Biogeochemical Behavior of Arsenic Species at Paranaguá Estuarine Complex, Southern Brazil

The behavior and dynamics of arsenic at Ilha do Mel, Guaraque?aba, and Paranaguá, located in the Paranaguá Estuarine Complex, Brazil, were investigated in this work. Samples were collected in March, September, and December of 2005. With respect to arsenic behavior, the total concentrations were higher for Paranaguá (22.5?±?2.5?μg?L^?1) on average, followed by the samples of Guaraque?aba (14.4?±?3.2?μg?L^?1) and Ilha do Mel (8.7?±?1.1?μg?L^?1). The concentrations found in this work were consistently greater when compared to other estuaries. The results can be attributed to geological factors. Nevertheless, it was also possible to realize that higher concentrations were found in Paranaguá, the more impacted environment. These results represent a strong indication that human activities in the area contribute to the enrichment of the estuary with this metalloid. Arsenic was mainly present in the dissolved phase, which corresponded to more than 70% of the total concentration. This behavior can represent a greater residence time of this metalloid in the water column. The marine phytoplankton presence was decisive in dictating the distribution of As in the waters of Paranaguá estuary. Organic species, which are considered the less toxic, were found in higher concentrations in the eutrophic areas such as Guaraque?aba and Paranaguá. This was a typical behavior during the summer probably due to higher biological activity.     

Formation and age of sphalerite mineralization in carbonate rocks of Bajocian age in the Swiss Jura Mountains: evidence of Mesozoic hydrothermal activity

A combination of petrographic and geochemical techniques was applied to better constrain the origin and evolution of the fluid systems responsible for the formation of disseminated, Cd-rich (up to 0.6 wt%), sphalerite (ZnS) mineralization in the northeastern part of the Jura Mountains, Switzerland. The Rb–Sr ages of sphalerite samples indicate that a main phase of sphalerite formation occurred near the boundary between the late Middle and early Late Jurassic, at around 162 Ma. The negative δ³⁴S values (?22.3 to ?5.3 ‰) suggest that biogenic sulfide sulfur was involved in ZnS precipitation. The strontium isotope composition is more radiogenic than that of contemporaneous seawater, reflecting the interaction of mineralizing fluids with silicate rocks. Lead isotope signatures are very uniform (²⁰⁶Pb^/204Pb = 18.63–18.67, ²⁰⁷Pb^/204Pb = 15.63–15.64, ²⁰⁸Pb^/204Pb = 38.51–38.63), indicating an isotopically well-homogenized fluid system. The basement rocks underlying the Jurassic strata are considered to be the main source of metals for the sphalerite mineralization. The migration of deep-sourced hydrothermal saline metal-bearing fluids into the Bajocian host carbonates containing sedimentary reduced sulfur resulted in the precipitation of sulfides. The period of sphalerite formation near the Middle–Late Jurassic boundary is characterized by enhanced tectonic and hydrothermal activity in Europe, related to the opening of the Central Atlantic and tectonic/thermal subsidence during spreading of the Alpine Tethys. Our study provides evidence that the Bajocian carbonate rocks in the Jura Mountains area were affected by the circulation of deep-sourced metal-bearing hydrothermal fluids in response to these continent-wide tectonothermal events. The presence of sphalerite mineralization and associated geochemical anomalies in Zn and Cd contents in carbonate rocks may also be used to trace basement features.     

Geochemistry of highly acidic mine water following disposal into a natural lake with carbonate bedrock

Acid mine drainage (AMD) from the Zn–Pb(–Ag–Bi–Cu) deposit of Cerro de Pasco (Central Peru) and waste water from a Cu-extraction plant has been discharged since 1981 into Lake Yanamate, a natural lake with carbonate bedrock. The lake has developed a highly acidic pH of ∼1. Mean lake water chemistry was characterized by 16,775 mg/L acidity as CaCO₃, 4330 mg/L Fe and 29,250 mg/L SO₄. Mean trace element concentrations were 86.8 mg/L Cu, 493 mg/L Zn, 2.9 mg/L Pb and 48 mg/L As, which did not differ greatly from the discharged AMD. Most elements showed increasing concentrations from the surface to the lake bottom at a maximal depth of 41 m (e.g. from 3581 to 5433 mg/L Fe and 25,609 to 35,959 mg/L SO₄). The variations in the H and O isotope compositions and the element concentrations within the upper 10 m of the water column suggest mixing with recently discharged AMD, shallow groundwater and precipitation waters. Below 15 m a stagnant zone had developed. Gypsum (saturation index, SI ∼ 0.25) and anglesite (SI ∼ 0.1) were in equilibrium with lake water. Jarosite was oversaturated (SI ∼ 1.7) in the upper part of the water column, resulting in downward settling and re-dissolution in the lower part of the water column (SI ∼ −0.7). Accordingly, jarosite was only found in sediments from less than 7 m water depth. At the lake bottom, a layer of gel-like material (∼90 wt.% water) of pH ∼1 with a total organic C content of up to 4.40 wet wt.% originated from the kerosene discharge of the Cu-extraction plant and had contaminant element concentrations similar to the lake water. Below the organic layer followed a layer of gypsum with pH 1.5, which overlaid the dissolving carbonate sediments of pH 5.3–7. In these two layers the contaminant elements were enriched compared to lake water in the sequence As < Pb ≈ Cu < Cd < Zn = Mn with increasing depth. This sequence of enrichment was explained by the following processes: (i) adsorption of As on Fe-hydroxides coating plant roots at low pH (up to 3326 mg/kg As), (ii) adsorption at increasing pH near the gypsum/calcite boundary (up to 1812 mg/kg Pb, 2531 mg/kg Cu, and 36 mg/kg Cd), and (iii) precipitation of carbonates (up to 5177 mg/kg Zn and 810 mg/kg Mn; all data corrected to a wet base). The infiltration rate was approximately equal to the discharge rate, thus gypsum and hydroxide precipitation had not resulted in complete clogging of the lake bedrocks.     

Spatial and Temporal Ion Dynamics on a Complex Hydrological System: The Lower Luján River (Buenos Aires,Argentina)

The interplay of the geochemistry of the lower stretch of the Luján River is analyzed with its natural geomorphology (basin features), local hydrometeorology (tidal regime and “sudestada” events) and the impact of polluted tributaries. Major ions, dissolved heavy metals and limnological variables were analyzed using multivariate techniques. The water quality of the mainstream of the Luján River, flowing through urbanized and industrialized areas is strongly and positively influenced by the input of the Paraná River through deltaic watercourses and is negatively impacted after receiving the discharge from polluted watercourses. The longitudinal spatial variations evidenced major discontinuities in the Lower Luján Basin, showing clearly the riverine and the deltaic water influenced zones. Seasonal variations were also marked and were either temperature driven or associated with the estuarine cycle and the “sudestada”.     

Net Primary Productivity of <Emphasis Type="Italic">Spartina densiflora</Emphasis> Brong in an SW Atlantic Coastal Salt Marsh

Coastal marshes are known as organic matter producers. The goal of this work is to study tiller demography, standing biomass, and net aerial primary productivity (NAPP) in a Spartina densiflora coastal wetland, using a method applied to permanent sample plots located at two sites differing in topographic location, a regularly flooded zone [relative low marsh (LM)] and an irregularly flooded one [relative high marsh (HM)]. Measurements were made every 2 months during the 2005–2007 period. The annual NAPP was estimated to be 2,599?±?705 gDW m^?2?year^?1 for the HM and 2,181?±?605 gDW m^?2?year^?1 and 602?±?154 gDW m^?2?year^?1 for the first and second period of the LM populations, respectively, showing a seasonal pattern reaching maximum values in summer. The reduced NAPP values of the LM sites in the second year was associated with an extremely high precipitation period related to the 2007–2008 El Niño event.     

Scaling properties and spatial organization of snow depth fields in sub‐alpine forest and alpine tundra

This paper reports on a study analysing the spatial distribution functions, the correlation structures, and the power spectral densities of high‐resolution LIDAR snow depths (～1 m) in two adjacent 500 m × 500 m areas in the Colorado Rocky Mountains, one a sub‐alpine forest the other an alpine tundra. It is shown how and why differences in the controlling physical processes induced by variations in vegetation cover and wind patterns lead to the observed differences in spatial organization between the snow depth fields of these environments. In the sub‐alpine forest area, the mean of snow depth increases with elevation, while its standard deviation remains uniform. In the tundra subarea, the mean of snow depth decreases with elevation, while its standard deviation varies over a wide range. The two‐dimensional correlations of snow depth in the forested area indicate little spatial memory and isotropic conditions, while in the tundra they indicate a marked directional bias that is consistent with the predominant wind directions and the location of topographic ridges and depressions. The power spectral densities exhibit a power law behaviour in two frequency intervals separated by a break located at a scale of around 12 m in the forested subarea, and 65 m in the tundra subarea. The spectral exponents obtained indicate that the snow depth fields are highly variable over scales larger than the scale break, while highly correlated below. Based on the observations and on synthetic snow depth fields generated with one‐ and two‐dimensional spectral techniques, it is shown that the scale at which the break occurs increases with the separation distance between snow depth maxima. In addition, the breaks in the forested area coincide with those of the corresponding vegetation height field, while in the tundra subarea they are displaced towards larger scales than those observed in the corresponding vegetation height field. Copyright © 2009 John Wiley & Sons, Ltd.     

Solving Kepler’s equation via Smale’s \alpha -theory

We obtain an approximate solution $\tilde{E}=\tilde{E}(e,M)$ of Kepler’s equation $E-e\sin (E)=M$ for any $e\in [0,1)$ and $M\in [0,\pi ]$ . Our solution is guaranteed, via Smale’s $\alpha $ -theory, to converge to the actual solution $E$ through Newton’s method at quadratic speed, i.e. the $n$ -th iteration produces a value $E_n$ such that $|E_n-E|\le (\frac{1}{2})^{2^n-1}|\tilde{E}-E|$ . The formula provided for $\tilde{E}$ is a piecewise rational function with conditions defined by polynomial inequalities, except for a small region near $e=1$ and $M=0$ , where a single cubic root is used. We also show that the root operation is unavoidable, by proving that no approximate solution can be computed in the entire region $[0,1)\times [0,\pi ]$ if only rational functions are allowed in each branch.