Analysis of stratigraphical sequences at Cocina Cave (Spain) using rare earth elements geochemistry

This study investigates the stratigraphical sequence of Cocina Cave (Spain) employing and testing for the first time the capability of rare earth elements as markers of human activities in caves. Located in Dos Aguas (Valencian Community, Spain), Cocina Cave is characterized by the presence of several Holocene archaeological deposits from the final Mesolithic to the present day and is a pivotal site for understanding the socio-ecological dynamics of the last hunter-gatherer inhabitants of the Iberian Peninsula and the transition to pastoral and agricultural economies in the Western Mediterranean. However, the identification of strata from particular time-periods in the cave is often difficult due to the homogeneity of layers, the poor archaeological record in some strata and the presence of severe disturbance phenomena. The methodological approach of this study consisted of cross-referencing rare earth elements and other chemical markers with the archaeological stratigraphical interpretation, in an attempt to not only support the identification of the anthropic contribution to the formation of Cocina Cave strata, but also to characterize and confirm different natural and occupational episodes, particularly those associated with hunter-gatherer, early agriculturalist, and shepherd activities. Sediments were collected from different excavation areas and analysed for major elements, trace elements, rare earth elements (REE), soil organic matter (SOM) amounts and pH. Multivariate statistics were employed to group samples according to their elemental profile, and these were then compared to the archaeological temporal interpretation. The obtained results showed that REE amount and fractionation geochemical processes were regulated by carbonates, phosphates and pH. The use of REE as markers was particularly useful as their concentrations and their calculated ratios and anomaly distributions were demonstrated to be highly consistent with the archaeological stratigraphical interpretation.     

Assessment of the acid drainage neutralization capacity and the toxic metals lixiviation of tailing from Guanajuato mining district,Mexico

In Mexico, many environmental problems are generated by large mining activities taking place in several mining districts. These mining activities produce great quantities of residues; large majorities of these have high sulfur content, which could generate acid drainage due to their interaction with the oxygen in the environment. The study area was located in the Mining District of Guanajuato, Mexico with abandoned tailings generated mainly by the gold and silver production. Two areas, called as Monte de San Nicolás (SN) and Peregrina (P) were selected for this study. The results study shows that there was no risk of production of acid drainage, since these tailings contained high amount of carbonates, which neutralized the generation of acidity and consequently decreased the possibility of leaching of some elements. However, not all elements leach in acid pH, as arsenic bound to oxyhydroxides, which is in a basic environment and its increased release by increasing the pH.     

Characterization of fluid inclusions from mineralized pegmatites of the Damara Belt,Namibia: insight into late-stage fluid evolution and implications for mineralization

Mineralogy and Petrology - Mineralized NYF and LCT pegmatites occur throughout the northeast-trending Neoproterozoic Damara Belt, Namibia. Mineralization in the pegmatites varies geographically,...     

Lanthanide sorption on smectitic clays in presence of cement leachates

Due to their potential retention capacity, clay minerals have been proposed for use in the engineered barriers for the storage of high-level radioactive actinides in deep geological waste repositories. However, there is still a lack of data on the sorption of actinides in clays in conditions simulating those of the repositories. The present article examines the sorption of two lanthanides (actinide analogues) in a set of smectitic clays (FEBEX bentonite, MX80 bentonite, hectorite, saponite, Otay montmorillonite, and Texas montmorillonite). Distribution coefficients (K_d) were determined in two media: water and 0.02 mol L⁻¹ Ca, the latter representing the cement leachates that may modify the chemical composition of the water in contact with the clay. The K_d values of the lanthanides used in the experiments (La and Lu) varied greatly (25-50 000 L kg⁻¹) depending on the ionic medium (higher values in water than in the Ca medium), the initial lanthanide concentration (up to three orders of magnitude decrease inversely with lanthanide concentration), and the examined clay (up to one order of magnitude for the same lanthanide and sorption medium). Freundlich and Langmuir isotherms were used to fit sorption data to allow comparison of the sorption parameters among smectites. The model based on the two-site Langmuir isotherms provided the best fit of the sorption data, confirming the existence of sorption sites with different binding energies. The sites with higher sorption affinity were about 6% of the total sorption capacity in the water medium, and up to 17% in the Ca medium, although in this latter site sorption selectivity was lower. The wide range of K_d values obtained regarding the factors examined indicated that the retention properties of the clays should also be considered when selecting a suitable clay for engineered barriers.     

Ultrasonic Spectral and Complexity Measurements on Brine and Oil Saturated Rocks

The effects of the rheological properties of fluids on the acoustic behavior of heterogeneous media like rocks are usually very difficult to characterize. We show here that, in ultrasonic tests and their spectral characterizations, signal attenuation is the most evident difference between water and oil saturated rock samples. Density effects, as explained by the inertial component of the Biot’s poroelastic theory, along with entropic analysis seem to provide a good understanding of the pore-fluid effects on the acoustic response of saturated rocks.     

Detection and 2d modelling of cavities using pole–dipole array

The resistivity method is often used in cave prospecting. In this paper the pole–dipole array ability to detect cavities at different depths and with different water contents is investigated. The research was performed using analogical and numerical modelling. According to the results, empty caves at a depth less than four times its diameter can be easily detected. The ability of the pole–dipole array to detect water-filled caves reaches a minimum at filling percentages of 30–50%. Overburden effects research shows that low resistivity overburden reduces the resolution capability of the array. This study shows that equivalent results can be obtained by modelling the empty caves as infinite resistivity bodies or, alternatively, as very high resistivity ones. The analysis of field data acquired in the Maciço Calcário Estremenho (Portugal) shows the practical importance of the pole–dipole array in cavities prospecting.     

Natural Variability of Shear Strength in a Granite Residual Soil from Porto

The renewal imposed by the Eurocodes regarding the methodologies of safety evaluation requires a statistical analysis of the variability of ground geotechnical parameters. However, the studies published in the reviewed literature do not cover the typical materials from the northeast region of Portugal—residual soils from granite—to which a strong heterogeneity is associated. Hence, a statistical characterization of the natural variability of a granite residual soil from Porto has been made through a significant amount of experimental tests, focusing on its geomechanical properties. In order to provide a database for probabilistic analysis of problems involving this type of soils, an appropriate statistical law has been used to model its variability, which has been quantified by means of coefficients of variation and scales of fluctuation.     

Reconstructing the Cryogenian–Ediacaran evolution of the Porongos fold and thrust belt,Southern Brasiliano Orogen,based on Zircon U–Pb–Hf–O isotopes

The Neoproterozoic geotectonic triad of the Brasiliano Orogen is reconstructed in southern Brazil from studies focused on the Porongos fold and thrust belt. We integrate field geology with isotopic studies of zircon U–Pb SHRIMP and Lu–Hf–O laser determinations in seven metasedimentary and three metavolcanic rock samples. The results indicate that the Porongos palaeo-basin was derived from mixed sources (3200–550 Ma), with major contributions from Rhyacian (2170 Ma) and Ediacaran (608 Ma) sources. Minor contributions from Archaean to Tonian sources are also registered. The maximum depositional age of the Porongos palaeo-basin is established by the age range of 650–550 Ma with T_DM model ages between 2.5 and 1.3 Ga. The reworked signature (ε_Hf values = ?34 to ?4) and the characteristic crustal magma reservoirs (δ¹⁸O ≥5.3 ‰) indicate that these sediments are equivalent to Neoproterozoic granites of the Dom Feliciano Belt. The episodic depositional history started in the Cryogenian (650 Ma) and lasted until the Ediacaran (most likely 570 Ma). A magmatic event of Tonian age is recorded in rhyodacite samples interleaved with the metasedimentary rocks and dated at 773, 801, and 809 Ma. The crustal evolution of the Sul-Riograndense Shield included mountain building, folding and thrusting and flexural subsidence in the foreland. An orogenic triad is revealed as the Pelotas Batholith, the Porongos fold and thrust belt and the Camaquã Basin, all part of the Dom Feliciano Belt.     

A New Appraisal of Sri Lankan BB Zircon as a Reference Material for LA‐ICP‐MS U‐Pb Geochronology and Lu‐Hf Isotope Tracing

A potential zircon reference material (BB zircon) for laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) U‐Pb geochronology and Hf isotope geochemistry is described. A batch of twenty zircon megacrysts (0.5–1.5 cm³) from Sri Lanka was studied. Within‐grain rare earth element (REE) compositions are largely homogeneous, albeit with some variation seen between fractured and homogeneous domains. Excluding fractured cathodoluminescence bright domains, the variation in U content for all analysed crystals ranged from 227 to 368 μg g^?1 and the average Th/U ratios were between 0.20 and 0.47. The Hf isotope composition (0.56–0.84 g/100 g Hf) is homogeneous within and between the grains – mean ¹⁷⁶Hf/¹⁷⁷Hf of 0.281674 ± 0.000018 (2s). The calculated alpha dose of 0.59 × 10¹⁸ g^?1 for a number of BB grains falls within the trend of previously studied, untreated zircon samples from Sri Lanka. Aliquots of the same crystal (analysed by ID‐TIMS in four different laboratories) gave consistent U‐Pb ages with excellent measurement reproducibility (0.1–0.4% RSD). Interlaboratory assessment (by LA‐ICP‐MS) from individual crystals returned results that are within uncertainty equivalent to the TIMS ages. Finally, we report on within‐ and between‐grain homogeneity of the oxygen isotope systematic of four BB crystals (13.16‰ VSMOW).     

Hydrostratigraphic analysis of the Darling River valley (Australia) using electromagnetic induction data and a spatially constrained algorithm for quasi-three-dimensional electrical conductivity imaging

Efforts are being made to improve the irrigation efficiency in the Murray-Darling River Basin, Australia, to deal with predicted rainfall decline and to reduce the incidence of secondary soil and water salinization. The latter commonly occurs as a result of locating water reservoirs upon relic drainage channels. To better manage irrigation, information is required about the spatial distribution of soil type and the stratigraphic features capable of redistributing deep-draining water. In previous research, electromagnetic (EM) induction instruments (e.g. EM38 and EM34) have been used to map the distribution of soil type, hydrological processes (e.g. deep drainage) and vadose-zone features. The aim of this research is to demonstrate how a joint inversion of EM38 and EM34 data, using a one-dimensional spatially constrained algorithm for quasi three-dimensional (quasi-3D) electrical conductivity imaging, can be used to infer the areal distribution of soil types and physiographic and hydrogeological units. The quasi-3D modeling of true electrical conductivity provides a framework for future environmental monitoring and management to mitigate the hydrological processes that drive localized secondary salinization in the study area.