrences of gold that have concentrations millions of times greater than the concentration of gold in Earth’s crust makes them important targets for exploration and resource development. The mechanisms by which such hyperenrichment occurs are enigmatic. The accepted wisdom is that this enrichment reflects the saturation and precipitation of gold from hydrothermal fluids. Laboratory experiments and measurements of active hydrothermal systems, however, have shown that the solubility of this noble metal is exceptionally low. Here, we demonstrate that this issue is resolved by the physical transport of gold in the solid state as nanoparticles and their flocculated aggregates, thereby explaining the paradox of bonanza gold ore formation., Aqueous complexation has long been considered the only viable means of transporting gold to depositional sites in hydrothermal ore-forming systems. A major weakness of this hypothesis is that it cannot readily explain the formation of ultrahigh-grade gold veins. This is a consequence of the relatively low gold concentrations typical of ore fluids (tens of parts per billion [ppb]) and the fact that these “bonanza” veins can contain weight-percent levels of gold in some epithermal and orogenic deposits. Here, we present direct evidence for a hypothesis that could explain these veins, namely, the transport of the gold as colloidal particles and their flocculation in nanoscale calcite veinlets. These gold-bearing nanoveinlets bear a remarkable resemblance to centimeter-scale ore veins in many hydrothermal gold deposits and give unique insight into the scale invariability of colloidal flocculation in forming hyperenriched gold deposits. Using this evidence, we propose a model for the development of bonanza gold veins in high-grade deposits. We argue that gold transport in these systems is largely mechanical and is the result of exceptionally high degrees of supersaturation that preclude precipitation of gold crystals and instead lead to the formation of colloidal particles, which flocculate and form much larger masses. These flocculated masses aggregate locally, where they are seismically pumped into fractures to locally form veins composed largely of gold. This model explains how bonanza veins may form from fluids containing ppb concentrations of gold and does not require prior encapsulation of colloidal gold particles in silica gel, as proposed by previous studies.

Whether giant porphyry ore deposits are the products of single, short-lived magmatic-hydrothermal events or multiple events over a prolonged interval is a topic of considerable debate. Previous studies, however, have all been devoted to porphyry Cu and Cu-Mo deposits. In this paper, we report high-precision isotope dilution-negative-thermal ionization mass spectrometric (ID-N-TIMS) molybdenite Re-Os ages for the newly discovered, world-class Chalukou porphyry Mo deposit (reserves of 2.46 Mt @ 0.087 wt % Mo) in NE China. Samples were selected based on a careful evaluation of the relative timing of the different vein types (i.e., A, B, and D veins), thereby ensuring that the suite of samples analyzed could be used to reliably determine the age and duration of mineralization. The molybdenite Re-Os geochronology reveals that hydrothermal activity at Chalukou involved two magmatic-hydrothermal events spanning an interval of 6.92 ± 0.16 m.y. The first event (153.96 ± 0.08/0.63/0.79 Ma, molybdenite ID-N-TIMS Re-Os age) was associated with the emplacement of a granite porphyry dated at 152.1 ± 2.2 Ma (zircon laser ablation-inductively coupled plasma-microscopic [LA-ICP-MS] U-Pb ages), and led to only minor Mo mineralization, accounting for 90%) was deposited in less than 650 kyr, between 147.67 ± 0.10/0.60/0.76 and 147.04 ± 0.12/0.72/0.86 Ma (molybdenite ID-N-TIMS Re-Os ages), coincident with the emplacement of a fine-grained porphyry at 148.1 ± 2.6 Ma (zircon LA-ICP-MS U-Pb ages). The high-precision Re-Os age determinations presented here show, contrary to the finding of a number of studies of porphyry Cu and Cu-Mo systems, that the giant Chalukou porphyry Mo deposit primarily formed in a single, short-lived (

The high mobility of boron during fluid-rock interaction makes it an effective tracer for the sources of magmatic and metamorphic fluids, as recorded in minerals such as tourmaline and muscovite. Although advances have been made in quantifying the fractionation of boron isotopes among different phases, boron isotope fractionation in complex silicate melts remains poorly understood. Here, we propose appropriate models for the BO 3 and BO 4 units in silicate melts covering a wide range of chemical compositions and boron coordination structures in silicate magmas, and report the results of a theoretical investigation of boron isotope fractionation among silicate melt, minerals and fluids using a first principles theoretical approach. A comparison of measured and calculated α factors in mineral-melt and fluid-melt systems shows good agreement, suggesting the applicability of a simplified treatment of boron coordination structures in silicate melt. The results of this study show that the proportion of trigonal/tetrahedral coordinated boron and the B/Si ordering in silicate tetrahedral layers control the boron isotope fractionation among different phases, and that the effect of chemical composition is minor (less than 2‰ at 600 K). The temperature-dependent boron isotope fractionations are described as 1000lnα mica-basic fluid = 0.8–2.4 × (1000/T) - 0.8 × (1000/T) 2, 1000lnα mica-acidic fluid = 7.0–14.0 × (1000/T) - 1.2 × (1000/T) 2 and 1000lnα mica-tur = 1.9–5.4 × (1000/T) -3.4 × (1000/T) 2 (T is temperature in Kelvins). At magmatic temperatures, ∆ 11B values between mineral/fluid and melt also vary with the proportion of the BO 4 unit in the melt. This study underpins the applicability of the white mica-tourmaline geothermometers and boron isotopes for fluid source identification, and also offers an explanation of boron isotope fractionation in systems that contain complex silicate melts.

International audience; The world-class, oxidized intrusion-related Canadian Malartic gold deposit, with reserves estimated at 5.56 Moz Au grading 1.10 g/t Au, and a total geological endowment of 16.3 Moz Au, is one of the largest gold deposits in the Archean Superior Province of Canada. The gold mineralization is hosted predominantly by Pontiac Group metasedimentary rocks, Piché Group metavolcanic rocks, and quartz monzodiorite to granodiorite porphyritic intrusions. The ore takes the form of a low-grade envelope of disseminated pyrite (0.35 to 1 g/t Au) grading inwards into higher grade (>1 g/t Au) stockwork and breccia zones. Hydrothermal alteration in the metase-dimentary rocks is zonally distributed around the fluid pathways. Proximal alteration is characterized by a microcline±albite-quartz replacement-type assemblage, with lesser phlogopite, calcite±Fe-dolomite, pyrite and rutile. The distal alteration assemblage comprises biotite, microcline±albite, phengite, quartz, calcite, pyrite and rutile. In this study, we assess the magnitude and distribution of fluid-rock interaction in the metasedimentary rocks of the Malartic district. The metaturbidites are separated into four lithotypes based on grain-size to reduce the effects of primary depositional processes on mass change calculations. Despite the variability in protolith composition, the metasedimentary rocks define a geochemically consistent, cogenetic sequence. The results of the mass transfer calculations indicate progressive gains in CO 2 , S, K 2 O and LOI, as well as Au, Te, W, Ag, As, Be, Sb, Bi, Mo and Pb, from background, to distal and proximal alteration zones (relative to the least-altered samples). Molar element ratio analysis (alkali/aluminum) indicates an increase in alkali metasomatism (K and Na) adjacent to the main hydrothermal fluid pathways, which is manifested by the progressive stabilization of microcline and albite at the expense of oligoclase, biotite and white mica. Ore-associated pathfinder elements delineate broad enrichment patterns around the deposit, and are used to understand hydrothermal fluid circulation in the Malartic district. A statistical approach based on a comparison of the mass change results with the background composition provides robust constraints on the magnitude and extent of the lithogeochemical haloes. Generally, the alteration forms envelopes that extend along the S 2 fabric, with the largest lithogeochemical anomalies (e.g., Au, W, Te and Ag) reaching up to 10 km in length, and 2 km in width. The results of this study demonstrate that whole-rock lithogeochemistry can provide a valuable tool with which to define vectors toward gold mineralization in a regional exploration context.

The solubility and speciation of Th in Cl-bearing solutions saturated in ThO2 was investigated experimentally at 150, 175, 200, 225 and 250 °C, and saturated water vapor pressure. At these experimental conditions (pH25°C T h 4 + + 2 O H - ↔ T h ( O H ) 2 2 + and T h 4 + + 4 O H - ↔ T h ( O H ) 4 0 . The logarithms of the formation constants determined for the first reaction are 23.91 ± 0.05, 24.79 ± 0.07, 25.78 ± 0.05, and 25.85 ± 0.05 for 175, 200, 225 and 250 °C, respectively, and 42.18 ± 0.06, 43.50 ± 0.07, 43.17 ± 0.08, and 43.74 ± 0.11 for the second reaction at the same temperatures. Formation constants could not be determined reliably for 150 °C. Extrapolations of our formation constants to 25 °C are in excellent agreement with the values determined at 25 °C by Neck and Kim (2001) and Ekberg et al. (2000). For natural systems buffered by thorianite (ThO2), the solubility determined in our study likely reflects a minimum, as the presence of additional ligands would lead to higher solubility.

The Khetri Copper Belt (KCB) in northwestern India contains several economically important hydrothermal Cu–(Au) deposits. Orebodies in these deposits are locally rich in monazite-(Ce). In this study, in situ U–Pb ages and Sm–Nd isotopic compositions of monazite-(Ce) are used to constrain the timing of mineralization and to better understand the genesis of the Cu–(Au) deposits. Monazite-(Ce) crystals were identified in the Madhan-Kudhan and Kolihan deposits in the KCB. Most monazite-(Ce) crystals in the two deposits show close textural associations with hydrothermal minerals (biotite, chlorite, and sulfide) and have low contents of ThO2 (mostly

Although it is well known that A-type granites are enriched in the rare earth elements (REE) and other high field strength elements (HFSE), the magmatic processes that concentrate these elements are still poorly understood. The 1.24 Ga Strange Lake pluton in northern Quebec-Labrador provides an extraordinary example of hyper-enrichment in the REE, Zr, and Nb in a peralkaline A-type granite. The pluton consists of two hypersolvus granite units (southern and northern) and a transsolvus granite, all of which contain perthitic alkali feldspar as the earliest major mineral; the transsolvus granite also contains separate albite and microcline crystals. Arfvedsonite, a sodic amphibole, occurs exclusively as phenocrysts in the transsolvus granite, whereas in the hypersolvus granite it is present as a late, interstitial phase. The primary HFSE minerals are zircon, monazite-(Ce), gagarinite-(Ce) and the pyrochlore group minerals. Magma evolution was monitored by the alumina content in the bulk rock, which decreases from the southern to the northern hypersolvus granite and is lowest in the transsolvus granite. Alkalinity indices and bulk Si, Fe, Rb, REE, Zr, Nb concentrations show the opposite trend. Alkali feldspar compositions mirror the trend shown by the bulk rock, i.e., decreasing Al contents are accompanied by increasing Si, Fe3+, REE, Zr and Nb contents. The major driving forces for the evolution of the hypersolvus magma prior to emplacement were the early separation of a fluoride melt from the silicate melt and the crystallization of alkali feldspar and HFSE-rich phases (zircon, monazite-(Ce), pyrochlore group). An alkali feldspar-rich crystal-mush containing LREE-fluoride melt droplets was emplaced as the least evolved southern hypersolvus granite. Massive fractionation of alkali feldspar led to a sharp increase in ƒH2O and F− activity in the magma chamber that triggered the crystallization of arfvedsonite and was followed by emplacement of the northern hypersolvus granite, which contained a higher proportion of LREE-fluoride melt droplets. Further evolution in the magma chamber led to a transition from a miaskitic to an agpaitic composition. The transsolvus granite was intruded in the form of a low viscosity crystal mush of alkali feldspar, quartz, arfvedsonite (after appreciable crystallization of arfvedsonite) and LREE-fluoride melt droplets. Upon emplacement, arfvedsonite (and gagarinite-(Ce)) crystals segregated as cumulates in response to a combination of flow differentiation and gravity settling. The immiscible fluoride melt accumulated in a volatile-rich residual silicate magma, which migrated to the top of the pluton where it formed the F-REE-rich cores of highly mineralized pegmatites.

This paper reports the results of a visible, near-infrared and short wave infrared (V-NIR-SWIR) spectroscopic study of the Nechalacho rare earth element (REE)-Nb-Zr deposit (Canada), associated rare metal pegmatites and select samples from other REE deposits. The zoning of minerals produced by hydrothermal alteration is traced using V-NIR-SWIR spectroscopic measurements in combination with geological, geochemical and mineralogical data. The minerals detected using V-NIR-SWIR spectroscopy (analcime, ankerite, biotite, chlorite, illite, REE-fluorocarbonates) display complex spatial distributions that were strongly controlled by the pathways and composition of multiple stages of hydrothermal fluids as well as the precursor lithology. Magmatic-hydrothermal analcime ± amphibole alteration was overprinted by regional biotite + magnetite + illite + ankerite + chlorite + REE-fluorocarbonate replacement. A qualitative mass change analysis indicates that the latter alteration (main-stage) was associated with significant gains in Mg and losses of Na at temperatures of ~300 °C, as indicated by the presence of phengitic to muscovitic illite. Low-temperature ankerite ± chlorite alteration was mainly fluid-controlled and associated with the formation of hydrothermal REE-fluorocarbonate minerals that crystallized as a result of the interaction of aqueous-carbonic hydrothermal fluids with eudialyte syenite protoliths, locally leading to leaching and re-deposition of light REE. The ankerite ± chlorite alteration also affected pegmatites peripheral to the Nechalacho intrusion and surrounding hydrothermally altered zones. Analysis of a variety of REE-mineral specimens and geochemically characterized bulk rock samples showed that the relative depths of the 741 and 864 nm NIR absorption features of Nd can be used as qualitative and quantitative proxies for the detection of the REE. In combination with fast measurement and processing capabilities, this allows field-based V-NIR-SWIR spectroscopy to be deployed as a powerful tool for regional and deposit-scale REE exploration, deposit characterization and mine production grade control.

The behavior of uranium in environments, ranging from those of natural systems responsible for the formation of uranium deposits to those of nuclear reactors providing 11% of the world’s electricity, is governed by processes involving high-temperature aqueous solutions. It has been well documented that uranium is mobile in aqueous solutions in its oxidized, U6+ state, whereas in its reduced, U4+ state, uranium has been assumed to be immobile. Here, we present experimental evidence from high temperature (>100 °C) acidic brines that invalidates this assumption. Our experiments have identified a new uranium chloride species (UCl4°) that is more stable under reducing than oxidized conditions. These results indicate that uranium is mobile under reducing conditions and necessitate a re-evaluation of the mobility of uranium, particularly in ore deposit models involving this metal. Regardless of the scenario considered, reducing conditions can no longer be considered a guarantee of uranium immobility., Ore deposits and nuclear reactors are greatly affected by the solubility and speciation of uranium at elevated (>100 °C) temperature. Here, the authors identify a new uranium chloride species (UCl40), which is mobile under reducing conditions, thereby necessitating a re-evaluation of uranium mobility.

Granites and pegmatites in the Strange Lake pluton underwent extreme enrichment in high field strength elements (HFSE), including the rare earth elements (REE). Much of this enrichment took place in the most altered rocks, and is expressed as secondary minerals, showing that hydrothermal fluids played an important role in HFSE concentration. Vasyukova et al. (2016) reconstructed a P-T-X path for the evolution of these fluids and provided evidence that hydrothermal activity was initiated by exsolution of fluid during crystallisation of border zone pegmatites (at ~450–500 °C and 1.1 kbar). This early fluid comprised a high salinity (25 wt% NaCl) aqueous phase and a CH4 + H2 gas. During cooling, the gas was gradually oxidised, first to higher hydrocarbons (e.g., C2H6, C3H8), and then to CO2, and the salinity decreased to 4 wt% (~250–300 °C), before increasing to 19 wt%, due to fluid-rock interaction (~150 °C). Here, we present crush-leach fluid inclusion data on the concentrations of the REE and major ligands at different stages of the evolution of the fluid. The chondrite-normalised REE profile of the fluid evolved from light REE (La-Nd)-enriched at high temperature (~400 °C, Stages 1–2a) to middle REE (Sm-Er)-enriched at 360 to 250 °C (Stages 2b–3) and strongly heavy REE (Tm-Lu)-enriched at low temperature (150 °C, Stage 5). These changes in the REE distribution were accompanied by changes in the concentrations of major ligands, i.e., Cl− was the dominant ligand in Stages 1, 2, 4 and 5, whereas HCO3− was dominant in Stage 3. Alteration of arfvedsonite to aegirine and/or hematite contributed strongly to the mobilisation of the REE. This alteration released middle REE (MREE) and heavy REE (HREE), which either partitioned into the fluid or precipitated directly as bastnasite-(Ce), ferri-allanite-(Ce) or gadolinite-(Y). Replacement of primary fluorbritholite-(Ce), which crystallised from an immiscible fluoride melt and altered to bastnasite-(Ce), was also important in mobilising the REE (MREE). This paper presents the first report of the distribution of the REE in an evolving hydrothermal fluid. Using this distribution, in conjunction with information on the changing physicochemical conditions, the study identifies the sources of REE enrichment, reconstructs the path of REE concentration, and evaluates the REE mineralising capacity of the fluid. Finally, this information is integrated into a predictive model for REE mobilisation applicable not only to Strange Lake but any REE ore-forming system, in which hydrothermal processes were important.

The ability to accurately determine the metal content of crude oils is necessary for reasons ranging from the need to identify the source of the oils (Ni and V) to removing components that might inhibit catalysis during refining or impact negatively on the environment during hydrocarbon combustion. Here we show that ashing followed by chemical oxidation and acid digestion, coupled with ICP-MS analysis, provides an accurate method for determining the concentration of metals in crude oil. Nickel and vanadium concentrations were measured in certified Ni and V oil standards and in various light, intermediate and heavy crude oils after application of a single vessel ashing-chemical oxidation-acid digestion sample preparation and storing technique. Prior to the ashing, chemical oxidation and acid digestion, an aliquot of the crude oil was placed in a 10 ml Pyrex™ culture tube and capped with quartz wool. The capped culture tubes were then subjected to thermal combustion, followed by chemical oxidation and leaching. The leachates and the aqueous standards were diluted and analyzed for their Ni and V contents using inductively coupled plasma mass spectrometry (ICP-MS). The measured concentrations of Ni in oil standards, reported to contain 1, 100, and 1000 mg kg−1 Ni (±2% error), were 1.1 ± 0.01, 99.8 ± 1.46, and 1025 ± 24 mg kg−1 respectively. The corresponding concentrations of V in these standards, reported to contain 2, 100, and 1000 mg kg−1 V, were measured to be 1.93 ± 0.06, 104 ± 1.3, and 1027 ± 7.5 mg kg−1, respectively. Crude oil samples, A, B, C, D and E, that varied significantly in their composition, and ranged from light to heavy, were determined to contain 5.59 ± 0.32, 4.05 ± 0.03, 6.22 ± 0.22, 33.8 ± 0.7 and 41.6 ± 3.5 mg kg−1 Ni, respectively. Their V contents were determined to be 11.98 ± 0.1, 12.2 ± 0.1, 16.5 ± 0.4, 34.7 ± 0.4, and 104 ± 8.9 mg kg−1, respectively. The results were thus repeatable on average to 4.1% and 2.75% for Ni and V, respectively; the repeatability was worst (∼8.5%) for crude oil E, a heavy (viscous) oil with a very high asphaltene content (27.2%). This modified single vessel ashing-digestion technique (combustion, chemical oxidation, acid leaching and storing) minimizes contamination and significantly reduces the loss of ash. Our results are repeatable, comparable to, and in some cases superior to those of other methods. The method is applicable to a wide range of crude oil compositions, is very accessible and robust, easy to use, and does not require costly equipment in preparing the samples for analysis by ICP-MS.

The speciation of U in NaCl-bearing solutions at temperatures up to 250 °C and concentrations of NaCl up to 1.5 m has been investigated using an in situ spectroscopic technique. The recorded spectra permit us to identify the species present in the solutions as UO22+, UO2Cl+, and UO2Cl2°. UO2Cl3− is also likely present at high temperatures and NaCl concentrations, but concentrations of this species are insufficient for derivation of the formation constants. No evidence was found for species of higher ligand (Cl−) number. Thermodynamic stability constants derived for these species show fair agreement with published data for 25 °C, but differ significantly from those predicted by an earlier high-temperature study (Dargent et al., 2013), which suggested that UO2Cl42− and UO2Cl53− contribute significantly to the mass balance of uranyl chloride complexes, especially at high temperature. In contrast, our data suggest that the main uranyl-chloride complex present in aqueous solutions at T > 150 °C and concentrations of NaCl relevant to natural hydrothermal systems is UO2Cl2°. The values of the logarithms of thermodynamic formation constants (β) for the reaction UO22+ + Cl− = UO2Cl+ are 0.02, 0.25, 0.55, 1.09, 1.59, and 2.28 derived at 25, 50, 100, 150, 200, and 250 °C, respectively. For the reaction UO22+ + 2Cl− = UO2Cl2° the values of log β derived at these temperatures are 0.4, 0.58, 0.74, 1.44, 2.18, and 3.42. Values of the formation constant estimated for uranyl-chloride species predict the high concentrations of U observed by Richard et al. (2011) in fluid inclusions of the giant McArthur River unconformity-type uranium deposit.