Geological and anthropogenic influences on sediment metal composition in the upper Paracatu River Basin, Brazil

This work reports a geochemical study of sediments from the upper Paracatu River Basin. The objective is to define the influences of Au, Zn, and Pb mineral deposits and mining activities on the sediment metal sources, distribution, and accretion. The samples were analyzed using ICP/OES, AAS, and XRD techniques and were treated with principal components analysis and the geo-accumulation index. The main geochemical processes that control the sediment composition are pyrite oxidation, muscovite weathering, carbonate dissolution, and the erosion of oxisols enriched with Zn and Pb. The upper Rico Stream has high Al, Fe, Cu, Cr, Co, and Mn concentrations due erosion of oxisols and pyrite oxidation and muscovite alteration present in the parental rock. The artisanal alluvial gold mining increased the primary rock-minerals?? weathering and Hg sediment concentration. The lower Escuro River and Santa Catarina Stream are enriched with Zn and Pb due the erosion of metal-rich soils formed over galena, sphalerite, calamine, and willemite mineral deposits located upstream. Elements such as Ca, Mg, and Ba have low concentrations throughout the sampled area due the high solubility of these metals-bearing minerals. The dispersion of metals is limited by the basin geomorphology and their affinity to silt-clayey minerals and Fe and Mn oxides and hydroxides in circumneutral pH waters.     

Evaluation of heavy metals and arsenic speciation discharged by the industrial activity on the Tinto-Odiel estuary, SW Spain

This study reports the annual amount of heavy metals discharged by industrial activity into the estuary of the Ría of Huelva (SW Spain). The findings showed that the discharged metals found in highest amounts were Fe (11 t y⁻¹), Zn (3.4 t y⁻¹) and Mo (0.88 t y⁻¹). There were other metals with high pollutant charge, such as Ti (232 kg y⁻¹), As (228 kg y⁻¹), Ni (195 kg y⁻¹), Pb (100 kg y⁻¹), Cr (39 kg y⁻¹) and Cd (33 kg y⁻¹). These results were compared with pollutants transported via the Tinto and Odiel rivers from abandoned mining activities in the Iberian Pyrite Belt (IPB), and it was deduced that the amounts spilled exclusively by industries were less than 1% in relation to the total discharge. Hence, the treatment of residues from the IPB should be the priority goal to improve water quality in the estuary.     

Compositional Bayesian indicator estimation

Indicator kriging is widely used for mapping spatial binary variables and for estimating the global and local spatial distributions of variables in geosciences. For continuous random variables, indicator kriging gives an estimate of the cumulative distribution function, for a given threshold, which is then the estimate of a probability. Like any other kriging procedure, indicator kriging provides an estimation variance that, although not often used in applications, should be taken into account as it assesses the uncertainty of the estimate. An alternative approach to indicator estimation is proposed in this paper. In this alternative approach the complete probability density function of the indicator estimate is evaluated. The procedure is described in a Bayesian framework, using a multivariate Gaussian likelihood and an a priori distribution which are both combined according to Bayes theorem in order to obtain a posterior distribution for the indicator estimate. From this posterior distribution, point estimates, interval estimates and uncertainty measures can be obtained. Among the point estimates, the median of the posterior distribution is the maximum entropy estimate because there is a fifty-fifty chance of the unknown value of the estimate being larger or smaller than the median; that is, there is maximum uncertainty in the choice between two alternatives. Thus in some sense, the latter is an indicator estimator, alternative to the kriging estimator, that includes its own uncertainty. On the other hand, the mode of the posterior distribution estimator, assuming a uniform prior, is coincidental with the simple kriging estimator. Additionally, because the indicator estimate can be considered as a two-part composition which domain of definition is the simplex, the method is extended to compositional Bayesian indicator estimation. Bayesian indicator estimation and compositional Bayesian indicator estimation are illustrated with an environmental case study in which the probability of the content of a geochemical element in soil being over a particular threshold is of interest. The computer codes and its user guides are public domain and freely available.     

Uphill diffusion,zero-flux planes and transient chemical solitary waves in garnet

Diffusion profiles in minerals are increasingly used to determine the duration of geological events. For this purpose, the distinction between growth and diffusion zoning is critical; it requires the understanding of complex features associated with multicomponent diffusion. Seed-overgrowth interdiffusion experiments carried out in the range 1,050–1,250°C at 1.3 GPa have been designed to quantify and better understand Fe–Mg–Ca interdiffusion in garnet. Some of the diffusion profiles measured by analytical transmission electron microscope show characteristic features of multicomponent diffusion such as uphill diffusion, chemical solitary waves, zero-flux planes and complex diffusion paths. We implemented three different methods to calculate the interdiffusion coefficients of the D matrix from the experimental penetration curves and determined that with Ca as the dependent component, the crossed coefficients of the D matrix are negative. Experiments and numerical simulations indicate that: (1) uphill diffusion in garnet can be observed indifferently on the three components Fe, Mg and Ca, (2) it takes the form of complementary depletion/repletion waves and (3) chemical waves occur preferentially on initially flat concentration profiles. Derived D matrices are used to simulate the fate of chemical waves in time, in finite crystals. These examples show that the flow of atoms in multicomponent systems is not necessarily unidirectional for all components; it can change both in space along the diffusion profile and in time. Moving zero-flux planes in finite crystals are transitory features that allow flux reversals of atoms in the diffusion zone. Interdiffusion coefficients of the D matrices are also analyzed in terms of eigenvalues and eigenvectors. This analysis and the experimental results show that depending on the composition of the diffusion couple, (1) the shape of chemical waves and diffusion paths changes; (2) the width of the diffusion zone for each component may or may not be identical; and (3) the width of diffusion calculated at a given D and duration may greatly vary. D matrices were retrieved from thirteen sets of diffusion profiles. Data were cast in Arrhenius relations. Linear regressions of the data yield activation energies equal to 368, 148, 394, 152 kJ mol⁻¹ at 1 bar and frequency factors D_o equal to 2.37 × 10⁻⁶, −4.46 × 10⁻¹⁶, −1.31 × 10⁻⁵, 9.85 × 10⁻¹⁵ m² s⁻¹ for [(D)\tilde]_FeFe^Ca \tilde{D}_{FeFe}^{Ca} , [(D)\tilde]_FeMg^Ca \tilde{D}_{FeMg}^{Ca} , [(D)\tilde]_MgFe^Ca \tilde{D}_{MgFe}^{Ca} , [(D)\tilde]_MgMg^Ca \tilde{D}_{MgMg}^{Ca} , respectively. These values can be used to calculate interdiffusion coefficients in Fe–Mg–Ca garnets and determine the duration of geological events in high temperature metamorphic or magmatic garnets.     

Extreme temperature scenarios in Mexicali,Mexico under climate change conditions

Extreme weather events can have severe consequences for the population and the environment. Therefore, in this study a temporal trend of annual temperatures was built with a time series from 1950 to 2010 for Mexicali, Mexico, and estimates of 5- to 100-year return periods are provided by modeling of summer maximum and winter minimum temperatures. A non-parametric Kendall’s tau test and the Sen’s slope estimator were used to compute trends. The generalized extreme value (GEV) distribution was applied to the approximation of block maxima and the generalized Pareto distribution (GPD) to values over a predetermined threshold. Due to the non-stationary characteristic of the series of temperature values, the temporal trend was included as a covariable in the location parameter and substantial improvements were observed, particularly with the extreme minimum temperature, compared to that obtained with the GEV with no covariable and with the GPD. A positive and significant statistically trend in both summer maximum temperature and winter minimum temperature was found. By the end of 21st century the extreme maximum temperature could be 2 to 3 °C higher than current, and the winter could be less severe, as the probabilistic model suggests increases of 7 to 9 °C in the extreme minimum temperature with respect to the base period. The foreseeable consequences on Mexicali city are discussed.     

Seasonal Diet Shifts and Overlap Between Two Sympatric Catfishes in an Estuarine Nursery

This study describes the seasonal feeding habits of different size classes of Cathorops spixii and Cathorops agassizii along an estuarine ecocline and the food overlap when different size classes occur together. These species were essentially zoobenthivorous, feeding mainly on Polychaeta Nereis sp., Copepoda Pseudodiaptomus acutus, Ostracoda Asterope sp., Gastropoda: Littorinidae, and Bivalvia Mytilus sp. and Anomalocardia brasiliana. However, during their life cycle and between different habitats and seasons, their trophic guild can change to zooplanktivore. The competition for resources was observed among C. spixii and C. agassizii, but was significantly reduced due to the seasonal diference in habitat use by different ontogenetic phases in the main channel of the estuary. The food niche separation was strongly influenced by environmental fluctuations, principally of salinity, resulting from rainfall and river inflow. High abundance of some preys, such as P. acutus (all estuary), Asterope sp. (upper and middle estuary), and Littorinidae (upper and lower estuary), could influence the significant diet overlap, principally during the rainy season, and call for more detailed studies of the benthic community structure. Moreover, dietary overlap was observed mainly between smaller sizes (intraspecific and/or interspecific) or between corresponding ontogenetic phases (interspecific), suggesting some differentiation in the diet in relation to the size class. Differences in prey type and size between the different ontogenetic phases of these ariids, principally among juveniles and adults, could be related to the size of the mouth, since adults are able to successfully capture larger preys or larger quantities of particular items.     

Using semivariogram parameter uncertainty in hydrogeological applications

Geostatistical estimation (kriging) and geostatistical simulation are routinely used in ground water hydrology for optimal spatial interpolation and Monte Carlo risk assessment, respectively. Both techniques are based on a model of spatial variability (semivariogram or covariance) that generally is not known but must be inferred from the experimental data. Where the number of experimental data is small (say, several tens), as is not unusual in ground water hydrology, the model fitted to the empirical semivariogram entails considerable uncertainty. If all the practical results are based on this unique fitted model, the final results will be biased. We propose that, instead of using a unique semivariogram model, the full range of models that are inside a given confidence region should be used, and the weight that each semivariogram model has on the final result should depend on its plausibility. The first task, then, is to evaluate the uncertainty of the model, which can be efficiently done by using maximum likelihood inference. The second task is to use the range of plausible models in applications and to show the effect observed on the final results. This procedure is put forth here with kriging and simulation applications, where the uncertainty in semivariogram parameters is propagated into the final results (e.g., the prediction of ground water head). A case study using log-transmissivity data from the Vega de Granada aquifer, in southern Spain, is given to illustrate the methodology.     

High-precision geoid determination in small areas: A case study in Doñana National Park (Spain)

Doñana National Park is an area of approximately 500 km² located on the SW coast of Spain that shows one of the greatest geoid gradients on the entire Iberian Peninsula, due to its peculiar tectonic characteristics. So, it is necessary to elaborate an accurate geoid model that can be used with GPS for precise surveying, since the existing ones are insufficient, due to their poor resolution and their limited adaptation to a small area with such a strong gradient. The least squares prediction method was tested in order to obtain the undulation from GPS/orthometric points. The results obtained were unsatisfactory because of the strong geoid gradient. In order to improve accuracy the remove-restore technique was used. Global geopotential model EIGEN-CG01C and a Digital Elevation Model (DEM) with a 25 × 25 m resolution and an accuracy better than 3 m were used. Thus, the final geometrical geoid obtained reaches the precision required by other disciplines (3 cm in any point within the Park). Particularly, the geoid model has allowed for the acquisition of a precision DEM that is essential to formulate a hydrodynamic model for the Doñana marsh functions.     

Katla volcano,Iceland: magma composition,dynamics and eruption frequency as recorded by Holocene tephra layers

The Katla volcano in Iceland is characterized by subglacial explosive eruptions of Fe–Ti basalt composition. Although the nature and products of historical Katla eruptions (i.e. over the last 1,100 years) at the volcano is well-documented, the long term evolution of Katla’s volcanic activity and magma production is less well known. A study of the tephra stratigraphy from a composite soil section to the east of the volcano has been undertaken with emphasis on the prehistoric deposits. The section records ∼8,400 years of explosive activity at Katla volcano and includes 208 tephra layers of which 126 samples were analysed for major-element composition. The age of individual Katla layers was calculated using soil accumulation rates (SAR) derived from soil thicknesses between ¹⁴C-dated marker tephra layers. Temporal variations in major-element compositions of the basaltic tephra divide the ∼8,400-year record into eight intervals with durations of 510–1,750 years. Concentrations of incompatible elements (e.g. K₂O) in individual intervals reveal changes that are characterized as constant, irregular, and increasing. These variations in incompatible elements correlate with changes in other major-element concentrations and suggest that the magmatic evolution of the basalts beneath Katla is primarily controlled by fractional crystallisation. In addition, binary mixing between a basaltic component and a silicic melt is inferred for several tephra layers of intermediate composition. Small to moderate eruptions of silicic tephra (SILK) occur throughout the Holocene. However, these events do not appear to exhibit strong influence on the magmatic evolution of the basalts. Nevertheless, peaks in the frequency of basaltic and silicic eruptions are contemporaneous. The observed pattern of change in tephra composition within individual time intervals suggests different conditions in the plumbing system beneath Katla volcano. At present, the cause of change of the magma plumbing system is not clear, but might be related to eruptions of eight known Holocene lavas around the volcano. Two cycles are observed throughout the Holocene, each involving three stages of plumbing system evolution. A cycle begins with an interval characterized by simple plumbing system, as indicated by uniform major element compositions. This is followed by an interval of sill and dyke system, as depicted by irregular temporal variations in major element compositions. This stage eventually leads to a formation of a magma chamber, represented by an interval with increasing concentrations of incompatible elements with time. The eruption frequency within the cycle increases from the stage of a simple plumbing system to the sill and dyke complex stage and then drops again during magma chamber stage. In accordance with this model, Katla volcano is at present in the first interval (i.e. simple plumbing system) of the third cycle because the activity in historical time has been characterized by uniform magma composition and relatively low eruption frequency.