Iron(II) oxide determination in rocks and minerals

The determination of FeO of geologic materials by modern instrumental methods (such as atomic absorption spectroscopy (AAS), inductively coupled plasma atomic emission spectroscopy (ICP-AES), X-ray fluorescence (XRF), etc.) cannot distinguish between different oxidation states of elements. In many cases, the oxidation state of Fe has to be known in order to perform several chemical calculations (norms, etc.) and discuss the reactions that occur during weathering, hydrothermal alteration and other processes. A modified Wilson method is proposed, giving reproducible results in a much shorter time than the classical method. Back-titration with potassium dichromate and an Fe(II) and ammonia sulphate solution is used, after dissolution of the sample powder in a heated HF/H₃PO₄ mixture and an ammonium vanadate solution. This modified method, tested with several international reference materials, gives reliable results, equivalent to the ones cited in the literature for the reference materials.     

Study of geothermal water intrusion due to groundwater exploitation in the Puebla Valley aquifer system, Mexico

Significant intrusion of geothermal water into fresh groundwater takes place in the Puebla Valley aquifer system, Mexico. The decline in the potentiometric surface due to the overexploitation of the groundwater induces this intrusion. This hydrological system comprises three aquifers located in Plio-Quaternary volcanic sediments and Mesozoic calcareous rocks. The hydraulic balance of the aquifer shows that the annual output exceeds the natural inputs by 12 million m³. Between 1973 and 2002, a drop in the potentiometric surface, with an 80 m cone of depression, was identified in a 5-km-wide area located southwest of the city of Puebla. Chemical analyses performed on water samples since 1990 have shown an increase in total dissolved solids (TDS) of more than 500 mg/L, coinciding with the region showing a cone of depression in the potentiometric surface. A three-dimensional flow and transport model, based on the hydrogeological and geophysical studies, was computed by using the MODFLOW and MT3D software. This model reproduces the evolution of the aquifer system during the last 30 years and predicts for 2010 an additional drawdown in the potentiometric surface of 15 m, and an increase in the geothermal water intrusion.     

Geotechnical Characterization by In situ and Lab Tests to the Back-Analysis of a Supported Excavation in Metro do Porto

This paper summarizes the geotechnical characterization conducted for the design and subsequent analysis of a strutted excavation in “Metro do Porto”. This region is geologically dominated by heterogeneous weathered granite masses with deep residual soil profiles. Local saprolitic soils exhibit, by their nature, a particular behavior characterized by very sensitive and weak relic micro-structures, due to their specific genesis. This study has included the interpretation of a significant volume of in situ test results, triaxial tests over undisturbed samples and monitoring data, giving rise to specific correlations between testing and design parameters. Real time monitoring enabled a back-analysis by FEM of a well instrumented section of the strutted excavation, which was calibrated taking into account the derived correlations and the deformability behavior of this specific geotechnical ambient. This geomaterial, although revealing very high initial stiffness values (for very small strain ranges) has shown low stiffness values for “medium to high” strain levels, reflecting a singular strong non-linearity in the stress-strain behavior.     

Controls on Quaternary coastal evolution of the east-northeastern coast of Brazil: roles of sea-level history, trade winds and climate

East-northeastern Brazil has a wave-dominated, micro- to meso-tidal coast, lying entirely within the southern Atlantic trade wind belt. Integration of geologic mapping, radiocarbon dating and vibracoring data shows that the Quaternary coastal evolution of this area was controlled by three major factors: (1) sea-level history; (2) trade winds; and (3) climate change.

Sea-level history. Along the east-northeastern coast of Brazil, relative sea level has fallen approximately 5 m during the last 5000 y. Correlation of this sea-level history with the evolution of beach-ridge, lagoonal and coastal plain deposits shows that: (1) sea-level rise favours the formation of barrier island—lagoonal systems and the construction of intralagoonal deltas; (2) sea-level lowering is not conductive to barrier island formation. Rather, lagoons and bays become emergent and beach-ridge plains rapidly prograde.

Trade winds. Sediment dispersal systems along the coastal zone of east-northeastern Brazil have been highly persistent since Pleistocene time, as deduced from beach-ridge orientation. This persistence results from the fact that sediment dispersal in wave-dominated settings is ultimately controlled by atmospheric circulation which, for the east-northeastern coast of Brazil is associated with the South Atlantic high-pressure cell. The remarkable stability of this cell through time, has allowed the accumulation of extensive beach-ridge plains at the longshore drift sinks located along the coast.

Climate change. Effects of Quaternary climate changes on coastal sedimentation are twofold. Climate changes may affect rainfall patterns, thus exerting an important control on coastal dune development. Along the coast of northeastern Brazil, active coastal dunes are only present in those areas in which at least four consecutive dry months occur during the year. Mapping of these areas has shown that dune development during the Holocene has been episodic, these episodes being probably controlled by variations in rainfall patterns associated with climate changes. Secondly, despite its overall stability, the position of the high-pressure cell has experienced small shifts in position during the Holocene in response to climate changes. Changes in wind direction associated with these shifts have induced modifications in the coastal dispersion system, which are recorded in the strandplains as small truncations in the beach-ridge alignments.

These results have important implications in understanding accumulation of ancient sandstone shoreline sequences.     

Assessment to the potential mobility and toxicity of metals and metalloids in soils contaminated by old Sb–Au and As–Au mines (NW Portugal)

The main purpose of this study is to assess arsenic and antimony availability in soils, as well as Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn availability in soils derived from the schist–metagraywacke complex close to old Sb–Au mines and in soils developed from Ordovician slates and close to an old As–Au mine in Portugal. The availability was determined using a European certified sequential extraction procedure (BCR). The results demonstrated that metalloids are not readily bioavailable, because they are mainly associated with the residual fraction. Arsenic and antimony proportions in exchangeable fractions are up to 3 and 1%, respectively. However, arsenic is up to 24% in oxy-hydroxide fractions, while antimony is up to 4% in them, demonstrating the highest bioavailability of arsenic compared to that of antimony, as metalloids are weakly bound to the soils in that fraction. Therefore, arsenic tends to be more toxic than antimony in all soils studied. However, the pseudo-total contents show that both metalloids are above the Italian and Dutch guidelines. Therefore, if physico-chemical changes occur arsenic and antimony will show higher potential environmental risk than evidenced by Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn.     

Sedimentological and provenance response to Cambrian closure of the Clymene ocean: The upper Alto Paraguai Group,Paraguay belt,Brazil

Final Gondwana amalgamation was marked by the closure of the Neoproterozoic Clymene ocean between the Amazonia craton and central Gondwana. The events which occurred in the last stage of this closure were recorded in the upper Alto Paraguai Group in the foreland of the Paraguay orogen. Outcrop-based facies analysis of the siliciclastic rocks of upper Alto Paraguai Group, composed of the Sepotuba and Diamantino Formations, was carried out in the Diamantino region, within the eastern part of the Barra dos Bugres basin, Mato Grosso state, central-western Brazil. The Sepotuba Formation is composed of sandy shales with planar to wave lamination interbedded with fine-grained sandstone with climbing ripple cross-lamination, planar lamination, swaley cross-stratification and tangential to sigmoidal cross-bedding with mud drapes, related to marine offshore deposits. The lower Diamantino Formation is composed of a monotonous, laterally continuous for hundreds of metres, interbedded siltstone and fine-grained sandstone succession with regular parallel lamination, climbing ripple cross-lamination and ripple-bedding interpreted as distal turbidites. The upper part of this formation consists of fine to medium-grained sandstones with sigmoidal cross-bedding, planar lamination, climbing ripple cross-lamination, symmetrical to asymmetrical and linguoid ripple marks arranged in lobate sand bodies. These facies are interbedded with thick siltstone in coarsening upward large-scale cycles related to a delta system. The Sepotuba Formation characterises the last transgressive deposits of the Paraguay basin representing the final stage of a marine incursion of the Clymene ocean. The progression of orogenesis in the hinterland resulted in the confinement of the Sepotuba sea as a foredeep sub-basin against the edge of the Amazon craton. Turbidites were generated during the deepening of the basin. The successive filling of the basin was associated with progradation of deltaic lobes from the southeast, in a wide lake or a restricted sea that formed after 541 ± 7 Ma. Southeastern to east dominant Neoproterozoic source regions were confirmed by zircon grains that yielded ages around 600 to 540 Ma, that are interpreted to be from granites in the Paraguay orogen. This overall regressive succession recorded in the Alto Paraguai Group represents the filling up of a foredeep basin after the final amalgamation of western Gondwana in the earliest Phanerozoic.     

The structure of the eastern border of the Andes in north-western Argentina

In the eastern border area of the Andes of north-western Argentina two structural units are represented: the Cordillera Oriental and the Sierras Subandinas.The Cordillera Oriental represents a structural unit of faulted blocks strongly uplifted in relation to the Sierras Subandinas. In the Cordillera Oriental, the metamorphic basement has been partially folded together with the sedimentary cover. In some cases the cover has been detached away from its substratum and folded independently of it.It was generally accepted that the Sierras Subandinas coincide with big asymmetrical anticlines produced in the cover rocks by tilting of rigid basement blocks. The detailed geological mapping of the region situated between the parallels 24° 45 and 26° latitude south and the meridians 64° 30 and 66° west has provided data that permit to modify considerably this scheme.The existence of important strike-slip faults running highly oblique to the main regional structural pattern and controlling the shape of the Sierras Subandinas folds has been verified. These highly oblique faults with strike-slip movements, that affect the whole region, are probably ancient lineaments reactivated during Andean diastrophism in Upper Pliocene to Early Pleistocene time.

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Zusammenfassung Im östlichen Grenzgebiet der Anden im nordwestlichen Argentinien liegen zwei strukturell unterschiedliche Einheiten vor, die Cordillera Oriental und die subandinen Sierren (Sierras Subandinas).Die Cordillera Oriental besteht aus Leistenschollen eines leicht metamorphisierten Sockels. Sie ist als Ganzes im Verhältnis zu den subandinen Sierren stark herausgehoben worden. In der Cordillera Oriental wurde dieser Sockel zum Teil zusammen mit seinen sedimentären Deckschichten verfaltet, zum Teil wurden sie aber auch von ihrem Unterlager abgeschert und unabhängig von ihm gefaltet.Bisher wurde allgemein angenommen, daß die subandinen Sierren aus großen assymmetrischen Falten aufgebaut werden, die in den Deckschichten durch Kippung starrer Blöcke im tieferen Untergrund hervorgerufen wurden. Die genaue geokartographische Aufnahme eines Gebietes zwischen den Breitenkreisen 24° 45 und 26° südl. Breite und den Längenkreisen 64° 30 und 66° westl. Länge erbrachte Daten, die es erlauben, diese Vorstellung erheblich zu modifizieren.Weit durchhaltende Seitenverschiebungen, die die übergeordneten Strukturen des gesamten Gebietes schräg durchziehen und die Gestalt der Falten in den Sierren erheblich beeinflussen, wurden nachgewiesen. Sie stellen wahrscheinlich alte, präandine Lineamente dar, die während der Anden-Orogenese im Jungtertiär bis Altpleistozän reaktiviert Wurden.

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Resumen En el borde oriental de los Andes del Noroeste Argentino están representadas dos unidades estructurales: la Cordillera Oriental y las Sierras Subandinas.La Cordillera Oriental es una unidad constituida por bloques fallados y, en conjunto, elevada con respecto a las Sierras Subandinas. En la Cordillera Oriental el basamento metamórfico ha sido parcialmente plegado junto con la cobertura sedimentaria. En algunos casos lo cobertura ha sido despegada de su substrato y plegada independientemente.En general se aceptaba que las Sierras Subandinas coincidian con grandes anticlinales asimétricos producidos en la cobertura sedimentaria por el basculamiento de bloques rígidos de basamento situados en el subsuelo. La cartografía geológica-estructural detallada de la región comprendida por los paralelos 24° 45 y 26° S y los meridianos 64° 30 y 66° W ha proporcionado datos que permiten modificar considerablemente este esquema.Se ha comprobado la existencia de importantes fallas transcurrentes, fuertemente oblicuas con respecto a la estructura regional, que han tenido profunda influencia sobre la forma de los pliegues subandinos. Estas fallas oblicuas son probablemente lineamientos antiguos en los que el diastrofismo Andico (Plioceno-Pleistoceno) ha producido considerables desplazamientos paralelos al rumbo de los mismos.

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Résumé Dans la bordure orientale des Andes du Nord-ouest de l'Argentine, deux unités structurales différentes sont présentes: les Sierras subandines et la Cordillère orientale.La Cordillère orientale est composée d'un socle faiblement métamorphique faillé en blocs fortement surélevés par rapport aux Sierras subandines. Dans la Cordillère orientale, ce socle métamorphique a été en partie plissé avec sa couverture sédimentaire; mais parfois celle-ci a été décolée de son substratum et plissé indépendentement.Jusqu'à présent, on admettait que les Sierras subandines sont constituées de grands anticlinaux assymétriques produits dans la couverture par l'ascension de blocs faillés du socle. La cartographie géologico-structurale detaillée de la région comprise entre les parallèles 24° 45 et 26° de latitude sud et les méridiens 64° 30 et 60° ouest conduit à modifier considérablement ce schéma.D'importants décrochements très obliques par rapport à la direction de la structure régionale et qui ont fortement influencé la forme des plis subandins sont probablement des accidents anciens rajeunis pendant le diastrophisme andin au cours du Pliocène supérieur et du Pléistocène inférieur.

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Ecotoxicological evaluation of dredged sediments from Rodrigo de Freitas Lagoon (Rio de Janeiro State,Brazil) using bioassays with earthworms and collembolans

The toxicity and metal bioavailability were studied in dredged sediments from Rodrigo de Freitas Lagoon (Rio de Janeiro, RJ, Brazil) using acute and avoidance tests with Eisenia andrei, and reproduction tests with Folsomia candida. The sediment was mixed with an artificial soil, and two natural soils (ferralsol and chernosol—representative Brazilian tropical soils) to obtain the following doses: 1, 3, 6, 12, 18, 24 and 30%. Total metal concentrations were determined in the sediment to support the interpretation of ecotoxicological data. Metal concentrations in the mixtures were in agreement with the threshold limits established by Brazilian law. However, significant avoidance responses were found on doses ≥?3% and were the most sensitive endpoint. Earthworm mortality found in artificial soil mixtures (LC50?=?3.9) suggests higher toxicity levels than those obtained in ferralsol (LC50?=?7.6%) and chernosol (11.0%) treatments. Earthworm mortality, avoidance responses and collembolan reproduction levels found in ferralsol mixtures (LC50?=?9.2; avoidance EC50?=?2.3%; reproduction EC50?=?2.8%) were higher compared to chernosol treatments (LC50?=?11.0%; avoidance EC50?=?4.3%; reproduction EC50?=?4.9%). The reduction of toxicity levels in chernosol mixtures is probably due to the abundance of expansive clay minerals in chernosols with capacity of adsorbing metals and other xenobiotic substances from soil pore water, decreasing metal bioavailability. Finally, threshold limits defined by Brazilian legislation for soil quality and land disposal of dredged sediments are not sufficient to prevent noxious effects on soil fauna and should be complemented with a preliminary ecotoxicological evaluation.