Behavior of epidote at high pressure and high temperature: a powder diffraction study up to 10 GPa and 1,200 K

The thermo-elastic behavior of a natural epidote [Ca_1.925 Fe_0.745Al_2.265Ti_0.004Si_3.037O₁₂(OH)] has been investigated up to 1,200 K (at 0.0001 GPa) and 10 GPa (at 298 K) by means of in situ synchrotron powder diffraction. No phase transition has been observed within the temperature and pressure range investigated. P–V data fitted with a third-order Birch–Murnaghan equation of state (BM-EoS) give V ₀ = 458.8(1)ų, K _T0 = 111(3) GPa, and K′ = 7.6(7). The confidence ellipse from the variance–covariance matrix of K _T0 and K′ from the least-square procedure is strongly elongated with negative slope. The evolution of the “Eulerian finite strain” vs “normalized stress” yields Fe(0) = 114(1) GPa as intercept values, and the slope of the regression line gives K′ = 7.0(4). The evolution of the lattice parameters with pressure is slightly anisotropic. The elastic parameters calculated with a linearized BM-EoS are: a ₀ = 8.8877(7) Å, K _T0(a) = 117(2) GPa, and K′(a) = 3.7(4) for the a-axis; b ₀ = 5.6271(7) Å, K _T0(b) = 126(3) GPa, and K′(b) = 12(1) for the b-axis; and c ₀ = 10.1527(7) Å, K _T0(c) = 90(1) GPa, and K’(c) = 8.1(4) for the c-axis [K _T0(a):K _T0(b):K _T0(c) = 1.30:1.40:1]. The β angle decreases with pressure, β_P(°) = β_P0 −0.0286(9)P +0.00134(9)P ² (P in GPa). The evolution of axial and volume thermal expansion coefficient, α, with T was described by the polynomial function: α(T) = α₀ + α₁ T ^−1/2. The refined parameters for epidote are: α₀ = 5.1(2) × 10⁻⁵ K⁻¹ and α₁ = −5.1(6) × 10⁻⁴ K^1/2 for the unit-cell volume, α₀(a) = 1.21(7) × 10⁻⁵ K⁻¹ and α₁(a) = −1.2(2) × 10⁻⁴ K^1/2 for the a-axis, α₀(b) = 1.88(7) × 10⁻⁵ K⁻¹ and α₁(b) = −1.7(2) × 10⁻⁴ K^1/2 for the b-axis, and α₀(c) = 2.14(9) × 10⁻⁵ K⁻¹ and α₁(c) = −2.0(2) × 10⁻⁴ K^1/2 for the c-axis. The thermo-elastic anisotropy can be described, at a first approximation, by α₀(a): α₀(b): α₀(c) = 1 : 1.55 : 1.77. The β angle increases continuously with T, with β_T(°) = β_T0 + 2.5(1) × 10⁻⁴ T + 1.3(7) × 10⁻⁸ T ². A comparison between the thermo-elastic parameters of epidote and clinozoisite is carried out.     

Origin of resources and trophic pathways in a large SW Atlantic estuary: An evaluation using stable isotopes

The Río de la Plata (34° 36′ S, 55° 58′ W; Argentina and Uruguay) estuary, one of the most important South American estuarine environments, is characterized by weak seasonal freshwater discharge, low tidal amplitude (<1 m), a wide and permanent connection to the sea, and a salt-wedge regime. Using stable isotope analysis, we explored the relative importance of the different sources of primary production in the food web. Our results show that phytoplankton and macrodetritus from terrestrial salt and freshwater marshes both contribute to the food web of the Río de la Plata estuary. On the basis of the sampled species, we identified four trophic levels. The clam Mactra isabelleana, the calanoid copepod Acartia tonsa, and the opossum shrimp Neomysis americana are the primary consumers. The rays Atlantoraja castelnaui and Squatina guggenheim and the shark Galeorhinus galeus are the top predators. The Río de la Plata food web shows an important input of nutrients derived from phytoplankton. Rays, sharks, and predatory gastropods reveal an important contribution of C4 plants (likely Spartina spp.). However, production derived from C3 plants is also important for some species. The fishes Brazilian menhaden, Brevoortia aurea; the stripped weakfish Cynoscion guatucupa; and the whitemouth croaker, Micropogonias furnieri, showed differences in their isotopic signatures as juveniles and adults, indicating different food sources, and they were therefore treated as different components of the food web. Our data suggest that detritus from salt and freshwater marshes is reaching the Río de la Plata estuary and can be an important allocthonous source of energy to this environment.     

The heating history of Vesta and the onset of differentiation

In this work, we study the link between the evolution of the internal structure of Vesta and thermal heating due to ²⁶Al and ⁶⁰Fe and long‐lived radionuclides, taking into account the chemical differentiation of the body and the affinity of ²⁶Al with silicates. We explored several thermal and structural scenarios differing in the available strength of energy due to the radiogenic heating and in the postsintering macroporosity. By comparing them with the data supplied by the HEDs and the Dawn NASA mission, we use our results to constrain the accretion and differentiation time as well as the physical properties of the core. Differentiation takes place in all scenarios in which Vesta completes its accretion in <1.4 Ma after the injection of ²⁶Al into the solar nebula. In all those scenarios where Vesta completes its formation in <1 Ma from the injection of ²⁶Al, the degree of silicate melting reaches 100 vol% throughout the whole asteroid. If Vesta completed its formation between 1 and 1.4 Ma after ²⁶Al injection, the degree of silicate melting exceeds 50 vol% over the whole asteroid, but reaches 100 vol% only in the hottest, outermost part of the mantle in all scenarios where the porosity is lower than 5 vol%. If the formation of Vesta occurred later than 1.5 Ma after the injection of ²⁶Al, the degree of silicate melting is always lower than 50 vol% and is limited only to a small region of the asteroid. The radiation at the surface dominates the evolution of the crust, which ranges in thickness from 8 to about 30 km after 5 Ma: a layer about 3–20 km thick is composed of primitive unmelted chondritic material, while a layer of about 5–10 km is eucritic.     

Iron-hydroxide clogging of public supply wells receiving artificial recharge: near-well and in-well hydrological and hydrochemical observations

Clogging of water wells by iron-hydroxide incrustations due to mixing of anoxic and oxic groundwater is a common well-ageing problem. The relation between well operation (on and off), the spatial and temporal variations in hydrochemistry outside and inside a supply well, and the distribution of clogging iron-hydroxides were studied in an artificial recharge well field in the Netherlands. Camera inspection, high-resolution multi-level water sampling outside the well and detailed in-well pH/EC/O₂ profiles revealed remarkable patterns. During pumping, the top of the upper well screen abstracted oxic filtrate, although the larger part of the in-well water column was anoxic. The column rapidly turned oxic after shutdown due to a downward short-circuiting of oxic water via the well. Within 15 d it became anoxic due to the slow advance of anoxic lake filtrate created by local changes in flow direction as the neighboring wells continued to pump. Severe clogging occurred where the oxic filtrate entered the well, while half-clogging of the upper well screen occurred due to less inflow of oxic filtrate on the lake side. Transport of iron flocs and bacterial slimes after shutdown seemed to clog the lower part of the well screen. Frequent on/off switching should be avoided in iron-clogged wells.     

An overview of physical and ecological processes in the Rio de la Plata Estuary

The Rio de la Plata is a large-scale estuary located at 35°S on the Atlantic coast of South America. This system is one of the most important estuarine environments in the continent, being a highly productive area that sustains valuable artisanal and coastal fisheries in Uruguay and Argentina. The main goals of this paper are to summarize recent knowledge on this estuary, integrating physical, chemical and biological studies, and to explore the sources and ecological meaning of estuarine variability associated to the stratification/mixing alternateness in the estuary. We summarized unpublished data and information from several bibliographic sources. From study cases representing different stratification conditions, we draw a holistic view of physical patterns and ecological processes of the stratification/mixing alternateness. This estuary is characterized by strong vertical salinity stratification most of the time (the salt-wedge condition). The head of the estuary is characterized by a well-developed turbidity front. High turbidity constrains their photosynthesis. Immediately offshore the turbidity front, water becomes less turbid and phytoplankton peaks. As a consequence, trophic web in the estuary could be based on two sources of organic matter: phytoplankton and plant detritus. Dense plankton aggregations occur below the halocline and at the tip of the salt wedge. The mysid Neomysis americana, a key prey for juvenile fishes, occurs all along the turbidity front. A similar spatial pattern is shown by one of the most abundant benthic species, the clam Mactra isabelleana. These species could be taken advantage of the particulate organic matter and/or phytoplankton concentrated near the front. Nekton is represented by a rich fish community, with several fishes breeding inside the estuary. The most important species in terms of biomass is Micropogonias furnieri, the main target for the coastal fisheries of Argentina and Uruguay. Two processes have been identified as producing partially stratified conditions: persistent moderate winds (synoptic scale), or low freshwater runoff (interannual scale). Less frequently, total mixing of the salt wedge occurs after several hours of strong winds. The co-dominance of diatoms (which proliferate in highly turbulent environments) and red tides dinoflagellates and other bloom taxa (better adapted to stratified conditions), would indicate great variability in the turbulence strength, probably manifested as pulses. Microplankton and ichthyoplankton assemblages defined for the stratified condition are still recognized during the partially mixed condition, but in this case they occupy the entire water column: vertical structure of the plankton featuring the stratified condition become lost. Bottom fish assemblages, on the contrary, shows persistence under the different stratification conditions, though the dominant species of the groups show some variations. Summarizing, the Río de la Plata Estuary is a highly variable environment, strongly stratified most of the time but that can be mixed in some few hours by strong wind events that occur in an unpredictable manner, generating stratification/partially mixed (less frequently totally mixed) pulses all along the year. At larger temporal scales, the system is under the effects of river discharge variations associated to the ENSO cycle, but their ecological consequences are not fully studied.     

Isotropic wavelets: a powerful tool to extract point sources from cosmic microwave background maps

It is the aim of this paper to introduce the use of isotropic wavelets to detect and determine the flux of point sources appearing in cosmic microwave background (CMB) maps. The most suitable wavelet to detect point sources filtered with a Gaussian beam is the 'Mexican Hat'. An analytical expression of the wavelet coefficient obtained in the presence of a point source is provided and used in the detection and flux estimation methods presented. For illustration the method is applied to two simulations (assuming Planck mission characteristics) dominated by CMB (100 GHz) and dust (857 GHz), as these will be the two signals dominating at low and high frequencies respectively in the Planck channels. We are able to detect bright sources above 1.58 Jy at 857 GHz (82 per cent of all sources) and above 0.36 Jy at 100 GHz (100 per cent of all), with errors in the flux estimation below 25 per cent. The main advantage of this method is that nothing has to be assumed about the underlying field, i.e. about the nature and properties of the signal plus noise present in the maps. This is not the case in the detection method presented by Tegmark & Oliveira-Costa. Both methods are compared, producing similar results.     

High-pressure X-ray and Raman study of a ferrian magnesian spodumene

The high-pressure behaviour of a synthetic P2₁/c ferrian magnesian spodumene, ^M2 (Li_0.85Mg_0.09Fe²⁺ _0.06)^M1(Fe³⁺ _0.85Mg_0.15)Si₂O₆, has been investigated using in situ single-crystal X-ray diffraction and Raman spectroscopy. No phase transition has been observed within the pressure range investigated. The isothermal equation of state up to 7 GPa was determined. V₀, K_T0 and K, simultaneously refined with a Murnaghan equation of state, are: V₀= 415.66(7) ų, K_T0=83(1) GPa and K=9.6(6). The magnitudes of the principal unit-strain coefficients were calculated and their ratios 1:2:3=1.00:1.85:2.81 at P=6.83 GPa indicate a very strong anisotropy. Monitoring of the intensity of b-type reflections (h+k= 2n+1) confirms that from room conditions up to 7 GPa the primitive lattice is maintained. Raman spectra have been collected up to 7.4 GPa. No change in the number of observed vibrational modes occurs in the pressure range investigated. At high frequency, the Raman doublet relative to the Si–O–Si vibrations of the two distinct tetrahedral chains is a broad band at room pressure, however, the frequency difference between the two modes increases with increasing pressure.Operating system: Windows NT     

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.     

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)°].