Magnesium isotope systematics of the lithologically varied Moselle river basin, France

Magnesium and strontium isotope signatures were determined during different seasons for the main rivers of the Moselle basin, northeastern France. This small basin is remarkable for its well-constrained and varied lithology on a small distance scale, and this is reflected in river water Sr isotope compositions. Upstream, where the Moselle River drains silicate rocks of the Vosges mountains, waters are characterized by relatively high ⁸⁷Sr/⁸⁶Sr ratios (0.7128-0.7174). In contrast, downstream of the city of Epinal where the Moselle River flows through carbonates and evaporites of the Lorraine plateau, ⁸⁷Sr/⁸⁶Sr ratios are lower, down to 0.70824.Magnesium in river waters draining silicates is systematically depleted in heavy isotopes (δ²⁶Mg values range from −1.2 to −0.7‰) relative to the value presently estimated for the continental crust and a local diorite (−0.5‰). In comparison, δ²⁶Mg values measured in soil samples are higher (∼0.0‰). This suggests that Mg isotope fractionation occurs during mineral leaching and/or formation of secondary clay minerals. On the Lorraine plateau, tributaries draining marls, carbonates and evaporites are characterized by low Ca/Mg (1.5-3.2) and low Ca/Sr (80-400) when compared to local carbonate rocks (Ca/Mg = 29-59; Ca/Sr = 370-2200), similar to other rivers draining carbonates. The most likely cause of the Mg and Sr excesses in these rivers is early thermodynamic saturation of groundwater with calcite relative to magnesite and strontianite as groundwater chemistry progressively evolves in the aquifer. δ²⁶Mg of the dissolved phases of tributaries draining mainly carbonates and evaporites are relatively low and constant throughout the year (from −1.4‰ to −1.6‰ and from −1.2‰ to −1.4‰, respectively), within the range defined for the underlying rocks. Downstream of Epinal, the compositions of the Moselle River samples in a δ²⁶Mg vs. ⁸⁷Sr/⁸⁶Sr diagram can be explained by mixing curves between silicate, carbonate and evaporite waters, with a significant contribution from the Vosgian silicate lithologies (>70%). Temporal co-variation between δ²⁶Mg and ⁸⁷Sr/⁸⁶Sr for the Moselle River throughout year is also observed, and is consistent with a higher contribution from the Vosges mountains in winter, in terms of runoff and dissolved element flux. Overall, this study shows that Mg isotopes measured in waters, rocks and soils, coupled with other tracers such as Sr isotopes, could be used to better constrain riverine Mg sources, particularly if analytical uncertainties in Mg isotope measurements can be improved in order to perform more precise quantifications.     

Exurbia from the bottom-up: Confronting empirical challenges to characterizing a complex system

We describe empirical results from a multi-disciplinary project that support modeling complex processes of land-use and land-cover change in exurban parts of Southeastern Michigan. Based on two different conceptual models, one describing the evolution of urban form as a consequence of residential preferences and the other describing land-cover changes in an exurban township as a consequence of residential preferences, local policies, and a diversity of development types, we describe a variety of empirical data collected to support the mechanisms that we encoded in computational agent-based models. We used multiple methods, including social surveys, remote sensing, and statistical analysis of spatial data, to collect data that could be used to validate the structure of our models, calibrate their specific parameters, and evaluate their output. The data were used to investigate this system in the context of several themes from complexity science, including have (a) macro-level patterns; (b) autonomous decision making entities (i.e., agents); (c) heterogeneity among those entities; (d) social and spatial interactions that operate across multiple scales and (e) nonlinear feedback mechanisms. The results point to the importance of collecting data on agents and their interactions when producing agent-based models, the general validity of our conceptual models, and some changes that we needed to make to these models following data analysis. The calibrated models have been and are being used to evaluate landscape dynamics and the effects of various policy interventions on urban land-cover patterns.     

Pressures of Crystallization of Icelandic Magmas

Iceland lies astride the Mid-Atlantic Ridge and was createdby seafloor spreading that began about 55 Ma. The crust is anomalouslythick (20–40 km), indicating higher melt productivityin the underlying mantle compared with normal ridge segmentsas a result of the presence of a mantle plume or upwelling centeredbeneath the northwestern edge of the Vatnajökull ice sheet.Seismic and volcanic activity is concentrated in 50 km wideneovolcanic or rift zones, which mark the subaerial Mid-AtlanticRidge, and in three flank zones. Geodetic and geophysical studiesprovide evidence for magma chambers located over a range ofdepths (1·5–21 km) in the crust, with shallow magmachambers beneath some volcanic centers (Katla, Grimsvötn,Eyjafjallajökull), and both shallow and deep chambers beneathothers (e.g. Krafla and Askja). We have compiled analyses ofbasalt glass with geochemical characteristics indicating crystallizationof ol–plag–cpx from 28 volcanic centers in the Western,Northern and Eastern rift zones as well as from the SouthernFlank Zone. Pressures of crystallization were calculated forthese glasses, and confirm that Icelandic magmas crystallizeover a wide range of pressures (0·001 to 1 GPa), equivalentto depths of 0–35 km. This range partly reflects crystallizationof melts en route to the surface, probably in dikes and conduits,after they leave intracrustal chambers. We find no evidencefor a shallow chamber beneath Katla, which probably indicatesthat the shallow chamber identified in other studies containssilica-rich magma rather than basalt. There is reasonably goodcorrelation between the depths of deep chambers (> 17 km)and geophysical estimates of Moho depth, indicating that magmaponds at the crust–mantle boundary. Shallow chambers (<7·1 km) are located in the upper crust, and probablyform at a level of neutral buoyancy. There are also discretechambers at intermediate depths (11 km beneath the rift zones),and there is strong evidence for cooling and crystallizing magmabodies or pockets throughout the middle and lower crust thatmight resemble a crystal mush. The results suggest that themiddle and lower crust is relatively hot and porous. It is suggestedthat crustal accretion occurs over a range of depths similarto those in recent models for accretionary processes at mid-oceanridges. The presence of multiple stacked chambers and hot, porouscrust suggests that magma evolution is complex and involvespolybaric crystallization, magma mixing, and assimilation. KEY WORDS: Iceland rift zones; cotectic crystallization; pressure; depth; magma chamber; volcanic glass     

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.     

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.     

Flood hazard delineation combining geomorphological and hydrological methods: an example in the Northern Iberian Peninsula

Flood mapping requires the combination and integration of geomorphological and hydrological-hydraulic methods; however, despite this, there is very little scientific literature that compares and validates both methods. Two types of analysis are addressed in the present article. On the one hand, maps of flood plains have been elaborated using geomorphological evidence and historical flood data in the mountainous area of northwestern Spain, covering an area of more then 232 km² of floodplains. On the other hand, a hydrometeorological model has been developed (Clark semidistributed unit hydrograph) in the Sarria River basin (155 km², NW Spain). This basin is not gauged, hence the model was subjected to a goodness-of-fit test of its parameter (curve number) by means of Monte Carlo simulation. The peak flows obtained by means of the hydrological model were used for hydraulic modeling (one-phase, one-dimensional and steady flow) in a 4 km² urban stretch of the river bed. The delineation of surface areas affected by floods since 1918, as well as those analyzed subsequent to the geomorphological study, reveals a high degree of reliability in the delineation of the flooded areas with frequent recurrence intervals (<50 years). If we compare these flooded surface areas with the estimate obtained by the hydrological-hydraulic method we can see that the latter method overestimates the extent of the surface water by 144% for very frequent recurrence intervals (>10 years) and underestimates it as the recurrence interval increases, by up to 80% less floodplain for exceptional events (>500 years). Finally, a management map is put forth combining the most reliable results available by integrating both methods. Originally presented at the Sixth International Conference on Geomorphology.     

Structural investigation of the synthetic CaAn(PO4)2 (An = Th and Np) cheralite-like phosphates

The crystallographic structures of the synthetic cheralite, CaTh(PO₄)₂, and its homolog CaNp(PO₄)₂ have been investigated by X-ray diffraction at room temperature. Rietveld analyses showed that both compounds crystallize in the monoclinic system and are isostructural to monazite LnPO₄ (Ln = La to Gd). The space group is P2₁/n (I.T. = 14) with Z = 2. The refined lattice parameters of CaTh(PO₄)₂ are a = 6.7085(8) Å, b = 6.9160(6) Å, c = 6.4152(6) Å, and β = 103.71(1)° with best fit parameters R _wp = 4.87%, R _p = 3.69% and R _B = 3.99%. For CaNp(PO₄)₂, we obtained a = 6.6509(5) Å, b = 6.8390(3) Å, c = 6.3537(8) Å, and β = 104.12(6)° and R _wp = 6.74%, R _p = 5.23%, and R _B = 6.05%. The results indicate significant distortions of bond length and angles of the PO₄ tetrahedra in CaTh(PO₄)₂ and to a lesser extent in CaNp(PO₄)₂. The structural distortions were confirmed by Raman spectroscopy of CaTh(PO₄)₂. A comparison with the isostructural compounds LnPO₄ (Ln = Ce and Sm) confirmed that the substitution of the large rare earth trivalent cations with Ca²⁺ and Th⁴⁺ introduces a distortion of the PO₄ tetrahedra.     

Mineralogy and geochemistry of El Dorado epithermal gold deposit, El Sauce district, central-northern Chile

Summary The El Dorado Au-Cu deposit is located in an extensive intra-caldera zone of hydrothermal alteration affecting Upper Cretaceous andesites of the Los Elquinos Formation at La Serena (≈ 29°47′S Lat., 70°43′W Long., Chile). Quartz-sulfide veins of economic potential are hosted by N25W and N20E fault structures associated with quartz-illite alteration (+supergene kaolinite). The main ore minerals in the deposit are pyrite, chalcopyrite ± fahlore (As/(As + Sb): 0.06−0.98), with electrum, sphalerite, galena, bournonite-seligmanite (As/(As + Sb): 0.21−0.31), marcasite, pyrrhotite being accessory phases. Electrum, with an Ag content between 32 and 37 at.%, occurs interstitial to pyrite aggregates or along pyrite fractures. Pyrite commonly exhibits chemical zonation with some zones up to 1.96 at.% As. Electron probe microanalyses of pyrite indicate that As-rich zones do not exhibit detectable Au values. Fluid inclusion microthermometry shows homogenization temperatures between 130 and 352 °C and salinities between 1.6 and 6.9 wt.% NaCl eq. Isotope data for quartz, ankerite and phyllosilicates and estimated temperatures show that δ¹⁸O and δD for the hydrothermal fluids were between 3 and 10‰ and between −95 and −75‰, respectively. These results suggest the mineralizing fluids were a mixture of meteoric and magmatic waters. An epithermal intermediate-sulfidation model is proposed for the formation of the El Dorado deposit. Author’s present address: J. Carrillo-Rosúa, Dpto. de Didáctica de las Ciencias Experimentales, Universidad de Granada, Campus de Cartuja, 18071, Granada, Spain     

Methodology of hydrogeological characterization of deep carbonate aquifers as potential reservoirs of groundwater. Case of study: the Jurassic aquifer of <Emphasis Type="Italic">El Maestrazgo</Emphasis> (Castellón,Spain)

A methodology for the characterization of deep carbonate aquifers has been developed and applied to El Maestrazgo Jurassic aquifer in Castellón, Spain. Characterization of these aquifer formations, located at more than 300 m deep, consisted of a previous phase of compilation, analysis and synthesis of the existing information about the area, followed by a coordinated combination of different speciality studies: geology, stratigraphy, structural analysis, hydrogeology, hydrochemistry, geophysics and remote sensing. Geological studies included geological mapping, definition of stratigraphical units and facies and structural analysis. The aim of the hydrogeology study was to define aquifer formations, recharge area, aquifer points inventory and groundwater flow directions for the establishment of piezometric and water quality observation nets. Special techniques were applied, like thermal infrared aerial images and the evaluation of submarine groundwater discharge by means of natural radium isotopes. Hydrochemical techniques, including majority elements characterization and stable isotopes (¹⁸O, ²H and ³H) determination, allowed classifying hydrochemical facies and establishing a renewal pattern for water within the system. Geophysics was useful in determining the aquifer geometry, the features of the basement and the petrophysical characteristics of the geological formations. Preliminary results show an important tectonic complexity and the possibilities for groundwater uses in the area of study.