Mono- and dicyclic unsaturated triterpenoid hydrocarbons in sediments from Lake Masoko (Tanzania) widely extend the botryococcene family

A mixture of C₃₃–C₃₇ botryococcenes and partially reduced derivatives was isolated from ca. 32,000 year old sediment from Lake Masoko, a freshwater crater lake in the Rungwe Range area (Tanzania). Botryococcenes and derivatives accounted for 246 μg/g dry sediment and for >92% of the hydrocarbon fraction; 1D and 2D nuclear magnetic resonance spectroscopy (NMR) and mass spectrometry allowed the structure of the dominant botryococcene (43% of hydrocarbon fraction) to be established, after purification using high performance liquid chromatography (HPLC). The compound is a novel tetraunsaturated dicyclic C₃₄ botryococcene and is named C₃₄ masokocene. Overall, the structures of six other novel botryococcenes and four partially reduced derivatives were tentatively assigned. The structures of the new biomarkers, three dicyclic C₃₄–C₃₆ botryococcenes (or masokocenes) and seven monocyclic C₃₄–C₃₇ analogues are discussed along with their biosynthetic relationship. The high abundance of such polyunsaturated compounds preserved in 32,000 year old sediment from the lake indicates an aquatic ecosystem dominated at the time by the green alga Botryococcus braunii, as well very good preservation of the organic matter.     

Paleosol at the Archean—Proterozoic contact in NW India revisited: Evidence for oxidizing conditions during paleo-weathering?

A number of fine-grained sericite bearing pelitic, schistose lithologies occur along the Archean (Banded Gneiss Complex)-Proterozoic (Aravalli Supergroup) contact (APC) in the Udaipur valley in NW Indian craton. These Al-rich lithologies (subsequently metamorphosed) have been described as ‘paleosols’, developed over a 3.3 Ga old Archean gneissic basement and are overlain by Paleoproterozoic Aravalli quartzite. The paleosol was developed between 2.5 and 2.1, coincident with the globally recognized Great Oxidation Event (GOE). In previous studies these paleosol sections were interpreted to have developed under reducing environment, however, the finding of a ‘ferricrete’ zone in the upper part of Tulsi Namla section (east of Udaipur) during the present study (in addition to earlier reported lithologies) has led to an alternative suggestion of oxygen-rich conditions during paleosol development. The Tulsi Namla paleosol section shows all the features characteristic of a complete paleosol section described from other Archean cratons. The paleosol includes sericite schist with kyanite as the prevalent Al-silicate in the lower part of profile while chloritoid and Fe-oxides typify the Fe-rich upper part. Alumina has remained immobile during the weathering process while Fe and Mn show a decrease in the lower part of the section and an abrupt rise in the upper part, in the ferricrete zone. The field and geochemical data indicate that the Tulsi Namla section is an in situ weathering profile and at least the upper part shows evidence of oxidizing conditions.     

Soil contamination from urban and industrial activity: example of the mining district of Linares (southern Spain)

The Linares region (southern Spain) has been subjected to two important sources of pollution: the intensive mining works and the urban-industrial activity. To obtain a geochemical characterisation of the soil, 31 trace elements were analysed and 669 soil samples were collected. By means of clustering analysis, we identified groups of elements and grid squares in which relations could be established concerning soil lithology, urban and industrial activities and the degree of pollution impact; in addition, we were able to characterise the geochemical background of the study area. The multivariate study led us to identify four factors. Particularly important was factor 2, which represented the elements associated with mineral paragenesis (Cu, Pb, As, Co, Mn, Zn, Sn, Ba). This factor also contains elements related with an urban-industrial activity, such as Pb, Cu, Zn, As and Ba. Furthermore, we identified factor 4, associating Ni, V and Cr, and which is related to the use of fuels.     

Doline probability map using logistic regression and GIS technology in the central Ebro Basin (Spain)

In the surroundings of Zaragoza, karstification processes are especially intense in covered karst areas where fluvial terraces lie directly on Tertiary evaporites. Since the beginning of Quaternary, these processes have lead to the development of collapse and subsidence dolines with a wide range of sizes, which have significant economic impacts. To reduce economic impact and increase safety, a regional analysis of this phenomenon is needed for spatial management. Therefore, a probability map of dolines was developed using logistic regression and geographic information system (GIS) techniques. This paper covers the selection of input data, manipulation of data using the GIS technology, and the use of logistic regression to generate a doline probability map. The primary variable in the doline development in this area is geomorphology, represented by the location of endorheic areas and different terrace levels. Secondary variables are the presence of irrigation and the water table gradient.     

Suitability analysis for sand and gravel extraction site location in the context of a sustainable development in the surroundings of Zaragoza (Spain)

Zaragoza city is located in the central Ebro Basin, in the Iberian Peninsula. The fluvial terraces formed by the Ebro River present a valuable resource of sand and gravel deposits. However, taking advantage of these available resources implies conflicts with other land use interests like urban and industrial development as well as agricultural use, which has also traditionally occupied the alluvial terraces. These deposits represent a substantial groundwater resource that should be preserved for future generations. The development of spatial decision support systems (SDSS) has greatly assisted efforts for solving land-use conflicts. These systems combine the benefits of geographic information systems (GIS) and decision support methodologies and are therefore suitable to manage sustainable development of urban areas. In this contribution, an extraction suitability map taking into consideration a variety of environmental criteria is created with the help of a SDSS. The method used is the analytical hierarchy process which is integrated in ArcGIS. Areas most suitable to sand and gravel extraction are located in the high terraces, and in those terraces covered by pediments where the thickness of resource is relatively high. These areas are far from valuable natural areas, outside areas most vulnerable to groundwater contamination, and beneath soils with poor irrigation characteristics.     

A new method of estimating the ratio between in situ rock stresses and tectonics based on empirical and probabilistic analyses

This paper describes a new procedure for assessing the ratio between in situ stresses in rock masses by means of K (K = σ_H / σ_v, being σ_H and σ_v principal stress) and tectonics for purposes of engineering geology and rock mechanics. The method combines the use of the logic decision tree and the empirical relationship between the Tectonic Stress Index, TSI, and a series of K in situ values obtained from an extensive database. The decision tree considers geological and geophysical factors affecting stress magnitudes both on the regional and local scale. The TSI index is defined by geological and geomechanical parameters. The method proposed provides an assessment of the magnitude of horizontal stresses of tectonic origin. Results for several regions of Europe are presented and the possible applications of the procedure are discussed.     

THERIA_G: a software program to numerically model prograde garnet growth

We present the software program THERIA_G, which allows for numerical simulation of garnet growth in a given volume of rock along any pressure–temperature–time (P–T–t) path. THERIA_G assumes thermodynamic equilibrium between the garnet rim and the rock matrix during growth and accounts for component fractionation associated with garnet formation as well as for intracrystalline diffusion within garnet. In addition, THERIA_G keeps track of changes in the equilibrium phase relations, which occur during garnet growth along the specified P–T–t trajectory. This is accomplished by the combination of two major modules: a Gibbs free energy minimization routine is used to calculate equilibrium phase relations including the volume and composition of successive garnet growth increments as P and T and the effective bulk rock composition change. With the second module intragranular multi-component diffusion is modelled for spherical garnet geometry. THERIA_G allows to simulate the formation of an entire garnet population, the nucleation and growth history of which is specified via the garnet crystal size frequency distribution. Garnet growth simulations with THERIA_G produce compositional profiles for the garnet porphyroblasts of each size class of a population and full information on equilibrium phase assemblages for any point along the specified P–T–t trajectory. The results of garnet growth simulation can be used to infer the P–T–t path of metamorphism from the chemical zoning of garnet porphyroblasts. With a hypothetical example of garnet growth in a pelitic rock we demonstrate that it is essential for the interpretation of the chemical zoning of garnet to account for the combined effects of the thermodynamic conditions of garnet growth, the nucleation history and intracrystalline diffusion. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.

Shale basins,sulfur-deficient ore brines and the formation of exhalative base metal deposits

The massive sulfide deposits of the Iberian Pyrite Belt are interbedded with felsic volcanic rocks and shale, and underlain by several thousand meters of siliciclastic sedimentary rocks known as the PQ Group. Isotope geochemistry and regional geology are both consistent with equilibration of the ore-forming fluids with the PQ Group, prior to ore deposition near the former seafloor. The average Cu:Zn:Pb ratio of the PQ Group rocks (ca. 26:55:19) is similar to the weighted average of all the massive sulfide orebodies combined (ca. 25:52:23).The genetic relationship between massive sulfide deposits and a siliciclastic sedimentary metal source is explained here by a thermodynamic model, proposing that mildly reducing redox conditions imposed by equilibration with the sedimentary rocks are most critical for the formation of an effective ore-forming fluid. Relatively metal-rich but organic-poor pyrite-bearing shale undergoing dewatering of saline pore fluids is an effective source for the generation of sulfur-deficient but relatively iron and base metal-rich brines. Thus, we propose that the giant deposits of the Iberian Pyrite Belt owe their existence not to exceptionally metal-enriched (e.g., magmatic) fluids, but to the existence of a fairly ordinary but large metal source in reactive siliciclastic sediments, combined with an underlying igneous heat source and a particularly efficient mechanism of sulfide precipitation by mixing with H₂S-rich fluids at or near the seafloor.Essentially similar mineral equilibria are imposed when saline fluids are buffered by typical continental basement rocks. Leaching of retrograde minerals and possibly residual salts from their magmatic or metamorphic prehistory is expected to generate similar, variably metal-rich but relatively sulfide-deficient fluids. Thus, the existence of mildly reducing rocks can be the dominant chemical control in the source of fluids generating many volcanogenic, Irish-type or sedex deposits, many of which are known to precipitate their metal load in response to biogenic sulfide addition at the ore deposition site.