Infrared spectroscopic properties of goethite: anharmonic broadening,long-range electrostatic effects and Al substitution

The infrared spectrum and its temperature dependence (20–320 K) were collected on a synthetic goethite sample (α-FeOOH). In addition, the infrared powder absorption spectrum of goethite and aluminum-substituted goethite was computed using ab initio quantum mechanical calculations based on density functional theory. This combined experimental and theoretical approach allows (1) the unequivocal assignment of absorption bands to the corresponding vibrational modes, (2) separate identification of the effects of the particle shape and of the aluminum substitution on the infrared spectrum, and (3) a discussion of the anharmonic properties and the origin of the line broadening in goethite. In particular, the two well-resolved OH bending absorption bands show different temperature evolution. Their detailed analysis suggests that the broadening of the band at ~800 cm^?1 cannot be described solely by a usual three-phonon process. The strong anharmonic behavior of this mode implies the addition of a four-phonon process, such as a pure dephasing process. In our calculations, the effect of the Hubbard U correction is also investigated and found to be most visible on the OH stretching and bending modes, in relation to the associated structural relaxation. The OH stretching frequencies decrease, leading to a better agreement with experimental frequencies, while the OH bending frequencies increase.     

Liquidus surfaces of ultracalcic primitive melts: formation conditions and sources

CaO-rich, Al₂O₃-poor ultracalcic primitive melts occur at mid-ocean-ridges, back-arc basins, ocean islands and volcanic arcs. They are subdivided into a nepheline-normative alkaline-rich, silica-poor group uniquely found in arcs and in hypersthene-normative fairly refractory melts which occur in all of the above environments. The high CaO contents (to 19.0 wt%) and CaO/Al₂O₃ ratios (to 1.8) exclude an origin from fertile lherzolites at volatile-absent conditions. Experimental investigation of the liquidus of a hypersthene-normative and a nepheline-normative ultracalcic melt results in quite distinct pressure-temperature conditions of multiple saturation: whereas the hypersthene-normative liquid saturates in olivine + clinopyroxene at 1.2 GPa and 1,410°C, this occurs at 0.2 GPa and 1,220°C for the nepheline-normative ultracalcic liquid. Our results in combination with melting experiments from the literature suggest that hypersthene-normative melts result from melting of a refractory olivine + clinopyroxene ± orthopyroxene source at elevated mantle temperatures. Contrasting, nepheline-normative ultracalcic melts form from wehrlitic cumulates in the arc crust; to account for the high alkaline and low silica contents, and the relatively low temperatures, source wehrlites must have contained amphibole.     

Latest Precambrian to Early Cambrian U–Pb zircon ages of augen gneisses from Calabria (Italy), with inference to the Alboran microplate in the evolution of the peri-Gondwana terranes

In situ U–Pb dating of zircons from five samples of Calabrian augen gneisses shows that their protoliths are Latest Precambrian to Early Cambrian in age (562 ± 15, 547 ± 7, 540 ± 4, 539 ± 16 and 526 ± 10 Ma), and contain Archaean (3.1 Ga), Palaeoproterozoic (1.7–2.4 Ga) and Neoproterozoic (0.6–0.9 Ga) inheritance. Geochemical signature of augen gneisses is typical of high-K calc-alkaline post-collisional magmatism. Their Sr–Nd isotopic compositions [0.7093 < (⁸⁷Sr/⁸⁶Sr)_i < 0.7139; −3.2 < ɛ_Nd(t) < −5.4; 1.5 < T _DM < 1.7 Ga] indicate the involvement of a crustal component in significant proportions. The Calabrian augen gneisses have, therefore, to be distinguished from the orthogneisses of Sardinia and northern Algeria, and from the porphyroids of Sicily, which are Middle Ordovician. By contrast, the Calabrian augen gneisses show a close similarity to the Pan-African post-collisional granitoids of the northern edge of the West African craton (e.g. the Moroccan Anti-Atlas). This suggests a peri-Gondwana origin and corroborates previous palaeogeodynamic reconstructions attributing the Alboran microplate to the northern margin of the West African craton.     

Behaviour of Li and its isotopes during metasomatism of French Massif Central lherzolites

Li behaviour and distribution in the mantle were investigated by ion microprobe in situ measurements on co-existing olivine (ol), orthopyroxene (opx), clinopyroxene (cpx) and amphibole (amp) in xenoliths from the French Massif Central. The fertile spinel lherzolites of this study record increasing degrees of mantle metasomatism, from unmetasomatised anhydrous samples through cryptically metasomatised samples to highly metasomatised amphibole-rich samples. In anhydrous lherzolites, Li is preferentially incorporated into olivine (1.1-1.4 ppm, average values) compared to pyroxenes (0.2-0.9 ppm). The hydrous samples clearly show enrichment of Li in ol (1.5-5.0 ppm), opx (1.1-2.4 ppm) and cpx (2.4-5.4 ppm), while amphibole incorporates less Li than the co-existing phases (0.8-1.3 ppm). Average δ⁷Li values range from +7.6 to +14.5‰ in ol, from 5.1 to +13.7‰ in opx and from 8.8 to +10.3‰ in cpx from the anhydrous lherzolites. A layered peridotite sample (Sdi) shows higher Li content in all phases, with lighter isotopic composition in opx and cpx (−0.6 and −2‰ average δ⁷Li values, respectively). In the hydrous lherzolites average δ⁷Li values both overlap and extend beyond these ranges in ol (up to 17.5 ‰) and in opx (up to 22.9‰), and vary widely in cpx (−2.7 to +9.7‰). Low δ⁷Li values are observed in some opx (−10.4‰) and cpx (−13‰) from sample Sdi, and in cpx from three hydrous samples (from −9.7 to −5.3‰). The different anhydrous phases from the hydrous samples show large intra-grain variations in Li isotopic ratios (e.g., up to 18‰) compared to the same phases from the anhydrous samples (mostly less than 6‰), excepting sample Sdi which has up to 20.4‰ variation in cpx. Similar to the anhydrous silicates, amphiboles show a wide variation of δ⁷Li values on the intra-grain scale (2-27‰). These variations are interpreted to result from fractionation processes during metasomatism by a silicate melt undergoing compositional changes as it percolates through and reacts with the peridotite phases. Thus Li abundances and isotopic in situ measurements are useful for tracing metasomatic processes but the heterogeneities observed in the samples preclude any identification of a specific mantle source by its Li signature.     

碧溪岭岩体中石榴橄榄岩的锆石显微结构及离子探针定年

对碧溪岭岩体中石榴橄榄岩的锆石进行了BSE和CL显微结构分析，并在此基础上用离子探针进行了锆石微区U－Pb定年。锆石CL图像显示其有明显的核边结构，核部具岩浆锆石，边部是变质增生锆石的特征。结合锆石的外形特征认为，边部的变质锆石是在超高压变质作用中重结晶形成的。离子探针分析结果在一致曲线图中构成不一致线，得到上下交点 年龄分别为824±39Ma和254±38Ma。结合CL图像认为上交点824±39Ma的年龄代表其原岩形成年龄，下交点254±38Ma为基超高压变质作用的年龄。另有少量较年龄的捕虏晶锆石，可能来自岩浆上升过程中同化混染的围岩。