Partitioning of Se, As, Sb, Te and Bi between monosulfide solid solution and sulfide melt - Application to magmatic sulfide deposits

The chalcogenes (S, Se, Te), semimetals (As, Sb) and the metal Bi are important ligands for noble metals and form a wide range of compositionally diverse minerals with the platinum-group elements (PGE). With the exception of S, few experimental data exist to quantify the behavior of these elements in magmatic sulfide systems. Here we report experimental partition coefficients for Se, Te, As, Sb, and Bi between monosulfide solid solution (mss) and sulfide melt, determined at 950 °C at a range of sulfur fugacities (fS2) bracketed by the Fe-FeS (metal-troilite) and the Fe_1−×S-S_x (mss-sulfur) equilibria. Selenium is shown to partition in mss-saturated sulfide melt as an anion replacing S²⁻. Arsenic changes its oxidation state with fS₂ from predominantly anionic speciation at low fS₂, to cationic speciation at high fS₂. The elements Sb, Te, and Bi are so highly incompatible with mss that they can only be present in sulfide melt as cations and/or as neutral metallic species. The partition coefficients derived fall with increasing atomic radius of the element. They also reflect the positions of the respective elements in the Periodic Table: within a group (e.g., As, Sb, Bi) the partition coefficients fall with increasing atomic radius, and within a period the elements of the 15th group are more incompatible with mss than the neighboring elements of the 16th group.     

Clay minerals in sediments of Portuguese reservoirs and their significance as weathering products from over-eroded soils: a comparative study of the Maranhão, Monte Novo and Divor Reservoirs (South Portugal)

The Southern region of Portugal is subjected to several forms of over-erosion. Most leached products, mainly composed of fine particles containing nutrients, metals or pesticides, are easily transported by river flows. When these are hindered by a physical barrier such as a dam, the particulate load accumulates on the bottom of the reservoirs, often leading to a pronounced decrease of water quality. Bottom sediments from three reservoirs were subjected to grain-size analysis and a study of clay minerals by X-ray diffraction. Most sediments contain a diverse set of clay minerals, mostly illites, smectites, chlorites and kaolinites. The nature of the clay minerals reflects the nature of the parent rocks. During the cycles of transport and temporary deposition, they may undergo significant chemical and physical transformations, which lead to an increase of expandable properties and therefore, to a higher cationic exchange capacity, determining its important role as vehicles of environmental pollutants.     

Assessing the control exerted by soil mineralogy in the fixation of potentially harmful elements in the urban soils of Lisbon,Portugal

The main purposes of this study are the textural, chemical and mineralogical characterization of the urban soils of Lisbon and the identification of probable relations between the several soil properties. The results are used to infer which soil properties control the superficial dispersion of potential harmful elements to human health. Soil sampling was carried out in 51 selected sites all through the city, under the criterion that such sites should be spaces usually frequented by children. The concentrations of 42 elements in the >2 mm soil size fraction were determined at a commercial laboratory in Canada (ActLabs, LTD), by ICP-MS/ICP-OES after an acid digestion with aqua regia. The soil mineralogy was determined by X-ray diffraction in the <2 and <62 μm size fractions. The results indicate that the urban soils have mainly a sandy texture and a main mineralogical assemblage of quartz, K-feldspar, plagioclase and calcite. In terms of clay minerals, smectite, illite and kaolinite are the main clays in the soil. Smectite and illite show a dichotomy in their distribution, with the smectites prevailing in the soils of the volcanic complex of Lisbon, which are classified as being residual, and illite prevailing in the remaining soils, which are considered mainly as man-made soils. Smectite seems to exert an important role in the fixation of Ni and Cr. The results of the geochemical study show that Ni and Cr have concentrations above the soil guideline value established to the UK and pose a probable risk to human health.     

Moisture and heat budgets of the south American monsoon system: climatological aspects

The climatology of the moisture and heat budget equation terms for subareas within the South American Monsoon System (SAMS) region is investigated for the 1958–2014 period considering the distinct phases of the Pacific Decadal Oscillation (PDO). These budget equations are applied to the data from the National Centers for Environmental Prediction (NCEP) Reanalysis project. Sources or sinks of moisture and heat are equation residues, referred to as residue and diabatic terms, respectively. Analyses are done for the Central Amazon Basin (CAM) and Western-Central Brazil (WCB) for three distinct periods, 1958–1976, 1977–1995, and 1996–2014, that correspond to the cold, warm, and undefined PDO phases. The differences among the PDO phases for each term are discussed. The CAM region acts dominantly as a moisture sink and heat source in all months during the three phases. On the other hand, in the WCB region, the monsoon characteristics are better defined, with a moisture sink (source) and a heat source (sink) during the wet (dry) season. The main result of the present analysis is the persistence of SAMS intensification signs in both CAM and WCB areas up to the last analyzed period (1996–2014), which is consistent with intense flooding in the Amazon Basin in 2008/2009, 2012, and 2014.     

Summer circulation patterns related to the upper tropospheric vortices over the Tropical South Atlantic

Summary Daily 200-hPa relative vorticity data have been used to study the dominant patterns related to the cyclonic vortices over the South Atlantic Ocean in the vicinities of northeast Brazil, during the 1980–1989 period. Reference modes were obtained through empirical orthogonal function (EOF) analysis of the 200-hPa filtered vorticity anomalies over northeast Brazil, considering all the southern hemisphere (SH) summers within the study period. The amplitude time series of the first reference mode, separately for each SH summer, was correlated with the corresponding filtered vorticity anomalies in a larger area extending from 20°N to 40°S and between 120°W and 20°W. The correlation patterns feature a wave-like structure along eastern South America, with three main centers: the first one, over the South Atlantic off the northeast Brazil coast, is associated with the cyclonic vortices; the second one, over eastern Brazil, represents the corresponding anomalously amplified ridges; and the third one, over southern Brazil/Uruguay, is related to the equatorward incursions of midlatitude upper level troughs. This wave-like pattern is consistent with the vortex formation mechanism suggested in previous works. Another wave-like pattern southwest-northeast oriented is evident over the tropical southeastern Pacific, for some years. The internannual variability of these patterns is discussed in this paper.With 9 Figures     

Tide circulation patterns in a coastal lagoon under sea-level rise

This study evaluates the patterns and effects of relative sea-level rise on the tidal circulation of the basin of the Ria Formosa coastal lagoon using a process-based model that is solved on an unstructured mesh. To predict the changes in the lagoon tidal circulation in the year 2100, the model is forced by tides and a static sea level. The bathymetry and the basin geometry are updated in response to sea-level rise for three morphological response scenarios: no bed updating, barrier island rollover, and basin infilling. Model results indicate that sea-level rise (SLR) will change the baseline current velocity patterns inside the lagoon over the ~100-year study period, due to a strong reduction in the area of the intertidal basin. The basin infilling scenario is associated with the most important adjustments of the tidal circulation (i.e., increases in the flood velocities and delays in the ebb tide), together with an increase in the cumulative discharges of the tidal inlets. Under sea-level rise and in the basin infilling scenario, the salt marshes and tidal flats experience increases in the tidal range and current asymmetry. Basin infilling changes the sediment flushing capacity of the lagoon, leading to the attenuation of the flood dominance in the main inlet and the strengthening of the flood dominance in the two secondary inlets. The predictions resulting from these scenarios provide very useful information on the long-term evolution of similar coastal lagoons that experience varying degrees of SLR. This study highlights the need for research focusing on the quantification of the physical and socio-economic impacts of SLR on lagoon systems, thus enabling the development of effective adaptation strategies.