Petrophysical properties, composition and deterioration of the Calatorao biogenic stone: case of the sculptures masonry of the Valley of the Fallen (Madrid, Spain)

The huge sculptures placed outdoors in the Valley of the Fallen Memorial Park (El Escorial, Madrid) made with blocks of Black-Limestone from Calatorao-Zaragoza, Spain (BLCZ) and disposed on a concrete core exhibit weathering traces, flaking, saline efflorescence and falling fragments, currently represent a danger for visitors. Frost action is important in the Valley of the Fallen by the large number of freeze–thaw cycles produced during Sculptures‘live under a temperate Mediterranean climate with severe seasonality. The formation of fissures facilitates the water transport within the rock and the salt- and ice-induced deterioration. Temperate climates with frequent freezing and thawing cycles can be the most effective drivers of the visible physical weathering. In order to propose a suitable weathering model, collected black-limestones from sculptures and Calatorao quarries were analyzed by optical microscopy, environmental scanning electron microscopy with energy dispersive spectrometry (ESEM-EDS), inductively coupled mass spectrometry (ICP-MS) and X-ray diffraction. Mercury intrusion porosimetry (MIP), nitrogen absorption and helium pycnometry techniques were used for pore analyses of the BLCZ micro-blocks (10 × 10 × 10 cm) described in terms of pore size distribution, pore volume and specific surface area. The appreciable amount of organic matter was isolated by solvent extraction, acid treatment, flotation and perborate degradation followed by Gas Chromatography–Mass Spectrometry (GC–MS), Analytical Pyrolysis (Py-GC/MS), Fourier Transformed Infrared Spectroscopy and Raman techniques. Both weathered and fresh BLCZ samples contained more than 90 % calcite shells with circa 10 % of pyrite (fresh samples) or iron hydroxides (weathered samples), quartz grains, claystone and fossil organic matter consisting of a condensed matrix with polyalkyl chains and polycyclic methoxyl-lacking aromatic structures. The petrophysical analyses revealed volumes of pores, sized <0.025 μm obtained by N₂ adsorption, of 3.18 × 10^?3 cm³ g^?1 while the measured porosity by MIP in the pore range from 0.005 to 200 μm was 3.30 × 10^?3 cm³ g^?1. These data could be explained by the existence of clay minerals and organic matter in the pore system less than 50 nm of diameter. Concerning BLCZ deterioration it was found that the porous framework of BLCZ was filled with sulphates formed from artificial cement observed in the sculptures inside trough a testing hole and from its intrinsic pyrite. The results suggested that although biological processes were not major agents in rock deterioration, there was also weak compatibility between sculptures‘constituents, (limestone, concrete and oxidized iron clamps) which under, continental Mediterranean conditions, were continuously releasing weathering compounds accelerating disruption of the cut-stone sculptures.     

ENSO as a natural experiment to understand environmental control of meiofaunal community structure

The sediments of the Bay of Concepción and the adjacent shelf underlie one of the most productive upwelling areas in the SE Pacific margin. Reports on factors controlling meiofaunal community structure in these kinds of organic‐rich and oxygen‐deficient habitats are scarce in the literature. In this study, five sites along a transect from the mid‐Bay of Concepción (27 m) to the outer shelf (120 m) were studied on fives dates (May, August, November 1997, and March and May 1998) in order to assess the dynamic relationships between sedimentary organic matter and metazoan meiofauna. The sampling period coincided with the 1997–1998 El Niño event. Sediment parameters investigated were the redox potential discontinuity depth, photosynthetic pigment concentrations (chlorophyll a and phaeopigments), organic carbon, nitrogen, total lipids, carbohydrates, and proteins. In general, lowest values of meiofauna abundance and biomass were found within the naturally eutrophic Bay of Concepción and towards the shelf break, while maximum values occurred at intermediate depths. During the whole period, the meiofaunal abundance was negatively correlated with the concentration of most of the biochemical components of organic matter, as well as with the sediment phaeopigment content. However, positive correlations were found with chlorophyll a derived indices and with bottom‐water oxygen content. Most of the sediment parameters displayed a seasonal cycle, but towards the beginning of 1998, an effect of the 1997–1998 El Niño was evident. Typical austral‐summer (i.e. oxygen‐deficient) conditions did not develop, and sedimentary parameters reflected a decreased input of phytodetritus. Along the transect, the magnitude of this effect on meiofauna varied among sites. An overall positive response, in terms of meiofaunal abundance was observed, probably due to the amelioration of low oxygen conditions in the sediment.     

Deposition of talc — kerolite–smectite — smectite at seafloor hydrothermal vent fields: Evidence from mineralogical,geochemical and oxygen isotope studies

Talc, kerolite–smectite, smectite, chlorite–smectite and chlorite samples from sediments, chimneys and massive sulfides from six seafloor hydrothermal areas have been analyzed for mineralogy, chemistry and oxygen isotopes. Samples are from both peridotite- and basalt-hosted hydrothermal systems, and basaltic systems include sediment-free and sediment-covered sites. Mg-phyllosilicates at seafloor hydrothermal sites have previously been described as talc, stevensite or saponite. In contrast, new data show tri-octahedral Mg-phyllosilicates ranging from pure talc and Fe-rich talc, through kerolite-rich kerolite–smectite to smectite-rich kerolite–smectite and tri-octahedral smectite. The most common occurrence is mixed-layer kerolite–smectite, which shows an almost complete interstratification series with 5 to 85% smectitic layers. The smectite interstratified with kerolite is mostly tri-octahedral. The degree of crystal perfection of the clay sequence decreases generally from talc to kerolite–smectite with lower crystalline perfection as the proportion of smectite layers in kerolite–smectite increases.Our studies do not support any dependence of the precipitated minerals on the type/subtype of hydrothermal system. Oxygen isotope geothermometry demonstrates that talc and kerolite–smectite precipitated in chimneys, massive sulfide mounds, at the sediment surface and in open cracks in the sediment near seafloor are high-temperature (> 250 °C) phases that are most probably the result of focused fluid discharge. The other end-member of this tri-octahedral Mg-phyllosilicate sequence, smectite, is a moderate-temperature (200–250 °C) phase forming deep within the sediment (～ 0.8 m). Chlorite and chlorite–smectite, which constitute the alteration sediment matrix around the hydrothermal mounds, are lower-temperature (150–200 °C) phases produced by diffuse fluid discharge through the sediment around the hydrothermal conduits. In addition to temperature, other two controls on the precipitation of this sequence are the silica activity and Mg/Al ratio (i.e. the degree of mixing of seawater with hydrothermal fluid). Higher silica activity favors the formation of talc relative to tri-octahedral smectite. Vent structures and sedimentary cover preclude complete mixing of hydrothermal fluid and ambient seawater, resulting in lower Mg/Al ratios in the interior parts of the chimneys and deeper in the sediment which leads to the precipitation of phyllosilicates with lower Mg contents. Talc and kerolite–smectite have very low trace- and rare earth element contents. Some exhibit a negative or flat Eu anomaly, which suggests Eu depletion in the original hydrothermal fluid. Such Eu depletion could be caused by precipitation of anhydrite or barite (sinks for Eu²⁺) deeper in the system. REE abundances and distribution patterns indicate that chlorite and chlorite–smectite are hydrothermal alteration products of the background turbiditic sediment.     

A parallel laboratory for simulation and visualization of seismic wavefields

The use of parallel computers makes simulation of elastic waves feasible throughout large structures by means of recent advances in domain decomposition methods. We introduce a competitive parallel algorithm for the propagation of elastic waves in complex heterogeneous media using finite-element discretization. This parallel method, called the multiblock method , performs more efficiently than classical domain decomposition techniques based on substructuration, such as the Schur complement technique. It reduces considerably the amount of communication amongst processors because the interface problem between subdomains is solved by taking advantage of Huygens' principle for wave propagation. We provide some numerical examples and detailed studies on the efficiency and performance of the algorithm, proving that it is competitive and less costly, from the computational viewpoint, than algorithms based on the Schur technique.     

Seismic evaluation of concrete dams via continuum damage models

In this paper a general methodology for the analysis of large concrete dams subjected to seismic excitation is outlined. It is valid both for gravity dams (2D representation) and arch dams (3D representation). The method allows for non-linear material behaviour of the dam, ‘transparent fictitious boundaries’ for dealing properly with in-coming and out-going seismic waves, and an efficient procedure to deal with dam-soil-fluid interaction. The mechanical behaviour of concrete is modelled using an isotropic damage model which allows for tension and compression damage, and exhibits stiffness recovery upon load reversals. Emphasis is placed in the treatment of fluid-structure interaction, regarding both formulation and efficiency aspects. A gravity dam and an arch dam are analysed subjected to artificially generated earthquakes of different intensities, and the results are used to study the degree of (un)safety of the dams.