Natural Arsenic Attenuation via Metal Arsenate Precipitation in Soils Contaminated with Metallurgical Wastes: I. Wet Chemical and Thermodynamic Evidences

Arsenic from natural and anthropogenic sources is a worldwide contaminant of aqueous environments, such as groundwater and soils. The present investigation was performed on Mexican soils contaminated with residues from metallurgical processes that have shown a natural As attenuation. Experimental aqueous arsenic extractions in these were successfully simulated for almost half of the soil samples using a database updated for all known metal arsenate formation constants, revealing the predominance of solubility-controlled As mobility via Pb, mixed Pb–Cu, and Ca arsenate solid formation. The relatively low total Fe/As ratios (2–13 w/w) present in the soils studied, together with the high and equivalent contents of As, Pb, and Cu in these, favor the precipitation process over As(V) adsorption to Fe oxides, despite a 2% average Fe content in the soils studied. Under these conditions bicarbonate was found to be a highly unsuitable extractant due to its indirect As release from the solid arsenates, via heavy metal carbonate precipitation processes.     

Evaluation of methods of spatial interpolation for monthly rainfall data over the state of Rio de Janeiro,Brazil

Five deterministic methods of spatial interpolation of monthly rainfall were compared over the state of Rio de Janeiro, southeast Brazil. The methods were the inverse distance weight (IDW), nearest neighbor (NRN), triangulation with linear interpolation (TLI), natural neighbor (NN), and spline tension (SPT). A set of 110 weather stations was used to test the methods. The selection of stations had two criteria: time series longer than 20 years and period of data from 1960 to 2009. The methods were evaluated using cross-validation, linear regression between values observed and interpolated, root mean square error (RMSE), coefficient of determination (r ²), coefficient of variation (CV, %), and the Willmott index of agreement (d). The results from different methods are influenced by the meteorological systems and their seasonality, as well as by the interaction with the topography. The methods presented higher precision (r ²) and accuracy (d, RMSE) during the summer and transition to autumn, in comparison with the winter or spring months. The SPT had the highest precision and accuracy in relation to other methods, in addition to having a good representation of the spatial patterns expected for rainfall over the complex terrain of the state and its high spatial variability.     

Changes in the onset and length of seasons from an ensemble of regional climate models over Spain for future climate conditions

This study analyses the length and onset of the four seasons based on the annual climatic cycle of maximum and minimum temperatures. Previous studies focused over climatically homogeneous mid-high latitude areas, employing fixed temperature thresholds (related to climatic features such as freezing point) that can be inadequate when different climate conditions are present. We propose a method related to the daily minimum and maximum temperature 25th and 75th point-dependent climatic percentiles. It is applied to an ensemble of regional climate models (RCMs) of 25-km horizontal resolution over the peninsular Spain and Balearic Islands, where a large variety of climatic regimes, from alpine to semi-desertic conditions, are present. First, baseline climate (1961–2000) ERA40-forced RCM simulations are successfully compared with the Spain02 daily observational database, following astronomical season length (around 90 days). This result confirms the validity of the proposed method and capability of the RCMs to describe the seasonal features. Future climate global climate model-forced RCMs (2071–2100) compared with present climate (1961–1990) simulations indicate the disappearance of winter season, a summer enlargement (onset and end) and a slight spring and autumn increase.     

Runoff and sediment yield from land under various uses in a Mediterranean mountain area: long‐term results from an experimental station

In this study we analyzed runoff and sediment yield from land under various traditional and current land uses in Mediterranean mountain areas, using long‐term data from an experimental station in the Aísa Valley, Central Spanish Pyrenees. Monitoring at this station has provided 20 years of data that can help explain the hydrological and geomorphological changes that have been observed at larger spatial scales, and also the changes that have occurred to some of the most characteristic landscapes of the Mediterranean middle mountains. In spite of the problems associated with the use of small experimental plots, the results obtained are consistent with other studies in the Mediterranean region, and confirm the strong influence of land use changes on runoff generation and sediment yield. The results indicate that: (i) cereal cultivation on steep slopes (both alternating cereal cultivation and fallow on sloping fields and shifting agriculture on the steepest slopes) represents a major problem for soil conservation. This explains the occurrence throughout the Mediterranean mountains of many degraded hillslopes, which show evidence of sheet wash erosion, rilling, gullying and shallow landsliding; (ii) farmland abandonment has led to a marked reduction in runoff and sediment yield as a consequence of rapid plant recolonization, particularly by dense shrubs; (iii) the natural transformation of abandoned fields into grazing meadows has reduced runoff and sediment yield. Land use trends in the Mediterranean mountains are mainly characterized by generalized farmland abandonment and a decrease in livestock pressure. From a hydrological and geomorphological point of view the main consequences have been a reduction in overland flow from the hillslopes, and a reduction in sediment sources, with differences up to one order of magnitude in sediment yield from dense shrub cover and grazing meadow areas compared with areas under shifting agriculture. Copyright © 2012 John Wiley & Sons, Ltd.     

Ecological quality assessment of small estuaries from the Portuguese coast based on benthic macroinvertebrate assemblages indices

Benthic macroinvertebrates communities are the most consistently emphasized biotic component of aquatic ecosystems and are one of the biological indicators required for assessment by the European Water Framework Directive. In this context, several indices based on these communities have been developed in order to assess ecological quality of estuarine systems. In the present work we used AMBI, M-AMBI, BENTIX and BAT to distinguish ecological status of five small estuarine systems of the Portuguese south and southwest coasts. Although indices outputs did not differ between systems and sampling seasons, results indicated that the metrics in which these indices are based could differentiate community structures as a result of two main gradients that force these communities: the natural variability, and the anthropogenic impact.     

Response of single benthic metrics and multi-metric methods to anthropogenic pressure gradients, in five distinct European coastal and transitional ecosystems

In recent times many benthic indices have been proposed to assess the ecological quality of marine waters worldwide. In this study we compared single metrics and multi-metric methods to assess coastal and transitional benthic status along human pressure gradients in five distinct environments across Europe: Varna bay and lake (Bulgaria), Lesina lagoon (Italy), Mondego estuary (Portugal), Basque coast (Spain) and Oslofjord (Norway). Hence, 13 single metrics (abundance, number of taxa, and several diversity and sensitivity indices) and eight of the most common indices used within the European Water Framework Directive (WFD) for benthic assessment were selected: index of size spectra (ISS), Benthic assessment tool (BAT), Norwegian quality index (NQI), Multivariate AMBI (M-AMBI), Benthic quality index (BQI), (Benthic ecosystem quality index (BEQI), Benthic index based on taxonomic sufficiency (BITS), and infaunal quality index (IQI). Within each system, sampling sites were ordered in an increasing pressure gradient according to a preliminary classification based on professional judgement. The different indices are largely consistent in their response to pressure gradient, except in some particular cases (i.e. BITS, in all cases, or ISS when a low number of individuals is present). Inconsistencies between indicator responses were most pronounced in transitional waters (i.e. IQI, BEQI), highlighting the difficulties of the generic application of indicators to all marine, estuarine and lagoonal environments. However, some of the single (i.e. ecological groups approach, diversity, richness) and multi-metric methods (i.e. BAT, M-AMBI, NQI) were able to detect such gradients both in transitional and coastal environments, being these multi-metric methods more consistent in the detection than single indices. This study highlights the importance of survey design and good reference conditions for some indicators. The agreement observed between different methodologies and their ability to detect quality trends across distinct environments constitutes a promising result for the implementation of the WFD’s monitoring plans. Moreover, these results have management implications, regarding the dangers of misclassification, uncertainty in the assessment, use of conflicting indices, and testing and validation of indices.     

Some Insights into Topographic,Elastic and Self-gravitation Interaction in Modelling Ground Deformation and Gravity Changes in Active Volcanic Areas

Surface displacements and gravity changes due to volcanic sources are influenced by medium properties. We investigate topographic, elastic and self-gravitation interaction in order to outline the major factors that are significant in data modelling. While elastic-gravitational models can provide a suitable approximation to problems of volcanic loading in areas where topographic relief is negligible, for prominent volcanoes the rough topography could affect deformation and gravity changes to a greater extent than self-gravitation. This fact requires the selection, depending on local relief, of a suitable model for use in the interpretation of surface precursors of volcanic activity. We use the three-dimensional Indirect Boundary Element Method to examine the effects of topography on deformation and gravity changes in models of magma chamber inflation/deflation. Topography has a significant effect on predicted surface deformation and gravity changes. Both the magnitude and pattern of the geodetic signals are significantly different compared to half-space solutions. Thus, failure to account for topographic effects in areas of prominent relief can bias the estimate of volcanic source parameters, since the magnitude and pattern of deformation and gravity changes depend on such effects.     

Witnessing North Atlantic westerlies variability from ships’ logbooks (1685–2008)

A monthly index based on the persistence of the westerly winds over the English Chanel is constructed for 1685–2008 using daily data from ships’ logbooks and comprehensive marine meteorological datasets. The so-called Westerly Index (WI) provides the longest instrumental record of atmospheric circulation currently available. Anomalous WI values are associated with spatially coherent climatic signals in temperature and precipitation over large areas of Europe, which are stronger for precipitation than for temperature and in winter and summer than in transitional seasons. Overall, the WI series accord with the known European climatic history, and reveal that the frequency of the westerlies in the eastern Atlantic during the twentieth century and the Late Maunder Minimum was not exceptional in the context of the last three centuries. It is shown that the WI provides additional and complementary information to the North Atlantic Oscillation (NAO) indices. The analysis of WI series during the industrial era indicates an overall good agreement with the winter and high-summer NAO, with the exception of several multidecadal periods of weakened correlation. These decoupled periods between the frequency and the intensity of the zonal flow are interpreted on the basis of several sources of non-stationarity affecting the centres of the variability of the North Atlantic and their teleconnections. Comparisons with NAO reconstructions and long instrumental indices extending back to the seventeenth century suggest that similar situations have occurred in the past, which call for caution when reconstructing the past atmospheric circulation from climatic proxies. The robustness and extension of its climatic signal, the length of the series and its instrumental nature make the WI an excellent benchmark for proxy calibration in Europe and Greenland.     

Scalar Fluxes Near a Tall Building in an Aligned Array of Rectangular Buildings

Scalar dispersion from ground-level sources in arrays of buildings is investigated using wind-tunnel measurements and large-eddy simulation (LES). An array of uniform-height buildings of equal dimensions and an array with an additional single tall building (wind tunnel) or a periodically repeated tall building (LES) are considered. The buildings in the array are aligned and form long streets. The sensitivity of the dispersion pattern to small changes in wind direction is demonstrated. Vertical scalar fluxes are decomposed into the advective and turbulent parts and the influences of wind direction and of the presence of the tall building on the scalar flux components are evaluated. In the uniform-height array turbulent scalar fluxes are dominant, whereas the tall building produces an increase of the magnitude of advective scalar fluxes that yields the largest component. The presence of the tall building causes either an increase or a decrease to the total vertical scalar flux depending on the position of the source with respect to the tall building. The results of the simulations can be used to develop parametrizations for street-canyon dispersion models and enhance their capabilities in areas with tall buildings.     

North Atlantic atmospheric circulation and surface wind in the Northeast of the Iberian Peninsula: uncertainty and long term downscaled variability

The variability and predictability of the surface wind field at the regional scale is explored over a complex terrain region in the northeastern Iberian Peninsula by means of a downscaling technique based on Canonical Correlation Analysis. More than a decade of observations (1992–2005) allows for calibrating and validating a statistical method that elicits the main associations between the large scale atmospheric circulation over the North Atlantic and Mediterranean areas and the regional wind field. In an initial step the downscaling model is designed by selecting parameter values from practise. To a large extent, the variability of the wind at monthly timescales is found to be governed by the large scale circulation modulated by the particular orographic features of the area. The sensitivity of the downscaling methodology to the selection of the model parameter values is explored, in a second step, by performing a systematic sampling of the parameters space, avoiding a heuristic selection. This provides a metric for the uncertainty associated with the various possible model configurations. The uncertainties associated with the model configuration are considerably dependent on the spatial variability of the wind. While the sampling of the parameters space in the model set up moderately impact estimations during the calibration period, the regional wind variability is very sensitive to the parameters selection at longer timescales. This fact illustrates that downscaling exercises based on a single configuration of parameters should be interpreted with extreme caution. The downscaling model is used to extend the estimations several centuries to the past using long datasets of sea level pressure, thereby illustrating the large temporal variability of the regional wind field from interannual to multicentennial timescales. The analysis does not evidence long term trends throughout the twentieth century, however anomalous episodes of high/low wind speeds are identified.