Late Carboniferous porphyry copper mineralization at La Voluntad,Neuquén,Argentina: Constraints from Re–Os molybdenite dating

The La Voluntad porphyry Cu–Mo deposit in Neuquén, Argentina, is one of several poorly known porphyry-type deposits of Paleozoic to Early Jurassic age in the central and southern Andes. Mineralization at La Voluntad is related to a tonalite porphyry from the Chachil Plutonic Complex that intruded metasedimentary units of the Piedra Santa Complex. Five new Re–Os molybdenite ages from four samples representing three different vein types (i.e., quartz–molybdenite, quartz–sericite–molybdenite and quartz–sericite–molybdenite ± chalcopyrite–pyrite) are identical within error and were formed between ~312 to ~316 Ma. Rhenium and Os concentrations range between 34 to 183 ppm and 112 to 599 ppb, respectively. The new Re–Os ages indicate that the main mineralization event at La Voluntad, associated to sericitic alteration, was emplaced during a time span of 1.7 ± 3.2 Ma and that the deposit is Carboniferous in age, not Permian as previously thought. La Voluntad is the oldest porphyry copper deposit so far recognized in the Andes and indicates the presence of an active magmatic arc, with associated porphyry style mineralization, at the proto-Pacific margin of Gondwana during the Early Pennsylvanian.     

Diagenesis, palaeoclimate and tectono-sedimentary influences on clay mineralogy and stable isotopes from Upper Cretaceous marine successions of the Basque-Cantabrian Basin (N Spain)

Clay mineralogy and whole-rock stable isotopes (δ¹⁸O and δ¹³C) of Upper Cretaceous marly sediments on the Basque-Cantabrian Basin have been integrated to determine the main effects of diagenesis, palaeoclimate and tectono-sedimentary factors in sections belonging to deep- (Barrika) and platform-marine (Isla de Castro, Villamartín and Olazagutía) settings.The mean values for the clay assemblages and δ¹⁸O exhibit notable differences among the sections, partially explainable by the influence of diagenesis. The Barrika sediments, with more diagenetically advanced illite-smectite (I-S) mixed-layer (R1, 70% illite), authigenic chlorite, and low δ¹⁸O (−4.05‰ PDB), experienced higher diagenetic grade than Isla de Castro and Olazagutía, which have R0 I-S (20% illite) and heavier δ¹⁸O. Villamartín was also affected by higher diagenesis than Isla de Castro and Olazagutía, given the occurrence of R1 I-S (60% illite) and low δ¹⁸O (−4.11‰ PDB). However, the absence of other clays in Villamartín (e.g. authigenic chlorite) is indicative of less diagenetic grade than Barrika. These results show the useful integration of clay mineralogy and stable isotopes to detect different diagenetic grades in distinct marine successions of the same basin.Despite being influenced by diagenesis, the clay mineralogy partially preserves its inherited signature. This allows detection of major contents of I-S and mica, and minor kaolinite, interpreted as indicative of warm palaeoclimatic conditions. High kaolinite content in Villamartín and absence of kaolinite in Isla de Castro, though, are considered to be a product of neither diagenesis nor palaeoclimatic influences. Instead, tectono-sedimentary causes, related to unsuitable conditions for clay formation and transport from the local source areas, contributed to original clay differences. The inferred effects of diagenesis, palaeoclimate and tectono-sedimentary factors make this work important to show the potentially great variety of controls on the clay mineralogy of marine sections, which are often uncritically treated in studies concerning the Late Cretaceous.     

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.     

Trace elements contamination of agricultural soils affected by sulphide exploitation (Iberian Pyrite Belt,Sw Spain)

Agricultural soils of the Riotinto mining area (Iberian Pyrite Belt) have been studied to assess the degree of pollution by trace elements as a consequence of the extraction and treatment of sulphides. Fifteen soil samples were collected and analysed by ICP-OES and INAA for 51 elements. Chemical analyses showed an As–Cu–Pb–Zn association related with the mineralisation of the Iberian Pyrite Belt. Concentrations were 19–994 mg kg⁻¹ for As, 41–4,890 mg kg⁻¹ for Pb, 95–897 mg kg⁻¹ for Zn and of 27–1,160 mg kg⁻¹ for Cu. Most of the samples displayed concentrations of these elements higher than the 90th percentile of the corresponding geological dominium, which suggests an anthropogenic input besides the bedrock influence. Samples collected from sediments were more contaminated than leptosols because they were polluted by leachates or by mining spills coming from the waste rock piles. The weathering of the bedrock is responsible for high concentrations in Co, Cr and Ni, but an anthropogenic input, such as wind-blown dust, seems to be indicative of the high content of As, Cu, Pb and Zn in leptosols. The metal partitioning patterns show that most trace elements are associated with Fe amorphous oxy-hydroxides, or take part of the residual fraction. According to the results obtained, the following mobility sequence is proposed for major and minor elements: Mn, Pb, Cd, > Zn, Cu > Ni > As > Fe > Cr. The high mobility of Pb, Cu and Zn involve an environmental risk in this area, even in soils where the concentrations are not so high.     

Space–time distribution of ancient and active alluvial karst subsidence: examples from the central Ebro Basin,Spain

Space and time variations of alluvial karst subsidence in the central Ebro Basin are analysed in trenches (paleodolines), aerial photographs (historical dolines) and field surveys (present-day active dolines). The measured subsidence rates, as well as a comparison between densities of paleodolines computed in randomly selected scan-lines and density of active dolines computed in maps, suggest that present-day subsidence in favourable areas is more intense than that of Pleistocene times. According to diachronic maps drawn from (a) different aerial photographs taken after 1946 and (b) field surveys on deformations in urbanized areas, subsidence behaved as a nearly steady process while the whole area was used for agriculture. In contrast, rapid changes (through periods of several tens of years) have occurred in urbanized areas, in which dolines expand their boundaries through small marginal collapses, shifting sharply their sinking centres to neighbouring sites. These rapid changes do not have an equivalent in observed paleodolines.     

Assessment of sandstone deterioration at Ta Keo temple (Angkor): first results and future prospects

A first application of geomorphological methods to the assessment of sandstone deterioration at Angkor is presented. Damage diagnosis was carried out on the first eastern tier of the central pyramid of the 1,000 year-old Ta Keo temple. Methods combine field observations and measurements at 230 sampling points, high-resolution lasergrammetry and stereophotogrammetry on a 2-m² test zone, and SEM observations. The first results indicate that decay operates through a synergistic combination of weathering phenomena dominated by scaling and solution, and exhibits a high spatial variability. Percentages of deteriorated surfaces vary from 17.6 to 93.8%, and average stone recession values from 0.00 to 2.71 cm (minimum) and 0.34 to 5.49 cm (maximum). On the test-zone, stereophotogrammetry and 3D-mapping of the present and reconstructed initial states using lasergrammetry indicate that erosion scars up to 6 cm deep have formed since 1963. On the whole, the amount of deteriorated surfaces more than tripled between 1963 and 2008. The degree of implication of salts in stone decay remains unclear for most efflorescences are composed of calcite (CaCO3), with secondary importance of barite (BaSO4) and gypsum (CaSO₄·2H₂O). Future prospects aim to evaluate the impact on stone decay of the clearing out of the temple from the forest in the 1920s.     

Environmental risk evaluation of the use of mine spoils and treated sewage sludge in the ecological restoration of limestone quarries

The ecologic restoration criteria in areas degraded from extraction activities require making use of their mine spoils. These materials do not meet fertility conditions to guarantee restoration success and therefore, need the incorporation of organic amendments to obtain efficient substratum. Reducing the deficiencies in the organic material and restoration material nutrients with the contribution of treated sewage sludge is proposed in this work. This experiment was based on a controlled study using columns. The work was conducted with two mine spoils, both very rich in calcium carbonate. The first mineral, of poor quality, came from the formation of aggregates of crushed limestone (Z). The other residual material examined originated in limestone extraction, formed by the levels of interspersed non-limestone materials and the remains of stripped soils (D). Two treatments were undertaken (30,000 and 90,000 kg/ha of sewage sludge), in addition to a control treatment. The water contribution was carried out with a device that simulated either short-duration rain or a flooding irrigation system in order to cover the surface and then percolate through the soil. The collection of leached water took place 24 h after the applications. Different parameters of the leached water were determined, including pH, electrical conductivity, nitrate anions, ammonium, phosphates, sulphates and chlorides. The values obtained for each irrigation application are discussed, and the nitrate values obtained were very elevated.     

Sediment Trend Analysis through the variation of granulometric parameters: A review of theories and applications

Spatial variations in grain-size parameters (i.e. grain-size trends) contain information on sediment transport patterns. Analytical procedures have been proposed using the grain-size trend to determine net sediment transport pathways. In the first part of this study, the fundamentals of the theory are presented through methods for analysing 1D and 2D variations. The methods used are critically discussed, while pointing out some severe problems. So far, these methods suffer from limitations leading to serious interpretational errors, making it necessary to take account of two kinds of uncertainties. Inputs uncertainties are linked to the physical sediment properties as well as procedures of sampling and analysis. Model uncertainties are then discussed for each step of the grain-size trend analysis. The validity of Sediment Trend Analysis under natural conditions is tested against published field studies to determine the most appropriate variation trend to use in a specific environment. Proposals are given for each step of the procedure for optimal use of the method using a Quality Assurance (QA) approach. Further developments are proposed, such as integration into a Geographic Information System.     

Diagenetic processes on metals in hypersaline mudflat sediments from a subtropical saltmarsh (SE Gulf of California): Postdepositional mobility and geochemical fractions

To understand the biogeochemical cycles of trace metals (Cd, Cu, Fe, Mn, Ni and Zn) in a hypersaline subtropical marsh, geochemical studies of both interstitial and solid phases were conducted on sediment cores from Chiricahueto marsh, SE Gulf of California. The sequential extraction procedure proposed by Tessier was used to estimate the percentages of the metals present in each geochemical phase of the sediment. Metal concentrations in the solid phase were found to be enriched in the upper layers and mainly associated with reactive fractions such as organic matter, Fe–Mn oxyhydroxides and carbonates (46–74% of Ni, Mn and Cd, and 11–19% of Cu and Zn). Principal factor analysis (PFA) and Spearman correlation analysis revealed a strong positive association of metals and their reactive phases with OC (the diagenetic component), and a negative or non-association with the mud content, Al, Fe and Li (the lithogenic component). Diagenetically released metals are mainly mobilized within hypersaline sediments by buoyancy transport (>90% of total flux) in response to an extreme salinity gradient by input of fresh groundwater (3–6 psu cm⁻¹). The molecular diffusion due to the gradient of metals in porewater (maximum and higher levels at 5–7 and below 20 cm depth, respectively) is significantly less important to the advective transport. Most of the metals mobilized by diffusion–advection processes are re-precipitated in the sediments by authigenic minerals, only <10% of most metals are extruded out to the overlying water column. Authigenic accumulation rates were estimated as 1.42–7.09 mg m⁻² a⁻¹ for Cd; 58.8–378 for Cu; 6922–17,985 for Fe; 38.2–345 for Mn; 20.8–263 for Ni; and 282–2956 mg m⁻² a⁻¹ for Zn. The Mn–Fe oxyhydroxides (40–85% of reactive metals) in the upper oxic–suboxic layers (<5 cm below surface) and sulfide minerals (75–97%) in anoxic sediment layers (7–18 cm) constitute the main scavengers for metals.     

Quantitative sinkhole hazard assessment. A case study from the Ebro Valley evaporite alluvial karst (NE Spain)

Quantitative sinkhole hazard assessments in karst areas allow calculation of the potential sinkhole risk and the performance of cost-benefit analyses. These estimations are of practical interest for planning, engineering, and insurance purposes. The sinkhole hazard assessments should include two components: the probability of occurrence of sinkholes (sinkholes/km² year) and the severity of the sinkholes, which mainly refers to the subsidence mechanisms (progressive passive bending or catastrophic collapse) and the size of the sinkholes at the time of formation; a critical engineering design parameter. This requires the compilation of an exhaustive database on recent sinkholes, including information on the: (1) location, (2) chronology (precise date or age range), (3) size, and (4) subsidence mechanisms and rate. This work presents a hazard assessment from an alluvial evaporite karst area (0.81 km²) located in the periphery of the city of Zaragoza (Ebro River valley, NE Spain). Five sinkholes and four locations with features attributable to karstic subsidence where identified in an initial investigation phase providing a preliminary probability of occurrence of 0.14 sinkholes/km² year (11.34% in annual probability). A trenching program conducted in a subsequent investigation phase allowed us to rule out the four probable sinkholes, reducing the probability of occurrence to 0.079 sinkholes/km² year (6.4% in annual probability). The information on the severity indicates that collapse sinkholes 10–15 m in diameter may occur in the area. A detailed study of the deposits and deformational structures exposed by trenching in one of the sinkholes allowed us to infer a modern collapse sinkhole approximately 12 m in diameter and with a vertical throw of 8 m. This collapse structure is superimposed on a subsidence sinkhole around 80 m across that records at least 1.7 m of synsedimentary subsidence. Trenching, in combination with dating techniques, is proposed as a useful methodology to elucidate the origin of depressions with uncertain diagnosis and to gather practical information with predictive utility about particular sinkholes in alluvial karst settings: precise location, subsidence mechanisms and magnitude, and timing and rate of the subsidence episodes.