First U–Pb SHRIMP age of the Hauterivian stage, Neuquén Basin, Argentina

A high-resolution ion-microprobe (SHRIMP) U–Pb zircon age from a tuff layer intercalated in the ammonoid bearing sedimentary succession of the Neuquén Basin in Argentina provides a robust geochronologic date to add to the absolute ages and to improve the relative chronology of the Early Cretaceous Hauterivian stage. The tuff layer appears interbedded between shales of the upper member (Agua de la Mula) of the Agrio Formation within the Spitidiscus riccardii ammonoid zone (base of the Late Hauterivian) yielding a date of 132.5 ± 1.3 Ma. This date confirms and supports an accurate correlation between the ammonoid biostratigraphy of the Neuquén Basin with the Western Mediterranean Province of the Tethys during the Early Cretaceous and matches with the most recently published time scale. It also casts doubts on the validity of K–Ar ages on glauconite-grains recently reported from the Lower Cretaceous of the Vocontian Basin of France.     

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.     

Biaxial test simulations using a packing of polygonal particles

The mechanical response of cohesionless granular materials under monotonic loading is studied by performing molecular dynamic simulations. The diversity of shapes of soil grains is modelled by using randomly generated convex polygons as granular particles. Results of the biaxial test obtained for dense and loose media show that samples achieve the same void ratio at large strains independent of their initial density state. This limit state resembles the so‐called critical state of soil mechanics, except for some stress fluctuations, which remain for large deformations. These fluctuations are studied at the micro‐mechanical level, by following the evolution of the co‐ordination number, force chains and the fraction of the sliding contacts of the sample. Copyright © 2007 John Wiley & Sons, Ltd.     

Mineralogy and geochemistry of platinum-group elements in the Aguablanca Ni-Cu deposit (SW Spain)

Summary The Aguablanca Ni-Cu-(PGE) magmatic sulphide deposit is associated with a magmatic breccia located in the northern part of the Aguablanca gabbro (SW, Iberia). Three types of ores are present: semi-massive, disseminated, and chalcopyrite-rich veined ore. The principal ore minerals are pyrrhotite, pentlandite and chalcopyrite. A relatively abundant platinum-group mineral (PGM) assemblage is present and includes merenskyite, melonite, michenerite, moncheite and sperrylite. Moreover, concentrations of base and precious metals and micro-PIXE analyses were obtained for the three ore-types. The mineralogy and the mantle-normalised chalcophile element profiles strongly suggest that semi-massive ore represents mss crystallisation, whereas the disseminated ore represents an unfractionated sulphide liquid and the chalcopyrite-rich veined ore a Cu-rich sulphide liquid. Palladium-bearing minerals occur commonly enclosed within sulphides, indicating a magmatic origin rather than hydrothermal. The occurrences and the composition of these minerals suggest that Pd was initially dissolved in the sulphides and subsequently exsolved at low temperatures to form bismutotellurides. Negative Pt and Au anomalies in the mantle-normalised chalcophile element profiles, a lack of Cu-S correlation and textural observations (such as sperrylite losing its euhedral shape when in contact with altered minerals) suggest partial remobilisation of Pt, Au and Cu by postmagmatic hydrothermal fluids after the sulphide crystallisation. Authors’ addresses: R. Pi?a, L. Ortega, R. Lunar, Departamento de Cristalografía y Mineralogía, Facultad de Geología, Universidad Complutense de Madrid, ES-28040 Madrid, Spain; F. Gervilla, Facultad de Ciencias, Instituto Andaluz de Ciencias de la Tierra, Universidad de Granada-CSIC, Avda. Fuentenueva, s/n, ES-18002 Granada, Spain     

Measuring and modelling temporal trends of 226Ra in waters of a Spanish estuary affected by the phosphate industry

The presence and temporal evolution (1990-2001) of (226)Ra in a tidal estuary affected by the phosphate industry has been investigated. Water samples collected in the course of four separate sampling campaigns were analysed for (226)Ra content using a gas flow proportional counter following Ba coprecipitation. Two (226)Ra sources have been identified: direct discharges from the industrial complex and run-off from a phosphogypsum pile. Although activity levels are similar, or even higher, than those found in other environments affected by the phosphate industry, there has been a general decrease in contamination since direct discharges ceased in 1998 due to new regulations from the EU. However, sediments are now acting as a source of Ra to the water column due to redissolution processes. A numerical model of the estuary has been developed to describe quantitatively the experimental results. The model solves the hydrodynamics and the dispersion equation of (226)Ra including interactions with sediments. Model results are, in general, in good agreement with observations.     

An aromatase inhibitor and tamoxifen decrease plasma levels of o,p'-DDT and its metabolites in Nile tilapia (Oreochromis niloticus)

The objective of this study was to determine if tamoxifen or an aromatase inhibitor (4-hydroxyandrostenedione; 4-OHA) affected plasma concentrations of o,p' -DDT and its metabolites, o,p'-DDD and o,p'-DDE, in mature tilapia. Male and female tilapia were injected 6 times intraperitoneally with o,p'-DDT (40 mg/kg) alone or in combination with 4-OHA (2 mg/kg) over a 12 day period. An additional group of male fish was injected with tamoxifen (5 mg/kg) plus o,p'-DDT. At the end of the treatment period, plasma samples were extracted and analyzed by GC/ECD. Females injected only with o,p'-DDT had significantly higher levels of o,p'-DDT compared with males. Interestingly, females and males treated concomitantly with o,p'-DDT and 4-OHA or tamoxifen had significantly lower concentrations of plasma o,p'-DDT (about 50%) compared with fish treated with only o,p'-DDT. These initial results suggest that an interaction between endocrine-active compounds occurs in vivo in tilapia and may involve alterations in metabolism of o,p'-DDT.     

Response of antioxidant systems to copper in the gills of the clam Ruditapes decussatus

Copper (Cu) is an essential element for biological systems, however, when present in excess, is toxic. Metallothioneins can play an important role in Cu homeostasis and detoxification. Moreover, Cu can catalyse the production of toxic hydroxyl radicals that cause lipid peroxidation but defence systems in the cells can limit the oxidative damage. The present study was performed to investigate the effect of three Cu concentrations (0.5, 2.5 and 25 μg l⁻¹) on the response of antioxidant enzyme activities (superoxide dismutase (SOD), catalase (CAT), selenium-dependent glutathion peroxidase and total glutathion peroxidase), total proteins, metallothioneins (MT), malondialdehyde (MDA) concentrations in the gills of the clam, Ruditapes decussatus. The activity of antioxidant enzymes and total proteins, MT and MDA concentrations were measured in the gills of the clams after 1, 3, 7, 14, 21 and 28 days of Cu exposure. Results indicate that Cu only induces an imbalance in the oxygen metabolism during the first week of Cu exposure due to a decrease in mitochondrial SOD and CAT, selenium-dependent and total glutathion peroxidase activities. Cu also causes lipid peroxidation, measured by the MDA formation, that was Cu dependent. In the gills of clams exposed to 25 μg Cu/l, the excess of Cu triggers the induction of MT synthesis after 3 days of exposure.     

A comparative mineralogical study of gas-related sediments of the Gulf of Cádiz

The Gulf of Cádiz area has been extensively surveyed in recent years and several gas-related fluid escape seafloor structures have been identified. In this study, gravity cores, collected during the ANASTASYA/00 and ANASTASYA/01 cruises, on mud volcanoes, hemipelagic sediments and dredged material from diapiric structures, have been studied. A comparative mineralogical analysis by XRD and SEM of samples from different areas has been performed in order to determine whether there is a characteristic mineralogy related to these fluid escape structures, and also to determine the origin of the mud matrix and constrain the depth of the parent units. The mineralogical analysis reflects the different origins of the different units described in the cores: hemipelagic material of the slope, clays that underlie the mud volcanoes and are discharged at the sea bottom surface, and authigenic and diagenetic minerals possibly involved in the anaerobic oxidation of methane in the mud volcano sediments.     

Horizontal spatial and temporal distribution patterns of nearshore larval fish assemblages at a temperate rocky shore

There have been no previous studies of the composition of nearshore larval fish assemblages along the coast of Portugal. We aimed to describe the composition and horizontal distribution patterns of larval fish assemblages and their temporal dynamics near a rocky reef at depths shallower than 13 m (inshore) and at two miles (3.70 km) from shore (offshore), as well as along transects perpendicular to the shoreline, from the reef to 10 miles offshore (18.52 km). Samples were taken using 5 min sub-surface trawls at the rocky shore of the Arrábida Marine Park (W Portugal). A total of 1021 larvae were collected, belonging to 61 taxa inshore and to 29 taxa offshore. Along transects, 626 larvae of 52 taxa were collected. Most larvae belonged to coastal species associated with rocky reefs. Total larval abundance and diversity were higher from May to July, which is consistent with the spawning activity of adults. Diversity and total larval abundance decreased significantly with increasing distance from shore, both in the inshore/offshore comparison and in the transects, where this decrease was evident at a very small spatial scale (within the first mile from the reef). Species assemblages differed in the pattern of distribution, with most species clearly associated to the extreme nearshore. The distribution patterns obtained were independent of the spawning mode of species. Results are discussed in the light of the possible physical mechanisms that can potentially act at the Arrábida Marine Park to facilitate larvae retention and the role of larval behaviour.     

Seasonal and inter-annual variation of mesozooplankton in the coastal upwelling zone off central-southern Chile

Zooplankton sampling at Station 18 off Concepción (36°30′S and 73°07′W), on an average frequency of 30 days (August 2002 to December 2005), allowed the assessment of seasonal and inter-annual variation in zooplankton biomass, its C and N content, and the community structure in relation to upwelling variability. Copepods contributed 79% of the total zooplankton community and were mostly represented by Paracalanus parvus, Oithona similis, Oithona nana, Calanus chilensis, and Rhincalanus nasutus. Other copepod species, euphausiids (mainly Euphausia mucronata), gelatinous zooplankton, and crustacean larvae comprised the rest of the community. Changes in the depth of the upper boundary of the oxygen minimum zone indicated the strongly seasonal upwelling pattern. The bulk of zooplankton biomass and total copepod abundance were both strongly and positively associated with a shallow (<20 m) oxygen minimum zone; these values increased in spring/summer, when upwelling prevailed. Gelatinous zooplankton showed positive abundance anomalies in the spring and winter, whereas euphausiids had no seasonal pattern and a positive anomaly in the fall. The C content and the C/N ratio of zooplankton biomass significantly increased during the spring when chlorophyll-a was high (>5 mg m⁻³). No major changes in zooplankton biomass and species were found from one year to the next. We concluded that upwelling is the key process modulating variability in zooplankton biomass and its community structure in this zone. The spring/summer increase in zooplankton may be largely the result of the aggregation of dominant copepods within the upwelling region; these may reproduce throughout the year, increasing their C content and C/N ratios given high diatom concentrations.