Rutile R632 – A New Natural Reference Material for U‐Pb and Zr Determination

A new natural rutile reference material is presented, suitable for U‐Pb dating and Zr‐in‐rutile thermometry by microbeam methods. U‐Pb dating of rutile R632 using laser ablation ICP‐MS with both magnetic sector field and quadrupole instruments as well as isotope dilution‐thermal ionisation mass spectrometry yielded a concordia age of 496 ± 2 Ma. The high U content (> 300 μg g^?1) enabled measurement of high‐precision U‐Pb ages despite its young age. The sample was found to have a Zr content of 4294 ± 196 μg g^?1, which makes it an excellent complementary reference material for Zr‐in‐rutile thermometry. Individual rutile grains have homogeneous compositions of a number of other trace elements including V, Cr, Fe, Nb, Mo, Sn, Sb, Hf, Ta and W. This newly characterised material significantly expands the range of available rutile reference materials relevant for age and temperature determinations.     

Evolution of fluids associated with metasedimentary sequences from Chaves (North Portugal)

In order to identify and characterise fluids associated with metamorphic rocks from the Chaves region (North Portugal), fluid inclusions were studied in quartz veinlets, concordant with the main foliation, in graphitic-rich and nongraphitic-rich lithologies from areas with distinct metamorphic grade. The study indicates multiple fluid circulation events with a variety of compositions, broadly within the C–H–O–N–salt system. Primary fluid inclusions in quartz contain low salinity aqueous–carbonic, H₂O–CH₄–N₂–NaCl fluids that were trapped near the peak of regional metamorphism, which occurred during or immediately after D2. The calculated P–T conditions for the western area of Chaves (CW) is P=300–350 MPa and T500 °C, and for the eastern area (CE), P=200–250 MPa and T=400–450 °C. A first generation of secondary fluid inclusions is restricted to discrete cracks at the grain boundaries of quartz and consists of low salinity aqueous–carbonic, H₂O–CO₂–CH₄–N₂–NaCl fluids. P–T conditions from the fluid inclusions indicate that they were trapped during a thermal event, probably related with the emplacement of the two-mica granites.

A second generation of secondary inclusions occurs in intergranular fractures and is characterised by two types of aqueous inclusions. One type is a low salinity, H₂O–NaCl fluid and the second consists of a high salinity, H₂O–NaCl–CaCl₂ fluid. These fluid inclusions are not related to the metamorphic process and have been trapped after D3 at relatively low P (hydrostatic)–T conditions (P<100 MPa and T<300 °C).

Both the early H₂O–CH₄–N₂–NaCl fluids in quartz from the graphitic-rich lithologies and the later H₂O–CO₂–CH₄–N₂–NaCl carbonic fluid in quartz from graphitic-rich and nongraphitic-rich lithologies seem to have a common origin and evolution. They have low salinity, probably resulting from connate waters that were diluted by the water released from mineral dehydration during metamorphism. Their main component is water, but the early H₂O–CH₄–N₂–NaCl fluids are enriched in CH₄ due to interaction with the C-rich host rocks.

From the early H₂O–CH₄–N₂–NaCl to the later aqueous–carbonic H₂O–CO₂–CH₄–N₂–NaCl fluids, there is an enrichment in CO₂ that is more significant for the fluids associated with nongraphitic-rich lithologies.

The aqueous–carbonic fluids, enriched in H₂O and CH₄, are primarily associated with graphitic-rich lithologies. However, the aqueous–carbonic CO₂-rich fluids were found in both graphitic and nongraphitic-rich units from both the CW and CE studied areas, which are of medium and low metamorphic grade, respectively.     

Regional retrograde alteration of sub-greenschist facies chlorite to smectite

Dioctahedral smectite is present as a retrograde alteration product of chlorite in Permian-Triassic red slates of the Malaguide Complex in Sierra de Espuña (Betic Cordillera). Mineral assemblages and textures, illite crystallinity indices, and fluid inclusion data indicate sub-greenschist facies conditions that reached at least 180°C in the higher-grade tectonic unit of the Malaguide Complex, preceding formation of smectite. Smectite, having K as the dominant interlayer cation, occurs ubiquitously intercalated with trioctahedral chlorite as thin packets of layers and as individual layers that commonly change to chlorite along layers. Although some chlorite is typically homogeneous and trioctahedral, much chlorite shows signs of alteration and has compositions corresponding to different degrees of smectite contaimination. The incompatibility of metamorphic grade with the occurrence of smectite, the general association of chlorite and smectite, and the textural relations collectively show that dioctahedral smectite is derived through replacement of trioctahedral chlorite. Such replacement occurs on a regional basis and demonstrates that caution must be used in interpreting the occurrence of smectite in pelites as being due to prograde processes. Alteration of trioctahedral chlorite under oxidizing conditions due to introduction of phreatic water after uplift of the Betic Cordillera is proposed as the cause of formation of smectite.     

Genetic and chemical relationships between berthierine,chlorite and cordierite in nodules associated to granitic pegmatites of Sierra Albarrana (Iberian Massif,Spain)

Chlorite and berthierine occur through alteration of cordierite within enclaves of metamorphic rocks transformed by the Sierra Albarrana pegmatites. The coexistence of both phyllosilicates allows us to study their stability relationships and to compare their chemical compositions. Samples showing incipient replacement of cordierite by small cryptocrystalline aggregates can be identified by X-ray diffraction (XRD) as berthierine with small quantities of chlorite. Electron Microprobe (EMP) analyses give mixed compositions of berthierine and cordierite. Samples with extensive replacement of cordierite by aggregates show similar characteristics to those with incipient replacement, but some small crystals are present. The last type of sample shows complete replacement of cordierite by crystals showing optical properties of chlorite and EMPA compositions coherent with chlorite or berthierine. Their XRD pattern corresponds to chlorite and their high resolution transmission electron microscopy (HRTEM) images only show perfect sequences of 14 Å lattice fringes. The cryptocrystalline aggregates of the samples with incipient and extensive replacement present coexistent areas of 14 Å and 7 Å lattice fringes that are intergrown at different levels: (1) large areas (> 1 m) of 7 Å layers; (2) packets of 7 Å layers between 14 Å layer areas, with visible 7 Å to 14 Å lateral changes; (3) random mixed-layers 7 Å/14 Å. Chlorite is the final stable product of alteration of cordierite, with berthierine as an intermediate metastable phase. Energy dispersive X-ray spectrometry microanalyses of 14 Å, 7 Å and (14+7) Å areas show lack of systematic differences in chemical compositions between both phyllosilicates which may be considered as true polymorphs.     

Future regional projections of extreme temperatures in Europe: a nonstationary seasonal approach

This paper analyzes changes of maximum temperatures in Europe, which are evaluated using two state-of-the-art regional climate models from the EU ENSEMBLES project. Extremes are expressed in terms of return values using a time-dependent generalized extreme value (GEV) model fitted to monthly maxima. Unlike the standard GEV method, this approach allows analyzing return periods at different time scales (monthly, seasonal, annual, etc). The study focuses on the end of the 20th century (1961?C2000), used as a calibration/validation period, and assesses the changes projected for the period 2061?C2100 considering the A1B emission scenario. The performance of the regional models is evaluated for each season of the calibration period against the high-resolution gridded E-OBS dataset, showing a similar South-North gradient with larger values over the Mediterranean basin. The inter-RCM changes in the bias pattern with respect to the E-OBS are larger than the bias resulting from a change in the boundary conditions from ERA-40 to ECHAM5 20c3m. The maximum temperature response to increased green house gases, as projected by the A1B scenario, is consistent for both RCMs. Under that scenario, results indicate that the increments for extremes (e.g. 40-year return values) will be two or three times higher than those for the mean seasonal temperatures, particularly during Spring and Summer in Southern Europe.     

Subfilter-scale Fluxes over a Surface Roughness Transition. Part I: Measured Fluxes and Energy Transfer Rates

A wind-tunnel experiment was designed and carried out to study the effect of a surface roughness transition on subfilter-scale (SFS) physics in a turbulent boundary layer. Specifically, subfilter-scale stresses are evaluated that require parameterizations and are key to improving the accuracy of large-eddy simulations of the atmospheric boundary layer. The surface transition considered in this study consists of a sharp change from a rough, wire-mesh covered surface to a smooth surface. The resulting magnitude jump in aerodynamic roughnesses, M = ln(z ₀₁/z ₀₂), where z ₀₁ and z ₀₂ are the upwind and downwind aerodynamic surface roughnesses respectively, is similar to that of past experimental studies in the atmospheric boundary layer. The two-dimensional velocity fields used in this study are measured using particle image velocimetry and are acquired at several positions downwind of the roughness transition as well as over a homogeneous smooth surface. Results show that the SFS stress, resolved strain rate and SFS transfer rate of resolved kinetic energy are dependent on the position within the boundary layer relative to the surface roughness transition. A mismatch is found in the downwind trend of the SFS stress and resolved strain rate with distance from the transition. This difference of behaviour may not be captured by some eddy-viscosity type models that parameterize the SFS stress tensor as proportional to the resolved strain rate tensor. These results can be used as a benchmark to test the ability of existing and new SFS models to capture the spatial variability SFS physics associated with surface roughness heterogeneities.     

An enhanced ensemble Kalman filter scheme incorporating model error in sequential coupling between flow and geomechanics

In this work, we construct a new methodology for enhancing the predictive accuracy of sequential methods for coupling flow and geomechanics while preserving low computational cost. The new computational approach is developed within the framework of the fixed-stress split algorithm procedure in conjunction with data assimilation based on the ensemble Kalman filter (EnKF). In this context, we identify the high-fidelity model with the two-way formulation where additional source term appears in the flow equation containing the time derivative of total mean stress. The iterative scheme is then interlaced with data assimilation steps, which also incorporate the modeling error inherent to the EnKF framework. Such a procedure gives rise to an “enhanced one-way formulation,” exhibiting substantial improvement in accuracy compared with the classical one-way method. The governing equations are discretized by mixed finite elements, and numerical simulation of a 2D slab problem between injection and production wells illustrate the tremendous achievement of the method proposed herein.     

Red micas from basal ignimbrites of Mt. Vulture (Italy): interlayer content appraisal by a multi-methodic approach

The crystal chemistry of red phlogopites from Mt. Vulture (Italy) ignimbrites has been studied by electron microprobe, secondary ion mass spectrometry (SIMS), single crystal structural investigation and Fourier transform infrared (FTIR) spectroscopy. The analysed phlogopite has Fe/(Fe + Mg) ∼ 0.35, TiO₂ (wt%): 2.8–5.0 and H₂O (wt%): 1.24–3.37. Infrared spectra revealed the presence of bands due to the NH₄⁺ and H₂O stretching and bending vibrations. The samples belong to the 1M polytype. The bimodal behaviour of several structural parameters allows red micas to be clustered into two distinct groups: K⁺ ↔ NH₄⁺, H₂O and M³⁺-vacancy substitutions dominate in the first group; M^3+,4+-oxy, in the second group. It has to be pointed out that quantitative analysis of hydrogen (via SIMS) together with the characterization of the local environment of the anionic site (via FTIR) are fundamental in assessing the correct structural formula and the substitution mechanisms in micas. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

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).