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.     

Radiation-induced defects in euclase: formation of O<Superscript>−</Superscript> hole and Ti<Superscript>3+</Superscript> electron centers

Irradiation techniques are often applied to gem minerals for color enhancement purposes. Natural green, blue and colorless specimens of rare gemological quality euclase, BeAlSiO₄(OH), from Brazil were irradiated with gamma rays in the dose range from 10 to 500 kGy. Although the colors of the different specimens were not strongly influenced, two different irradiation-induced paramagnetic defect centers were found by electron paramagnetic resonance (EPR). The first one is an O⁻ hole center interacting with one Al neighbor and the second is a Ti³⁺ electron center. The EPR angular rotation patterns of both irradiation-induced defects were measured and analyzed. The results suggest that O⁻ hole centers are formed by dissociation of the hydroxyl ions, similar as in topaz crystals. In euclase the OH⁻ ions interconnect distorted Al octahedra and Be tetrahedra in O₅ positions. During irradiation, the electrons are captured by titanium ions (Ti⁴⁺ + e⁻), leading to the formation of paramagnetic Ti³⁺ ions. From the EPR rotation patterns it is clear that these ions substitute for Al ions. The spin Hamiltonian parameters of the irradiation-induced defects are analyzed and compared to similar defect centers in other mineral specimens. Thermal annealing experiments show that the O⁻ hole centers and Ti³⁺ electron centers are directly connected through the radiation process.     

Mineral equilibrium constraints on the feasibility of diffusive H2O-fluxed melting in the continental crust

Generation of granitic melt is believed to occur predominantly by melting through the breakdown of hydrous minerals. However, melting due to the influx of H₂O has been recognized in anatectic amphibolite facies tonalitic grey gneisses, metagreywackes and low-P metapelites, and has consequently been proposed as an alternative mechanism for the generation of granitic melt. Melting induced by H₂O addition is recognized from voluminous melt production at relatively low temperature, where hydrous minerals are stable and anhydrous minerals are preferentially consumed during melting. Mineral equilibrium modelling to determine the P–T conditions, melt volumes, melting reactions and viable H₂O sources reveals that the process is not restricted to specific compositions or P–T conditions, although lower pressure and lithologies with a low hydrous mineral content are more favourable. Melting reactions in all lithologies primarily consume quartz and feldspars to yield 5–6 mol.% melt for each mol.% of H₂O added. remains constant at ~0.70 to 0.77 during progressive melting as long as alkali feldspar is present. Once alkali feldspar is exhausted, plagioclase becomes the main reactant, producing more tonalitic melt compositions with gradually higher . Our results demonstrate that, at the site of melting, melting is driven by diffusion of H₂O into the target rock along chemical potential gradients, rather than the advective flow of a mechanically distinct water-rich fluid phase. Melting will initiate and proceed as long as a gradient exists between the H₂O source and target lithology. Our calculations show that an ordinary magma, such as an I-type magma with typical H₂O content, has a high enough to be a viable H₂O source, allowing diffusive H₂O-fluxed melting to produce melt proportions and fertility comparable to that of dehydration melting. However, high degrees of partial melting require a considerable amount of H₂O, which necessitates a continuously advecting H₂O source such as a magma conduit or melt-bearing shear zone. A magmatic H₂O source at emplacement level will undergo a similar amount of crystallization as the melt fraction produced in the target rock such that there will be no net melt production. Considering that shear-zone hosted magma conduits are localized features, diffusive H₂O-fluxed melting is likely to only be viable in a small fraction of the anatectic orogenic crust. Although it may play an important role in locally raising melt volumes and modifying magma chemistry through mingling and hybridization, it does not appear to, of itself, be able to generate significant volumes of granitic melt.     

Intact ash and charred litter reduces susceptibility to rain splash erosion post‐wildfire

This paper describes the changes in soil water repellency and soil hydrological and erosional responses to rainfall at small‐plot scale, arising from a prescribed fire immediately following burning and one year later in a Mediterranean heathland in the area of the Strait of Gibraltar (southern Spain). Very little research has been carried out about the modifications on the ground surface after fire immediately after burning. A prescribed fire was conducted to study short‐term changes of the ground surface immediately and one year following burning. After a prescribed fire, a homogeneous charred litter layer and ash‐bed covered the mineral soil surface. This cover stayed stable on the soil surface during a period of seven days, until strong winds redistributed litter and ashes. The hydrophobicity of the exposed surface (litter and ashes) decreased considerably in relation with the litter layer properties before the fire. Ponding, runoff coefficients and soil loss were determined using simulated rainfall over the litter layer, the ash‐bed and the bare soil. Significant differences were not detected between pre‐ and post‐fire soil loss rates while a charred litter and thick ash layer were present on the ground surface. Runoff and erosion rates increased and time to ponding and runoff decreased when the charred litter and ash layers were artificially removed and the bare soil was exposed. Although wildfires will increase soil erodibility, the trends observed in this study suggest that this increased susceptibility to erosion from rainsplash processes may be limited to some degree while an intact ash and charred litter layer is still present. Copyright © 2009 John Wiley & Sons, Ltd.     

A nonhomogeneous Poisson process geostatistical model

This paper introduces a new geostatistical model for counting data under a space-time approach using nonhomogeneous Poisson processes, where the random intensity process has an additive formulation with two components: a Gaussian spatial component and a component accounting for the temporal effect. Inferences of interest for the proposed model are obtained under the Bayesian paradigm. To illustrate the usefulness of the proposed model, we first develop a simulation study to test the efficacy of the Markov Chain Monte Carlo (MCMC) method to generate samples for the joint posterior distribution of the model’s parameters. This study shows that the convergence of the MCMC algorithm used to simulate samples for the joint posterior distribution of interest is easily obtained for different scenarios. As a second illustration, the proposed model is applied to a real data set related to ozone air pollution collected in 22 monitoring stations in Mexico City in the 2010 year. The proposed geostatistical model has good performance in the data analysis, in terms of fit to the data and in the identification of the regions with the highest pollution levels, that is, the southwest, the central and the northwest regions of Mexico City.     

Late Holocene marine productivity changes in Northern Patagonia-Chile inferred from a multi-proxy analysis of Jacaf channel sediments

A multi-proxy approach based on organic (organic carbon, alkenones, and C/N) and inorganic geochemical proxies (biogenic opal, inorganic carbon, Fe, Ti, and Ca) preserved in the sediments of the Jacaf channel (CF7-PC33; 44°21′S, 72°58′W, 510 m water depth), Chilean fjords, yields evidence of major past productivity fluctuations in accordance with climatic changes over the last ∼1800 years. The downcore record clearly shows two productivity/climate modes. The first period, prior to 900 cal yr BP, is characterized by decreased marine productivity and a reduced continental signal, pointing to diminished precipitation and runoff. In contrast, the second period between ∼750 cal yr BP and the late 1800s (top of core) is illustrated by elevated productivity and an increased continental signal, suggesting higher precipitation and runoff. Both time intervals are separated by a relatively abrupt transition of ∼150 years which roughly coincides with the beginning of the Little Ice Age. The increased content of freshwater diatoms and Chrysophyte cysts that characterize the last 200 years of the latter mode coincides with a significant decrease in the carbonate content of the sediment; together they further indicate increased terrigenous contributions and decreased marine carbonate productivity at the end of the Little Ice Age. The correspondence between our record and other paleoclimate studies carried out in South America and Antarctica demonstrates that the Chilean fjord area of Northern Patagonia is not just sensitive to local climatic variability but also to regional and possibly global variability.     

Changes in ostracod assemblages and morphologies during lake‐level variations of Lago Cardiel (49°S), Patagonia,Argentina, over the last 15.6 ka

Changes in the ostracod assemblages from two sediment cores collected from Lago Cardiel in southeastern Patagonia (49°S) reflect the main regional abrupt climatic changes over the last 15.6 cal. ka BP. Shifts in species abundance and switches in dominances suggest that these were mainly driven by variable salinity. During the Late Pleistocene, Limnocythere rionegroensis was abundant and dominant, indicating waters with high salinity and prevalence of evaporative processes. Between 12.6 and 10.8 cal. ka BP, Lago Cardiel expanded markedly and reached an Early Holocene highstand of +55 m above present lake level. A major change in ostracod assemblage in which Limnocythere patagonica appears as the dominant species in parallel with the disappearance of L. rionegroensis and Eucypris aff. cecryphalium mirrored this transitional period between the cold and dry Late Pleistocene and the humid and warm Early Holocene. Over the last 4 cal. ka BP, L. rionegroensis returned to the species assemblage and Riocypris whatleyi increased its abundance pointing towards increasing salinities. The variations in size, shape and ornamentation of L. rionegroensis and R. whatleyi fossil valves were examined using geometric morphometric techniques and further compared to those of modern Patagonian sites. Limnocythere rionegroensis specimens displayed high morphological variability during the evolution of Lago Cardiel. More specifically, the switch in reproductive mode – from sexual to parthenogenetic– and the increase in valve ornamentation around 12.7 cal. ka BP suggest that these changes were promoted by the hydrological alteration that occurred in the Late Pleistocene. This exercise provides a robust range of morphological variation for these proxies, which will be useful in further taxonomic and palaeoenvironmental studies adding more information about different factors influencing the observed morphological trends.     

Paleohydrological Changes in Highland Desert Rivers and Human Occupation, 7000‐3000 Cal. Yr B.P., South‐Central Andes,Argentina

This article focuses on local paleohydrological changes experienced by the Las Pitas and Miriguaca Rivers in the south‐central Andes of Argentina and their impacts on hunter‐gatherers as they transitioned to food‐producing communities 7000–3000 cal. yr B.P. Paleoenvironmental reconstruction based on geomorphology, alluvial sedimentology, and diatom evidence indicates a dry phase of reduced streamflow between ca. 6700 and 4800 cal. yr B.P. for the Las Pitas River, and 6600 and 3000 cal. yr B.P. for the Miriguaca River. A phase of more humid environmental conditions commenced after ca. 4900 cal. yr B.P. along the Las Pitas River, and after 3000 cal. yr B.P. along the Miriguaca River. Differences in the chronology and magnitude of hydrological changes along both rivers are related to topographic and hydrological characteristics of their respective watersheds. Higher catchment elevation and enhanced orographic precipitation favored greater sensitivity for the Las Pitas River to short humid events during the middle‐to‐late Holocene. The archaeological evidence suggests that the paleohydrological changes within these catchments played a significant role in human occupational dynamics such that the Las Pitas River offered better environmental conditions for human occupation relative to the Miriguaca River as foragers increasingly relied on plant and animal domestication.     

Paleomagnetic and rock magnetic study of the Yaxcopoil‐1 impact breccia sequence,Chicxulub impact crater (Mexico)

Abstract— Results of a detailed paleomagnetic and rock magnetic study of samples of the impact breccia sequence cored in the Yaxcopoil‐1 (Yax‐1) borehole between about 800 m and 896 m are presented. The Yax‐1 breccia sequence occurs from 794.63 m to 894.94 m and consists of redeposited melt‐rich, clast‐size sorted, fine‐grained suevites; melt‐rich, no clast‐size sorting, medium‐grained suevites; coarse suevitic melt agglomerates; coarse melt‐rich heterogeneous suevites; brecciated suevites; and coarse carbonate and silicate melt suevites. The low‐field susceptibility ranges from ?0.3 to 4018 times 10^?6 SI, and the NRM intensity ranges from 0.02 mA/m up to 37510 mA/m. In general, the NRM intensity and magnetic susceptibility present wide ranges and are positively correlated, pointing to varying magnetic mineral contents and textures of the melt‐rich breccia sequence. The vectorial composition and magnetic stability of NRM were investigated by both stepwise alternating field and thermal demagnetization. In most cases, characteristic single component magnetizations are observed. Both upward and downward inclinations are present through the sequence, and we interpret the reverse magnetization as the primary component in the breccias. Both the clasts and matrix forming the breccia appear to have been subjected to a wide range of temperature/pressure conditions and show distinct rock magnetic properties. An extended interval of remanence acquisition and secondary partial or total remagnetization may explain the paleomagnetic results.