The degree of trace metal pyritization in subtidal sediments of a mariculture area: application to the assessment of toxic risk

Four 2–3 m sediment cores were taken at the sites on the periphery of mussel raft concentrations in the subtidal zone of the inner Ría de Vigo (Galicia, NW Spain) with a view to evaluate the potential risk to mariculture from sediment-borne trace elements (As, Cd, Cr, Cu, Mn, Ni, Pb and Zn). The distribution of each of these elements in reactive, organic, pyrite and silicate-bound fractions was determined at 64 samples, and these data were used to calculate the degree of trace metal pyritization (DTMP) of each metal/metalloid. In the top 10–20 cm, relatively oxic conditions led to As, Cd, Cu, Pb and Zn having large reactive fractions due to their association with Fe and Mn oxyhydroxides. At lower levels, anoxic conditions favoured by intense diagenesis led to the precipitation of trace metals and metalloids as sulphides, with or without association with pyrite. Particularly large pyrite fractions in the 20–100 cm layer are attributed to the organic matter of this layer being more marine in origin than that of deeper sediments. DTMP was greatest for Cu and As, and least for Pb, Zn and Cr. The risk of trace element toxicity in the event of disturbances instituting oxic conditions in these sediments is discussed.     

Overview and status of estuarine microphytobenthos ecological research in South Africa

This article presents a historical overview of estuarine microphytobenthos (MPB) research in South Africa published over the period 1950 to the present, highlighting major milestones, challenges and estuarine management problems, as well as future research needs within the South African context. The studies that were covered comprise peer-reviewed books and journal articles on relevant research conducted in any estuarine environment during the period reviewed. There was a general increase in MPB research outputs over the decades, from only two publications in the 1950s, to over 20 outputs between 2010 and the present. Whereas the MPB studies in South Africa cover a broad spectrum of themes, the research priorities in these works have changed from taxonomically biased studies to those of ecologically based research. Research in the 1950s and 1960s was exclusively taxonomic in nature, with the first ecological investigation incorporating MPB being produced in the 1970s. By the 1980s, ecological studies dominated the research outputs and this trend has persisted to the present. The 1990s and 2000s saw the rise of research into the role of fresh water as a driver of MPB dynamics, whereas the period 2010 to the present saw an increase in more diverse ecological themes, ranging from an autecological investigation to food-web studies and the assessment of multiple drivers of MPB dynamics. However, the majority of studies have focused on either diatoms or estimates of overall MPB biomass. Moreover, there is a regional underrepresentation that runs broadly along biogeographic lines, with the bulk of the work having been conducted in the warm-temperate and subtropical zones of South Africa. Challenges and future research needs for the region are outlined, as is the need to expand MPB research to include other aspects of the biology and ecology of this flora.     

Evaluating cost-effective strategies for meeting regional CO2 targets

Various climate protocol proposals oblige different industrialized countries to reduce CO₂ and other greenhouse gas emissions. In principle, the total costs of these obligations could be substantially reduced if emission reductions are implemented in regions with low marginal costs for CO₂ reduction. This has been difficult to quantify because of lack of models with suitable regional and sectoral detail. In this paper we perform these calculations by taking advantage of the capability of the IMAGE 2 model to compute regional emissions and costs. Two main options are examined for allocating emission reductions required of industrialized regions in a cost effective manner: (1) allocating them among industrialized regions (2) allocating them among all world regions. The cost savings for each of these options are presented. The main conclusions are that (a) it is of great importance for the cost comparisons of protocols to use a well defined baseline scenario and clearly formulated targets, and (b) large economic benefits, in the order of 35–65%, can accrue from joint-implementation agreements which allocate investments on the basis of net marginal costs of CO₂ emission reduction.     

Isopropylxanthate ions uptake by modified natural zeolite and removal by dissolved air flotation

This work describes a laboratory study concerning the adsorption of isopropylxanthate ions onto modified zeolites particles. The separation of the loaded carrier and their removal, from aqueous solutions, was conducted by flocculation followed by dissolved air flotation, DAF. The zeolite employed was a natural sample (approximately 48% clinoptilolite and 30% mordenite) which was previously treated with sodium ions (activation) and modified with copper ions (Cu–Z) before the xanthate ions uptake. Adsorption capacities (q_m) for Cu–Z were 0.34 meq g^− 1 for the powdered form, and 1.12 meq g^− 1 for the floc form. The adsorption capacity for the floc form appears to involve an enhanced electrostatic adsorption due to the positive sites on the floc surface. In all cases, the isopropylxanthate concentration in the treated water was found to be negligible (< 0.04 mg L^{− 1}). The flotation technique showed to be a fast process, requires a low recycle ratio (20%) in air saturated water, and the treated water ended up with a very low residual turbidity (6.8 NTU). It is believed that this adsorption–flotation technique, here named adsorptive particulate flotation, using activated and modified natural zeolite has a high potential as an alternative for pollutants removal (copper and isopropylxanthate ions) from waste mining effluents.     

Thermo-optical detection of defects and decarbonation in natural smithsonite

Natural hydrothermal ZnCO₃ crystal aggregates are nominally anhydrous phases with interfacial water, with substitutional divalent cations and decarbonation c. 300°C. All these common features must be involved during the experimental heating of a thermoluminescence (TL) glow curve up to 500°C: dehydration–dehydroxylation, phase transition and ion transition of point defects in Zn²⁺ positions. A representative specimen of natural smithsonite was analysed by X-ray fluorescence spectrometry, field emission scanning electron microscopy (FESEM) with a chemical probe of energy dispersive spectrometer, high temperature in situ X-ray diffraction, differential scanning calorimetry, differential thermal analyses coupled to thermogravimetry, TL, radioluminescence and high resolution spectra thermoluminescence (3DTL), to gain an overview of the spectra emission and defects linkages modified by heating from room temperature up to 500°C. The ZnCO₃ specimen contains minor amounts of Ca, Cu, Cr, Cd, Pb, Ce, Co, Ni, Mn and Fe. Under FESEM, it displays CaCO₃ clusters and oscillatory zoning distribution with lamellae ranging from Ca_0.11Zn_0.89 to Ca_0.19Zn_0.81. The analytical results suggest assignments of defects and processes to measured 3DTL emission bands, as follows: (1) peak at ~260°C, ~360 nm bonds, breaking during the thermal decarbonation process; (2) peak ~120°C, ~340 nm: non-bridging oxygen centres associated to a complex dehydration–dehydroxylation process and (3) peak at ~170°C, ~650 nm, crystal field effects on the thermoluminescence of Mn²⁺ centres and associated transitional elements in the ZnCO₃ phase. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Interplay between detrital and diagenetic processes since the last glacial maximum on the northwest Iberian continental shelf

Integrated analyses of magnetic, geochemical and textural data on six cores from the northwestern Iberian continental shelf allowed the reconstruction of the paleoenvironmental evolution of this area since the last glacial maximum (LGM). Four sedimentary units were identified, representing a succession from fluvial and subaerial settings to high and finally low-energy marine deposits subsequent to the post-LGM sea-level rise. The uppermost unit was deposited during the Holocene and its magnetic properties were controlled by the interplay between detrital input and early diagenetic reductive dissolution of magnetic minerals. Identification of a primary steady-state early diagenetic signal allowed the recognition of periods of increased detrital input, bounded by intervals of lower detrital input and intensified reductive diagenesis related to intensified upwelling in the area. These paleoenvironmental alternations are consistent with the climatic evolution of the late Holocene. During the Roman Warm Period and Medieval Warm Period, the combined effect of greater humidity and intense agricultural and mining activities led to a greater erosion and transport of detrital sediments to the shelf. In contrast, enhanced diagenetic reduction intervals, caused by upwelling intensification, were roughly coincident with the colder Dark Ages and the Little Ice Age.     

Zeta potential of single and polymer-coated microbubbles using an adapted microelectrophoresis technique

The zeta potential of microbubbles, generated by injecting pressurised air into water and then releasing the pressure, was determined in the absence and presence of different polyacrylamides. Air was dissolved in either water or solutions of cationic, anionic, amphoteric or nonionic polymers at a constant pressure of four atmospheres. The charge of the bubbles at the shear-zeta plane was measured using a modified microelectrophoresis glass cell, held at a stationary level, at varying pH (2.0–12.0). Known practical problems with this technique were solved, and these solutions are described in detail. The anionic, amphoteric and nonionic polymers increased the negative charge of the bubbles, but the isoelectric point (iep) remained constant at about pH 2.0. Conversely, in the presence of the cationic polymer, the bubbles exhibited positive surface charges between pH 2.0 and 8.0 and an iep of pH 8.0. The results revealed the existence of an important interaction mechanism between air bubbles and polymeric macromolecules; neither this mechanism nor its practical implications have been reported in the literature to date, especially in the treatment of wastewater by flocculation followed by dissolved air flotation (DAF).     

Rapid fish stock depletion in previously unexploited seamounts: the case of Beryx splendens from the Sierra Leone Rise (Gulf of Guinea)

Fish stocks associated with seamounts may be particularly susceptible to overexploitation. From January to July 2001, the Spanish Oceanographic Institute (IEO) conducted an experimental fishing survey entitled ‘Palguinea-2001’ on the seamounts of the Sierra Leone Rise. Beryx splendens (commonly called alfonsino) is the main commercial demersal fish associated with this area. The aim of this study was to investigate the effects of a demersal longline fishery targeting B. splendens on the previously unexploited small Machucambo Seamount over a short time-scale, and also to consider trends in pooled catch rate at another four seamounts. During 110 fishing days at Machucambo, a total catch of 207 tonnes of B. splendens was taken with a fishing effort of 1 309 070 hooks. A spectral analysis and red-noise spectra procedure (REDFIT) algorithm was used to identify the red-noise spectrum from the gaps in the observed time-series of catch per unit effort by weight. Our results show the potential impact of longline fishing pressure on an unexploited ecosystem – after approximately 50 fishing days, the stock appeared to decline substantially, as reflected by a marked drop in catch per unit effort. The apparent rapid decline of the stock might be related to the small size and the virgin state of the Sierra Leone seamounts. The results could be extrapolated to similar small seamounts elsewhere.     

Cosmic impact versus terrestrial origin of the Azuara structure (Spain): A review

Abstract— The Azuara structure is the largest one proposed so far in Spain as possibly related to a cosmic impact event. A review of the evidence set forward in favor of and against its cosmic origin indicates that the discussion is not yet finished. Some megascopic features (inverted stratigraphy, megabreccia, negative gravity anomalies) and shock‐metamorphic effects (planar deformational features) have been described in relation with the structure, although their real significance has been questioned and is still being debated. Comparison with other similar‐sized verified impacts suggests that unequivocal impactogenic features are yet to be found before the Azuara structure can be related to a cosmic impact. Until then, the Azuara structure should be considered as an unverified impact structure, and should not be included in global comprehensive maps of terrestrial impact structures.     

Groundwater recharge in semi-arid carbonate aquifers under intensive use: the Estepa Range aquifers (Seville, southern Spain)

Quantifying groundwater recharge in carbonate aquifers located in semi-arid regions and subjected to intensive groundwater use is no easy task. One reason is that there are very few available methods suitable for application under such climatic conditions, and moreover, some of the methods that might be applied were originally designed with reference to non-carbonate aquifers. In addition, it is necessary to take into account the fact that, in any given aquifer, groundwater recharge is modified by the groundwater exploitation. Here we focus on four methods selected to assess their suitability for estimating groundwater recharge in carbonate aquifers affected by intensive exploitation. The methods were applied to the Estepa Range aquifers of Seville, southern Spain, which are subjected to different degrees of exploitation. Two conventional methods were used: chloride mass balance and daily soil–water balance. These results were compared with the results obtained by means of two non-conventional methods, designed for application to the carbonate aquifers of southern Spain: the APLIS and ERAS methods. The results of the different methods are analogous, comparable to those obtained in nearby non-exploited carbonate aquifers, confirming their suitability for use with carbonate aquifers in either natural or exploited regimes in a semi-arid climate.