Trace elements in Holocene sediments of the southern Doñana National Park (SW Spain): historical pollution and applications

The multidisciplinary analysis of core sediments from Doñana National Park, south Spain, permits to delimitate both the paleoenvironmental changes and the geochemical evolution of this area during the Holocene. In a first phase (10–6.5 kyr cal), this area was occupied by freshwater/brackish marshes with periodical alternation of dry periods and humid intervals. In a second phase, these marshes were inundated during the Flandrian transgression (~6.5 kyr cal), with the deposition of bioclastic sands. The third phase (6.5–3.6 kyr cal) is characterized by the transition to an old lagoon, with unpolluted, bottom sediments. The geochemical concentrations of these clayey sediments can be used as a geochemical background for present-day and future environmental evaluations of this area. In the following 600 years approximately, two tsunamis caused the partial infilling of this area with bioclastic, marine sediments. In the interval comprised between these two tsunamis, this lagoon was polluted with heavy metals derived from historical mining activities. This environmental contamination represents one of the oldest evidences of mining pollution in the world (>3 kyr cal BP).     

HTP21/c–C2/c phase transition and kinetics of Fe2+–Mg order–disorder of an Fe-poor pigeonite: implications for the cooling history of ureilites

A natural Ca-poor pigeonite (Wo₆En₇₆Fs₁₈) from the ureilite meteorite sample PCA82506-3, free of exsolved augite, was studied by in situ high-temperature single-crystal X-ray diffraction. The sample, monoclinic P2₁/c, was annealed up to 1,093°C to induce a phase transition from P2₁/c to C2/c symmetry. The variation with increasing temperature of the lattice parameters and of the intensity of the b-type reflections (h + k = 2n + 1, present only in the P2₁/c phase) showed a displacive phase transition P2₁/c to C2/c at a transition temperature T _Tr = 944°C, first order in character. The Fe–Mg exchange kinetics was studied by ex situ single-crystal X-ray diffraction in a range of temperatures between the closure temperature of the Fe–Mg exchange reaction and the transition temperature. Isothermal disordering annealing experiments, using the IW buffer, were performed on three crystals at 790, 840 and 865°C. Linear regression of ln k _D versus 1/T yielded the following equation: ln k_\textD = - 3717( ±416)/T(K) + 1.290( ±0.378);    (R² = 0.988) \ln \,k_{\text{D}} = - 3717( \pm 416)/T(K) + 1.290( \pm 0.378);\quad (R^{2} = 0.988) . The closure temperature (T _c) calculated using this equation was ∼740(±30)°C. Analysis of the kinetic data carried out taking into account the e.s.d.'s of the atomic fractions used to define the Fe–Mg degree of order, performed according to Mueller’s model, allowed us to retrieve the disordering rate constants C ₀ K _dis⁺ for all three temperatures yielding the following Arrhenius relation: ln( C₀ K_\textdis ⁺ ) = ln K₀ - Q/(RT) = 20.99( ±3.74) - 26406( ±4165)/T(K);    (R² = 0.988) \ln \left( {C_{0} K_{\text{dis}}^{ + } } \right) = \ln \,K_{0} - Q/(RT) = 20.99( \pm 3.74) - 26406( \pm 4165)/T(K);\quad (R^{2} = 0.988) . An activation energy of 52.5(±4) kcal/mol for the Fe–Mg exchange process was obtained. The above relation was used to calculate the following Arrhenius relation modified as a function of X _Fe (in the range of X _Fe = 0.20–0.50): ln( C₀ K_\textdis ⁺ ) = (21.185 - 1.47X_\textFe ) - \frac(27267 - 4170X_\textFe )T(K) \ln \left( {C_{0} K_{\text{dis}}^{ + } } \right) = (21.185 - 1.47X_{\text{Fe}} ) - {\frac{{(27267 - 4170X_{\text{Fe}} )}}{T(K)}} . The cooling time constant, η = 6 × 10⁻¹ K⁻¹ year⁻¹ calculated on the PCA82506-3 sample, provided a cooling rate of the order of 1°C/min consistent with the extremely fast late cooling history of the ureilite parent body after impact excavation.     

Chemistry of the Ferraria thermal water, S. Miguel Island, Azores: mixing and precipitation processes

The Ferraria thermal water emerges at the sea level in the Ferraria lava delta (western edge of S. Miguel Island, Azores) with temperature of ca. 60°C and pH varying between 5.4 and 6.2. It is of sodium chloride type, resulting from ca. 50% seawater mixing with an acid brackish, at ≈100°C, denoting the presence of significant CO₂(g) and the progress of water–rock interactions in open system conditions. The thermal Na–Cl water is strongly enriched with Sr and Mn and, comparatively, has low concentrations in Al, Fe and As. These elements are removed from the solution as critical conditions for the formation of several neo-formed mineral phases are gradually attained. Thermodynamic equilibrium calculations are consistent with this interpretation, showing that the thermal fluid can precipitate Fe³⁺-(hydr-)oxides, kaolinite and non-crystalline silica. Wells logging show fracture planes and pores fully/partly filled up with polyphase botryoidal aggregates mostly composed of goethite + ferrihydrite and displaying variable adsorbed contents of Si, P and As. These neo-formed phases result from the pristine fluid oxidation due to seawater mixing; its precipitation is easily affected by pH and redox variations of the brackish, due to volcanic gases pressure alterations, and fluid pressure or flow-velocity oscillation in the fractured aquifer.     

Aquifer development planning to supply a seaside resort: a case study in Goa,India

Using the hydrogeological and socio-economic data derived from a European Commission research project on the measurement, monitoring and sustainability of the coastal environment, two optimization models have been applied to satisfy the future water resources needs of the coastal zone of Bardez in Goa, India. The number of tourists visiting Goa since the 1970s has risen considerably, and roughly a third of them go to Bardez taluka, prompting growth in the tourist-related infrastructure in the region. The optimization models are non-linear mixed integer models that have been solved using GAMS/DICOPT++ commercial software. Optimization models were used, firstly, to indicate the most suitable zones for building seaside resorts and wells to supply the tourist industry with an adequate amount of water, and secondly, to indicate the best location for wells to adequately supply pre-existing hotels. The models presented will help to define the optimal locations for the wells and the hydraulic infrastructures needed to satisfy demand at minimum cost, taking into account environmental constraints such as the risk of saline intrusion.

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Résumé A l’aide de données hydrogéologiques et socio-économiques, dérivées d’un projet de recherche de la Commission Européenne sur l’étude, la surveillance et la durabilité de l’environnement c?tier, deux modèles d’optimisation ont été appliqués en vue de satisfaire les besoins futurs en ressources en eau de la zone c?tière de Bardez au Goa en Inde. Le nombre de touristes qui visitent le Goa depuis les années 70 a considérablement augmenté et environ un tiers d’entre eux se rend à Bardez taluka, ce qui encourage la croissance des infrastructures liées au tourisme dans la région. Les modèles d’optimisation sont des modèles non linéaires mixtes en nombres entiers qui ont été résolus en utilisant le logiciel commercial GAMS/DICOPT++. Les modèles d’optimisation ont été utilisés pour indiquer premièrement les zones les plus appropriées pour construire des stations balnéaires et des puits pour approvisionner en quantité d’eau suffisante l’industrie touristique, et deuxièmement pour indiquer la meilleure localisation de puits pour l’alimentation des h?tels préexistants. Les modèles présentés aideront à définir les localisations optimales des puits et des infrastructures hydrauliques nécessaires à la satisfaction de la demande à un co?t minimum, tout en prenant en compte les contraintes environnementales, tel que le risque d’intrusion saline.

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Resumen Se han aplicado dos modelos de optimización en base a datos socio-económicos e hidrogeológicos derivados de un proyecto de investigación de la Comisión Europea sobre medición, monitoreo y sostenibilidad del ambiente costero para satisfacer las necesidades futuras de recursos hídricos de la zona costera de Bardez en Goa, India. El número de turistas que visita Goa desde la década de 1970′s ha subido considerablemente y cerca de un tercio de ellos van a Bardez taluka impulsando el crecimiento en la infraestructura turística de la región. Los modelos de optimización son modelos de números enteros mixtos no-lineales que se han resuelto usando el programa comercial GAMS/DICOPT++. Los modelos de optimización se usaron, primero para indicar las zonas más adecuadas para la construcción de centros de diversión en las márgenes del océano y pozos para abastecer la industria turística con una adecuada cantidad de agua, y segundo, para indicar la mejor localización de pozos para el abastecimiento de hoteles pre-existentes. Los modelos que se presentan ayudarán a definir las localizaciones óptimas para los pozos y las infraestructuras hidráulicas necesarias para satisfacer la demanda al mínimo costo, tomando en consideración restricciones ambientales tal como el riesgo de intrusión salina.

     

Partitioning,bioavailability and origin of heavy metals from the Nador Lagoon sediments (Morocco) as a basis for their management

Nador Lagoon sediments show low trace element concentrations, and, in relation to the lagoon geochemical baseline, only some anomalies for As, Cd, Cu and Pb in the NW of the lagoon deserve to be outstanding. The distribution of major, minor and trace elements in the lagoon allows a breakdown in four zones. Between “Beni Ensar” and “Atelouane” (zone A), a quite confined zone rich in organic matter and S, the most important trace-element anomalies (As, Cd, Co, Cu, Mn, Pb, Zn) were found, mainly around industry and old mining activities. In the surrounding of the city of Nador (zone B), the anomalies correspond to Mn, Cu and Zn. The coastal barrier and Kebdana channel (zone C) show moderately concentrations of Cd, Cr and Ni at specific sites. The less polluted area is the SE of the lagoon (zone D), with no outstanding anomaly. In lagoon sediments, metal bioavailability is very low. The metal partitioning patterns show that Cu, Pb and Zn present a low availability because they are bounded to the residual, non-mobile phases of the sediments. Only in some sites, the fraction was associated with organic matter, which could be liberated easily. Arsenic is concentrated in both the residual phases and the organic matter, the latter being more available. Cadmium is mainly concentrated in some samples in the interchangeable fraction, which could be considered as a potentially toxic element because it is easily released. Concerning the origin of these trace elements, those found in zone A correspond mostly to a natural source by weathering of mount Gourougou volcanic rocks (As, Co, Cu, Pb and Zn), and to an anthropogenic origin (Cd) owing to the presence of industry and old mines. In zone B, contributions of Cu and Zn enter the lagoon through soil weathering and river-borne, and as anthropogenic pollution from urban wastes. In zone C the most important pollutant is Cd deduced to be of anthropogenic origin from the close industry and intensive agriculture area. In spite of the intense socio-economic activities developed in the Nador Lagoon (agriculture, industry, fishing, tourism) trace element concentrations in the sediments are low and with scarce bioavailability. Only the NW sector is relativity polluted because of geogenic features.     

Large to intermediate-scale aquifer heterogeneity in fine-grain dominated alluvial fans (Cenozoic As Pontes Basin,northwestern Spain): insight based on three-dimensional geostatistical reconstruction

Facies reconstructions are used in hydrogeology to improve the interpretation of aquifer permeability distribution. In the absence of sufficient data to define the heterogeneity due to geological processes, uncertainties in the distribution of aquifer hydrofacies and characteristics may appear. Geometric and geostatistical methods are used to understand and model aquifer hydrofacies distribution, providing models to improve comprehension and development of aquifers. However, these models require some input statistical parameters that can be difficult to infer from the study site. A three-dimensional reconstruction of a kilometer scale fine-grain dominated Cenozoic alluvial fan derived from more than 200 continuously cored, closely spaced, and regularly distributed wells is presented. The facies distributions were reconstructed using a genetic stratigraphic subdivision and a deterministic geostatistical algorithm. The reconstruction is only slightly affected by variations in the geostatistical input parameters because of the high-density data set. Analysis of the reconstruction allowed identification in the proximal to medial alluvial fan zones of several laterally extensive sand bodies with relatively higher permeability; these sand bodies were quantified in terms of volume, mean thickness, maximum area, and maximum equivalent diameter. These quantifications provide trends and geological scenarios for input statistical parameters to model aquifer systems in similar alluvial fan depositional settings.     

The Precambrian of the Anti-Atlas (Morocco): A geochronological synthesis

Twenty total rock Rb/Sr isochrons ($\text{λ}{}^{87}\text{Rb}\text{= 1.47 · 10}{}^{\mathrm{?11}}\text{yr}{}^{\mathrm{?1}}$) and many individual data, mainly obtained by the K/Ar and Rb/Sr methods, on total rocks and minerals show that the orogenic story of the Precambrian of the Anti-Atlas, which was studied in its western and central parts, began with the Eburnean orogeny (1900-1650 m.y.). Up to now there is no good evidence of an older basement, even if the rather high initial ratio (0.707–0.709) of some Eburnean granites might suggest that such a basement exists at depth. There is also no geochronological evidence of plutonism until in early Panafrican time (680 m.y.) there started a period of intense magmatic and thermal activity which was ended by the emplacement of late post-tectonic granites at 530-520 m.y.The late Panafrican acid volcanism does not generally give suitable material for Rb/Sr dating, because of the great mobility of the radiogenic strontium in such a material even under very weak thermal conditions.