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The Fregeneda-Almendra pegmatite field of the Iberian Massif represents a typical expression of peraluminous rare-metal magmatism that occurred over western Europe at the end of the Variscan orogeny. It is the host for two main types of Li-mineralized intrusions, identified at the scale of the Variscan belt, including petalite- or spodumene-rich pegmatites, as well as Li-mica-rich pegmatites, for which the origin of mineralogical-chemical differences is not yet understood. Here, we provide cassiterite and columbite-group mineral (CGM) U-Pb ages along with oxide, mica and phosphate mineral compositions for Li-pegmatites from the Fregeneda-Almendra field in order to assess their petrogenesis and tectonic-magmatic context of emplacement. U-Pb geochronology indicates that petalite-rich and Li-mica-rich pegmatites were mostly emplaced sub-synchronously from 315 ± 6 to 308 ± 6 Ma, during strike-slip deformation and granitic magmatism within an anatectic dome bounding the pegmatite field. U-Pb data and pegmatite geographic zonation suggest that Li-pegmatites were sourced from buried equivalents of leucogranites and migmatites from the dome. Li-pegmatites experienced a complex crystallization including K-feldspar, petalite, topaz, Nb-Ta-Fe-Mn-rich cassiterite, amblygonite-group minerals (AGM) and CGM as early magmatic phases, followed by lepidolite for Li-mica-rich pegmatites. At the magmatic-hydrothermal transition, notably leading to the formation of Nb-Ta-Mn-Fe-poor cassiterite hosting CGM inclusions, earlier minerals were resorbed by muscovite and albite. A later F-rich hydrothermalism is locally reflected by zinnwaldite overgrowths on muscovite. Cassiterite, CGM and micas from petalite-rich pegmatites show lower Mn/Fe ratios and higher Ti contents, along with lower Zr-Ga contents for cassiterite, than that from Li-mica-rich pegmatites. Such behavior is consistent with a magmatic differentiation process whereby Ti content decreased and the degree of Mn-Fe geochemical fractionation and solubilities of Ga and Zr increased in the melts, possibly in relation with high fluorine activity. In Li-mica-rich pegmatites, AGM equilibrated with a melt with up to 2 wt% F, similar to that in equilibrium with lepidolite (1–3 wt%). In petalite-rich pegmatites, the relatively high F concentration of the melts equilibrated with AGM (≤ 1.5 wt% F) contrasts with the liquid equilibrated with muscovite (< 0.5 wt% F). This can be accounted for by muscovite crystallization after the exsolution of a F-rich aqueous phase at the magmatic-hydrothermal transition. Relatively similar F contents in the initial melts of petalite- and Li-mica-rich pegmatites support the hypothesis that the stability of lepidolite does not only involve high F but also a low H2O/F activity ratio. For the Fregeneda-Almendra Li-mica-rich pegmatites, this could be explained by a decrease of melt H2O solubility due to a relatively low pressure of emplacement.

In phosphorites, the content and distribution of rare earth elements are linked to the environment of phosphogenesis. This paper focuses on the question of sources and processes controlling the rare earth element content of apatite from Belgian phosphorites formed during three major phosphogenic events in the Lower Palaeozoic, Late Cretaceous and Cenozoic. To constrain sources and processes, new data include petrological, mineralogical (including cathodoluminescence and Raman spectroscopy) and in situ trace element and Sr and O isotope analyses of apatite. Fluorapatite from Lower Palaeozoic P‐rich conglomerates has the greatest rare earth element enrichment. It is affected by metamorphism that led to deformation of apatite nodules and formation of garnet porphyroblast inclusions. The role of Fe‐oxyhydroxides in element scavenging is highlighted by some apatite nodules that maintain their primary middle rare earth element enrichment, while others are characterized by altered rare earth element patterns resulting from competition for these elements between co‐crystallizing minerals during deformation. A systematic shift towards lower δ18O and radiogenic Sr isotopic composition compared to contemporaneous seawater indicate interaction with 18O‐depleted meteoric fluids and a crustal component. By contrast, carbonate‐rich fluorapatite from the Late Cretaceous phosphatic chalk mostly keeps its primary trace element and isotopic signatures (close to seawater), although an external rare earth element addition is noted, as well as rare earth element redistribution induced by diagenetic alteration. Cenozoic carbonate fluorapatite nodules mostly present flat rare earth element patterns that are indicative of a detrital influence. Slight changes in rare earth element distribution are assigned to post‐depositional alteration, which also led to an increase in radiogenic Sr, with unchanged δ18O compared to seawater. The methodology followed here efficiently helps in deciphering the processes that modified the chemistry of apatite in the frame of major phosphogenic events. [ABSTRACT FROM AUTHOR]

The Puy-les-Vignes W deposit, located in the northwestern French Massif Central (FMC), is a rare occurrence of a wolframite-mineralized hydrothermal breccia pipe hosted in high-grade metamorphic gneisses. We present an integrated study of this deposit aiming to characterize the ore-forming hydrothermal system in link with the Variscan late-orogenic evolution of the FMC. Based on a set of representative samples from the host rocks and mineralization, we describe a detailed paragenetic sequence and we provide the major and trace element geochemistry of the granitic rocks and W–Nb–Ta–Sn–Ti oxide minerals, in situ U/Pb and 40Ar/39Ar geochronology, and a fluid inclusion study of quartz and wolframite. We demonstrate that the formation of this W-mineralized breccia pipe results from a multistage development related to four major episodes during the late Carboniferous. The first episode corresponds to the emplacement of an unexposed peraluminous granite at ca. 324 Ma, which generated microgranite dykes exposed at the present-day surface. The second episode is the formation of the quartz-supported breccia pipe and wolframite mineralization at ca. 318 Ma at a paleodepth of 7 km. The mineralizing fluids have a H2O–NaCl–CO2–CH4–N2 composition, a moderate-salinity ( 400 °C) during lithostatic to hydrostatic pressure variations caused by hydrofracturing of the host rocks. Wolframite deposition is interpreted to result from a W-rich intermediate-density magmatic fluid that exsolved from an evolved leucogranite and interacted with volatile-rich metasedimentary country rocks and/or possibly mixed with low-salinity metamorphic fluids of deep origin. The third episode corresponds to magmatic-hydrothermal Nb–Ta mineralization overprinting the W-mineralized system interpreted to be related to the intrusion at ca. 311 Ma of a rare-metal granite, which is part of a regional peraluminous rare-metal magmatism during the 315–310 Ma period. Finally, the last episode corresponds to disseminated Bi ± Au–Ag mineralization emplaced at ca. 300 Ma, which shares similar mineralogical features with late Carboniferous orogenic gold deposits in the FMC. The Puy-les-Vignes W deposit records, therefore, a multistage and long-lived development that extends over a timespan of 25 million years in a regional setting dominated by protracted peraluminous magmatism and high-temperature and low-pressure metamorphism. Although the local environment of ore deposition is atypical, our results show that the mineral assemblages, alteration styles, and fluid characteristics of the Puy-les-Vignes breccia pipe are similar to those of other peri-granitic W deposits in the FMC.

The in situ (U‐Th‐Sm)/He and U/Pb laser‐ablation double‐dating procedure is a valuable method that can provide a large dataset relatively efficiently in contrast with conventional bulk helium thermochronometry. In this study, we evaluate the potential age error associated with the double ablation procedure and report the in situ (U‐Th‐Sm)/He double‐ablation dating of 249 zircons from the Fish Canyon Tuff locality. With LA‐ICP‐MS pseudo‐depth profiling and 3D numerical modelling, we show that the concentric double‐ablation procedure in minerals with U‐Th‐Sm zoning can generate a significant (U‐Th‐Sm)/He age error (positive or negative), resulting in over‐scattering and/or an offset of the mean age. Pseudo‐depth profiling is insufficient to predict the individual age error, partly because of the superimposed ablations. To evaluate the consequence of this inherent bias, we confront a synthetic age distribution to the error expected for U‐Th‐Sm zoned zircons analysed with double‐ablation (U‐Th‐Sm)/He thermochronometry. As expected, a strong age bias causes the spreading of peak ages, downgrading the original signal. Yet, the throughput of the ablation‐based method can allow intra‐ and inter‐sample peak age identification and comparison, and the coupling of (U‐Th‐Sm)/He and U/Pb ages extends our ability to deconvolute a multimodal age spectrum. [ABSTRACT FROM AUTHOR]

Laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) is used to compare the suitability of four cassiterite (SnO2) materials (SPG, Yankee, AY‐4 and Jian‐1), and three matrix‐mismatched reference materials (NIST SRM 612, NIST SRM 614 and 91500 zircon) for normalisation of U‐Pb and Pb‐Pb isotope ratios in cassiterite. The excess variance of ages determined by LA‐ICP‐MS is estimated to be ±0.33% for 207Pb/206Pb vs. 208Pb/206Pb isochron ages and ± 1.8% and for U‐Pb ages. Incorporation of this excess variance in cassiterite ages is necessary for realistic uncertainties. 207Pb‐206Pb ages are advantageous for dating Precambrian cassiterite such as SPG compared with U‐Pb ages as matrix effect on instrumental mass fractionation of Pb isotopes are generally considered to be minor. We note minor bias in 207Pb/206Pb vs. 208Pb/206Pb isochron ages (~ 0.6%) when using either the NIST SRM 614 or 91500 zircon reference materials and emphasise the requirement for uncertainty propagation of all sources of error and reference materials with comparable U and Pb mass fraction to the cassiterite. The 238U/206Pb isotopic ratios from normalisation to matrix‐mismatched reference materials show varied results, which emphasises the need to use matrix‐matched reference materials for calculating U‐Pb ages. When cross‐calibrated against each other, LA‐ICP‐MS U‐Pb ages of the ca. 1535 Ma SPG, ca. 245 Ma Yankee and ca. 155 Ma Jian‐1 cassiterites are all consistent with their ID‐TIMS values. [ABSTRACT FROM AUTHOR]