Synchrotron-based X-ray study of iron oxide transformations in terraces from the Tinto-Odiel river system: Influence on arsenic mobility

Simultaneous analysis of micro-X-ray diffraction (μ-XRD) and micro-X-ray fluorescence (μ-XRF) based on synchrotron light sources, and electron microprobe (EMP) analyses, were performed on iron terrace samples taken from Tinto-Odiel river system from the Iberian Pyrite Belt (IBP, SW Iberian Peninsula). Iron terraces are formed during the oxidation and precipitation of dissolved iron along the riverbeds impacted by acid mine drainage (AMD). This paper includes the study of actively-forming current terraces and fossil terraces isolated from the stream courses due to the river migration over time. The results of the study of current terrace samples from AMD-affected streams of two IPB abandoned mines (Tinto Santa Rosa and Cueva de la Mora) showed that fresh precipitates at the surface are composed primarily of metastable schwertmannite, which is gradually transformed at depth over short-time scales into goethite. Sediments of ancient terraces are composed mainly of goethite, which most likely originated from the re-crystallization of a precursor schwertmannite. However, at century-time scale, goethite partially re-crystallizes to hematite due to diagenetic processes. The transformation rate of goethite into hematite is negatively correlated with grain size and the crystallinity of goethite. Moreover, this transformation is accompanied by an increase in grain size and a decrease in surface area of hematite, and a concomitant decrease in arsenic trapped in the solid. This increase in the arsenic mobility during the diagenetic maturation should be considered in the development of conceptual and analytical models describing long-term fate, transport and bioavailability of arsenic in environmental systems.     

An Analytical Model for Hydraulic Fracturing in Shallow Bedrock Formations

A theoretical method is proposed to estimate post‐fracturing fracture size and transmissivity, and as a test of the methodology, data collected from two wells were used for verification. This method can be employed before hydrofracturing in order to obtain estimates of the potential hydraulic benefits of hydraulic fracturing. Five different pumping test analysis methods were used to evaluate the well hydraulic data. The most effective methods were the Papadopulos‐Cooper model (1967), which includes wellbore storage effects, and the Gringarten‐Ramey model (1974), known as the single horizontal fracture model. The hydraulic parameters resulting from fitting these models to the field data revealed that as a result of hydraulic fracturing, the transmissivity increased more than 46 times in one well and increased 285 times in the other well. The model developed by dos Santos (2008) , which considers horizontal radial fracture propagation from the hydraulically fractured well, was used to estimate potential fracture geometry after hydrofracturing. For the two studied wells, their fractures could have propagated to distances of almost 175 m or more and developed maximum apertures of about 2.20 mm and hydraulic apertures close to 0.30 mm. Fracturing at this site appears to have expanded and propagated existing fractures and not created new fractures. Hydraulic apertures calculated from pumping test analyses closely matched the results obtained from the hydraulic fracturing model. As a result of this model, post‐fracturing geometry and resulting post‐fracturing well yield can be estimated before the actual hydrofracturing.     

The pyrogeography of sub-Saharan Africa: a study of the spatial non-stationarity of fire–environment relationships using GWR

This study analyses the relationship between fire incidence and some environmental factors, exploring the spatial non-stationarity of the phenomenon in sub-Saharan Africa. Geographically weighted regression (GWR) was used to study the above relationship. Environment covariates comprise land cover, anthropogenic and climatic variables. GWR was compared to ordinary least squares, and the hypothesis that GWR represents no improvement over the global model was tested. Local regression coefficients were mapped, interpreted and related with fire incidence. GWR revealed local patterns in parameter estimates and also reduced the spatial autocorrelation of model residuals. All the covariates were non-stationary and in terms of goodness of fit, the model replicates the data very well (R ² = 87%). Vegetation has the most significant relationship with fire incidence, with climate variables being more important than anthropogenic variables in explaining variability of the response. Some coefficient estimates exhibit locally different signs, which would have gone undetected by a global approach. This study provides an improved understanding of spatial fire–environment relationships and shows that GWR is a valuable complement to global spatial analysis methods. When studying fire regimes, effects of spatial non-stationarity need to be incorporated in vegetation-fire modules to have better estimates of burned areas and to improve continental estimates of biomass burning and atmospheric emissions derived from vegetation fires.     

Marine debris ingestion by Magellanic penguins, Spheniscus magellanicus (Aves: Sphenisciformes), from the Brazilian coastal zone

Magellanic penguins (Spheniscus magellanicus) are non-breeding winter visitors to the Brazilian coast. In 2008 and 2010, plastic items and other marine debris were found in the stomachs and intestines of 15% of 175 dead penguins collected in the Lagos Region of the state of Rio de Janeiro. One bird had its stomach perforated by a plastic straw, which may have caused its death. There are few records of penguins ingesting plastic litter, but previous studies have found similar levels of debris ingestion among Magellanic penguins stranded on the Brazilian coast (35.8% of 397 birds). The high incidence of marine debris in this species in Brazil may result at least in part from the predominance of juveniles reaching these waters, as juvenile penguins may have a broader diet than adults. It is unclear to what extent plastic ingestion affects the mortality rate in this species and whether the incidence in stranded birds reflects that in the entire population. The present study addresses the increasing impact of plastic debris on marine life.     

In situ Re–Os isotopic analysis of platinum-group minerals from the Mayarí-Cristal ophiolitic massif (Mayarí-Baracoa Ophiolitic Belt,eastern Cuba): implications for the origin of Os-isotope heterogeneities in podiform chromitites

Chromitite pods in the Mayarí-Cristal ophiolitic massif (eastern Cuba) were formed in the Late Cretaceous when island arc tholeiites and MORB-like back-arc basin basalts reacted with residual mantle peridotites and generated chromite-rich bodies enclosed in dunite envelopes. Platinum-group minerals (PGM) in the podiform chromitites exhibit important Os-isotope heterogeneities at the kilometric, hand sample and thin section scales. ¹⁸⁷Os/¹⁸⁸Os calculated at the time of chromitite crystallization (~90 Ma) ranges between 0.1185 and 0.1295 (γOs = −7.1 to +1.6, relative to enstatite chondrite), and all but one PGM have subchondritic ¹⁸⁷Os/¹⁸⁸Os. Grains in a single hand sample have initial ¹⁸⁷Os/¹⁸⁸Os that spans from 0.1185 to 0.1274, and in one thin section it varies between 0.1185 and 0.1232 in two PGM included in chromite which are only several millimeters apart. As the Os budget of a single micrometric grain derives from a mantle region that was at least several m³ in size, the variable Os isotopic composition of PGM in the Mayarí-Cristal chromitites probably reflects the heterogeneity of their mantle sources on the 10–100 m scale. Our results show that this heterogeneity was not erased by pooling and mingling of individual melt batches during chromitite crystallization but was transferred to the ore deposits on mineral scale. The distribution of the Os model ages calculated for PGM shows four main peaks, at ~100, 500, 750 and 1,000 Ma. These variable Os model ages reflect the presence of different depleted domains in the oceanic (Pacific-related) upper mantle of the Greater Antilles paleo-subduction zone. The concordance between the age of crystallization of the Mayarí-Cristal chromitites and the most recent peak of the Os model age distribution in PGM supports that Os in several grains was derived from fertile domains of the upper mantle, whose bulk Os isotopic composition is best approximated by that of enstatite chondrites; on the other hand, most PGM are crystallized by melts that tapped highly refractory mantle sources.     

Relationship between tilt changes and effusive-explosive episodes at an andesitic volcano: the 2004–2005 eruption at Volcán de Colima,México

Continuous tilt changes during the 2004–2005 effusive-explosive episodes at Volcán de Colima (México) were recorded simultaneously by two tiltmeters installed on opposite sides of the volcano at elevations of 2200 m and 3060 m above sea level. Data indicate that the 2004 lava extrusion was preceded by an inflation accompanied by a deflation. The 2005 explosion sequences were associated with a deflationary–inflationary tilt. The period between the 2004 extrusion and the 2005 explosions was characterized by an inflationary tilt during a 3 month period. Two deformation sources were located. The first was situated at a depth between 300 m and 1800 m beneath the crater at the northern flank of the volcano and was responsible for volcano deformation during the preliminary September 2004 stage, the October 2004 extrusion, and the initial stage of the transition period and the March 2005 explosion sequence. The second source was located at a depth between 1800 m and 2800 m beneath the crater at the southern flank of the volcano and was responsible for volcano deformation during the final stage of the transition period and the May–June 2005 explosion sequence.     

On the crystal structure and compressional behavior of talc: a mineral of interest in petrology and material science

The crystal structure of a natural triclinic talc (1Tc polytype) [with composition: (Mg_2.93Fe_0.06)_Σ2.99(Al_0.02Si_3.97)_Σ3.99O₁₀(OH)_2.10] has been investigated by single-crystal X-ray diffraction at 223 and 170 K and by single-crystal neutron diffraction at 20 K. Both the anisotropic X-ray refinements (i.e. at 223 and 170 K) show that the two independent tetrahedra are only slightly distorted. For the two independent Mg-octahedra, the bond distances between cation-hydroxyl groups are significantly shorter than the others. The ditrigonal rotation angle of the six-membered ring of tetrahedra is modest (α ~ 4°). The neutron structure refinement shows that the hydrogen-bonding scheme in talc consists of one donor site and three acceptors (i.e. trifurcated configuration), all the bonds having O···O ≤ 3.38 Å, H···O ~ 2.8 Å, and O–H···O ~ 111–116°. The three acceptors belong to the six-membered ring of tetrahedra juxtaposed to the octahedral sheet. The vibrational regime of the proton site appears being only slightly anisotropic. The elastic behavior of talc was investigated by means of in situ synchrotron single-crystal diffraction up to 16 GPa (at room temperature) using a diamond anvil cell. No evidence of phase transition has been observed within the pressure range investigated. P–V data fit, with an isothermal third-order Birch-Murnaghan equation of state, results as follows: V ₀ = 454.7(10) Å³, K _T0 = 56(3) GPa, and K′ = 5.4(7). The “Eulerian finite strain” versus “normalized stress” plot yields: Fe(0) = 56(2) GPa and K′ = 5.3(5). The compressional behavior of talc is strongly anisotropic, as reflected by the axial compressibilities (i.e. β(a):β(b):β(c) = 1.03:1:3.15) as well as by the magnitude and orientation of the unit-strain ellipsoid (with ε ₁:ε ₂:ε ₃ = 1:1.37:3.21). A comparison between the elastic parameters of talc obtained in this study with those previously reported is carried out.     

Hydromechanical Analysis of Masonry Gravity Dams and their Foundations

A numerical model for the hydromechanical analysis of masonry dams based on the discrete element method is presented. The dam and the rock foundation are represented as block assemblies, and a coupled flow-stress analysis is performed in an integrated manner for the entire system. Complex block shapes may be obtained by assembling elementary blocks into macroblocks, allowing the application of the model to situations ranging from equivalent continuum to fully discontinuum analysis. A contact formulation was developed based on an accurate edge–edge approach, incorporating mechanical and hydraulic behavior. The main numerical aspects are described, with an emphasis in the flow analysis explicit algorithm. An application to an existing masonry dam is presented, analyzing its present condition, with excessive seepage, and the proposed rehabilitation intervention. An evaluation of sliding failure mechanisms was also performed, showing the expected improvement in the safety of the structure.     

Debris-flow susceptibility of upland catchments

Over the last three decades, many regional studies in mountain ranges under temperate climate revealed that it is possible to discriminate debris-flow and fluvial fans from morphometric indicators measured at the scale of the catchment and the fan itself. The most commonly used indicators are the Melton index (R), a normalized index of the gravitational energy of the catchment, and the fan slope (S). A wide range of thresholds have been proposed for discriminating purpose, but these are generally based on a small population of catchments and may be highly influenced by ambiguous fans included in the data set. A database of 620 upland catchments from several mountain ranges under temperate climate was compiled from the literature to propose robust discriminant morphometric thresholds for debris-flow versus fluvial responses. Linear discriminant analysis (LDA) and logistic regression (LR) were performed using the whole data set, and a leave-one-out cross-validation was used to evaluate performances of the models. Sensitivity and specificity scores obtained for LDA and LR were 0.96 and 0.73, and 0.95 and 0.75, respectively. It is also shown that the channel slope above which debris-flow is observed decreases with the gravitational energy of the catchment. Limitations of the morphometric discrimination are discussed.     

Strutted Excavation in Soft Soil Incorporating a Jet-Grout Base Slab: Analysis Considering the Consolidation Effect

The influence of the consolidation on a strutted excavation in soft soil is analysed using a computer code based on the finite element method. A base jet-grout slab is considered in order to improve stability against bottom heave failure and minimize wall displacements. The numerical model incorporates the Biot consolidation theory (coupled formulation of the flow and equilibrium equations) with soil constitutive relations simulated by the p–q–θ critical state model. Special emphasis is given to the analysis, during and after the construction period, of the pore pressures, shear stresses, stress levels and displacements in the ground, as well as strut compression loads, wall displacements and bending moments, earth pressures on the wall faces and compression loads and bending moments on the jet-grout slab. The safety factor against bottom heave is also evaluated from the finite element analysis considering formulations of the critical state soil mechanics, and also compared to values obtained with traditional methods that use limit equilibrium approach and bearing capacity fundamentals.