(137)Cs baseline levels in the Mediterranean and Black Sea: a cross-basin survey of the CIESM Mediterranean Mussel Watch programme

The common mussel Mytilus galloprovincialis was selected as unique biomonitor species to implement a regional monitoring programme, the CIESM Mediterranean Mussel Watch (MMW), in the Mediterranean and Black Seas. As of today, and upon standardization of the methodological approach, the MMW Network has been able to quantify (137)Cs levels in mussels from 60 coastal stations and to produce the first distribution map of this artificial radionuclide at the scale of the entire Mediterranean and Black Seas. While measured (137)Cs levels were found to be very low (usually < 1 Bq kg(-1) wet wt) (137)Cs activity concentrations in the Black Sea and North Aegean Sea were up to two orders of magnitude higher than those in the western Mediterranean Basin. Such effects, far from representing a threat to human populations or the environment, reflect a persistent signature of the Chernobyl fallout in this area.     

Mineralogy, geochemistry and geological significance of tourmaline-rich rocks from the Paleozoic Cinco Villas massif (western Pyrenees, Spain)

Tourmaline-rich rocks associated with clastic metasedimentary rocks of Carboniferous age occur in the Cinco Villas massif, western Pyrenees. Three types of tourmaline-rich rocks were distinguished: (1) Fine-grained stratiform tourmaline-rich rocks, which are associated with carbonaceous metapelites (TR1); (2) stratabound tourmaline-rich rocks, associated with metapelites in the contact aureole of the Aya granitoid pluton (TR2); (3) stratabound to massive tourmaline-rich rocks, associated with psammopelites in contact with granites and pegmatites (TR3). Tourmalines belong to the schorl–dravite solid solution series and have a wide compositional range, from nearly end-member dravite for TR1 tourmalines to schorl for TR3 tourmalines; TR2 tourmalines have intermediate compositions. The Fe/(Fe+Mg) typically varies between 0.02 and ≈0.55, increasing from TR1 to TR3. The TR1 tourmalines commonly display a discontinuous chemical zoning with Fe-rich green cores (8–8.5% FeO) and Mg-rich colorless rims (10–11% MgO). In contrast, crystals that exhibit fine growth lamellae appear to lack significant chemical zoning. Oxygen and hydrogen isotope compositions also reveal major differences between TR1 and TR3 tourmalines, the former displaying heavier δ¹⁸O values (17.7–19‰) and δD values (−35 to −42‰) than TR3 tourmalines 11 to 13‰ and −47 to −76‰, respectively. The TR2 tourmalines show intermediate values of 11.3 to 14.6‰ for δ¹⁸O and −40 to −55‰ for δD. Linear and continuous chemical variations obtained for major and trace elements of the whole rocks reflect mixing between clay-rich and quartz-rich end-members, indicative that some tourmaline-rich rocks contain a significant detrital component. Chondrite normalized REE (rare earth element) patterns of tourmaline-rich rocks are similar to those of surrounding unaltered clastic metasediments, except for some TR1 rocks which are characterized by low contents of ΣREE. Mass-balance calculations show that tourmaline-forming processes plus metamorphism led to mass and volume changes at mesoscopic scales (≈10% for the TR1 tourmalinites). Silicon, Fe, Mn, and REE elements were partially lost from sedimentary rocks, whereas Mg and particularly B were added to pelitic sediments. Available data, nevertheless, do not allow an assessment of the boron source. Formation of the TR1 tourmaline-rich rocks probably was the net result of several processes, including direct precipitation from B-rich hydrothermal fluids or colloids, early diagenetic reactions of carbonaceous pelitic sediments with these fluids, and subsequent recrystallization during regional metamorphism. The TR2 tourmaline-rich rocks mainly developed by metamorphic recrystallization of TR1. Tourmaline-rich rocks and veins adjacent to pegmatites and granitic rocks (TR3) are the result of boron metasomatism; the primary boron having been recycled from stratiform tourmalinites during regional metamorphism and magmatism. Received: 18 November 1996 / Accepted: 25 April 1997     

The Differential Geochemical Behavior of Arsenic and Phosphorus in the Water Column and Sediments of the Saguenay Fjord Estuary, Canada

The distribution and partitioning of dissolved andparticulate arsenic and phosphorus in the water columnand sediments of the Saguenay Fjord in Quebec, Canada,are compared. In addition, selective and/or sequentialextractions were carried out on the suspendedparticulate matter (SPM) and solid sediments tocontrast their geochemical behaviors in this naturalaquatic system.Results of our analyses show that both arsenic andsoluble reactive phosphate are actively scavenged fromthe water column by settling particles. Upon theiraccumulation at the sediment-water interface some Asand P may be released to porewaters following thedegradation of organic matter to which they areassociated. The porewater concentrations are, however,limited by their strong affinity for authigenic,amorphous iron oxyhydroxides which accumulate in theoxic sediments near the sediment-water interface.The geochemical behavior of arsenic and phosphorusdiverge most strikingly upon the development of anoxicconditions in the sediments. Following their burial inthe anoxic zone, amorphous iron oxyhydroxides arereduced and dissolved, releasing phosphate and arsenicto the porewaters. We observed, however, thatporewater arsenic concentrations increase at shallowerdepths than phosphate in the sediments. The reductionof arsenate, As(V), to arsenite, As(III), and itsdesorption prior to the reductive dissolution of thecarrier phase(s) may explain this observation.Driven by the strong concentration gradientestablished in the suboxic zone, phosphate diffuses uptowards the oxic layer where it is readsorbed byauthigenic iron oxyhydroxides. In the organic-rich andrapidly accumulating sediments at the head of theFjord, porewater sulfate depletion and the resultingabsence of a sulfide sink for Fe(II), may lead to theformation of vivianite in the fermentation zone, apotential sink for phosphate. Arsenite released to theporewaters in the suboxic and anoxic zones of thesediments diffuses either down, where it is adsorbedto or incorporated with authigenic iron sulfides, orup towards the oxic boundary. Arsenite appears tomigrate well into the oxic zone where it may beoxidized by authigenic manganese oxides before beingadsorbed by iron oxyhydroxides present at the samedepth. Whereas, in the absence of authigenic carbonatefluorapatite precipitation, the ability of oxicsediments to retain mineralized phosphate is afunction of their amorphous iron oxyhydroxide content,arsenic retention may depend on the availability ofmanganese oxides, the thickness of the oxic layer and,its co-precipitation with iron sulfides at depth.     

The Gulf of California: Review of ecosystem status and sustainability challenges

The Gulf of California is unique because of its geographical location and conformation. It hosts diverse ecosystems and important fisheries that support industry and provide livelihood to coastal settlements. It is also the site of interests and problems, and an intense interaction among managers, producers, and conservationists. In this report, we scrutinize the abiotic (hydrography, climate, ocean circulation, and chemistry) and biotic (phyto- and zooplankton, fish, invertebrates, marine mammals, birds, and turtles) components of the marine ecosystem, and some particular aspects of climate variability, endemisms, harmful algal blooms, oxygen minimum layer, and pollution. We also review the current conditions and conflicts around the main fisheries (shrimp, small and large pelagic fishes, squid, artisanal and sportfishing), the most important human activity in the Gulf of California. We cover some aspects of management and conservation of fisheries, especially the claimed overexploitation of fish resources and the ecosystems, and review proposals for creating networks of marine protected areas. We conclude by identifying main needs for information and research, particularly the integration of data bases, the implementation of models and paleoreconstructions, establishment of monitoring programs, and the evaluation of fishing impacts and management actions.     

OSL dating of the Middle Palaeolithic Hotel California site,Sierra de Atapuerca,north‐central Spain

In this study we present optically stimulated luminescence (OSL) dating results obtained at one of the most important open‐air Middle Palaeolithic sites in the Sierra de Atapuerca foothills – Hotel California. We also assess the possibility of obtaining extended‐range OSL chronologies for a nearby Middle Pleistocene fluvial deposit using several novel methods, namely OSL dating of individual quartz ‘supergrains’, multi‐grain aliquot thermally transferred OSL (TT‐OSL) dating and the first application of a single‐grain TT‐OSL dating procedure. Four single‐grain OSL ages constrain the Middle Palaeolithic occupation of Hotel California to between 71±6 and 48±3 ka. The Hotel California single‐grain equivalent dose (D_e) distributions are highly overdispersed and contain several dose populations, which are probably attributable to post‐depositional sediment mixing, partial bleaching and intrinsic scatter. The reliability of multi‐grain aliquot OSL dating is compromised by the complex underlying D_e dispersion affecting these samples, as well as by biasing multi‐grain averaging effects. Extended‐range OSL and TT‐OSL chronologies for the nearby Pico River terrace are consistent with each other and with broad independent age control. These experimental approaches yield a weighted average age of 348±16 ka for terrace T_A9 of the Arlanzón River sequence. Our results highlight the benefits of comparing ages obtained using several OSL methodologies to improve the robustness of luminescence chronologies. They also demonstrate the potential that single‐grain OSL techniques offer for establishing improved age constraints on the many other Middle Palaeolithic sites found at Atapuerca and elsewhere across north‐central Spain.     

The Cretaceous sediment-hosted copper deposits of San Marcos (Coahuila,Northeastern Mexico): An approach to ore-forming processes

In the San Marcos ranges of Cuatrociénegas, NE Mexico, several sediment-hosted copper deposits occur within the boundary between the Coahuila Block, a basement high mostly granitic in composition and Late Paleozoic to Triassic in age, and the Mesozoic Sabinas rift basin. This boundary is outlined by the regional-scale synsedimentary San Marcos Fault. At the basin scale, the copper mineralization occurs at the top of a ～1000 m thick red-bed succession (San Marcos Formation, Berrisian), a few meters below a conformable, transitional contact with micritic limestones (Cupido Formation, Hauterivian to Aptian). It consists of successive decimeter-thick roughly stratiform copper-rich horizons placed just above the red-beds, in a transitional unit of carbonaceous grey-beds grading to micritic limestones. The host rocks are fine- to medium-grained arkoses, with poorly sorted and subangular to subrounded grains. The detrital grains are cemented by quartz and minor calcite; besides, late iron oxide grain-coating cement occurs at the footwall unmineralized red-beds. The source area of the sediments, indicated by their modal composition, is an uplifted basement. The contents of SiO₂ (40.70–87.50 wt.%), Al₂O₃ (5.91–22.00 wt.%), K₂O (3.68–12.50 wt.%), Na₂O (0.03–2.03 wt.%) and CaO (0.09–3.78 wt.%) are within the ranges expected for arkoses. Major oxide ratios indicate that the sedimentary-tectonic setting was a passive margin.The outcropping copper mineralization essentially consists in a supergene assemblage of chrysocolla, malachite and azurite. All that remains of the primary mineralization are micron-sized chalcocite grains shielded by quartz cement. In addition, pyrite subhedral grains occur scattered throughout the copper-mineralized horizons. In these weathered orebodies copper contents range between 4.24 and 7.72 wt.%, silver between 5 and 92 ppm, and cobalt from 8 to 91 ppm. Microthermometric measurements of fluid inclusions in quartz and calcite crystals from footwall barren veinlets gave temperatures of homogenization between 98 °C and 165 °C, and ice-melting temperatures between ?42.5 °C and ?26.1 °C.The primary copper mineralization formed during the early diagenesis, contemporary with the active life of the Sabinas Basin. The mineralizing fluids were dense, near neutral, moderately oxidized brines that originally formed from seawater that, driven by gravity, infiltrated to the deepest parts of the basin and dissolved evaporites. As a result, they became hydrothermal fluids of moderate temperature capable of leaching high amounts of copper. The source of this metal could be mafic detrital grains and iron oxides of the underlying Jurassic and Lower Cretaceous red-beds. Copper precipitation took place when the brines passed through the redox boundary marked by the transition from red- to grey-beds. The upward movement of the brines was promoted by a high heat flow that allowed their convective circulation and their ascent along the synsedimentary San Marcos Fault.     

On classical iterative subdomain methods for the Stokes–Darcy problem

Within classical iterative subdomain methods, the problems in the subdomains are solved alternately by only using data on the interface provided from the other subdomains. Methods of this type for the Stokes–Darcy problem that use Robin boundary conditions on the interface are reviewed. Their common underlying structure and their main differences are identified. In particular, it is clarified that there are different updating strategies for the interface conditions. For small values of fluid viscosity and hydraulic permeability, which are relevant in applications from geosciences, it is shown in numerical studies that only one of these updating strategies leads to an efficient numerical method, if it is used with appropriate parameters in the Robin conditions.