Effects of temperature on the crystal structure of epidote: a neutron single-crystal diffraction study at 293 and 1,070 K

The effects of temperature on the crystal structure of a natural epidote [Ca_1.925 Fe_0.745Al_2.265Ti_0.004Si_3.037O₁₂(OH), a = 8.890(6), b = 5.630(4), c = 10.150(6) Å and β = 115.36(5)°, Sp. Gr. P2₁ /m] have been investigated by means of neutron single-crystal diffraction at 293 and 1,070 K. At room conditions, the structural refinement confirms the presence of Fe³⁺ at the M₃ site [%Fe(M3) = 73.1(8)%] and all attempts to refine the amount of Fe at the M(1) site were unsuccessful. Only one independent proton site was located. Two possible hydrogen bonds, with O(2) and O(4) as acceptors [i.e. O(10)–H(1)···O(2) and O(10)–H(1)···O(4)], occur. However, the topological configuration of the bonds suggests that the O(10)–H(1)···O(4) is energetically more favourable, as H(1)···O(4) = 1.9731(28) Å, O(10)···O(4) = 2.9318(22) Å and O(10)–H(1)···O4 = 166.7(2)°, whereas H(1)···O(2) = 2.5921(23) Å, O(10)···O(2) = 2.8221(17) Å and O(10)–H(1)···O2 = 93.3(1)°. The O(10)–H(1) bond distance corrected for “riding motion” is 0.9943 Å. The diffraction data at 1,070 K show that epidote is stable within the T-range investigated, and that its crystallinity is maintained. A positive thermal expansion is observed along all the three crystallographic axes. At 1,070 K the structural refinement again shows that Fe³⁺ share the M(3) site along with Al³⁺ [%Fe(M3)_1,070K = 74(2)%]. The refined amount of Fe³⁺ at the M(1) is not significant [%Fe(M1)_1,070K = 1(2)%]. The tetrahedral and octahedral bond distances and angles show a slight distortion of the polyhedra at high-T, but a significant increase of the bond distances compared to those at room temperature is observed, especially for bond distances corrected for “rigid body motions”. The high-T conditions also affect the inter-polyhedral configurations: the bridging angle Si(2)–O(9)–Si(1) of the Si₂O₇ group increases significantly with T. The high-T structure refinement shows that no dehydration effect occurs at least within the T-range investigated. The configuration of the H-bonding is basically maintained with temperature. However, the hydrogen bond strength changes at 1,070 K, as the O(10)···O(4) and H(1)···O(4) distances are slightly longer than those at 293 K. The anisotropic displacement parameters of the proton site are significantly larger than those at room condition. Reasons for the thermal stability of epidote up to 1,070 K observed in this study, the absence of dehydration and/or non-convergent ordering of Al and Fe³⁺ between different octahedral sites and/or convergent ordering on M(3) are discussed.     

Analysis and simulation of magma mixing processes in 3D

Magma mixing structures from the lava flow of Lesbos (Greece) are analyzed in three dimensions using a technique that, starting from the serial sections of rock cubes, allows the reconstruction of the spatial distribution of magmas inside rocks. Two main kinds of coexisting structures are observed: (i) “active regions” (AR) in which magmas mix intimately generating wide contact surfaces and (ii) “coherent regions” (CR) of more mafic magma that have a globular shape and do not show large deformations. The intensity of mingling is quantified by calculating both the interfacial area (IA) between interacting magmas and the fractal dimension of the reconstructed structures. Results show that the fractal dimension is linearly correlated with the logarithm of interfacial area allowing discrimination among different intensities of mingling.

The process of mingling of magmas is simulated using a three-dimensional chaotic dynamical system consisting of stretching and folding processes. The intensity of mingling is measured by calculating the interfacial area between interacting magmas and the fractal dimension, as for natural magma mixing structures. Results suggest that, as in the natural case, the fractal dimension is linearly correlated with the logarithm of the interfacial area allowing to conclude that magma mixing can be regarded as a chaotic process.

Since chemical exchange and physical dispersion of one magma inside another by stretching and folding are closely related, we performed coupled numerical simulations of chaotic advection and chemical diffusion in three dimensions. Our analysis reveals the occurrence in the same system of “active mixing regions” and “coherent regions” analogous to those observed in nature. We will show that the dynamic processes are able to generate magmas with wide spatial heterogeneity related to the occurrence of magmatic enclaves inside host rocks in both plutonic and volcanic environments.     

Time relationships between volcanism–plutonism–alteration–mineralization in Cu-stratabound ore deposits from the Michilla mining district,northern Chile: a <Superscript>40</Superscript>Ar/<Superscript>39</Superscript>Ar geochronological approach

The Michilla mining district comprises one of the most important stratabound and breccia-style copper deposits of the Coastal Cordillera of northern Chile, hosted by the Middle Jurassic volcanic rocks of the La Negra Formation. ⁴⁰Ar/³⁹Ar analyses carried out on igneous and alteration minerals from volcanic and plutonic rocks in the district allow a chronological sequence of several magmatic and alteration events of the district to be established. The first event was the extrusion of a thick lava series of the La Negra Formation, dated at 159.9 ± 1.0 Ma (2σ) from the upper part of the series. A contemporaneous intrusion is dated at 159.6 ± 1.1 Ma, and later intrusive events are dated at 145.5 ± 2.8 and 137.4 ± 1.1 Ma, respectively. Analyzed alteration minerals such as adularia, sericite, and actinolite apparently give valid ⁴⁰Ar/³⁹Ar plateau and miniplateau ages. They indicate the occurrence of several alteration events at ca. 160–163, 154–157, 143–148, and 135–137 Ma. The first alteration event, being partly contemporaneous with volcanic and plutonic rocks, was probably produced in a high thermal gradient environment. The later events may be related either to a regional low-grade hydrothermal alteration/metamorphism process or to plutonic intrusions. The Cu mineralization of the Michilla district is robustly bracketed between 163.6 ± 1.9 and 137.4 ± 1.1 Ma, corresponding to dating of actinolite coexisting with early-stage chalcocite and a postmineralization barren dyke, respectively. More precisely, the association of small intrusives (a dated stock from the Michilla district) with Cu mineralization in the region strongly suggests that the main Michilla ore deposit is related to a magmatic/hydrothermal event that occurred between 157.4 ± 3.6 and 163.5 ± 1.9 Ma, contemporaneous or shortly after the extrusion of the volcanic sequence. This age is in agreement with the Re–Os age of 159 ± 16 Ma obtained from the mineralization itself (Tristá-Aguilera et al., Miner Depos, 41:99–105,2006).     

H-bonding scheme and cation partitioning in axinite: a single-crystal neutron diffraction and Mössbauer spectroscopic study

The crystal chemistry of a ferroaxinite from Colebrook Hill, Rosebery district, Tasmania, Australia, was investigated by electron microprobe analysis in wavelength-dispersive mode, inductively coupled plasma–atomic emission spectroscopy (ICP–AES), ⁵⁷Fe Mössbauer spectroscopy and single-crystal neutron diffraction at 293 K. The chemical formula obtained on the basis of the ICP–AES data is the following: \( ^{X1,X2} {\text{Ca}}_{4.03} \,^{Y} \left( {{\text{Mn}}_{0.42} {\text{Mg}}_{0.23} {\text{Fe}}^{2 + }_{1.39} } \right)_{\varSigma 2.04} \,^{Z1,Z2} \left( {{\text{Fe}}^{3 + }_{0.15} {\text{Al}}_{3.55} {\text{Ti}}_{0.12} } \right)_{\varSigma 3.82} \,^{T1,T2,T3,T4} \left( {{\text{Ti}}_{0.03} {\text{Si}}_{7.97} } \right)_{\varSigma 8} \,^{T5} {\text{B}}_{1.96} {\text{O}}_{30} \left( {\text{OH}} \right)_{2.18} \). The ⁵⁷Fe Mössbauer spectrum shows unambiguously the occurrence of Fe²⁺ and Fe³⁺ in octahedral coordination only, with Fe²⁺/Fe³⁺ = 9:1. The neutron structure refinement provides a structure model in general agreement with the previous experimental findings: the tetrahedral T1, T2, T3 and T4 sites are fully occupied by Si, whereas the T5 site is fully occupied by B, with no evidence of Si at the T5, or Al or Fe³⁺ at the T1–T5 sites. The structural and chemical data of this study suggest that the amount of B in ferroaxinite is that expected from the ideal stoichiometry: 2 a.p.f.u. (for 32 O). The atomic distribution among the X1, X2, Y, Z1 and Z2 sites obtained by neutron structure refinement is in good agreement with that based on the ICP–AES data. For the first time, an unambiguous localization of the H site is obtained, which forms a hydroxyl group with the oxygen atom at the O16 site as donor. The H-bonding scheme in axinite structure is now fully described: the O16–H distance (corrected for riding motion effect) is 0.991(1) Å and an asymmetric bifurcated bonding configuration occurs, with O5 and O13 as acceptors [i.e. with O16···O5 = 3.096(1) Å, H···O5 = 2.450(1) Å and O16–H···O5 = 123.9(1)°; O16···O13 = 2.777(1) Å, H···O13 = 1.914(1) Å and O16–H···O13 = 146.9(1)°].     

Diel feeding of the transparent goby Aphia minuta (Pisces,Gobiidae) in the Northwestern Adriatic Sea in spring time

The present study provides the first estimate of the daily ration for a goby species in the Mediterranean Sea, using a new approach to determine the mass of fish stomach contents through the sum of individual prey dry mass derived indirectly from prey size. Diel feeding activity and daily ration of the pelagic goby Aphia minuta were studied under natural conditions in the coastal waters off Comacchio (Northwestern Adriatic Sea) during the spring season. A total of 318 individuals of A. minuta, collected by 14 trawls carried out on 4 consecutive days, was examined for gut contents. The diel pattern of the vacuity index and the stomach fullness index indicated that A. minuta has nocturnal feeding behaviour. The daily ration, computed over a period of 16 h, was equivalent to 2.23% wet body mass.     

Internal tidal bore warm fronts and settlement of invertebrates in central Chile

We studied the occurrence of large high frequency temperature fluctuations and their potential association with settlement of intertidal invertebrates during the spring/summer period 1999/2000 at Las Cruces, on the coast of central Chile. Our results showed the existence of internal tidal bores, characterized by sharp drops in water temperature at the surface and near the bottom, and subsequent temperature increases, which occurred with a semidiurnal periodicity. Measured currents support the hypothesis of alternating onshore and offshore movement of warm-water fronts. The frequency of the events varied through the summer and their amplitude seems to be modulated by onshore winds. The strongest events were observed when strong onshore winds occurred in late afternoon hours and the entire water column showed a semidiurnal temperature signal. Highest values of chlorophyll concentration in the intertidal zone and daily settlement of bivalves, gastropods and crustaceans were observed at times when conditions were favorable for occurrence of internal tidal bores. Results suggest that internal tidal bore warm fronts could play an important role in the transport of neustonic larval invertebrates and the delivery of phytoplankton to at least some intertidal sites along the coast of Chile.     

Echelle-mepsicron time-resolved spectroscopy of the dwarf nova SS Cygni

High dispersion time-resolved spectrograms of the dwarf nova SS Cygni, obtained with the Echelle-Mepsicron system, show double peaked emission lines with a complex profile. The intensity of the H line appears to be modulated by the orbital period. Radial velocity measurements of the wings of H and of the absorption line system of the late-type star yield semiamplitude values of K_em=101±6 km s^–1 and K_ab=151±7 km s^–1, respectively. Radial velocity measurements of the blue and red peaks and of the central absorption of H reveal a synchronous movement with the broad wings, although there is some evidence of a narrow component probably associated with a hot spot in the disk or a chromospheric emission line from the secondary star. The H modulation, the double profile and recently discovered UBV light variations support an inclination angle i 50°. The masses of the primary are M_p=0.60 M and M_s=0.40 M, respectively. A detailed analysis of the absorption lines reveals a spectral type of K2V.Paper presented at the IAU Colloquium No. 93 Cataclysmic Variables. Recent Multi-Frequency Observations and Theoretical Developments, held at Dr. Remeis-Sternwarte Bamberg, F.R.G., 16–19 June, 1986.     

Three dimensional elasto‐plastic interface for embedded beam elements with interaction surface for the analysis of lateral loading of piles

This paper presents a numerical formulation for a three dimensional elasto‐plastic interface, which can be coupled with an embedded beam element in order to model its non‐linear interaction with the surrounding solid medium. The formulation is herein implemented for lateral loading of piles but is able to represent soil‐pile interaction phenomena in a general manner for different types of loading conditions or ground movements. The interface is formulated in order to capture localized material plasticity in the soil surrounding the pile within the range of small to moderate lateral displacements. The interface is formulated following two different approaches: (i) in terms of beam degrees of freedoms; and (ii) considering the displacement field of the solid domain. Each of these alternatives has its own advantages and shortcomings, which are discussed in this paper. The paper presents a comparison of the results obtained by means of the present formulation and by other well‐established analysis methods and test results published in the literature. Copyright © 2016 John Wiley & Sons, Ltd.