Abstract. Recent advances in laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) open new perspectives for quantification of trace metals and metalloids in mineral-hosted fluid inclusions and glass-hosted gas bubbles. This work is devoted to a new method applied to quantify element concentrations (at parts-per-million and weight percent levels) in natural and synthetic fluid inclusions and gas bubbles by using only an external calibrator in cases where internal standardization is unavailable. For example, this method can be applied to calculate element (metal and metalloid) concentrations in carbonic (C–O–H) fluid inclusions and bubbles. The method is devoted to measuring incompatible (with the host mineral and glass) trace elements originally dissolved into the trapped fluid. The method requires precise estimation of the fluid density, the inclusion/bubble volume or average radius, and measurement of the laser ablation crater radius by independent microanalytical techniques as well as accurate data on the concentration of major/minor elements compatible with the host mineral (or host glass). This method, applicable for analyses of hydrous carbonic fluid inclusions and gas bubbles hosted in silicate minerals and glasses, relies on the absence of a matrix effect between fluid, host mineral and daughter phases (silicate, oxide or sulfide) and the external calibrator (e.g., reference silicate glasses) during the LA-ICP-MS analysis, an assumption validated by the use of femtosecond lasers.
Monazite and rutile occurring in hydrothermally altered W mineralizations, in the Echassières district of the French Massif Central (FMC), were dated by U-Pb isotopic systematics using in-situ Laser ablation-inductively coupled plasma–quadrupole mass spectrometry (LA-ICP-MS). The resulting dates record superimposed evidence for multiple percolation of mineralizing fluids in the same area. Cross-referencing these ages with cross-cutting relationships and published geochronological data reveals a long history of more than 50 Ma of W mineralization in the district. These data, integrated in the context of the Variscan belt evolution and compared to other major W provinces in the world, point to an original geodynamic-metallogenic scenario. The formation, probably during the Devonian, of a quartz-vein stockwork (1st generation of wolframite, called wolframite “a”; >360 Ma) of porphyry magmatic arc affinity is analogous to the Sn-W belts of the Andes and the Nanling range in China. This stockwork was affected by Barrovian metamorphism, induced by tectonic accretion and crustal thickening, during the middle Carboniferous (360 to 350 Ma). Intrusion of a concealed post-collisional peraluminous Visean granite, at 333 Ma, was closely followed by precipitation of a second generation of wolframite (termed “b”), from greisen fluids in the stockwork and host schist. This W-fertile magmatic episode has been widely recorded in the Variscan belt of central Europe, e.g. in the Erzgebirge, but with a time lag of 10–15 Ma. During orogenic collapse, a third magmatic episode was characterized by the intrusion of numerous rare-metal granites (RMG), which crystallized at ~310 Ma in the FMC and in Iberia. One of these, the Beauvoir granite in the Echassières district, led to the formation of the wolframite “c” generation during greisen alteration.
Hydrothermal gold deposits commonly form during protracted multistage ore-forming processes, however, discriminating among different ore-forming fluids and tracing their origin to unique or different repositories is a challenging task. The Huilvshan gold deposit in West Junggar (Xinjiang province, NW China), was affected by three hydrothermal stages and thus provides an opportunity to examine complex ore-forming processes. The deposit consists of gold-bearing quartz-sulfide veins and disseminated sulfides, hosted within Early Carboniferous basalts and tuffs. Three stages of hydrothermal pyrite (Py1, Py2, and Py3) were identified. Gold is only present in Py2 where it occurs as native gold inclusion and in invisible form. Anhedral Py1, disseminated in the altered basalt, is characterized by higher Ni (13.7 to 635 ppm) concentrations than Py2 and Py3. Euhedral-subhedral Py2 is the richest in Au (1.46 to 25.7 ppm) among three stages of pyrite. Py3 is subdivided into grains with zonal texture (Py3a) and irregular grains (Py3b). Both sub-types have high Sb (56.8 to 1599 ppm) and Tl (0.02 to 68.7 ppm) concentrations. In situ δ34S values of Py1 (-6.0 to 2.7 ‰) are similar to those of Py2 (-5.9 to 3.9 ‰), whereas Py3 has extremely negative δ34S values (-44.3 to-18.0 ‰). Ar-Ar ages of hydrothermal muscovite coexisting with Py2 indicate that the Huilvshan gold deposit formed at ∼300 Ma. The sulfur isotopic systematics of Py1 and Py2, close spatial and temporal relationship between the Huilvshan gold deposit and adjacent felsic intrusions, and paucity of regional metamorphic rocks in the region all suggest that hydrothermal fluids in stage I (Py1) and II (Py2) were derived from magmatism. On the other hand, stage III pyrite and associated sulfides more likely precipitated from a hydrothermal fluid that circulated in tuffs, based on the extremely negative δ34S values of Py3, similar to those measured from framboidal pyrite in the host tuffs. Therefore, textural, trace elemental and sulfur isotope data from pyrite suggest different sources for the hydrothermal fluids in the Huilvshan gold deposit, and that magmatic activity may have contributed the most to the main ore-forming stage. The genesis of this Huilvshan gold deposit could provide significant insights into the origin of other hydrothermal gold deposits that show multiple sulfide generations.