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.     

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.     

Palynological characterization of gassy sediments in the inner part of Ría de Vigo (NW Spain). New chronological and environmental data

Palynological characterization of the pollen assemblages from core ZV-01 offers a reliable age record of shallow ‘gas seal’ and ‘gas reservoir’ sediments from the Ría de Vigo (NW Spain). Gassy sediments show a direct correspondence with the palynological assemblage zones (LPAZ) 2, 3 and 4, which range in age from 950 to 1510 a.d. for the interval 81–176 cm where gas is found. The facies acting as a seal would correspond to the sedimentation in the ria starting from 1510 a.d. These assemblages also provide significant data which make it possible to reconstruct the palaeoenvironmental changes recorded in the sedimentary infill of the Ría de Vigo. The gassy horizon corresponds to the phase when riparian and mesophilous forest were better represented. This coincides with a relative high abundance of Lingulodinium machaerophorum, which indicates that the waters of the ria had been less renewed by oceanic waters and had a plentiful supply of continental nutrients. At that time, anoxic conditions resulted from restricted vertical circulation of seawater and/or high biological productivity. The dinocyst assemblages overlying and underlying the gassy horizon in core ZV-01 are clearly different from those concomitant with the accumulation of the gassy sediments. This suggests that oceanographic conditions in the Ría de Vigo may have changed several times during the time interval covered by our record. The weaker relationship between L. machaerophorum/Spiniferites spp., and simultaneous significant increases in Impagidinium spp. and Bitectatodinium tepikiense may indicate a greater intrusion of colder, more oceanic waters into the Ría de Vigo, which may have provoked intensification in upwelling during two periods, ca. 700–850 a.d. and ca. 1500–1750 a.d.     

The Huelva (Spain) Tsunami-Ready Station and Its Interaction with Storm Emma (March 2018)

Abstract

The sea level station operating since 1996 at Mazagón (Huelva, Spain) has been progressively upgraded to fit tsunami warning requirements, due to its location in one of the main regions at risk. Its radar water level sensor was complemented in 2017, with the addition of a pressure sensor. The performance of both sea level sensors and their response to sea level oscillations, at different frequencies, is assessed. Particular emphasis is put on the effect of extreme events, such as Storm Emma, when alternative methods to obtain 1-min data are tested, in contrast to the one based on arithmetic means. The overall differences are small, for the whole period of study (centered-root-mean-square-error below 1?cm, for 5-min, and hourly data; similar tidal parameters and sea level oscillations with periods between 30?s and 5?min). However, during Storm Emma, the pressure sensor presents sensibly lower readings than the radar, with the centered-root-mean-square-error rising to 80?mm on the March 2^nd 2018. A new method to compute 1-min data, based on medians, reduced this value to 10?mm for the same day.     

Influence of upwelling and river runoff interaction on phytoplankton assemblages in a Middle Galician Ria and Comparison with northern and southern rias (NW Iberian Peninsula)

The first oceanographic research (hydrography, nutrient salts, chlorophyll, primary production and phytoplankton assemblages) in a Middle Galician Ria was carried out in Corme-Laxe during 2001, just a year before the Prestige oil spill, being the only reference to evaluate eventual changes in the phytoplankton community. Due to the small size of this ria (6.5 km²), oceanographic processes were driven by the continental water supplied by Anllons River during the wet season (20–30 m³ s⁻¹ in winter), and the strong oceanic influence from the nearby shelf during the dry season. The annual cycle showed a spring bloom with high levels of chlorophyll (up to 14 μg Chl-a L⁻¹) and primary production (3 g C m⁻² d⁻¹) and a summer upwelling bloom (up to 8 μg Chl-a L⁻¹ and 10 g C m⁻² d⁻¹) where the proximity of the Galician upwelling core (<13.5 °C at sea surface) favors the input of upwelled seawater (up to 9 μM of nitrate and silicate) to the bottom ria layer, even during summer stratification events (primary production around 2 g C m⁻² d⁻¹). Thus, phytoplankton assemblages form a “continuum” from spring to autumn with a predominance of diatoms and overlapping species between consecutive periods; only in autumn dinoflagellates and flagellates characterized the phytoplankton community. In the Middle Rias as Corme-Laxe, the nutrient values, Chl-a, primary production and phytoplankton abundance for productive periods were higher than those reported for the Northern (Ria of A Coruña) and Southern Rias (Ria of Arousa) for year 2001; this suggests the importance of the hydrographic events occurring in the zone of maximum upwelling intensity of the Western Iberian Shelf, where a lack of annual cycles studies exists.