THERIA_G: a software program to numerically model prograde garnet growth

We present the software program THERIA_G, which allows for numerical simulation of garnet growth in a given volume of rock along any pressure–temperature–time (P–T–t) path. THERIA_G assumes thermodynamic equilibrium between the garnet rim and the rock matrix during growth and accounts for component fractionation associated with garnet formation as well as for intracrystalline diffusion within garnet. In addition, THERIA_G keeps track of changes in the equilibrium phase relations, which occur during garnet growth along the specified P–T–t trajectory. This is accomplished by the combination of two major modules: a Gibbs free energy minimization routine is used to calculate equilibrium phase relations including the volume and composition of successive garnet growth increments as P and T and the effective bulk rock composition change. With the second module intragranular multi-component diffusion is modelled for spherical garnet geometry. THERIA_G allows to simulate the formation of an entire garnet population, the nucleation and growth history of which is specified via the garnet crystal size frequency distribution. Garnet growth simulations with THERIA_G produce compositional profiles for the garnet porphyroblasts of each size class of a population and full information on equilibrium phase assemblages for any point along the specified P–T–t trajectory. The results of garnet growth simulation can be used to infer the P–T–t path of metamorphism from the chemical zoning of garnet porphyroblasts. With a hypothetical example of garnet growth in a pelitic rock we demonstrate that it is essential for the interpretation of the chemical zoning of garnet to account for the combined effects of the thermodynamic conditions of garnet growth, the nucleation history and intracrystalline diffusion. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.

A transdisciplinary analysis of water problems in the mountainous karst areas of Morocco

Water management and engineering in the karstic High Atlas of Morocco are difficult tasks under the prevailing geological, hydrogeological, geomorphological, vegetational and climatic conditions. It is important to be able to understand and predict the characteristics and availability of water for future water planning in the region under changing climatic and agricultural conditions. An interdisciplinary analysis of problems and adequate hydrological modelling tools developed by geologists, hydrologists and biologists are necessary. The karst areas of the High Atlas Mountains are characterised by impermeable triassic basalt underlying substantial subsurface reservoirs with high potential discharge rates. The karst groundwater aquifers are extensive but largely unknown in dimension, probably with a hierarchical network of groundwater flow paths. It is estimated that approximately 70% of the surface water is directly lost to groundwater. Steep landslide- and debris flow prone slopes exist next to coarse-grained, highly porous river beds. Infrequent, high intensity rainfall or snowmelt causes a particularly high flood risk to these karst areas. In addition, agriculture and land use changes have degraded the karst areas. The most important driving forces for degradation include permanent overgrazing even during droughts and the use of firewood by a continually growing population. Large scale degradation of vegetation has occurred in the oro-mediterranean (mountainous Mediterranean) zone, between 2600 and 3400 m which coincides with the most important zone for karstic groundwater creation. The combination of high amounts of groundwater flow and rapid surface flow due to sparse vegetation has increased the problems of flood flow.     

Water and sanitation in the Buenos Aires metropolitan region: Fragmented markets, splintering effects?

This paper discusses the provision of water and sanitation services and the related urban impacts in Buenos Aires circa 2005. The first part of the paper focuses on the metropolitan region (BAMR) which is larger than the area served by the Aguas Argentinas S.A. (AASA) concession (i.e. the capital and its conurbano). It highlights a form of institutional fragmentation that is reflected in the diverse management practices of the numerous service providers and results in differentiated levels of and access to services. The paper discusses the technical, economic and regulatory factors that have historically resulted in this institutional fragmentation. The second part of the article focuses on AASA’s water concession agreement. It demonstrates that, although the agreement had an in-built splintering logic, its implementation led to a more “integrated approach” based on the “reality on the ground”. On the whole, the conclusion regarding the application of the splintering urbanism concept to Buenos Aires is a mixed one and depends on the scale of observation. Although at regional level (BAMR), a form of “institutional fragmentation” would appear to be obvious, it is the result of a long and complex historical process and, while recent neo-liberal reforms in service provisions have “cemented” this fragmentation, they did not actually cause it. If we take the AASA service area in isolation, the trend in the decade following the contracting out of the service has been one of improved service provision and access—although this was not achieved through increased integration of the supply system. Finally, in the case of the Buenos Aires metropolitan region, the splintering urbanism thesis defended by Marvin and Graham needs to be nuanced in several significant ways.     

Geochemistry, petrology and ages of the lunar meteorites Kalahari 008 and 009: New constraints on early lunar evolution

Kalahari 008 and 009 are two lunar meteorites that were found close to each other in Botswana. Kalahari 008 is a typical lunar anorthositic breccia; Kalahari 009 a monomict breccia with basaltic composition and mineralogy. Based on minor and trace elements Kalahari 009 is classified as VLT (very-low-Ti) mare basalt with extremely low contents of incompatible elements, including the REE. The Lu-Hf data define an age of 4286 ± 95 Ma indicating that Kalahari 009 is one of the oldest known basalt samples from the Moon. It provides evidence for lunar basalt volcanism prior to 4.1 Ga (pre-Nectarian) and may represent the first sample from a cryptomare. The very radiogenic initial ¹⁷⁶Hf/¹⁷⁷Hf (εHf = +12.9 ± 4.6), the low REE, Th and Ti concentrations indicate that Kalahari 009 formed from re-melting of mantle material that had undergone strong incompatible trace element depletion early in lunar history. This unusually depleted composition points toward a hitherto unsampled basalt source region for the lunar interior that may represent a new depleted endmember source for low-Ti mare basalt volcanism. Apparently, the Moon became chemically very heterogeneous at an early stage in its history and different cumulate sources are responsible for the diverse mare basalt types.Evidence that Kalahari 008 and 009 may be paired includes the similar fayalite content of their olivine, the identical initial Hf isotope composition, the exceptionally low exposure ages of both rocks and the fact that they were found close to each other. Since cryptomaria are covered by highland ejecta, it is possible that these rocks are from the boundary area, where basalt deposits are covered by highland ejecta. The concentrations of cosmogenic radionuclides and trapped noble gases are unusually low in both rocks, although Kalahari 008 contains slightly higher concentrations. A likely reason for this difference is that Kalahari 008 is a polymict breccia containing a briefly exposed regolith, while Kalahari 009 is a monomict brecciated rock that may never have been at the surface of the Moon.Altogether, the compositions of Kalahari 008 and 009 permit new insight into early lunar evolution, as both meteorites sample lunar reservoirs hitherto unsampled by spacecraft missions. The very low Th and REE content of Kalahari 009 as well as the depletion in Sm and the lack of a KREEP-like signature in Kalahari 008 point to a possible source far from the influence of the Procellarum-KREEP Terrane, possibly the lunar farside.     

The pathway of mercury in contaminated waters determined by association with organic carbon (Tagus Estuary,Portugal)

Reactive dissolved Hg (Hg_R), non-reactive dissolved Hg (Hg_NR), particulate Hg (Hg_P), dissolved organic C (DOC), particulate organic C (POC), salinity and other interpretative parameters were determined in water samples collected in the North Channel and in adjacent areas of the Tagus estuary (Portugal). Higher concentrations of both dissolved and particulate Hg in the North Channel indicate a pollution source and raise the possibility of Hg escaping to adjacent areas by tidal action. This transport was confirmed by the increase of Hg_R with salinity and Hg_NR with DOC, along a longitudinal axis paralleling the North Channel. Apparently, Hg leaving this channel is progressively complexed by inorganic and organic ligands. Near the mouth of the estuary, values decreased reflecting dilution with seawater. Moreover the Hg_P:POC ratio also increased seaward, suggesting mixing with Hg enriched particles that escaped the North Channel, or incorporation of dissolved Hg species in river-derived particles. These results suggest that the pathway of anthropogenic Hg in contaminated waters may be identified by their enrichment in organic matter, both in the dissolved and particulate fraction.     

Weibull statistical analysis of granite bending strength

Summary  This paper describes and discusses the adequacy of Weibull statistical analysis to analyse the bending strength of granite. The experimental results show that strength variability is related with a specific origin of failure. This conclusion is based on analysing the influence of the surface condition (extrinsic defects) on the bending strength results treated by the Weibull statistics. The conclusions drawn from this study have been validated by analysing the results of the critical flaw dimension estimated by applying the linear elastic fracture mechanics (LEFM) formulae. Results obtained from fractographic examination also have been used to describe the location of the origin of the fracture and understand the distribution of defects; i.e., there is a unimodal distribution of defects (intrinsic defects), despite the fact that some outlier values are normally observed in the fractured surfaces. Correspndence: P. M. Amaral, Department of Materials Engineering, Instituto Superior Técnico, Technical University of Lisbon, Av. Rovisco Pais, 1049-001 Lisboa, Portugal     

Origins of high pH mineral waters from ultramafic rocks, Central Portugal

This paper reviews the geochemical, isotopic (²H, ¹⁸O, ¹³C, ³H and ¹⁴C) and numerical modelling approaches to evaluate possible geological sources of the high pH (11.5)/Na–Cl/Ca–OH mineral waters from the Cabeço de Vide region (Central-Portugal). Water–rock interaction studies have greatly contributed to a conceptual hydrogeological circulation model of the Cabeço de Vide mineral waters, which was corroborated by numerical modelling approaches. The local shallow groundwaters belong to the Mg–HCO₃ type, and are derived by interaction with the local serpentinized rocks. At depth, these type waters evolve into the high pH/Na–Cl/Ca–OH mineral waters of Cabeço de Vide spas, issuing from the intrusive contact between mafic/ultramafic rocks and an older carbonate sequence. The Cabeço de Vide mineral waters are supersaturated with respect to serpentine indicating that they may cause serpentinization. Magnesium silicate phases (brucite and serpentine) seem to control Mg concentrations in Cabeço de Vide mineral waters. Similar δ²H and δ¹⁸O suggest a common meteoric origin and that the Mg–HCO₃ type waters have evolved towards Cabeço de Vide mineral waters. The reaction path simulations show that the progressive evolution of the Ca–HCO₃ to Mg–HCO₃ waters can be attributed to the interaction of meteoric waters with serpentinites. The sequential dissolution at CO₂ (g) closed system conditions leads to the precipitation of calcite, magnesite, amorphous silica, chrysotile and brucite, indicating that the waters would be responsible for the serpentinization of fresh ultramafic rocks (dunites) present at depth. The apparent age of Cabeço de Vide mineral waters was determined as 2790 ± 40 a BP, on the basis of ¹⁴C and ¹³C values, which is in agreement with the ³H concentrations being below the detection limit.     

The passivation of calcite by acid mine water. Column experiments with ferric sulfate and ferric chloride solutions at pH 2

Column experiments, simulating the behavior of passive treatment systems for acid mine drainage, have been performed. Acid solutions (HCl or H₂SO₄, pH 2), with initial concentrations of Fe(III) ranging from 250 to 1500 mg L⁻¹, were injected into column reactors packed with calcite grains at a constant flow rate. The composition of the solutions was monitored during the experiments. At the end of the experiments (passivation of the columns), the composition and structure of the solids were measured. The dissolution of calcite in the columns caused an increase in pH and the release of Ca into the solution, leading to the precipitation of gypsum and Fe–oxyhydroxysulfates (Fe(III)–SO₄–H⁺ solutions) or Fe–oxyhydroxychlorides (Fe(III)–Cl–H⁺ solutions). The columns worked as an efficient barrier for some time, increasing the pH of the circulating solutions from 2 to 6–7 and removing its metal content. However, after some time (several weeks, depending on the conditions), the columns became chemically inert. The results showed that passivation time increased with decreasing anion and metal content of the solutions. Gypsum was the phase responsible for the passivation of calcite in the experiments with Fe(III)–SO₄–H⁺ solutions. Schwertmannite and goethite appeared as the Fe(III) secondary phases in those experiments. Akaganeite was the phase responsible for the passivation of the system in the experiments with Fe(III)–Cl–H⁺ solutions.     

Quantitative sinkhole hazard assessment. A case study from the Ebro Valley evaporite alluvial karst (NE Spain)

Quantitative sinkhole hazard assessments in karst areas allow calculation of the potential sinkhole risk and the performance of cost-benefit analyses. These estimations are of practical interest for planning, engineering, and insurance purposes. The sinkhole hazard assessments should include two components: the probability of occurrence of sinkholes (sinkholes/km² year) and the severity of the sinkholes, which mainly refers to the subsidence mechanisms (progressive passive bending or catastrophic collapse) and the size of the sinkholes at the time of formation; a critical engineering design parameter. This requires the compilation of an exhaustive database on recent sinkholes, including information on the: (1) location, (2) chronology (precise date or age range), (3) size, and (4) subsidence mechanisms and rate. This work presents a hazard assessment from an alluvial evaporite karst area (0.81 km²) located in the periphery of the city of Zaragoza (Ebro River valley, NE Spain). Five sinkholes and four locations with features attributable to karstic subsidence where identified in an initial investigation phase providing a preliminary probability of occurrence of 0.14 sinkholes/km² year (11.34% in annual probability). A trenching program conducted in a subsequent investigation phase allowed us to rule out the four probable sinkholes, reducing the probability of occurrence to 0.079 sinkholes/km² year (6.4% in annual probability). The information on the severity indicates that collapse sinkholes 10–15 m in diameter may occur in the area. A detailed study of the deposits and deformational structures exposed by trenching in one of the sinkholes allowed us to infer a modern collapse sinkhole approximately 12 m in diameter and with a vertical throw of 8 m. This collapse structure is superimposed on a subsidence sinkhole around 80 m across that records at least 1.7 m of synsedimentary subsidence. Trenching, in combination with dating techniques, is proposed as a useful methodology to elucidate the origin of depressions with uncertain diagnosis and to gather practical information with predictive utility about particular sinkholes in alluvial karst settings: precise location, subsidence mechanisms and magnitude, and timing and rate of the subsidence episodes.     

Sur la présence de nickel dans un gisement de bauxite près de Mégare

Résumé L'exploitation récente d'un gisement de bauxite près de Mégare (Grèce) a fait apparaître sur les calcaires de base une concentration verte d'oxyde de nickel relativement élevée. La présence dans le gisement d'argiles rouges, renfermant de fortes proportions d'oxyde de fer avec des teneurs relativement faibles en alumine et des traces d'oxyde de nickel, induit à penser qu'il s'agit d'un produit latéritique dérivé d'une roche ultrabasique et transporté ultérieurement sur la région calcaire karstifiée avec ses remplissages bauxitiques. L'étude se termine par une hypothèse sur la genèse de ce gîte singulier.

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The recent mining of a bauxite deposit near Megara (Greece) has shown on the footwall limestone a relatively high concentration of a green nickel oxide. The occurrence in the same deposit of red clays with a rather high percentage of iron oxide and a low content of alumina, together with some traces of nickel, induces to think that this material is composed of a lateritic soil derived from an ultrabasic rock and subsequently transported on karstified limestone with its bauxitic fillings. — The study ends with an hypothesis on the genesis of this unusual deposit.