Espectroscopia mecânica em ruteno-cupratos: mobilidade de vacâncias de oxigênio intersticial

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Environmental changes in the western Amazônia: morphological framewor, geochemistry, palynology and radiocarbon dating data

Os sedimentos do lago Coari, de ambiente de terra firme esculpido nos depósitos do Plio-Pleistocenos, e o Acará, típico lago de várzea e ambos formados nos sedimentos quaternários da planície de inundação do médio Solimões, no oeste da Amazônia, Brasil, foram estudados para investigar as condições ambientais durante sua formação. Este estudo inclui dados da composição mineralógica, química, isótopos de Pb, palinologia, datações de radiocarbono e a configuração morfológica dos lagos obtida por imagens SRTM. As condições geológica e ambiental dos lagos variam e sugerem que suas evoluções refletem processos autogenéticos em condições de floresta úmida e chuvosa. Embora caulinita, quartz, muscovita, illita e esmectita sejam os principais minerais em ambos os lagos, a geoquímica indica fonte distinta, os sedimentos do lago Acará têm maior concentração de Al2O3, Fe2O3, FeO, CaO, K2O, MgO, Na2O, P2O5, Ba, V, Cu, Ni, Zn, Pb, Sr, Li, Y e La e têm mais Pb radiogênico que os sedimentos do lago Coari. As idades de radiocarbono sugerem que há aproximadamente 10160 anos AP o lago Coari iniciou o desenvolvimento devido a avulsão do rio Solimões, enquanto o lago Acará foi formado devido ao abandono de meandro do rio Solimões e retendo o domínio das gramíneas nas suas praias há aproximadamente 3710 anos AP.

Geologia, petrografia e geoquímica das associações leucograníticas e TTG arqueanos da área de Nova Canadá (PA) Domínio Carajás

O mapeamento geológico realizado na área de Nova Canadá, porção sul do Domínio Carajás, aliado aos estudos petrográficos e geoquímicos, permitiram a caracterização de pelo menos três novas unidades que antes estavam inseridas no contexto geológico do Complexo Xingu. São elas: (i) Leucogranodiorito Nova Canadá, que é constituído por rochas leucogranodioríticas mais enriquecidas em Al₂O₃, CaO, Na₂O, Ba, Sr e na razão Sr/Y, que mostram fortes afinidades geoquímicas com a Suíte Guarantã do Domínio Rio Maria, as quais também podem ser correlacionadas aos TTGs Transicionais do Cráton Yilgarn. Estas rochas apresentam padrão ETR levemente fracionado, mostram baixas razões (La/Yb)N e anomalias negativas de Eu ausentes ou discretas; (ii) Leucogranito Velha Canadá, caracterizado pelos conteúdos mais elevados de SiO₂, Fe₂O₃, TiO₂, K₂O, Rb, HFSE (Zr, Y e Nb), das razões K₂O/Na₂O, FeOt/(FeOt+MgO), Ba/Sr e Rb/Sr. Apresentam dois padrões distintos de ETR: (a) baixas à moderadas razões (La/Yb)N com anomalias negativas de Eu acentuadas; e (b) moderadas à altas razões (La/Yb)N, com anomalias negativas de Eu discretas e um padrão côncavo dos ETRP. Em diversos aspectos, as rochas do granito Velha Canadá mostram fortes afinidades com os leucogranitos potássicos tipo Xinguara e Mata Surrão do Domínio Rio Maria, assim como aqueles da região da Canaã dos Carajás e mais discretamente com os granitos de baixo Ca do Cráton Yilgarn. Para a origem das rochas do Leucogranodiorito Nova Canadá é admitida a hipótese de cristalização fracionada a partir de líquidos com afinidade sanukitóide, seguido por processos de mistura entre estes e líquidos de composição trondhjemítica, enquanto que para aquelas de alto K do Leucogranito Velha Canadá, acreditase na fusão parcial de metatonalitos tipo TTG em diferentes níveis crustais, para gerar líquidos com tais características; e (iii) associações trondhjemíticas com afinidade TTG de alto Al₂O₃, Na₂O e baixo K₂O, compatíveis com os granitoides arqueanos da série cálcioalcalina tonalítica-trondhjemítica de baixo potássio. Foram distinguidas duas variedades: (a) biotita-trondhjemito com estruturação marcada pelo desenvolvimento de feições que indicam atuação de pelo menos dois eventos deformacionais em estágios sin- a pós-magmáticos, como bandamentos composicionais, dobras e indícios de migmatização; e (b) muscovita ± biotita trondhjemito que é distinguido da variedade anterior pela presença da muscovita, saussuritização do plagioclásio, textura equigranular média e atuação discreta da deformação com o desenvolvimento de uma foliação E-W de baixo angulo. A primeira variedade destes litotipos, que ocorre predominantemente na porção norte, tem ocorrência restrita. Com intensa deformação e prováveis feições de anatexia (migmatitos) podem indicar que estas rochas tenham sido afetadas por um retrabalhamento crustal, ligado à geração dos leucogranitos dominantemente descritos na área. Os trondhjemitos do sul da área são mais enriquecidos em Fe₂O₃, MgO, TiO₂, CaO, Zr, Rb, e na razão Rb/Sr em relação aos trondhjemitos da porção norte da área. Estas exibem ainda padrões fracionados de ETR, com variações nos conteúdos de ETRP, além da ausência de anomalias de Eu e Sr, e baixos conteúdos de Y e Yb. Tais feições são tipicamente atribuídas à magmas gerados por fusão parcial de uma fonte máfica em diferentes profundidades, com aumento da influência da granada no resíduo e a falta de plagioclásio tanto na fase residual como na fracionante. Em uma análise geral, a disposição dos trends geoquímicos evolutivos de ambas as variedades sugere que estas unidades não são comagmáticas. As afinidades geoquímicas entre as rochas da área de Nova Canadá com aquelas do Domínio Mesoarqueano Rio Maria, poderiam nos levar a entender a região de Nova Canadá como uma extensão do Rio Maria para norte, enquanto que para aquelas do Leucogranito Velha Canadá, que são mais jovens e geradas já no Neoarqueano, se descarta a idéia de associação com os mesmos eventos tectono-magmáticos que atuaram em Rio Maria.

Planificación y diagnóstico de base de las playas no vírgenes de "sol y baño" (Tópicos actualizados a 2014 para redactar planes de manejo). Aplicación al caso de la Playa de Las Canteras (Las Palmas de Gran Canaria)

[ES]Respecto a la gestión de las playas de sol y baño, se presentan 4 bloques de prácticas con sus soportes teóricos, que se denominan, por sus alcances conceptuales y procedimentales: cálculo de calidades DAFO cuantitativas y contrastables para un campo de aplicación dado en la Ordenación del Territorio (imprescindible en un diagnóstico ambiental de situación), evaluación de impactos ambientales heredados como parte del diagnóstico ambiental de situación, redacción de proyectos, propuestas y planteamientos (con sus acciones específicas), en relación con la Ordenación del Territorio, y puesta en valor de proyectos de Ordenación del Territorio (cualificación, cuantificación, catalogación y clasificación). Cada uno de los bloques de prácticas contiene: una base teórica, una batería de enunciados de ejercicios, y sus correspondientes soluciones. Los casos prácticos presentados satisfacen a las tareas propias de los gestores de un territorio y, en particular, se ajustan a las competencias profesionales asignadas a la materia de Planificación y Gestión del Litoral de grado de la ULPGC, generados a partir de los objetivos establecidos y que se alcanzan a través de los contenidos conceptuales, procedimentales y actitudinales, de una Ordenación del Territorio.

Gestión del litoral : caso de la playa urbana de "sol y baño" de Las Canteras (Las Palmas de Gran Canaria)

[ES]Respecto a la gestión de las playas de sol y baño, se presentan 4 bloques de prácticas con sus soportes teóricos, que se denominan, por sus alcances conceptuales y procedimentales: cálculo de calidades DAFO cuantitativas y contrastables para un campo de aplicación dado en la Ordenación del Territorio, evaluación de impactos ambientales heredados como parte del diagnóstico ambiental de situación, redacción de proyectos en relación con la Ordenación del Territorio, y puesta en valor de proyectos de Ordenación del Territorio. Cada uno de los bloques de prácticas contiene: una base teórica, una batería de enunciados de ejercicios, y sus correspondientes soluciones. Los casos prácticos presentados satisfacen a las tareas propias de los gestores de un territorio.

Gestión del litoral : herramientas para la planificación de playas vírgenes de arena como recurso de sol y baño : (rediseñadas y calibradas en el Parque Natural del Cabo de Gata-Níjar, España)

[ES]Se pretende disponer de herramientas que midan calidades ambientales de playas vírgenes de arena, respecto a su uso sustentable como recursos de sol y baño. Estas herramientas son los Análisis DAFO cuantitativos y las Evaluaciones de Impactos heredados. Para rediseñarlas y calibrarlas, se opta por las playas del Parque Natural del Cabo de Gata-Níjar (Almería, España). Se recurre a la formulación de sus patrones de comportamiento morfodinámico para identificar y definir algunos de sus descriptores y factores ambientales del campo en consideración. Las medidas se harían a partir del árbol involucrado de objetivos, de observaciones in situ, de las variables aisladas, y del rescate de muchos descriptores y factores ambientales de las playas urbanas de sol y baño.

Petrogenesis of rift-related tephrites, phonolites and trachytes (Central European Volcanic Province, Rhon, FRG): Constraints from Sr, Nd, Pb and O isotopes

The volcanic rocks of the Rhön area (Central European Volcanic Province, Germany) belong to a moderately alkali basaltic suite that is associated with minor tephriphonolites, phonotephrites, tephrites, phonolites and trachytes. Based on isotope sytematics (87Sr/86Sr: 0.7033–0.7042; 143Nd/144Nd: 0.51279–0.51287; 206Pb/204Pb: 19.1–19.5), the inferred parental magmas formed by variable degrees of partial melting of a common asthenospheric mantle source (EAR: European Asthenospheric Reservoir of Cebriá and Wilson, 1995). Tephrites, tephriphonolites, phonotephrites, phonolites and trachytes show depletions and enrichments in some trace elements (Sr, Ba, Nb, Zr, Y) indicating that they were generated by broadly similar differentiation processes that were dominated by fractionation of olivine, clinopyroxene, amphibole, apatite and titaniferous magnetite ± plagioclase ± alkalifeldspar. The fractionated samples seem to have evolved by two distinct processes. One is characterized by pure fractional crystallization indicated by increasing Nb (and other incompatible trace element) concentrations at virtually constant 143Nd/144Nd ~ 0.51280 and 87Sr/86Sr ~ 0.7035. The other process involved an assimilation–fractional crystallization (AFC) process where moderate assimilation to crystallization rates produced evolved magmas characterized by higher Nb concentrations at slightly lower 143Nd/144Nd down to 0.51275. Literature data for some of the evolved rocks show more variable 87Sr/86Sr ranging from 0.7037 to 0.7089 at constant 143Nd/144Nd ~ 0.51280. These features may result from assimilation of upper crustal rocks by highly differentiated low-Sr (< 100 ppm Sr) lavas. However, based on the displacement of the differentiated rocks from this study towards lower 143Nd/144Nd ratios and modeled AFC processes in 143Nd/144Nd vs. 87Sr/86Sr and 207Pb/204Pb vs. 143Nd/144Nd space assimilation of lower crustal rocks seems more likely. The view that assimilation of lower crustal rocks played a role is confirmed by high-precision double-spike Pb isotope data that reveal higher 207Pb/204Pb ratios (15.62–15.63) in the differentiated rocks than in the primitive basanites (15.58–15.61). This is compatible with incorporation of radiogenic Pb from lower crustal xenoliths (207Pb/204Pb: 15.63–15.69) into the melt. However, 206Pb/204Pb ratios are similar for the differentiated rocks (19.13–19.35) and the primitive basanites (19.12–19.55) implying that assimilation involved an ancient crustal end member with a higher U/Pb ratio than the mantle source of the basanites. In addition, alteration-corrected δ18O values of the differentiated rocks range from c. 5 to 7‰ which is the same range as observed in the primitive alkaline rocks. This study confirms previous interpretations that highlighted the role of AFC processes in the evolution of alkaline volcanic rocks in the Rhön area of the Central European Volcanic Province.

Rb, Sr, Sm and Nd concentrations and isotopic composition of basalts from DSDP Leg 74 (Table 1)

Basement intersected in DSDP holes 525A, 528 and 527 on the Walvis Ridge consists of submarine basalt flows and pillows with minor intercalated sediments. These holes are situated on the crest and mid and lower northwest flank of a NNW-SSE-trending ridge block which would have closely paralleled the paleo mid-ocean ridge (Rabinowitz and LaBrecque, 1979 doi:10.1029/JB084iB11p05973, Moore et al. (1983 doi:10.1130/0016-7606(1983)94<907:TWRTDS>2.0.CO;2). The basalts were erupted approximately 70 m.y. ago, an age equivalent to that of immediately adjacent oceanic crust in the Angola Basin and coraistent with formation at the paleo mid-ocean ridge (Moore et al., 1983). The basalt types vary from aphyric quartz tholeiites on the ridge crest to highly plagioclase phyric olivine tholeiites on the ridge flank. These show systematic differences in incompatible trace element and isotopic composition. Many element and isotope ratio pairs form systematic trends with the ridge crest basalts at one end and the highly phyric ridge flank basalts at the other. The low 143Nd/144Nd (0.51238), 206Pb/204Pb (17.54), 207Pb/204Pb (15.47), 208Pb/204Pb (38.14) and high 87Sr/86Sr (0.70512) ratios of the ridge crest basalts suggest derivation from an old Nd/Sm-, Rb/Sr- and Pb/U-enriched mantle source. This isotopic signature is similar to that of alkaline basalts on Tristan da Cunha but offset to significantly lower Nd and Pb isotopic ratios. The isotopic ratio trends may be extrapolated beyond the ridge flank basalts with higher 143Nd/144Nd (0.51270), 206Pb/204Pb (18.32), 207Pb/204Pb (15.52), 208Pb/204Pb (38.77) and lower 87Sr/86Sr (0.70417) ratios in the direction of increasingly Nd/Sm-, Rb/Sr- and Pb/U-depleted source compositions. These isotopic correlations are equally consistent with mixing of depleted and enriched end member melts or partial melting of an inhomogeneous, variably enriched mantle source. However, observed Zr-Ba-Nb-Y interelement relationships are inconsistent with any simple two-component model of magma mixing, as might result from the rise of a lower mantle plume through the upper mantle. Incompatible element and Pb isotopic systematics also preclude extensive involvement of depleted (N-type) MORB material or its mantle sources. In our preferred petrogenetic model the Walvis Ridge basalts were derived by partial melting of mantle similar to an enriched (E-type) MORB source which had become heterogeneous on a small scale due to the introduction of small-volume melts and metasomatic fluids.

Petrology and geochemistry of volcanic rocks from ODP Sites 134-827, 134-829 and 134-830

Igneous rocks recovered from Ocean Drilling Program (ODP) Leg 134 Sites 827, 829, and 830 at the toe of the forearc slope of New Hebrides Island Arc were investigated, using petrography, mineral chemistry, major and trace element, and Sr, Nd, and Pb isotopic analyses. Basaltic and andesitic clasts, together with detrital crystals of plagioclase, pyroxenes, and amphiboles embedded in sed-lithic conglomerate or volcanic siltstone and sandstone of Pleistocene age, were recovered from Sites 827 and 830. Petrological features of these lava clasts suggest a provenance from the Western Belt of New Hebrides Island Arc; igneous constituents were incorporated into breccias and sandstones, which were in turn reworked into a second generation breccia. Drilling at Site 829 recovered a variety of igneous rocks including basalts and probably comagmatic dolerites and gabbros, plus rare ultramafic rocks. Geochemical features, including Pb isotopic ratios, of the mafic rocks are intermediate between midocean ridge basalts and island arc tholeiites, and these rocks are interpreted to be backarc basin basalts. No correlates of these mafic rocks are known from Espiritu Santo and Malakula islands, nor do they occur in the Pleistocene volcanic breccias at Sites 827 and 830. However, basalts with very similar trace element and isotopic compositions have been recovered from the northern flank of North d'Entrecasteaux Ridge at Site 828. It is proposed that igneous rocks drilled at Site 829 represent material from the North d'Entrecasteaux Ridge accreted onto the over-riding Pacific Plate during collision. An original depleted mantle harzburgitic composition is inferred for a serpentinite clast recovered at 407 meters below seafloor (mbsf) in Hole 829A. Its provenance is a matter of speculation. It could have been brought up along a deep thrust fault affecting the Pacific Plate at the colliding margin, or analogous to the Site 829 basaltic lavas, it may represent material accreted from the North d'Entrecasteaux Ridge.

Composition of volcanic rocks from the Alchan Basin, Northwestern Primorie

Geological, petrochemical, and geochemical data are reported for volcanic rocks of a Cretaceous pull-apart basin in the Tan Lu strike-slip system, Asian continental margin. A comparison of these volcanic rocks with magmatic rocks from typical Cenozoic transform margins in the western North America and rift zones of Korea made it possible to distinguish some indicator features of transform-margin volcanic rocks. Magmatic rocks from strike-slip extension zones bear island-arc, intraplate, and occasionally depleted MORB geochemical signatures. In addition to calc-alkaline rocks there are bimodal volcanic series. The rocks are characterized by high K2O, MgO, and TiO2 contents. They show variable enrichment in LILE relative to HFSE, which is typical of island-arc magmas. At the same time they are rich in compatible transition elements, which is a characteristic of intraplate magmas. Trace element distribution patterns normalized to MORB or primitive mantle usually show a negative Ta-Nb anomaly typical of suprasubduction settings. Their Ta/Nb ratio is lower, whereas Ba/Nb, Ba/La, and La/Yb ratios are higher than those of some MORB and OIB. In terms of trace element systematics, for example, Ta-Th-Hf, Ba/La-(Ba/La)_n, (La/Sm)_n-La/Hf, and others, they fall within the area of mixing of magmas from several sources (island arc, intraplate, and depleted reservoirs). Magmatic rocks of transform settings show a sigmoidal chondrite-normalized REE distribution pattern with a negative slope of LREE, depletion in MREE, and an enriched or flat HREE pattern. Magmas with mixed geochemical characteristics presumably originated in a transform margin setting in local extension zones under influence of mantle diapirs, which caused metasomatism and melting of the lithosphere at different levels, and mixing of melts from different sources in variable proportions.

Petrology and chemistry of ODP Site 134-828 magmatic rocks

Petrography, major and trace elements, mineral chemistry, and Sr, Nd, and Pb isotopic ratios are reported for igneous rocks drilled on the northern flank of the North d'Entrecasteaux Ridge (NDR) during Ocean Drilling Program (ODP) Leg 134 Site 828. These rocks comprise a breccia unit beneath a middle Eocene foraminiferal ooze. Both geophysical characteristics and the variety of volcanic rocks found at the bottom of Holes 828A and 828B indicate that a very immature breccia or scree deposit was sampled. Basalts are moderately to highly altered, but primary textures are well preserved. Two groups with different magmatic affinities, unrelated to the stratigraphic height, have been distinguished. One group consists of aphyric to sparsely plagioclase + clinopyroxene-phyric basalts, characterized by high TiO2 (~2 wt%) and low Al2O3 (less than 15 wt%) contents, with flat MORB-normalized incompatible element patterns and LREE-depleted chondrite-normalized REE patterns. This group resembles N-MORB. The other group comprises moderately to highly olivine + plagioclase-phyric basalts with low TiO2 (<1 wt%) and high Al2O3 (usually >15 wt%) contents, and marked HFSE depletion and LFSE enrichment. Some lavas in this group are picritic, with relatively high modal olivine abundances, and MgO contents up to 15 wt%. Both the basalts and picritic basalts of this group reflect an influence by subduction-related processes, and have compositions transitional between MORB and IAT. Lavas with similar geochemical features have been reported from small back-arc basins such as the Mariana Trough, Lau Basin, Sulu Sea, and the North Fiji Basin and are referred to as back-arc basin basalts. However, regional tectonic considerations suggest that the spreading that produced these backarc basin basalts may have occurred in the forearc region of the southwest-facing island arc that existed in this region in the Eocene.

Lithogeochemical and isotope (Rb-Sr, Sm-Nd, Pb-Pb whole rock and Lu-Hf zircon) composition of samples from the Shackleton Range, East Antarctica

Three distinct, spatially separated crustal terranes have been recognised in the Shackleton Range, East Antarctica: the Southern, Eastern and Northern Terranes. Mafic gneisses from the Southern Terrane provide geochemical evidence for a within-plate, probably back-arc origin of their protoliths. A plume-distal ridge origin in an incipient ocean basin is the favoured interpretation for the emplacement site of these rocks at c. 1850 Ma, which, together with a few ocean island basalts, were subsequently incorporated into an accretionary continental arc/supra-subduction zone tectonic setting. Magmatic underplating resulted in partial melting of the lower crust, which caused high-temperature granulite-facies metamorphism in the Southern Terrane at c. 1710-1680 Ma. Mafic and felsic gneisses there are characterised by isotopically depleted, positive Nd and Hf initials and model ages between 2100 and 2000 Ma. They may be explained as juvenile additions to the crust towards the end of the Palaeoproterozoic. These juvenile rocks occur in a narrow, c. 150 km long E-W trending belt, inferred to trace a suture that is associated with a large Palaeoproterozoic accretionary orogenic system. The Southern Terrane contains many features that are similar to the Australo-Antarctic Mawson Continent and may be its furthermost extension into East Antarctica. The Eastern Terrane is characterised by metagranitoids that formed in a continental volcanic arc setting during a late Mesoproterozoic orogeny at c. 1060 Ma. Subsequently, the rocks experienced high-temperature metamorphism during Pan-African collisional tectonics at 600 Ma. Isotopically depleted zircon grains yielded Hf model ages of 1600-1400 Ma, which are identical to Nd model ages obtained from juvenile metagranitoids. Most likely, these rocks trace the suture related to the amalgamation of the Indo-Antarctic and West Gondwana continental blocks at ~600 Ma. The Eastern Terrane is interpreted as the southernmost extension of the Pan-African Mozambique/Maud Belt in East Antarctica and, based on Hf isotope data, may also represent a link to the Ellsworth-Whitmore Mountains block in West Antarctica and the Namaqua-Natal Province of southern Africa. Geochemical evidence indicates that the majority of the protoliths of the mafic gneisses in the Northern Terrane formed as oceanic island basalts in a within-plate setting. Subsequently the rocks were incorporated into a subduction zone environment and, finally, accreted to a continental margin during Pan-African collisional tectonics. Felsic gneisses there provide evidence for a within-plate and volcanic arc/collisional origin. Emplacement of granitoids occurred at c. 530 Ma and high-temperature, high-pressure metamorphism took place at 510-500 Ma. Enriched Hf and Nd initials and Palaeoproterozoic model ages for most samples indicate that no juvenile material was added to the crust of the Northern Terrane during the Pan-African Orogeny but recycling of older crust or mixing of crustal components of different age must have occurred. Isotopically depleted mafic gneisses, which are spatially associated with eclogite-facies pyroxenites, yielded late Mesoproterozoic Nd model ages. These rocks occur in a narrow, at least 100 km long, E-W trending belt that separates alkaline ocean island metabasalts and within-plate metagranitoids from volcanic arc metabasalts and volcanic arc/syn-collisional metagranitoids in the Northern Terrane. This belt is interpreted to trace the late Neoproterozoic/early Cambrian Pan-African collisional suture between the Australo-Antarctic and the combined Indo-Antarctic/West Gondwana continental blocks that formed during the final amalgamation of Gondwana.

Estrategias de monitorización de CO2 y otros gases en los estudios de análogos naturales

La Universidad Politécnica de Madrid (UPM) y la Università degli Studi di Firenze (UniFi), bajo la coordinación técnica de AMPHOS21, participan desde 2009 en el proyecto de investigación “Estrategias de Monitorización de CO2 y otros gases en el estudio de Análogos Naturales”, financiado por la Fundación Ciudad de la Energía (CIUDEN) en el marco del Proyecto Compostilla OXYCFB300 (http://www.compostillaproject.eu), del Programa “European Energy Program for Recovery - EEPR”. El objetivo principal del proyecto fue el desarrollo y puesta a punto de metodologías de monitorización superficiales para su aplicación en el seguimiento y control de los emplazamientos donde se realice el almacenamiento geológico de CO2, analizando técnicas que permitan detectar y cuantificar las posibles fugas de CO2 a la atmósfera. Los trabajos se realizaron tanto en análogos naturales (españoles e italianos) como en la Planta de Desarrollo Tecnológico de Almacenamiento de CO2 de Hontomín. Las técnicas analizadas se centran en la medición de gases y aguas superficiales (de escorrentía y manantiales). En cuanto a la medición de gases se analizó el flujo de CO2 que emana desde el suelo a la atmósfera y la aplicabilidad de trazadores naturales (como el radón) para la detección e identificación de las fugas de CO2. En cuanto al análisis químico de las aguas se analizaron los datos geoquímicos e isotópicos y los gases disueltos en las aguas de los alrededores de la PDT de Hontomín, con objeto de determinar qué parámetros son los más apropiados para la detección de una posible migración del CO2 inyectado, o de la salmuera, a los ambientes superficiales. Las medidas de flujo de CO2 se realizaron con la técnica de la cámara de acúmulo. A pesar de ser una técnica desarrollada y aplicada en diferentes ámbitos científicos se estimó necesario adaptar un protocolo de medida y de análisis de datos a las características específicas de los proyectos de captura y almacenamiento de CO2 (CAC). Donde los flujos de CO2 esperados son bajos y en caso de producirse una fuga habrá que detectar pequeñas variaciones en los valores flujo con un “ruido” en la señal alto, debido a actividad biológica en el suelo. La medida de flujo de CO2 mediante la técnica de la cámara de acúmulo se puede realizar sin limpiar la superficie donde se coloca la cámara o limpiando y esperando al reequilibrio del flujo después de la distorsión al sistema. Sin embargo, los resultados obtenidos después de limpiar y esperar muestran menor dispersión, lo que nos indica que este procedimiento es el mejor para la monitorización de los complejos de almacenamiento geológico de CO2. El protocolo de medida resultante, utilizado para la obtención de la línea base de flujo de CO2 en Hontomín, sigue los siguiente pasos: a) con una espátula se prepara el punto de medición limpiando y retirando el recubrimiento vegetal o la primera capa compacta de suelo, b) se espera un tiempo para la realización de la medida de flujo, facilitando el reequilibrio del flujo del gas tras la alteración provocada en el suelo y c) se realiza la medida de flujo de CO2. Una vez realizada la medición de flujo de CO2, y detectada si existen zonas de anomalías, se debe estimar la cantidad de CO2 que se está escapando a la atmósfera (emanación total), con el objetivo de cuantificar la posible fuga. Existen un amplio rango de metodologías para realizar dicha estimación, siendo necesario entender cuáles son las más apropiadas para obtener el valor más representativo del sistema. En esta tesis se comparan seis técnicas estadísticas: media aritmética, estimador insegado de la media (aplicando la función de Sichel), remuestreo con reemplazamiento (bootstrap), separación en diferentes poblaciones mediante métodos gráficos y métodos basados en criterios de máxima verosimilitud, y la simulación Gaussiana secuencial. Para este análisis se realizaron ocho campañas de muestreo, tanto en la Planta de Desarrollo Tecnológico de Hontomón como en análogos naturales (italianos y españoles). Los resultados muestran que la simulación Gaussiana secuencial suele ser el método más preciso para realizar el cálculo, sin embargo, existen ocasiones donde otros métodos son más apropiados. Como consecuencia, se desarrolla un procedimiento de actuación para seleccionar el método que proporcione el mejor estimador. Este procedimiento consiste, en primer lugar, en realizar un análisis variográfico. Si existe una autocorrelación entre los datos, modelizada mediante el variograma, la mejor técnica para calcular la emanación total y su intervalo de confianza es la simulación Gaussiana secuencial (sGs). Si los datos son independientes se debe comprobar la distribución muestral, aplicando la media aritmética o el estimador insesgado de la media (Sichel) para datos normales o lognormales respectivamente. Cuando los datos no son normales o corresponden a una mezcla de poblaciones la mejor técnica de estimación es la de remuestreo con reemplazamiento (bootstrap). Siguiendo este procedimiento el máximo valor del intervalo de confianza estuvo en el orden del ±20/25%, con la mayoría de valores comprendidos entre ±3,5% y ±8%. La identificación de las diferentes poblaciones muestrales en los datos de flujo de CO2 puede ayudar a interpretar los resultados obtenidos, toda vez que esta distribución se ve afectada por la presencia de varios procesos geoquímicos como, por ejemplo, una fuente geológica o biológica del CO2. Así pues, este análisis puede ser una herramienta útil en el programa de monitorización, donde el principal objetivo es demostrar que no hay fugas desde el reservorio a la atmósfera y, si ocurren, detectarlas y cuantificarlas. Los resultados obtenidos muestran que el mejor proceso para realizar la separación de poblaciones está basado en criterios de máxima verosimilitud. Los procedimientos gráficos, aunque existen pautas para realizarlos, tienen un cierto grado de subjetividad en la interpretación de manera que los resultados son menos reproducibles. Durante el desarrollo de la tesis se analizó, en análogos naturales, la relación existente entre el CO2 y los isótopos del radón (222Rn y 220Rn), detectándose en todas las zonas de emisión de CO2 una relación positiva entre los valores de concentración de 222Rn en aire del suelo y el flujo de CO2. Comparando la concentración de 220Rn con el flujo de CO2 la relación no es tan clara, mientras que en algunos casos aumenta en otros se detecta una disminución, hecho que parece estar relacionado con la profundidad de origen del radón. Estos resultados confirmarían la posible aplicación de los isótopos del radón como trazadores del origen de los gases y su aplicación en la detección de fugas. Con respecto a la determinación de la línea base de flujo CO2 en la PDT de Hontomín, se realizaron mediciones con la cámara de acúmulo en las proximidades de los sondeos petrolíferos, perforados en los ochenta y denominados H-1, H-2, H-3 y H-4, en la zona donde se instalarán el sondeo de inyección (H-I) y el de monitorización (H-A) y en las proximidades de la falla sur. Desde noviembre de 2009 a abril de 2011 se realizaron siete campañas de muestreo, adquiriéndose más de 4.000 registros de flujo de CO2 con los que se determinó la línea base y su variación estacional. Los valores obtenidos fueron bajos (valores medios entre 5 y 13 g•m-2•d-1), detectándose pocos valores anómalos, principalmente en las proximidades del sondeo H-2. Sin embargo, estos valores no se pudieron asociar a una fuente profunda del CO2 y seguramente estuvieran más relacionados con procesos biológicos, como la respiración del suelo. No se detectaron valores anómalos cerca del sistema de fracturación (falla Ubierna), toda vez que en esta zona los valores de flujo son tan bajos como en el resto de puntos de muestreo. En este sentido, los valores de flujo de CO2 aparentemente están controlados por la actividad biológica, corroborado al obtenerse los menores valores durante los meses de otoño-invierno e ir aumentando en los periodos cálidos. Se calcularon dos grupos de valores de referencia, el primer grupo (UCL50) es 5 g•m-2•d-1 en las zonas no aradas en los meses de otoño-invierno y 3,5 y 12 g•m-2•d-1 en primavera-verano para zonas aradas y no aradas, respectivamente. El segundo grupo (UCL99) corresponde a 26 g•m-2•d- 1 durante los meses de otoño-invierno en las zonas no aradas y 34 y 42 g•m-2•d-1 para los meses de primavera-verano en zonas aradas y no aradas, respectivamente. Flujos mayores a estos valores de referencia podrían ser indicativos de una posible fuga durante la inyección y posterior a la misma. Los primeros datos geoquímicos e isotópicos de las aguas superficiales (de escorrentía y de manantiales) en el área de Hontomín–Huermeces fueron analizados. Los datos sugieren que las aguas estudiadas están relacionadas con aguas meteóricas con un circuito hidrogeológico superficial, caracterizadas por valores de TDS relativamente bajos (menor a 800 mg/L) y una fácie hidrogeoquímica de Ca2+(Mg2+)-HCO3 −. Algunas aguas de manantiales se caracterizan por concentraciones elevadas de NO3 − (concentraciones de hasta 123 mg/l), lo que sugiere una contaminación antropogénica. Se obtuvieron concentraciones anómalas de of Cl−, SO4 2−, As, B y Ba en dos manantiales cercanos a los sondeos petrolíferos y en el rio Ubierna, estos componentes son probablemente indicadores de una posible mezcla entre los acuíferos profundos y superficiales. El estudio de los gases disueltos en las aguas también evidencia el circuito superficial de las aguas. Estando, por lo general, dominado por la componente atmosférica (N2, O2 y Ar). Sin embargo, en algunos casos el gas predominante fue el CO2 (con concentraciones que llegan al 63% v/v), aunque los valores isotópicos del carbono (<-17,7 ‰) muestran que lo más probable es que esté relacionado con un origen biológico. Los datos geoquímicos e isotópicos de las aguas superficiales obtenidos en la zona de Hontomín se pueden considerar como el valor de fondo con el que comparar durante la fase operacional, la clausura y posterior a la clausura. En este sentido, la composición de los elementos mayoritarios y traza, la composición isotópica del carbono del CO2 disuelto y del TDIC (Carbono inorgánico disuelto) y algunos elementos traza se pueden considerar como parámetros adecuados para detectar la migración del CO2 a los ambientes superficiales. ABSTRACT Since 2009, a group made up of Universidad Politécnica de Madrid (UPM; Spain) and Università degli Studi Firenze (UniFi; Italy) has been taking part in a joint project called “Strategies for Monitoring CO2 and other Gases in Natural analogues”. The group was coordinated by AMPHOS XXI, a private company established in Barcelona. The Project was financially supported by Fundación Ciudad de la Energía (CIUDEN; Spain) as a part of the EC-funded OXYCFB300 project (European Energy Program for Recovery -EEPR-; www.compostillaproject.eu). The main objectives of the project were aimed to develop and optimize analytical methodologies to be applied at the surface to Monitor and Verify the feasibility of geologically stored carbon dioxide. These techniques were oriented to detect and quantify possible CO2 leakages to the atmosphere. Several investigations were made in natural analogues from Spain and Italy and in the Tecnchnological Development Plant for CO2 injection al Hontomín (Burgos, Spain). The studying techniques were mainly focused on the measurements of diffuse soil gases and surface and shallow waters. The soil-gas measurements included the determination of CO2 flux and the application to natural trace gases (e.g. radon) that may help to detect any CO2 leakage. As far as the water chemistry is concerned, geochemical and isotopic data related to surface and spring waters and dissolved gases in the area of the PDT of Hontomín were analyzed to determine the most suitable parameters to trace the migration of the injected CO2 into the near-surface environments. The accumulation chamber method was used to measure the diffuse emission of CO2 at the soil-atmosphere interface. Although this technique has widely been applied in different scientific areas, it was considered of the utmost importance to adapt the optimum methodology for measuring the CO2 soil flux and estimating the total CO2 output to the specific features of the site where CO2 is to be stored shortly. During the pre-injection phase CO2 fluxes are expected to be relatively low where in the intra- and post-injection phases, if leakages are to be occurring, small variation in CO2 flux might be detected when the CO2 “noise” is overcoming the biological activity of the soil (soil respiration). CO2 flux measurements by the accumulation chamber method could be performed without vegetation clearance or after vegetation clearance. However, the results obtained after clearance show less dispersion and this suggests that this procedure appears to be more suitable for monitoring CO2 Storage sites. The measurement protocol, applied for the determination of the CO2 flux baseline at Hontomín, has included the following steps: a) cleaning and removal of both the vegetal cover and top 2 cm of soil, b) waiting to reduce flux perturbation due to the soil removal and c) measuring the CO2 flux. Once completing the CO2 flux measurements and detected whether there were anomalies zones, the total CO2 output was estimated to quantify the amount of CO2 released to the atmosphere in each of the studied areas. There is a wide range of methodologies for the estimation of the CO2 output, which were applied to understand which one was the most representative. In this study six statistical methods are presented: arithmetic mean, minimum variances unbiased estimator, bootstrap resample, partitioning of data into different populations with a graphical and a maximum likelihood procedures, and sequential Gaussian simulation. Eight campaigns were carried out in the Hontomín CO2 Storage Technology Development Plant and in natural CO2 analogues. The results show that sequential Gaussian simulation is the most accurate method to estimate the total CO2 output and the confidential interval. Nevertheless, a variety of statistic methods were also used. As a consequence, an application procedure for selecting the most realistic method was developed. The first step to estimate the total emanation rate was the variogram analysis. If the relation among the data can be explained with the variogram, the best technique to calculate the total CO2 output and its confidence interval is the sequential Gaussian simulation method (sGs). If the data are independent, their distribution is to be analyzed. For normal and log-normal distribution the proper methods are the arithmetic mean and minimum variances unbiased estimator, respectively. If the data are not normal (log-normal) or are a mixture of different populations the best approach is the bootstrap resampling. According to these steps, the maximum confidence interval was about ±20/25%, with most of values between ±3.5% and ±8%. Partitioning of CO2 flux data into different populations may help to interpret the data as their distribution can be affected by different geochemical processes, e.g. geological or biological sources of CO2. Consequently, it may be an important tool in a monitoring CCS program, where the main goal is to demonstrate that there are not leakages from the reservoir to the atmosphere and, if occurring, to be able to detect and quantify it. Results show that the partitioning of populations is better performed by maximum likelihood criteria, since graphical procedures have a degree of subjectivity in the interpretation and results may not be reproducible. The relationship between CO2 flux and radon isotopes (222Rn and 220Rn) was studied in natural analogues. In all emissions zones, a positive relation between 222Rn and CO2 was observed. However, the relationship between activity of 220Rn and CO2 flux is not clear. In some cases the 220Rn activity indeed increased with the CO2 flux in other measurements a decrease was recognized. We can speculate that this effect was possibly related to the route (deep or shallow) of the radon source. These results may confirm the possible use of the radon isotopes as tracers for the gas origin and their application in the detection of leakages. With respect to the CO2 flux baseline at the TDP of Hontomín, soil flux measurements in the vicinity of oil boreholes, drilled in the eighties and named H-1 to H-4, and injection and monitoring wells were performed using an accumulation chamber. Seven surveys were carried out from November 2009 to summer 2011. More than 4,000 measurements were used to determine the baseline flux of CO2 and its seasonal variations. The measured values were relatively low (from 5 to 13 g•m-2•day-1) and few outliers were identified, mainly located close to the H-2 oil well. Nevertheless, these values cannot be associated to a deep source of CO2, being more likely related to biological processes, i.e. soil respiration. No anomalies were recognized close to the deep fault system (Ubierna Fault) detected by geophysical investigations. There, the CO2 flux is indeed as low as other measurement stations. CO2 fluxes appear to be controlled by the biological activity since the lowest values were recorded during autumn-winter seasons and they tend to increase in warm periods. Two reference CO2 flux values (UCL50 of 5 g•m-2•d-1 for non-ploughed areas in autumn-winter seasons and 3.5 and 12 g•m-2•d-1 for in ploughed and non-ploughed areas, respectively, in spring-summer time, and UCL99 of 26 g•m-2•d-1 for autumn-winter in not-ploughed areas and 34 and 42 g•m-2•d-1 for spring-summer in ploughed and not-ploughed areas, respectively, were calculated. Fluxes higher than these reference values could be indicative of possible leakage during the operational and post-closure stages of the storage project. The first geochemical and isotopic data related to surface and spring waters and dissolved gases in the area of Hontomín–Huermeces (Burgos, Spain) are presented and discussed. The chemical and features of the spring waters suggest that they are related to a shallow hydrogeological system as the concentration of the Total Dissolved Solids approaches 800 mg/L with a Ca2+(Mg2+)-HCO3 − composition, similar to that of the surface waters. Some spring waters are characterized by relatively high concentrations of NO3 − (up to 123 mg/L), unequivocally suggesting an anthropogenic source. Anomalous concentrations of Cl−, SO4 2−, As, B and Ba were measured in two springs, discharging a few hundred meters from the oil wells, and in the Rio Ubierna. These contents are possibly indicative of mixing processes between deep and shallow aquifers. The chemistry of the dissolved gases also evidences the shallow circuits of the Hontomín– Huermeces, mainly characterized by an atmospheric source as highlighted by the contents of N2, O2, Ar and their relative ratios. Nevertheless, significant concentrations (up to 63% by vol.) of isotopically negative CO2 (<−17.7‰ V-PDB) were found in some water samples, likely related to a biogenic source. The geochemical and isotopic data of the surface and spring waters in the surroundings of Hontomín can be considered as background values when intra- and post-injection monitoring programs will be carried out. In this respect, main and minor solutes, the isotopic carbon of dissolved CO2 and TDIC (Total Dissolved Inorganic Carbon) and selected trace elements can be considered as useful parameters to trace the migration of the injected CO2 into near-surface environments.

Cu-NirK from Haloferax mediterranei as an example of metalloprotein maturation and exportation via Tat system

The green Cu-NirK from Haloferax mediterranei (Cu-NirK) has been expressed, refolded and retrieved as a trimeric enzyme using an expression method developed for halophilic Archaea. This method utilizes Haloferax volcanii as a halophilic host and an expression vector with a constitutive and strong promoter. The enzymatic activity of recombinant Cu-NirK was detected in both cellular fractions (cytoplasmic fraction and membranes) and in the culture media. The characterization of the enzyme isolated from the cytoplasmic fraction as well as the culture media revealed important differences in the primary structure of both forms indicating that Hfx. mediterranei could carry out a maturation and exportation process within the cell before the protein is exported to the S-layer. Several conserved signals found in Cu-NirK from Hfx. mediterranei sequence indicate that these processes are closely related to the Tat system. Furthermore, the N-terminal sequence of the two Cu-NirK subunits constituting different isoforms revealed that translation of this protein could begin at two different points, identifying two possible start codons. The hypothesis proposed in this work for halophilic Cu-NirK processing and exportation via the Tat system represents the first approximation of this mechanism in the Halobacteriaceae family and in Prokarya in general.

Exploring Multi-Component Superconducting Compounds by a High-Pressure Method and Ceramic Combinatorial Chemistry

In this short review, we provide some new insights into the material synthesis and characterization of modern multi-component superconducting oxides. Two different approaches such as the high-pressure, high-temperature method and ceramic combinatorial chemistry will be reported with application to several typical examples. First, we highlight the key role of the extreme conditions in the growth of Fe-based superconductors, where a careful control of the composition-structure relation is vital for understanding the microscopic physics. The availability of high-quality LnFeAsO (Ln = lanthanide) single crystals with substitution of O by F, Sm by Th, Fe by Co, and As by P allowed us to measure intrinsic and anisotropic superconducting properties such as Hc2, Jc. Furthermore, we demonstrate that combinatorial ceramic chemistry is an efficient way to search for new superconducting compounds. A single-sample synthesis concept based on multi-element ceramic mixtures can produce a variety of local products. Such a system needs local probe analyses and separation techniques to identify compounds of interest. We present the results obtained from random mixtures of Ca, Sr, Ba, La, Zr, Pb, Tl, Y, Bi, and Cu oxides reacted at different conditions. By adding Zr but removing Tl, Y, and Bi, the bulk state superconductivity got enhanced up to about 122 K.