Analysis of Sediments and Soils by X-Ray Fluorescence Spectrometry Using Matrix Corrections Based on Fundamental Parameters

Wavelength dispersive X-ray fluorescence spectrometry (WD-XRF) is widely used for the analysis of soils and sediments using well characterised procedures. However, difficulties can occur with samples such as unknowns containing small amounts of ore materials and samples collected from contaminated sites where trace elemental concentrations can exceed the concentration range for routine analysis. We studied the performance of a commercially available method, based on fundamental parameters (FP) to correct matrix effects. The spectrometer was originally calibrated with elemental or simple compound calibrants. Samples were analysed as pressed powder pellets. Eighteen sediment and soil reference materials, three of them with certified values for some of their constituents, were used to evaluate accuracy, by comparing results with recommended values and their standard deviations (RV ± 2s) or certified values and their confidence intervals (CV ± Cl). When results fell systematically outside these intervals, calibrations were refined with geochemical reference materials. The best agreement of results with recommended and certified values was obtained when the contents of H₂O and C in each sample were included as matrix constituents during calculations. The detection limits of trace elements tended to be relatively high, because the measuring conditions employed were not maximised for sensitivity. The main advantage of the method tested was that it enabled the analysis of samples with high concentrations of trace elements and the determination of elements such as F, Bi, Sb and W, which are not commonly included in quantitative XRF analysis of geological samples.     

Palynological Evidence for Climatic Change and Human Activity during the Holocene on Minorca (Balearic Islands)

Four pollen diagrams from Minorca (Balearic Islands) have been correlated with other previously studied sequences from Majorca and Minorca to define a Holocene landscape sequence for the region from 8000 yr B.P. to the present. The lower part of the pollen diagrams reflects a climatic phase with more rain and less-marked seasonality than today. Significant quantities ofCorylus, Buxus,and mesophilous taxa are found. In the middle part, between 5000 and 4000 yr B.P., a strong change is recorded in composition and structure of the vegetational landscape, with vegetation appearing that was adapted to Mediterranean conditions. This episode coincided with the first human colonization of the island and also with a widespread climatic change in the western Mediterranean region. The change in taxa was complex and some sclerophyllous taxa suchOleaplayed an important role in the transformation of the landscape physiognomy from the mid-Holocene until the present. Although human activities have removed much of the Mediterranean vegetation on the Balearic Islands, it seems clear that the changes have been brought about, in part, by increasing dryness.     

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.

     

Application of integrated methods in mapping waste disposal areas

An integrated suite of environmental methods was used to characterize the hydrogeological, geological and tectonic regime of the largest waste disposal landfill of Crete Island, the Fodele municipal solid waste site (MSW), to determine the geometry of the landfill (depth and spatial extent of electrically conductive anomalies), to define the anisotropy caused by bedrock fabric fractures and to locate potential zones of electrically conductive contamination. A combination of geophysical methods and chemical analysis was implemented for the characterization and management of the landfill. Five different types of geophysical surveys were performed: (1) 2D electrical resistance tomography (ERT), (2) electromagnetic measurements using very low frequencies (VLF), (3) electromagnetic conductivity (EM31), (4) seismic refraction measurements (SR), and (5) ambient noise measurements (HVSR). The above geophysical methods were used with the aim of studying the subsurface properties of the landfill and to define the exact geometrical characteristics of the site under investigation.     

Petrogenetic links between lepidolite-subtype aplite-pegmatite,aplite veins and associated granites at Segura (central Portugal)

In the Segura area, Variscan S-type granites, aplite veins and lepidolite-subtype granitic aplite-pegmatite veins intruded the Cambrian schist-metagraywacke complex. The granites are syn D3. Aplite veins also intruded the granites. Two-mica granite and muscovite granite have similar ages of 311.0 ± 0.5 Ma and 312.9 ± 2.0 Ma but are not genetically related, as indicated by their geochemical characteristics and (⁸⁷Sr/⁸⁶Sr)₃₁₁ values. They correspond to distinct pulses of magma derived by partial melting of heterogeneous metapelitic rocks. Major and trace elements suggest fractionation trends for: (a) muscovite granite and aplite veins; (b) two-mica granite and lepidolite-subtype aplite-pegmatite veins, but with a gap in most of these trends. Least square analysis for major elements, and modeling of trace elements, indicate that the aplite veins were derived from the muscovite granite magma by fractional crystallization of quartz, plagioclase, K-feldspar and ilmenite. This is supported by the similar (⁸⁷Sr/⁸⁶Sr)₃₁₁ and δ¹⁸O values and the behavior of P₂O₅ in K-feldspar and albite. The decrease in (⁸⁷Sr/⁸⁶Sr)₃₁₁ and strong increase (1.6‰) in δ¹⁸O from two-mica granite to lepidolite-subtype aplite-pegmatite veins, and the behaviors of Ca, Mn and F of hydroxylapatite indicate that these veins are not related to the two-mica granite.     

Petrogenesis of the mafic igneous rocks of the Betic Cordilleras: A field, petrological and geochemical study

Mafic igneous rocks are widespread in the Nevado-Filábride Complex, the lowermost metamorphic unit of the internal zones of the Betic Cordilleras. They form intrusive, small, discontinuous bodies, predominantly dikes with subordinate small lava flows. The entire complex underwent alpine compressional metamorphism during the Paleogene continental collision, resulting in eclogites and blueschists in the mafic bodies and high-pressure assemblages in the intruded metasediments. Locally, weakly metamorphosed or completely unmetamorphosed igneous rocks with the same textural features occur as patches surrounded by eclogitized igneous rocks. The bulk rock chemistry of unmetamorphosed and completely metamorphosed mafic igneous rocks is consistent with an alkaline to transitional tholeiitic magmatism with typical within-plate geochemical characteristics. All but a few samples are nepheline normative and display REE and trace element characteristics typical of continental, rift-related magmatism. This conclusion is strongly supported by the mineral chemistry of the major constituents, in particular the calcic Ti-rich character of clinopyroxene, the lack of orthopyroxene, and the occurrence of kaersutitic amphibole. Incompatible trace element abundances and Sr and Nd isotopes support the provenance of these magmas from a variably metasomatized previously depleted sub-continental lithospheric mantle source. Received: 5 July 1999 / Accepted: 28 February 2000     

Integrated provenance analysis of a convergent retroarc foreland system: U–Pb ages,heavy minerals,Nd isotopes,and sandstone compositions of the Middle Magdalena Valley basin,northern Andes,Colombia

Sediment provenance analysis remains a powerful method for testing hypotheses on the temporal and spatial evolution of uplifted source regions, but issues such as recycling, nonunique sources, and pre- and post-depositional modifications may complicate interpretation of results from individual provenance techniques. Convergent retroarc systems commonly contain sediment sources that are sufficiently diverse (continental magmatic arc, fold–thrust belt, and stable craton) to enable explicit provenance assessments. In this paper, we combine detrital zircon U–Pb geochronology, heavy mineral identification, Nd isotopic analyses, conventional sandstone petrography, and paleocurrent measurements to reconstruct the clastic provenance history of a long-lived sedimentary basin now exposed in an intermontane zone of the northern Andean hinterland of Colombia. The Middle Magdalena Valley basin, situated between the Central Cordillera and Eastern Cordillera, contains a 5–10 km-thick succession of Upper Cretaceous to Quaternary fill. The integrated techniques show a pronounced change in provenance during the Paleocene transition from the lower to upper Lisama Formation. We interpret this as a shift from an eastern cratonic source to a western Andean source composed of magmatic-arc rocks uplifted during initial shortening of the Central Cordillera. The appearance of detrital chloritoid and a shift to more negative ε_Nd(t=0) values in middle Eocene strata of the middle La Paz Formation are attributed to shortening-related exhumation of a continental basement block (La Cira–Infantas paleohigh), now buried, along the axis of the Magdalena Valley. The diverse provenance proxies also show distinct changes during middle to late Eocene deposition of the Esmeraldas Formation that likely reflect initial rock uplift and exhumation of the fold–thrust belt defining the Eastern Cordillera. Upsection, detrital zircon U–Pb ages and heavy mineral assemblages for Oligocene and younger clastic deposits indicate that the Mesozoic sedimentary cover of the Eastern Cordillera was recycled during continued Cenozoic shortening. Our multidisciplinary provenance study refines the tectonic history of the Colombian Andes and demonstrates that uncertainties related to sediment recycling, nonunique sources, source heterogeneity, and climate in interpreting provenance data can be minimized via an integrated approach.     

Short time-scale impacts of hydropeaking on benthic invertebrates in an Alpine stream (Trentino,Italy)

The impact of a single hydropeaking event was studied in the Alpine stream Noce Bianco. Four stations were selected, one upstream and three, respectively, at 0.25, 6, and 8 km downstream from a hydropower plant. We collected drifting invertebrates during a planned water release that increased the discharge 7-fold. At the onset of the hydropeaking wave the number of invertebrates lost from the riverbed per minute to the drift increased 9-fold at the first downstream station and the same effects propagated 8 km downstream. The drift was composed mainly of aquatic insect larvae (Chironomidae, Plecoptera, Ephemeroptera Baetidae, and Psychodidae, with Chironomidae as the most abundant taxon at all stations) and partly by larval and adult riparian insects, and by Oligochaeta, which were particularly abundant at the station 6 km downstream. We monitored drift for 30 min from the start of the water release: peaks in drifting invertebrates occurred within 5–10 min of the beginning of the hydropeaking wave, and most of the invertebrates were washed out within the first 15 min of the water release. The different timeframes were possibly due to habitat preferences (most of the taxa that increased in the drift at the arrival of the wave were associated with algae and organic debris, which were washed off quickly by the increase in discharge) and/or behavioral adaptations (other taxa initially resisted the shear stress and began to drift with a delay of 5–10 min). The temporal pattern and drift composition corresponded well with those reported in literature, and indicate that repeated high-flow events of similar magnitude cause considerable losses from benthic populations to drift.