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.     

Hydraulic modeling of flood pulses in the Middle Bussento Karst System (MBSKS), UNESCO Cilento Global Geopark,southern Italy

Karst systems provide water for domestic and industrial uses and for generating hydropower, but they can also create fluvial hazards, such as upstream back‐flooding and downstream karst flash‐flood events. However, these hazards are difficult to foresee due to the complex recharge‐discharge processes as well as the lack of information on the inside of the system, which has often not been completely surveyed by speleologists or explored by boreholes. To overcome these difficulties, hydro‐chemical data from the monitoring system in the Middle Bussento Karst System (MBSKS), one of the first Experimental Karst Systems in southern Italy, were recorded and previously discussed. Based on shared background in flood karst hydraulic modeling, this paper describes the conceptual premises and rationale of a general‐purpose hydraulic model that is suitable both for the MBSKS and for other Mediterranean, multi‐recharge, mature, conduit‐dominated karst systems. To test the reliability of the model, simulations of time–space behavior and response are performed using natural and artificial flood pulses “as tracers”, considering a “pulse” as a significant variation in water quantity and/or quality. The results of the model explain the interactions between allogenic, autogenic, and anthropogenic recharges from differentiated sources and phreatic conduit systems. These results also clarify the overall response of karst springs at typical time scales of flood pulses. Table acronym name     

Impact of lightning on organic matter-rich soils: influence of soil grain size and organic matter content on underground fires

A detailed study was carried out on a piece of land that had been struck by lightning during the violent rainstorm that raged over the Island of S?o Miguel (Azores Archipelago) in late October 2006. Temperature and gas measurements (CO₂, CO, H₂S and CH₄) were performed in four study trenches, dug in an area of ∼3 m², where an underground fire had been initiated by the impact with a lightning stroke, followed by the emission of a column of gases and smoke. The soil under study was originally a well-pedogenized about 80 cm thick bed, made of volcanic clayey to silty tephra fallouts and contained 5.5–9.7% of organic matter. The underground fire was monitored for one week and revealed a peak release of 404 ppm CO and 3.4% CO₂ originating from a horizon located about 45 cm under the soil surface. Measurements of temperature, performed one week after the impact, indicated a maximum value of 326°C inside the soil, while 516.5°C were measured on the surface of a lava block interred about 20 cm under the surface. Subsequently, a stratigraphic and sedimentologic study proved the role of the grain-size of the soil and of the organic matter content of the different horizons of the impact area, in determining the ratio between anoxic/oxidised combustion conditions and in the progress of the process itself. It was also noticed that combustion was not total all over in the soil bed and that the process had slightly migrated toward SW during the observation period. The combustion process went on for about ten days, in spite of several other violent rainstorms, until it was artificially extinguished through the excavations made to obtain study trenches. This particular circumstance evidenced the potential natural hazard represented by this kind of atmospheric event, especially in a land where the volcanic nature of the soil may easily mislead inexperienced observers and, consequently, delay proper action.     

Metasomatic events recorded in ultramafic xenoliths from the Hyblean area (Southeastern Sicily, Italy)

Three types of ultramafic xenoliths from the Hyblean area (Sicily) show prime evidence for mantle metasomatism, namely: 1) Spinel-facies depleted harzburgite veined by phlogopite-bearing clinopyroxenite; 2) Amphibole-bearing harzburgite; and 3) Al-spinel websterite. (2) and (3) exhibit glassy pockets having respectively mugearitic and basanitic compositions, but a little amount of glass with low Ca and very low alkalis in (2). Glasses generally show trace element distributions consistent with the partial melting of pargasite-dominated mineral assemblages. Abundant Ca-Mg-carbonate globules immersed in these glassy pockets testify to immiscibility between silicate and carbonatite melts. Silicate melts and hydrous-silicate supercritical fluids, which underwent phase separation during fluxing throughout the semi-brittle lithospheric mantle, may account for such metasomatizing processes. The nature and abundance of some fluid-mobile elements in glasses and hydrous minerals (especially the Ca-poor glass, with B?=?59 ppm, Li?=?27 ppm, Ba?=?700 ppm and phlogopite, with Ba?=?8,465 ppm, Sr?=?260 ppm, F?=?5,700 ppm) suggest that some hydrous fluids may derive from hydrothermally altered oceanic crust. Conversely, metasomatizing silicate melts probably have a deep-seated origin. These results confirm previous suggestions on the key role of mantle metasomatism in the origin of some alkaline Hyblean magmas.     

Exploring lava‐flow hazards at Pico Island,Azores Archipelago (Portugal)

Pico, the youngest island of the Azores Archipelago (Portugal), is characterized by a central volcano and a 30‐km‐long fissure zone. Its eruption rate is the highest of the Azores islands, with more than 35 eruptions in the last 2000 years. Here, we estimate the lava‐flow hazard for Pico Island by combining the vent opening probability derived from the spatial distribution of eruptive fissures, the classes of expected eruptions inferred from the physical and chemical characteristics of historical eruptions, and the lava‐flow paths simulated by the MAGFLOW model. The most likely area to host new eruptions is along a WNW–ESE trend centred on the central volcano, with the highest hazard affecting the two main residential zones of Lajes do Pico and Madalena. Our analysis is the first attempt to assess the lava‐flow hazard for Pico Island, and may have important implications for decision‐making in territorial management and future land‐use planning.     

Neural network approach to prediction of temperatures around groundwater heat pump systems

A fundamental aspect in groundwater heat pump (GWHP) plant design is the correct evaluation of the thermally affected zone that develops around the injection well. This is particularly important to avoid interference with previously existing groundwater uses (wells) and underground structures. Temperature anomalies are detected through numerical methods. Computational fluid dynamic (CFD) models are widely used in this field because they offer the opportunity to calculate the time evolution of the thermal plume produced by a heat pump. The use of neural networks is proposed to determine the time evolution of the groundwater temperature downstream of an installation as a function of the possible utilization profiles of the heat pump. The main advantage of neural network modeling is the possibility of evaluating a large number of scenarios in a very short time, which is very useful for the preliminary analysis of future multiple installations. The neural network is trained using the results from a CFD model (FEFLOW) applied to the installation at Politecnico di Torino (Italy) under several operating conditions. The final results appeared to be reliable and the temperature anomalies around the injection well appeared to be well predicted.     

Aliphatic hydrocarbons in metasomatized gabbroic xenoliths from Hyblean diatremes (Sicily): Genesis in a serpentinite hydrothermal system

Many tholeiite gabbro xenoliths from the Hyblean tuff-breccia deposits (Sicily, southern Italy) present mineralogical and geochemical evidence for hydrothermal alteration at different temperatures and water/rock ratios. In some cases, the primary mineral assemblage has been entirely replaced by Na-rich alkali feldspar, chlorite/smectite interlayers, zeolites, aegirine–augite, titanite, zircon etc. Hence the chemical composition of such metasomatic rocks displays larger amounts of volatiles, alkalis, Zr, Hf, U, Th and lower Ca, Mg, Fe with respect to the original gabbro. Five hydrothermally altered gabbroic xenoliths were selected for thermal decrepitation and bulk gas analyses by quadrupole mass spectrometry. All the samples analyzed display the same Electron Impact-Direct Pyrolysis Mass spectra (EI-DPMS). These show a series of peaks differing by 14 mass units due to loss of methylene groups (–CH₂), by a fragmentation process typical of saturated aliphatic and aliphatic–aromatic hydrocarbons. In addition, Fourier Transform Infrared (FT-IR) spectra of the samples present several bands typical of vibration frequencies of aliphatic hydrocarbons. The high-molecular-weight hydrocarbons observed probably originated from Fischer–Tropsch-type (FT-t) synthesis in the high temperature section of a serpentinite-hosted hydrothermal system. This suggestion may lend support to the recent hypothesis regarding the original oceanic nature of the Hyblean lithospheric basement.     

Estimates of effective permeability for non-Newtonian fluid flow in randomly heterogeneous porous media

An understanding of the interplay between non-Newtonian effects in porous media flow and field-scale domain heterogeneity is of great importance in several engineering and geological applications. Here we present a simplified approach to the derivation of an effective permeability for flow of a purely viscous power–law fluid with flow behavior index n in a randomly heterogeneous porous domain subject to a uniform pressure gradient. A standard form of the flow law generalizing the Darcy’s law to non-Newtonian fluids is adopted, with the permeability coefficient being the only source of randomness. The natural logarithm of the permeability is considered a spatially homogeneous and correlated Gaussian random field. Under the ergodic hypothesis, an effective permeability is first derived for two limit 1-D flow geometries: flow parallel to permeability variation (serial-type layers), and flow transverse to permeability variation (parallel-type layers). The effective permeability of a 2-D or 3-D isotropic domain is conjectured to be a power average of 1-D results, generalizing results valid for Newtonian fluids under the validity of Darcy’s law; the conjecture is validated comparing our results with previous literature findings. The conjecture is then extended, allowing the exponents of the power averaging to be functions of the flow behavior index. For Newtonian flow, novel expressions for the effective permeability reduce to those derived in the past. The effective permeability is shown to be a function of flow dimensionality, domain heterogeneity, and flow behavior index. The impact of heterogeneity is significant, especially for shear-thinning fluids with a low flow behavior index, which tend to exhibit channeling behavior.     

Inter-annual variability of wet season freshwater plume extent into the Great Barrier Reef lagoon based on satellite coastal ocean colour observations

Riverine freshwater plumes are the major transport mechanism for nutrients, sediments and pollutants into the Great Barrier Reef (GBR) lagoon and connect the land with the receiving coastal and marine waters. Knowledge of the variability of the freshwater extent into the GBR lagoon is relevant for marine park management to develop strategies for improving ecosystem health and risk assessments. In this study, freshwater extent has been estimated for the entire GBR lagoon area from daily satellite observations of the Moderate Resolution Imaging Spectroradiometer (MODIS) between 2002 and 2010. To enable a reliable mapping of freshwater plumes we applied a physics-based coastal ocean colour algorithm, that simultaneously retrieves chlorophyll-a, non-algal particulate matter and coloured dissolved organic matter (CDOM), from which we used CDOM as a surrogate for salinity (S) for mapping the freshwater extent.