The External Tanger Unit (Intrarif sub-Domain,External Rifian Zones,Morocco): an interdisciplinary study

The External Tanger Unit represents one of the most complete Cretaceous-Miocene successions in the central areas of the Internal Intrarif sub-Domain (External Rif Zones, Morocco). An interdisciplinary study has been carried out to propose a new characterization of this unit which would allow a better comprehension of the confused and complex relationships among different units of the same sub-domain. The results achieved can be summarized as follows: (1) redefinition of the stratigraphic (litho-, bio-, and chrono-) record and introduction of a new, informal lithostratigraphic terminology; (2) recognition of two main depositional sequences (lower-middle Eocene p.p. and lower Oligocene p.p.-lower Miocene p.p.) separated by extended gaps (latest Cretaceous-early Eocene p.p. and middle Eocene p.p.-early Oligocene p.p.); (3) reconstruction of the evolution of the sedimentary realm, and of the relationships between tectonics and sedimentation; and (4) comparison between the upper Cretaceous-Miocene stratigraphic record and tectonic events of the Intrarif, which is located in the western external portion of the Maghrebian Flysch Basin, and the equivalent sedimentary record of the eastern portion of this basin in the Tunisian Tell. More in general, our results allowed (i) a first reconstruction of the Cretaceous-Miocene main tectono-sedimentary events; (ii) a more detailed location of the sedimentary suite in the external African Margin in the context of a wider palaeogeographic framework; and (iii) the definition of the main stages of the geological evolution of the area.     

Plankton carbon metabolism and air–water CO2 fluxes at a hypereutrophic tropical estuary

Multiple biotic and abiotic drivers regulate the balance between CO₂ assimilation and release in surface waters. In the present study, we compared in situ measurements of plankton carbon metabolism (primary production and respiration) to calculated air–water CO₂ fluxes (based on abiotic parameters) during 1 year (2008) in a hypereutrophic tropical estuary (Recife Harbor, NE Brazil – 08°03′S, 34°52′W) to test the hypothesis that high productivity leads to a net CO₂ flux from the atmosphere. The calculated CO₂ fluxes through the air–water interface (FCO₂) were negative throughout the year (FCO₂: –2 to –9 mmol C·m^?2·day^?1), indicating that Recife Harbor is an atmospheric CO₂ sink. Respiration rates of the plankton community ranged from 2 to 45 mmol C·m^?2·hr^?1. Gross primary production ranged from 0.2 to 281 mmol C·m^?2·hr^?1, exceeding respiration during most of the year (net autotrophy), except for the end of the wet season, when the water column was net heterotrophic. The present results highlight the importance of including eutrophic tropical shallow estuaries in global air–water CO₂ flux studies, in order to better understand their role as a sink of atmospheric CO₂.     

Another look at the calculation of fallout tephra volumes

The calculation of volumes of fallout tephra layers is difficult because of the nonlinear dependence of thickness on area and because of the extrapolations required at the vent and in distal regions. Calculation using the trapezoidal rule, straight lines on log-log plots of area versus thickness, straight lines on plots of log thickness versus area^1/2, and the crystal-concentration method are reviewed and the problems with each method discussed. The method using straight lines on plots of log thickness versus area^1/2 is the most geologically reasonable because most deposits thin exponentially from source and therefore plot as straight lines using these coordinates. Errors and uncertainties in previous derivations for using this method are discussed and more general formulas presented. The method is also used to gain perspective on the missing distal volumes calculated by the crystal-concentration method compared to those calculated based only on isopach data.     

Mechanisms of fine extinction band development in vein quartz: new insights from correlative light and electron microscopy

Fine extinction bands (FEBs) (also known as deformation lamellae) visible with polarized light microscopy in quartz consist of a range of nanostructures, inferring different formation processes. Previous transmission electron microscopy studies have shown that most FEB nanostructures in naturally deformed quartz are elongated subgrains formed by recovery of dislocation slip bands. Here we show that three types of FEB nanostructure occur in naturally deformed vein quartz from the low-grade metamorphic High-Ardenne slate belt (Belgium). Prismatic oriented FEBs are defined by bands of dislocation walls. Dauphiné twin boundaries present along the FEB boundaries probably formed after FEB formation. In an example of two sub-rhombohedral oriented FEBs, developed as two sets in one grain, the finer FEB set consists of elongated subgrains, similar to FEBs described in previous transmission electron microscopy studies. The second wider FEB set consists of bands with different dislocation density and fluid-inclusion content. The wider FEB set is interpreted as bands with different plastic strain associated with the primary growth banding of the vein quartz grain. The nanometre-scale fluid inclusions are interpreted to have formed from structurally bounded hydroxyl groups that moreover facilitated formation of the elongate subgrains. Larger fluid inclusions aligned along FEBs are explained by fluid-inclusion redistribution along dislocation cores. The prismatic FEB nanostructure and the relation between FEBs and growth bands have not been recognized before, although related structures have been reported in experimentally deformed quartz.     

Hydrofluoric Acid‐Free Digestion of Geological Samples for the Quantification of Rare Earth Elements by Inductively Coupled Plasma‐Optical Emission Spectrometry

Rare earth elements (REEs) are very important to technological development as well as to geochemical and environmental studies. In this work, hydrofluoric acid (HF) was replaced by condensed phosphoric acid (CPA) in the digestion of geological samples, and the quantification of REEs was performed by inductively coupled plasma‐optical emission spectrometry (ICP‐OES). Six international reference materials (RMs), named DC86318, CGL 111, CGL 124, CGL 126, OKA‐2 and COQ‐1 and three Brazilian ore samples, named Araxá, Catalão and Pitinga were analysed. Only zircon and xenotime, which are potential REE‐bearing minerals, were not completely dissolved. Nevertheless, no REE associated with zircon was detected. The investigated digestion method presented many advantages: It was relatively fast (3 h), avoided fluoride precipitation, it was less hazardous because handling diluted H₃PO₄ is safer than HF, NH₄F or NH₄HF₂ aqueous solutions, it preserved the quartz fittings of the measurement equipment and the final solution contained lower levels of total dissolved solids than those produced by the fusion method.     

Oxygen isotope exchange and disequilibrium between calcite and tremolite in the absence and presence of an experimental C–O–H fluid

Oxygen isotope exchange between minerals during metamorphism can occur in either the presence or the absence of aqueous fluids. Oxygen isotope partitioning among minerals and fluid is governed by both chemical and isotopic equilibria during these processes, which progress by intragranular and intergranular diffusion as well as by surface reactions. We have carried out isotope exchange experiments in two- and three-phase systems, respectively, between calcite and tremolite at high temperatures and pressures. The two-phase system experiments were conducted without fluid either at 1 GPa and 680 °C for 7 days or at 500 MPa and 560 °C for 20 days. Extrapolated equilibrium fractionations between calcite and tremolite are significantly lower than existing empirical estimates and experimental determinations in the presence of small amounts of fluid, but closely match calculated fractionations by means of the increment method for framework oxygen in tremolite. The small fractionations measured in the direct calcite–tremolite exchange experiments are interpreted by different rates of oxygen isotope exchange between hydroxyl oxygen, framework oxygen and calcite during the solid–solid reactions where significant recrystallization occurs. The three-phase system experiments were accomplished in the presence of a large amount of fluid (CO₂+H₂O) at 500 MPa and 560 °C under conditions of phase equilibrium for 5, 10, 20, 40, 80, 120, 160, and 200 days. The results show that oxygen isotope exchange between minerals and fluid proceeds in two stages: first, through a mechanism of dissolution-recrystallization and very rapidly; second, through a mechanism of diffusion and very slowly. Synthetic calcite shows a greater rate of isotopic exchange with fluid than natural calcite in the first stage. The rate of oxygen diffusion in calcite is approximately equal to or slightly greater than that in tremolite in the second stage. A calculation using available diffusion coefficients for calcite suggests that grain boundary diffusion, rather than volume diffusion, has been the dominant mechanism of oxygen transport between the fluid and the mineral grains in the later stage.Editorial responsibility: T.L. Grove     

Field multi-step limestone and MgO passive system to treat acid mine drainage with high metal concentrations

Passive treatment systems have become one of the most sustainable and feasible ways of remediating acid mine drainage (AMD). However, conventional treatments show early clogging of the porosity or/and coating of the reactive grains when high acidity and metal concentrations are treated. The performance of fine-grained reagents dispersed in a high porosity matrix of wood shavings was tested as an alternative to overcome these durability problems. The system consisted of two tanks of 3 m³ filled with limestone sand and wood shavings, and one tank of 1 m³ with caustic magnesia powder and wood shavings, separated by several oxidation cascades and decantation ponds. The system treated about 1.5 m³/day of AMD containing an average of 360 mg/L Fe, 120 mg/L Al, 390 mg/L Zn, 10 mg/L Cu, 300 μg/L As and 140 μg/L Pb, a mean pH of 3.08 and a net acidity of 2500 mg/L as CaCO₃ equivalent. The water reached pH 5 and 6 in the first and second limestone tanks, respectively (suitable to remove trivalent metals); and pH 8–9 in the MgO tank (suitable to remove divalent metals). After 9 months of operation, the system achieved an average removal of 100% Al, Cu, As, Pb, more than 70% Fe, about 25% Zn and 80% acidity. Goethite, schwertmannite, hydrobasaluminite, amorphous Al(OH)₃ and gypsum were the main precipitates in the two limestone tanks. Precipitation of divalent metals (Fe (II), Zn, and traces of Cd, Ni and Co) were complete inside the third tank of MgO, but preferential flow along the walls was responsible for its low treatment performance. Goethite, gypsum, Zn-schulenbergite and sauconite are the crystalline solid phases identified in the MgO tank.     

Species composition and diversity of woody communities along an elevational gradient in tropical Dwarf Cloud Forest

Elucidating woody community diversity and structure change along environmental gradients is still a central issue of tropical forest ecology. We have evaluated changes in alpha and beta diversity, community composition and structure of woody communities along an elevational gradient in Dwarf Cloud Forests, Southeast Brazil. We selected five areas along an elevational gradient(1,300-1,600 m asl), and randomly allocated 10 plots(10 m × 20 m) in each area in the Ibitipoca State Park(ISP), Serra da Mantiqueira, southeastern Brazil. All woody species(diameter at breast height ≥ 5.0 cm) were collected for taxonomic identification. Thus, we analysed the woody communities based on a phytosociological approach. Overall, 147 species and 37 families were recorded, distributed in 2,303 individuals. No differences in the species richness pattern were observed between areas using the rarefaction and extrapolation curves. Significant differences in species composition and structure between areas were observed. The high beta diversity observed, corroborated by the Jaccard coefficient, increases with decreasing altitude. Our results showed that woody communities in the studied Dwarf Cloud Forests have a higher diversity and structural variability along elevational gradient.     

Hydrogeological origin of the CO2-rich mineral water of Vilajuïga in the Eastern Pyrenees (NE Catalonia,Spain)

The mineral water of Vilajuïga village in Alt Empordà (NE Catalonia, Spain) owes its uniqueness to an emanation of geogenic CO₂ that modifies groundwater hydrochemistry to produce a differentiated HCO₃–Na- and CO₂-rich groundwater among the usual Ca–HCO₃ type found in this region. A hydrogeological conceptual model attributes its occurrence to the intersection of two faults: La Valleta and Garriguella-Roses. The former provides a thrust of metamorphic over igneous rocks, formed during the Paleozoic, over a layer of ampelitic shale that, from a hydrogeological perspective, acts as a confining layer. The Garriguella-Roses normal fault, which originated during the Neogene, permits the degassing of geogenic CO₂ that is attributed to volcanic activity occurring in the Neogene. Groundwater mixing from the metamorphic and igneous rock units plus the local occurrence of CO₂ creates a HCO₃–Na water that still holds free-CO₂ in solution. Interaction with the gas phase is restricted at the intersection of the two faults. Radiocarbon dating, after correcting for geogenic dead carbon, estimates an age of 8,000 years BP. The low tritium content (0.7 TU) indicates that Vilajuïga water is a mix of “older” groundwater recharged in the metamorphic rocks of the Albera range and “younger” groundwater from the igneous rocks of the Rodes range, over a recharge area of 45 km² and a maximum elevation of 600 m. Given its origin as rare groundwater in the southern slope of the Eastern Pyrenees, purposeful monitoring is necessary to evaluate the groundwater vulnerability and anticipate impacts from nearby wells and climate-change effects.