High-T phase transition of synthetic ANaB(LiMg)CMg5Si8O22(OH)2 amphibole: an X-ray synchrotron powder diffraction and FTIR spectroscopic study

The synthetic amphibole Na_0.95(Li_0.95Mg_1.05)Mg₅Si₈O₂₂(OH)₂ was studied in situ at high-T, using IR OH-stretching spectroscopy and synchrotron X-ray powder diffraction. At room-T the sample has P2₁ /m symmetry, as shown by the FTIR spectrum. It shows in the OH region two well-defined and intense absorptions at 3,748 and 3,712 cm⁻¹, respectively, and two minor bands at 3,667 and 3,687 cm⁻¹. The main bands are assigned to the two independent O–H groups in the primitive structure. The two minor bands evidencing the presence of small amount of vacant A-site (^A□_0.05). With increasing T, these bands shift continuously and merge into a unique absorption at high temperature. A change as a function of increasing T is revealed by the evolution of the refined unit-cell parameters, whose trend shows a transition to C2/m at about 320–330°C. The spontaneous scalar strain, fitted with a tricritical 2–6 Landau potential, gives a T _c of 325(10)°C (β parameter = 0.27). Comparison with the second-order P2₁ /m ⇔ C2/m phase transition at 255°C for synthetic amphibole ^ANa_0.8^B(Na_0.8Mg_1.2)^CMg₅Si₈O₂₂(OH)₂ indicates that the substitution of Na with Li at the B-sites strongly affects the thermodynamic character and the T _c of the phase transition. The comparison of LNMSH amphiboles with cummingtonitic ones shows that the high-T thermodynamic behaviour is affected by A-site occupancy.     

Argon isotope fractionation induced by stepwise heating

Noble gas isotopes are widely used to elucidate the history of the rocks in which they have been trapped, either from distinct reservoirs or by accumulation following radioactive decay. To extract noble gases from their host rocks, stepwise heating is the most commonly used technique to deconvolve isotopically different components, e.g., atmospheric, in situ radiogenic, or excess radiogenic from mantle or crustal reservoirs. The accurate determination of the isotopic composition of these different components is of crucial importance, e.g., for ages obtained by ⁴⁰Ar-³⁹Ar stepheating plateaus. However, diffusion theory-based model calculations predict that the stepwise thermal extraction process from mineral phases induces isotope fractionation and, hence, adulterates the original composition. Such effects are largely unconsidered, as they are small and a compelling experimental observation is lacking. We report the first unequivocal evidence for significant mass fractionation of argon isotopes during thermal extraction, observed on shungite, a carbon-rich Precambrian sedimentary rock. The degree of fractionation, as monitored by ³⁸Ar/³⁶Ar and ⁴⁰Ar/³⁶Ar ratios, very well agrees with theoretical predictions assuming an inverse square root dependence of diffusion coefficient and atomic mass, resulting in easier extraction of lighter isotopes. Hence, subatmospheric ⁴⁰Ar/³⁶Ar ratios obtained for argon extracted at low temperatures may not represent paleoatmospheric argon. Shungite argon resembles modern atmospheric composition, but constraints on the timing of trapping appear difficult to obtain, as shungites are multicomponent systems.In ⁴⁰Ar-³⁹Ar stepwise heating, the isotope fractionation effect could cause systematic underestimations of plateau ages, between 0.15 and 0.4% depending on age, or considerably higher if samples contain appreciable atmospheric Ar. The magnitude of this effect is similar to the presently achieved uncertainties of this increasingly precise dating technique. Our results also indicate the importance of thermally activated diffusion as a possible fractionation mechanism, e.g., for hydrothermal gas exhalations, or for carbonaceous carrier phases such as “Q” in meteorites that have been suggested as carriers of highly fractionated noble gas residues from the early solar nebula.     

Long-term deforestation in NW Spain: linking the Holocene fire history to vegetation change and human activities

The Holocene fire regime is thought to have had a key role in deforestation and shrubland expansion in Galicia (NW Spain) but the contribution of past societies to vegetation burning remains poorly understood. This may be, in part, due to the fact that detailed fire records from areas in close proximity to archaeological sites are scarce. To fill this gap, we performed charcoal analysis in five colluvial soils from an archaeological area (Campo Lameiro) and compared the results to earlier studies from this area and palaeo-ecological literature from NW Spain. This analysis allowed for the reconstruction of the vegetation and fire dynamics in the area during the last ca 11 000 yrs. In the Early Holocene, Fabaceae and Betula sp. were dominant in the charcoal record. Quercus sp. started to replace these species around 10 000 cal BP, forming a deciduous forest that prevailed during the Holocene Thermal Maximum until ～5500 cal BP. Following that, several cycles of potentially fire-induced forest regression with subsequent incomplete recovery eventually led to the formation of an open landscape dominated by shrubs (Erica sp. and Fabaceae). Major episodes of forest regression were (1) ～5500–5000 cal BP, which marks the mid-Holocene cooling after the Holocene Thermal Maximum, but also the period during which agropastoral activities in NW Spain became widespread, and (2) ～2000–1500 cal BP, which corresponds roughly to the end of the Roman Warm Period and the transition from the Roman to the Germanic period. The low degree of chronological precision, which is inherent in fire history reconstructions from colluvial soils, made it impossible to distinguish climatic from human-induced fires. Nonetheless, the abundance of synanthropic pollen indicators (e.g. Plantago lanceolata and Urtica dioica) since at least ～6000 cal BP strongly suggests that humans used fire to generate and maintain pasture.     

The use of the exponent K(q) function to delimit homogeneous regions in regional frequency analysis of extreme annual daily rainfall

The regional frequency analysis of extreme annual rainfall data is a useful methodology in hydrology to obtain certain quantile values when no long data series are available. The most crucial step in the analysis is the grouping of sites into homogeneous regions. This work presents a new grouping criterion based on some multifractal properties of rainfall data. For this purpose, a regional frequency analysis of extreme annual rainfall data from the Maule Region (Chile) has been performed. Daily rainfall data series of 53 available stations have been studied, and their empirical moments scaling exponent functions K(q) have been obtained. Two characteristics parameters of the K(q) functions (γ_max and K(0)) have been used to group the stations into three homogeneous regions. Only five sites have not been possible to include into any homogenous regions, being the local frequency analysis of extreme daily rainfall the most appropriate method to be used at these locations. Copyright © 2014 John Wiley & Sons, Ltd.     

Low-order stabilized finite element for the full Biot formulation in soil mechanics at finite strain

This article presents a novel finite element formulation for the Biot equation using low-order elements. Additionally, an extra degree of freedom is introduced to treat the volumetric locking steaming from the effective response of the medium; its balance equation is also stabilized. The accuracy of the proposed formulation is demonstrated by means of numerical analyses.     

Pre‐Alpine discordant granitic dikes in the metamorphic core of the Betic Cordillera: tectonic implications

Pegmatite dikes bearing andalusite crosscut foliation S₂ in Alpujarride gneisses and schists. Post‐S₂ andalusite is transposed by a foliation S₃, defined by fibrolite, which affects the dikes. The dikes represent highly differentiated granitic magmas with low REE and Zr contents and a positive Eu anomaly. U‐Pb SHRIMP dating of magmatic zircons provided Pan‐African ages (cores) and late Variscan ages (rims). However, U‐rich rims also provided metamorphic Alpine ages, supporting a polyorogenic tectonometamorphic history for pre‐Mesozoic Alpujarride rocks.     

The multi-component Hekla Ö Tephra,Iceland: a complex widespread mid-Holocene tephra layer

Large Plinian eruptions from Hekla volcano, Iceland, produce compositionally zoned tephra used as key markers in tephrochronology. However, spatial variations in chemical composition of a tephra layer may complicate its identification. An example is the 5950–6180 cal a bp Hekla Ö tephra layer, which shows compositional spread from rhyolite, dacite and andesite to basalt. In soil sections north of Hekla, the SiO₂ content of the tephra glass reaches 76 wt% in the lowest unit of the Hekla Ö deposit and decreases to 62–63 wt% in the uppermost unit. Intermingled within the whole deposit are basalt tephra grains having 46–47 wt% SiO₂. The composition of the basalt glass includes primitive basalt and a more evolved basalt (MgO >6 and <6 wt%, respectively). Together with literature data, the Hekla Ö tephra and the so-called T-Tephra/Hekla-T are most likely from contemporaneous eruptions of different vents on the Hekla volcanic system, forming a single important marker tephra (Hekla ÖT) deposited over 80% of Iceland. Identification is complicated by its spatial compositional heterogeneity, such as systematic decrease in SiO₂ content from the east to the west of Hekla volcano. Consequently, an individual tephra layer from a large explosive eruption can have different composition at different locations. © 2020 John Wiley & Sons, Ltd.     

Crustal segments in the North Patagonian Massif,Patagonia: An integrated perspective based on Sm–Nd isotope systematics

New insights on the Paleozoic evolution of the continental crust in the North Patagonian Massif are presented based on the analysis of Sm–Nd systematics. New evidence is presented to constrain tectonic models for the origin of Patagonia and its relations with the South American crustal blocks. Geologic, isotopic and tectonic characterization of the North Patagonian Massif and comparison of the Nd parameters lead us to conclude that: (1) The North Patagonian Massif is a crustal block with bulk crustal average ages between 2.1 and 1.6 Ga T_DM (Nd) and (2) At least three metamorphic episodes could be identified in the Paleozoic rocks of the North Patagonian Massif. In the northeastern corner, Famatinian metamorphism is widely identified. However field and petrographic evidence indicate a Middle to Late Cambrian metamorphism pre-dating the emplacement of the ca. 475 Ma granitoids. In the southwestern area, are apparent 425–420 Ma (?) and 380–360 Ma metamorphic peaks. The latter episode might have resulted from the collision of the Antonia terrane; and (3) Early Paleozoic magmatism in the northeastern area is coeval with the Famatinian arc. Nd isotopic compositions reveal that Ordovician magmatism was associated with attenuated crust. On the southwestern border, the first magmatic recycling record is Devonian. Nd data shows a step by step melting of different levels of the continental crust in the Late Palaeozoic. Between 330 and 295 Ma magmatism was likely the product of a crustal source with an average 1.5 Ga T_DM (Nd). Widespread magmatism represented by the 295–260 Ma granitoids involved a lower crustal mafic source, and continued with massive shallower-acid plutono volcanic complexes which might have recycled an upper crustal segment of the Proterozoic continental basement, resulting in a more felsic crust until the Triassic. (4) Sm–Nd parameters and detrital zircon age patterns of Early Paleozoic (meta)-sedimentary rocks from the North Patagonian Massif and those from the neighboring blocks, suggest crustal continuity between Eastern Sierras Pampeanas, southern Arequipa-Antofalla and the northeastern sector of the North Patagonian Massif by the Early Paleozoic. This evidence suggests that, at least, this corner of the North Patagonian Massif is not allochthonous to Gondwana. A Late Paleozoic frontal collision with the southwestern margin of Gondwana can be reconcilied in a para-autochthonous model including a rifting event from a similar or neighbouring position to its post-collision location. Possible Proterozoic or Early Paleozoic connections of the NPM with the Kalahari craton or the western Antartic blocks should be investigated.