M1, M2 site populations and distortion parameters in synthetic Mg-Fe orthopyroxenes from Mössbauer spectra and X-ray structure refinements

Synthetic orthopyroxenes free of trivalent cations Mg _x Fe _2-x Si₂O₆ (x=0; 1; 1.6) were investigated using both Mössbauer spectroscopy (MS) and single-crystal X-ray diffraction (XRD) in order to compare the results obtained on the same samples by the two techniques. The Mg-Fe distribution over M1 and M2 octahedral sites was determined on compounds with x = 1 and x=1.6, unheated and annealed at 650, 850 and 1040° C for 29 to 42 hours to obtain different degrees of order. The data obtained by the two techniques are in very good agreement, thus suggesting, for these compositions, the absence of systematic errors. The investigation of a synthetic compound with x=0 (ferrosilite) confirmed that the accuracy of both methods is very good. The observed small discrepancies between the results are not significant if compared with the relevant standard deviations which, for both methods, were derived by leastsquares calculations. The best fit is obtained for Fe(M1)/ Fe(tot) parameters that, in both methods, are directly calculated without using data from chemical analysis. For the unheated samples the values by MS and XRD are respectively: 0.185(9) and 0.180(4) for x = 1.6; 0.282(8) and 0.285(2) for x=1; 0.503(7) and 0.502(1) for x=0. For all the investigated samples the correlation between the geometrical distortion parameters, calculated by X-ray refinement, and the quadrupole splitting values, measured by Mössbauer spectroscopy, agrees with the theoretical model of Ingalls (1964).     

High-temperature emplacement of the Cerro Galán and Toconquis Group ignimbrites (Puna plateau,NW Argentina) determined by TRM analyses

Estimates of pyroclastic flow emplacement temperatures in the Cerro Galán ignimbrite and Toconquis Group ignimbrites were determined using thermal remanent magnetization of lithic clasts embedded within the deposits. These ignimbrites belong to the Cerro Galán volcanic system, one of the largest calderas in the world, in the Puna plateau, NW Argentina. Temperature estimates for the 2.08-Ma Cerro Galán ignimbrite are retrieved from 40 sites in 14 localities (176 measured clasts), distributed at different distances from the caldera and different stratigraphic heights. Additionally, temperature estimates were obtained from 27 sample sites (125 measured clasts) from seven ignimbrite units forming the older Toconquis Group (5.60–4.51 Ma), mainly outcropping along a type section at Rio Las Pitas, Vega Real Grande. The paleomagnetic data obtained by progressive thermal demagnetization show that the clasts of the Cerro Galán ignimbrite have one single magnetic component, oriented close to the expected geomagnetic field at the time of emplacement. Results show therefore that most of the clasts acquired a new magnetization oriented parallel to the magnetic field at the moment of the ignimbrite deposition, suggesting that the clasts were heated up to or above the highest blocking temperature (T _b) of the magnetic minerals (T _b = 580°C for magnetite; T _b = 600–630°C for hematite). We obtained similar emplacement temperature estimations for six out of the seven volcanic units belonging to the Toconquis Group, with the exception of one unit (Lower Merihuaca), where we found two distinct magnetic components. The estimation of emplacement temperatures in this latter case is constrained at 580–610°C, which are lower than the other ignimbrites. These estimations are also in agreement with the lowest pre-eruptive magma temperatures calculated for the same unit (i.e., 790°C; hornblende–plagioclase thermometer; Folkes et al. 2011b). We conclude that the Cerro Galán ignimbrite and Toconquis Group ignimbrites were emplaced at temperatures equal to or higher than 620°C, except for Lower Merihuaca unit emplaced at lower temperatures. The homogeneity of high temperatures from proximal to distal facies in the Cerro Galán ignimbrite provides constraints for the emplacement model, marked by a relatively low eruption column, low levels of turbulence, air entrainment, surface–water interaction, and a high level of topographic confinement, all ensuring minimal heat loss.     

HTP21/c–C2/c phase transition and kinetics of Fe2+–Mg order–disorder of an Fe-poor pigeonite: implications for the cooling history of ureilites

A natural Ca-poor pigeonite (Wo₆En₇₆Fs₁₈) from the ureilite meteorite sample PCA82506-3, free of exsolved augite, was studied by in situ high-temperature single-crystal X-ray diffraction. The sample, monoclinic P2₁/c, was annealed up to 1,093°C to induce a phase transition from P2₁/c to C2/c symmetry. The variation with increasing temperature of the lattice parameters and of the intensity of the b-type reflections (h + k = 2n + 1, present only in the P2₁/c phase) showed a displacive phase transition P2₁/c to C2/c at a transition temperature T _Tr = 944°C, first order in character. The Fe–Mg exchange kinetics was studied by ex situ single-crystal X-ray diffraction in a range of temperatures between the closure temperature of the Fe–Mg exchange reaction and the transition temperature. Isothermal disordering annealing experiments, using the IW buffer, were performed on three crystals at 790, 840 and 865°C. Linear regression of ln k _D versus 1/T yielded the following equation: ln k_\textD = - 3717( ±416)/T(K) + 1.290( ±0.378);    (R² = 0.988) \ln \,k_{\text{D}} = - 3717( \pm 416)/T(K) + 1.290( \pm 0.378);\quad (R^{2} = 0.988) . The closure temperature (T _c) calculated using this equation was ∼740(±30)°C. Analysis of the kinetic data carried out taking into account the e.s.d.'s of the atomic fractions used to define the Fe–Mg degree of order, performed according to Mueller’s model, allowed us to retrieve the disordering rate constants C ₀ K _dis⁺ for all three temperatures yielding the following Arrhenius relation: ln( C₀ K_\textdis ⁺ ) = ln K₀ - Q/(RT) = 20.99( ±3.74) - 26406( ±4165)/T(K);    (R² = 0.988) \ln \left( {C_{0} K_{\text{dis}}^{ + } } \right) = \ln \,K_{0} - Q/(RT) = 20.99( \pm 3.74) - 26406( \pm 4165)/T(K);\quad (R^{2} = 0.988) . An activation energy of 52.5(±4) kcal/mol for the Fe–Mg exchange process was obtained. The above relation was used to calculate the following Arrhenius relation modified as a function of X _Fe (in the range of X _Fe = 0.20–0.50): ln( C₀ K_\textdis ⁺ ) = (21.185 - 1.47X_\textFe ) - \frac(27267 - 4170X_\textFe )T(K) \ln \left( {C_{0} K_{\text{dis}}^{ + } } \right) = (21.185 - 1.47X_{\text{Fe}} ) - {\frac{{(27267 - 4170X_{\text{Fe}} )}}{T(K)}} . The cooling time constant, η = 6 × 10⁻¹ K⁻¹ year⁻¹ calculated on the PCA82506-3 sample, provided a cooling rate of the order of 1°C/min consistent with the extremely fast late cooling history of the ureilite parent body after impact excavation.     

Did the “Autochthonous” European foreland of Corsica Island (France) experience Alpine subduction?

Despite the important role played by the Sardinia‐Corsica block in the reconstruction of the Western Mediterranean geodynamics, the extent of involvement of the “Autochthonous” European margin exposed in Corsica (France) (i.e., Hercynian Corsica) in the Alpine orogeny remains uncertain. Stratigraphic and sedimentological studies in the post‐Variscan deposits on the Hercynian Corsica are scarce and even scarcer are the structural and metamorphic constraints. To face these uncertainties, we present new stratigraphic, structural and metamorphic data from the area of Razzo Bianco, Central Corsica, where a complete sequence belonging to the European continental margin is exposed. Field and structural investigations demonstrate that the sequence represents the easternmost edge of the downgoing European plate. Metamorphic studies on the Eocene deposits indicate that the margin was buried at depth up to blueschist facies conditions and, subsequently, it was progressively exhumed mainly through the activation of oblique top‐to‐the NW shear zones.     

Towards a predictive model to assess the natural position of the Posidonia oceanica seagrass meadows upper limit

The upper portion of the meadows of the protected Mediterranean seagrass Posidonia oceanica occurs in the region of the seafloor mostly affected by surf-related effects. Evaluation of its status is part of monitoring programs, but proper conclusions are difficult to draw due to the lack of definite reference conditions. Comparing the position of the meadow upper limit with the beach morphodynamics (i.e. the distinctive type of beach produced by topography and wave climate) provided evidence that the natural landwards extension of meadows can be predicted. An innovative model was therefore developed in order to locate the region of the seafloor where the meadow upper limit should lie in natural conditions (i.e. those governed only by hydrodynamics, in absence of significant anthropogenic impact). This predictive model was validated in additional sites, which showed perfect agreement between predictions and observations. This makes the model a valuable tool for coastal management.     

Long-term model of planimetric and bathymetric evolution of a tidal lagoon

This model is based on the concept of transport concentration, defined as the time-averaged concentration in a given location of a lagoon, which determines the long-term net transport of sediments as the sum of a dispersive and an advective flux. Dispersive net flux of sediments is due to the alternate components of the tidal flow, while the advective net flux of sediments is due to the residual (Eulerian) component of the tidal, fluvial and littoral flow and possibly to the asymmetry between flow and ebb tide.