The thermal stability of sideronatrite and its decomposition products in the system Na2O–Fe2O3–SO2–H2O

The thermal stability of sideronatrite, ideally Na₂Fe³⁺(SO₄)₂(OH)·3(H₂O), and its decomposition products were investigated by combining thermogravimetric and differential thermal analysis, in situ high-temperature X-ray powder diffraction (HT-XRPD) and Fourier transform infrared spectroscopy (HT-FTIR). The data show that for increasing temperature there are four main dehydration/transformation steps in sideronatrite: (a) between 30 and 40 °C sideronatrite transforms into metasideronatrite after the loss of two water molecules; both XRD and FTIR suggest that this transformation occurs via minor adjustments in the building block. (b) between 120 and 300 °C metasideronatrite transforms into metasideronatrite II, a still poorly characterized phase with possible orthorhombic symmetry, consequently to the loss of an additional water molecule; X-ray diffraction data suggest that metasideronatrite disappears from the assemblage above 175 °C. (c) between 315 and 415 °C metasideronatrite II transforms into the anhydrous Na₃Fe(SO₄)₃ compound. This step occurs via the loss of hydroxyl groups that involves the breakdown of the [Fe³⁺(SO₄)₂(OH)] _∞ ^2? chains and the formation of an intermediate transient amorphous phase precursor of Na₃Fe(SO₄)₃. (d) for T > 500 °C, the Na₃Fe(SO₄)₃ compound is replaced by the Na-sulfate thenardite, Na₂SO₄, plus Fe-oxides, according to the Na₃Fe³⁺(SO₄)₃ → 3/2 Na₂(SO₄) + 1/2 Fe₂O₃ + SO_x reaction products. The Na–Fe sulfate disappears around 540 °C. For higher temperatures, the Na-sulfates decomposes and only hematite survives in the final product. The understanding of the thermal behavior of minerals such as sideronatrite and related sulfates is important both from an environmental point of view, due to the presence of these phases in evaporitic deposits, soils and sediments including extraterrestrial occurrences, and from the technological point of view, due to the use of these materials in many industrial applications.     

Place and people: spatializing degrees of bonding and bridging social capital in Lisbon (Portugal)

GeoJournal - Broad academic interest in measuring social relationships within an urban context has grown over recent decades. Significant research attention is focused on where social synergies...     

Sources and behavior of arsenic and trace elements in groundwater and surface water in the Poopó Lake Basin,Bolivian Altiplano

Water management in semiarid and arid catchments such as the Poopó Lake Basin requires improved understanding of the complex behavior of the various contaminants, which affect the drinking water quality and considered as crucial for sustainable development of the region. Mechanisms of arsenic (As) release in the surface and groundwater were studied. Hydrochemical data for surface water (4 samples) and groundwater (28 samples) were collected in a small watershed in the Poopó catchment at the highland of the Bolivian Andes (Altiplano). All of them show high electrical conductivity values and moderately oxidizing conditions. The surface water contains high concentration of sulfate and the trace elements As, Zn and Pb in the zone affected by acid mine drainage. There is a large variability of the concentration of As and of the trace elements in the groundwater in the five different regions within the Poopó catchment. The metal concentrations sensitive to changes of redox state and results of speciation modeling suggest that As (V) is a predominant aqueous species, which conforms to the prevailing oxidizing conditions in the shallow groundwater environment. Two generalized trends for As distribution were identified in groundwater: (a) high concentrations are found in the arid zone (100–250 μg/L) in the southern (region III) and in the northwestern (region V) regions, and (b) low concentrations (<50 μg/L) are found in the remaining part of the basin (region I, II and IV). However, the spatial distribution within these regions needs to be investigated further. A conclusion from the present study is that there are multiple sources of As as well as other trace elements (such as Cd, Mn and Zn) in the Poopó Lake Basin. Among the sources and the processes which led to the mobility of As and other trace metals in the region are: (a) weathering of sulfide minerals, (b) oxidation of pyrite and/or arsenopyrite in mineralized areas and (c) desorption from hydrous ferric oxide (HFO) surfaces. In non-mining areas, volcanic ash is suggested to be a significant source of As.     

Late Variscan “Basin and Range” magmatism and tectonics in the Central Alps: evidence from U-Pb geochronology

Abstract

Towards the end of the Variscan orogeny, volcano-sedimentary basins were formed within the mountain hell. U-Pb age determinations on zircons of volcanic and plutonic rocks from intramontane basins of the Central Alps allows us to define the age of two volcano-sedimentary units: The former one was dated older than 333 Ma (probably Visean), the younger one was deposited in a short time span between 303 and 298 Ma (Stephanien). The latter contains tuffs (303 ± 4 Ma), ignimbrites and microgranites (299 ± 2 Ma) and intrusive rhyolites (300 ± 2 Ma) that are all coeval within analytical precision. Granitoid rocks intruded into the volcano-sedimentary rocks at 333 ± 2 Ma, 310 ± 3 Ma and 298 ± 2 Ma. An angular unconformity between the older and the younger units in the Tö di area (Aar massif) indicates uplift and erosion between 310 and 303 Ma.

Our results suggest the existence of two periods of late Variscan extension (or transtension) in the Alpine realm, both combined with magmatic activity. The extensional event of Stephaniun age is characterized by a short duration of only a few million years, between 303 and 298 Ma, comprising tectonic activity, volcanism and plutonism. The plutonic rocks are characterized by a dominant lithospheric mantle component, which was contaminated by different amounts of crostai material and might have been increasingly influenced by aslhcnos-pherie mantle melts in the course of crostai thinning. The ealc-alkaline geochemical characteristics of the granites may be explained as an inherited source feature.

The overall tectonic style and the mode of magmatism resembles the situation of the Basin-and-Kange Province (eastern USA). Consequently there is no need to invoke a late-Variscan Andean-type subduction to explain the geochemical composition of the magmatic rocks. We conclude that late-orogenic extension is an important tectonic stage of the Variscan orogeny, which lasted for some 50 million years. The extension led to thinning of the crust and upwelling of hot mantle, causing high heat flow, intrusion of mantle melts and formation of huge volumes of acid melts.     

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.     

Detection and 2d modelling of cavities using pole–dipole array

The resistivity method is often used in cave prospecting. In this paper the pole–dipole array ability to detect cavities at different depths and with different water contents is investigated. The research was performed using analogical and numerical modelling. According to the results, empty caves at a depth less than four times its diameter can be easily detected. The ability of the pole–dipole array to detect water-filled caves reaches a minimum at filling percentages of 30–50%. Overburden effects research shows that low resistivity overburden reduces the resolution capability of the array. This study shows that equivalent results can be obtained by modelling the empty caves as infinite resistivity bodies or, alternatively, as very high resistivity ones. The analysis of field data acquired in the Maciço Calcário Estremenho (Portugal) shows the practical importance of the pole–dipole array in cavities prospecting.     

Supportive elements to the decision-making process in the emergency planning of the Angra dos Reis Nuclear Power Complex,Brazil

Accidents in nuclear power plants are problems of great complexity, mainly due to their consequences, such as the population evacuation from the enterprise influence area. The decision-making and emergency plans must be well articulated and require good local geographic space knowledge and the interactions of their environments. This study is a contribution to the emergency plans for the Almirante Álvaro Alberto Nuclear Power Plant, currently the only nuclear complex in Brazil, located in Angra dos Reis, Rio de Janeiro. The study confirmed the region’s main geoenvironmental aspects as winds and rainfall, landslides and population density were evaluated as important elements in the local emergency process. Their integrated analysis supported scenario identification and critical regional points and highlighted population evacuation escape routes. These important results characterized the support to local emergency management actions and guidelines. Furthermore, the geographic information systems was configured as an integrated spatial and temporal analysis platform to associate meteorological, geological/geomorphological and socio-economic data, playing a key role to support the evacuation planning in the event of nuclear power plant accidents.     

A New Appraisal of Sri Lankan BB Zircon as a Reference Material for LA‐ICP‐MS U‐Pb Geochronology and Lu‐Hf Isotope Tracing

A potential zircon reference material (BB zircon) for laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) U‐Pb geochronology and Hf isotope geochemistry is described. A batch of twenty zircon megacrysts (0.5–1.5 cm³) from Sri Lanka was studied. Within‐grain rare earth element (REE) compositions are largely homogeneous, albeit with some variation seen between fractured and homogeneous domains. Excluding fractured cathodoluminescence bright domains, the variation in U content for all analysed crystals ranged from 227 to 368 μg g^?1 and the average Th/U ratios were between 0.20 and 0.47. The Hf isotope composition (0.56–0.84 g/100 g Hf) is homogeneous within and between the grains – mean ¹⁷⁶Hf/¹⁷⁷Hf of 0.281674 ± 0.000018 (2s). The calculated alpha dose of 0.59 × 10¹⁸ g^?1 for a number of BB grains falls within the trend of previously studied, untreated zircon samples from Sri Lanka. Aliquots of the same crystal (analysed by ID‐TIMS in four different laboratories) gave consistent U‐Pb ages with excellent measurement reproducibility (0.1–0.4% RSD). Interlaboratory assessment (by LA‐ICP‐MS) from individual crystals returned results that are within uncertainty equivalent to the TIMS ages. Finally, we report on within‐ and between‐grain homogeneity of the oxygen isotope systematic of four BB crystals (13.16‰ VSMOW).