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.     

大别山双河超高压榴辉岩中变质锆石；离子探针和微区结构研究

对南大别双河超高压岩板榴辉岩中锆石进行了阴极发光、喇曼光谱、U- Pb和氧同位素离子探针微区分析。发现大部分锆石具有核边结构 ,其核和边有明显不同的 U ,Th,Pb含量、Th/ U比、2 0 6 Pb/ 2 38U年龄和δ1 8O值。锆石边部具有变质锆石的结构和化学特征 ,核部具有岩浆锆石向变质锆石变化的过渡特征。 17个点 U - Pb同位素分析中大多数为不一致年龄 ,由 14个正向不一致点所构成的不一致线与一致曲线的上、下交点年龄分别为 2 4 89± 2 5和 2 4 8± 16 Ma,它们代表了榴辉岩原岩形成时间和前进变质至峰期变质过程中原岩岩浆锆石重结晶和变质增生作用的时间 ,大别山变质锆石的成因是复杂的 ,它既可以是变质新生锆石 ,呈独立的颗粒或原岩岩浆锆石的增生边 ,也可以是由原岩锆石在固相或流体存在下的重结晶作用形成。不同程度的重结晶作用是超高压条件下双河榴辉岩原岩岩浆锆石发生的主要的物理化学变化 ,它导致锆石中 U、Th、Pb和Th/ U比的降低和岩浆振荡环带的消退