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.     

Impact evaluation on groundwater of the infiltration of an urban wastewater geopurification system placed over a detrital aquifer in a semiarid region (Spain)

Over a period of 4 years and 4 months, the geopurification installations at Dehesas de Guadix (Granada, Spain) were monitored to determine the impact on soil and groundwater of the controlled discharge of urban wastewater, and also to identify the best indicators of the entry of the recharged water into the aquifer. The installations are located in an area where the climate is Mediterranean sub-arid, with an average precipitation of less than 287 mm/year, and a rate of evapotranspiration that is almost three times greater. The system was controlled by determining the balance of majority nutrients and boron in the soil and in the groundwater, both at the points affected directly by the wastewater discharge and at others. The quantity of mass discharged was relatively large (COD 14,656 g/m², NO₃ 85 g/m², NO₂ 4 g/m², NH₄ 2,425 g/m², PO₄ 1,143 g/m², K 1,531 g/m², B 63 g/m²). It was observed that the elimination of nutrients within the soil (COD 97.5%, PO₄ 94.4%, K 59.17%, N _total 18.8%, B 12.69%) was very efficient except for the nitrogen, which nevertheless did not reach the groundwater, as it was eliminated at deep levels of the unsaturated zone. Only 12.69% of the boron was removed, and appreciable, increasing amounts of this element did reach the groundwater. Unexpectedly, none of the majority nutrients behaved as a reliable indicator of the impact on groundwater; despite this, the boron and the bicarbonate did clearly reflect the arrival of the recharged water, and are proposed as the best indicators.     

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.     

Determination of fluid/melt partition coefficients by LA-ICPMS analysis of co-existing fluid and silicate melt inclusions: Controls on element partitioning

Analyses of co-existing silicate melt and fluid inclusions, entrapped in quartz crystals in volatile saturated magmatic systems, allowed direct quantitative determination of fluid/melt partition coefficients. Investigations of various granitic systems (peralkaline to peraluminous in composition, log fO₂ = NNO−1.7 to NNO+4.5) exsolving fluids with various chlorinities (1-14 mol/kg) allowed us to assess the effect of these variables on the fluid/melt partition coefficients (D). Partition coefficients for Pb, Zn, Ag and Fe show a nearly linear increase with the chlorinity of these fluid (D_Pb ∼ 6 ∗ m_Cl, D_Zn ∼ 8 ∗ m_Cl, D_Ag ∼ 4 ∗ m_Cl, D_Fe ∼ 1.4 ∗ m_Cl, where m_Cl is the molinity of Cl). This suggests that these metals are dissolved primarily as Cl-complexes and neither oxygen fugacity nor the composition of the melt affects significantly their fluid/melt partitioning. By contrast, partition coefficients for Mo, B, As, Sb and Bi are highest in low salinity (1-2 mol/kg Cl) fluids with maximum values of D_Mo ∼ 20, D_B ∼ 15, D_As ∼ 13, D_Sb ∼ 8, D_Bi ∼ 15 indicating dissolution as non-chloride (e.g., hydroxy) complexes. Fluid/melt partition coefficients of copper are highly variable, but highest between vapor like fluids and silicate melt (D_Cu ? 2700), indicating an important role for ligands other than Cl. Partition coefficients for W generally increase with increasing chlorinity, but are exceptionally low in some of the studied brines which may indicate an effect of other parameters. Fluid/melt partition coefficients of Sn show a high variability but likely increase with the chlorinity of the fluid (D_Sn = 0.3-42, D_W = 0.8-60), and decrease with decreasing oxygen fugacity or melt peraluminosity.     

Sedimentary petrology and geochemistry of siliciclastic rocks from the upper Jurassic Tordillo Formation (Neuquén Basin, western Argentina): Implications for provenance and tectonic setting

The Upper Jurassic Tordillo Formation is exposed along the western edge of the Neuquén Basin (west central Argentina) and consists of fluvial strata deposited under arid/semiarid conditions. The pebble composition of conglomerates, mineralogical composition of sandstones and pelitic rocks, and major- and trace-element geochemistry of sandstones, mudstones, and primary pyroclastic deposits are evaluated to determine the provenance and tectonic setting of the sedimentary basin. Conglomerates and sandstones derived almost exclusively from volcanic sources. The stratigraphic sections to the south show a clast population of conglomerates dominated by silicic volcanic fragments and a predominance of feldspathic litharenites. This framework composition records erosion of Triassic–Jurassic synrift volcaniclastic rocks and basement rocks from the Huincul arch, which was exhumed as a result of Late Jurassic inversion. In the northwestern part of the study area, conglomerates show a large proportion of mafic and acidic volcanic rock fragments, and sandstones are characterised by a high content of mafic volcanic rock fragments and plagioclase. These data suggest that the source of the sandstones and conglomerates was primarily the Andean magmatic arc, located west of the Neuquén Basin. The clay mineral assemblage is interpreted as the result of a complex set of factors, including source rock, climate, transport, and diagenesis. Postdepositional processes produced significant variations in the original compositions, especially the fine-grained deposits. The Tordillo sediments are characterised by moderate SiO₂ contents, variable abundances of K₂O and Na₂O, and a relatively high proportion of ferromagnesian elements. The degree of chemical weathering in the source area, expressed as the chemical index of alteration, is low to moderate. The major element geochemistry and Th/Sc, K/Rb, Co/Th, La/Sc, and Cr/Th values point to a significant input of detrital volcanic material of calcalkaline felsic and intermediate composition. However, major element geochemistry is not useful for interpreting the tectonic setting. Discrimination plots based on immobile trace elements, such as Ti, Zr, La, Sc, and Th, show that most data lie in the active continental margin field. Geochemical information is not sufficiently sensitive to differentiate the two different source areas recognized by petrographic and modal analyses of conglomerates and sandstones.