(Table 1) List of samples with carbonate mineralogy, stable isotope, and accessory-mineral information

Petrographic and stable-isotope (d13C, d18O) patterns of carbonates from the Logatchev Hydrothermal Field (LHF), the Gakkel Ridge (GR), and a Late Devonian outcrop from the Frankenwald (Germany) were compared in an attempt to understand the genesis of carbonate minerals in marine volcanic rocks. Specifically, were the carbonate samples from modern sea floor settings and the Devonian analog of hydrothermal origin, low-temperature abiogenic origin (as inferred for aragonite in serpentinites from elsewhere on the Mid-Atlantic Ridge), or biogenic origin? Aragonite is the most abundant carbonate mineral in serpentinites from the two modern spreading ridges and occurs within massive sulfides of the LHF. The precipitation and preservation of aragonite suggests high Mg2+ and sulfate concentrations in fluids. Values of d18OPDB as high as +5.3 per mill for serpentinite-hosted aragonite and as high as +4.2 per mill for sulfide-hosted aragonite are consistent with precipitation from cold seawater. Most of the corresponding d13C values indicate a marine carbon source, whereas d13C values for sulfide-hosted aragonite as high as +3.6 per mill may reflect residual carbon dioxide in the zone of methanogenesis. Calcite veins from the LHF, by contrast, have low d18OPDB (-20.0 per mill to -16.1 per mill) and d13C values (-5.8 per mill to -4.5 per mill), indicative of precipitation from hydrothermal solutions (~129°-186°C) dominated by magmatic CO2. Calcite formation was probably favored by fluid rock interactions at elevated temperatures, which tend to remove solutes that inhibit calcite precipitation in seawater (Mg2+ and sulfate). Devonian Frankenwald calcites show low d18O values, reflecting diagenetic and metamorphic overprinting. Values of d13C around 0 per mill for basalt-hosted calcite indicate seawater-derived inorganic carbon, whereas d13C values for serpentinite-hosted calcite agree with mantle-derived CO2 (for values as low as -6 per mill) with a contribution of amagmatic carbon (for values as low as -8.6 per mill), presumably methane. Secondary mineral phases from the LHF for which a biogenic origin appears feasible include dolomite dumbbells, clotted carbonate, and a network of iron- and silica-rich filaments.

Extensive boiling as a precipitation mechanism for precious and base metal ores, Bienaventurada Mine, Huancavelica, Perú

The Bienaventurada mine operates a polymetallic Ag-Pb-Zn (Cu, Au) vein system of the low sulphidation epithermal type. Fluid inclusions, FI, are abundant in quartz, sphalerite and adularia. FI petrography demonstrates typical primary growth zoning which occurs frequently in crystalline quartz, and defines the most common primary FI. These are usually very small, but several types of primary, P, and secondary, S, FI Assemblages (FIAs) comprising FI of measurable size (3 to > 100 μm) can also be identified through careful petrographic work. The fluids are aqueous and undersaturated, and no evidence of CO2 was found; the degree of fill is usually high (~70-80 %) in the L-rich inclusions, but extremely low in V-rich inclusions. The measured microthermometric values are very consistent in the FIAs selected; they are for the most part roughly similar in the P and S assemblages: the median is typically ~258ºC for total homogenization temperatures, Th, and -1.5 ºC for ice melting temperatures, Tm (corresponding to 2.57 wt% NaCl eq). The widespread occurrence of L-rich and V-rich FI in the same FIA and the consistent Th values point to an extensive boiling system along the vein. In these conditions, Th equals T of trapping, and the ores are assumed to have been precipitated from an aqueous low salinity boiling fluid, of likely meteoric origin, at some 250-280º C, under ~500 m hydrostatic head.

Estudio de la reactividad álcali-sílice originada por componentes reactivos minoritarios

El objetivo de la presente tesis se enmarca dentro del estudio del estado de hormigones de presas, desarrollado en los últimos años en el Laboratorio Central del CEDEX, en el que se ratifica que una de las causas más importantes del deterioro de obras hidráulicas en España es la reacción álcali-sílice. La tesis que se presenta pretende contribuir al mejor conocimiento de la reacción álcali sílice con fines normativos preventivos, abordando los aspectos relativos a la identificación de áridos reactivos en el hormigón. El conocimiento de los áridos reactivos en España (origen de la reactividad, tipos de reacción y su comportamiento, así como las herramientas disponibles para su detección) es imprescindible para evitar la futura aparición de esta patología en nuevas estructuras, ya sea evitando el uso de áridos reactivos o tomando las medidas preventivas necesarias si su utilización es inevitable. A partir del Estudio Bibliográfico realizado se han detectado diversas lagunas en la identificación y caracterización de áridos de reacción rápida, cuya característica principal es que son reactivos con concentraciones muy bajas de diferentes componentes reactivos. Para resolver las lagunas identificadas se ha planeado un estudio experimental, consistente en el análisis de áridos cuya reactividad es conocida porque han sido empleados en obras afectadas por la reacción álcali sílice. Sobre el árido grueso extraído de estas estructuras se han realizado una serie de ensayos normalizados (estudio petrográfico, ensayo acelerado de probetas de mortero, ensayo Gel Pat y ensayos químicos). El análisis de los resultados experimentales ha permitido conocer las limitaciones reales en áridos reactivos españoles de las diferentes técnicas existentes, tratando de minimizarlas para áridos cuya reactividad es debida a componentes minoritarios (áridos de reacción rápida). Además, se ha evaluado la utilización de la difracción de rayos X (no normalizada) y la creación de un nuevo ensayo (Gel Pat Modificado). Finalmente, el estudio experimental ha permitido fijar una metodología de ensayo para el estudio de áridos reactivos por su contenido en componentes minoritarios (áridos de reacción rápida). The objective of this Thesis fits into the research program developed in CEDEX the last years and focused on the durability of concrete in Dams. This research work confirms that one of the main problems related to the deterioration of hydraulic structures is the alkali silica reaction. This Thesis aims to contribute to a better understanding of alkali-silica reaction, for preventive regulation purposes, considering the aspects related to the identification of reactive aggregates. The knowledge of Spanish reactive aggregates (origin of the reactivity, types of reaction and their behavior, and the tools available to detect and describe them) is essential to avoid the appearance of this pathology in new structures, either not using the reactive aggregate or taking the necessary preventive measures available in bibliography if the use of the reactive aggregate is inevitable. From the State-of –the-Art developed, several gaps have been detected in the detection and description of rapid reactive aggregates, which main characteristic if that they are reactive with low content of some reactive components. An experimental programme has been designed to solve these gaps, consisting on studying the reactivity of aggregates used in Spanish structures affected by the alkali silica reaction. Several Standard Tests have been carried out on coarse aggregates removed from the affected structures (Petrographic description, Accelerated Mortar Bar Test, Gel Pat Test and Chemical Tests). The analysis of the results obtained in Spanish reactive aggregates allows to know the advantages and limitations of each test, trying to minimize the disadvantages to detect Spanish reactive aggregates because of the minority content of rapid reactive components (rapid reactive aggregates). Moreover, X ray diffraction (not standardized) has been tested to detect rapid reactive aggregates and also a new test has been developed for the same purpose (Optimized Gel Pat Test). Finally, the experimental programme has made possible to define a methodology for detection of Spanish rapid reactive aggregates.

Ferromanganese nodules and micro-hardgrounds associated with the Cadiz Contourite Channel (NE Atlantic): Palaeoenvironmental records of fluid venting and bottom currents

Ferromanganese nodule fields and hardgrounds have recently been discovered in the Cadiz Contourite Channel in the Gulf of Cadiz (850–1000 m). This channel is part of a large contourite depositional system generated by the Mediterranean Outflow Water. Ferromanganese deposits linked to contourites are interesting tools for palaeoenviromental studies and show an increasing economic interest as potential mineral resources for base and strategic metals. We present a complete characterisation of these deposits based on submarine photographs and geophysical, petrographic, mineralogical and geochemical data. The genesis and growth of ferromanganese deposits, strongly enriched in Fe vs. Mn (av. 39% vs. 6%) in this contourite depositional system result from the combination of hydrogenetic and diagenetic processes. The interaction of the Mediterranean Outflow Water with the continental margin has led to the formation of Late Pleistocene–Holocene ferromanganese mineral deposits, in parallel to the evolution of the contourite depositional system triggered by climatic and tectonic events. The diagenetic growth was fuelled by the anaerobic oxidation of thermogenic hydrocarbons (δ13CPDB=−20 to −37‰) and organic matter within the channel floor sediments, promoting the formation of Fe–Mn carbonate nodules. High 87Sr/86Sr isotopic values (up to 0.70993±0.00025) observed in the inner parts of nodules are related to the influence of radiogenic fluids fuelled by deep-seated fluid venting across the fault systems in the diapirs below the Cadiz Contourite Channel. Erosive action of the Mediterranean Outflow Water undercurrent could have exhumed the Fe–Mn carbonate nodules, especially in the glacial periods, when the lower core of the undercurrent was more active in the study area. The growth rate determined by 230Thexcess/232Th was 113±11 mm/Ma, supporting the hypothesis that the growth of the nodules records palaeoenvironmental changes during the last 70 ka. Ca-rich layers in the nodules could point to the interaction between the Mediterranean Outflow Water and the North Atlantic Deep Water during the Heinrich events. Siderite–rhodochrosite nodules exposed to the oxidising seabottom waters were replaced by Fe–Mn oxyhydroxides. Slow hydrogenetic growth of goethite from the seawaters is observed in the outermost parts of the exhumed nodules and hardgrounds, which show imprints of the Mediterranean Outflow Water with low 87Sr/86Sr isotopic values (down to 0.70693±0.00081). We propose a new genetic and evolutionary model for ferromanganese oxide nodules derived from ferromanganese carbonate nodules formed on continental margins above the carbonate compensation depth and dominated by hydrocarbon seepage structures and strong erosive action of bottom currents. We also compare and discuss the generation of ferromanganese deposits in the Cadiz Contourite Channel with that in other locations and suggest that our model can be applied to ferromanganiferous deposits in other contouritic systems affected by fluid venting.