Controlling factors and environmental implications of mercury contamination in urban and agricultural soils under a long-term influence of a chlor-alkali plant in the North–West Portugal

This study aims at assessing the extent of total mercury (Hg) contamination in urban and agricultural soils under long-term influence of a chlor-alkali plant, located at about 1 km away from a town centre. Moreover, it aims at identifying the main factors controlling Hg contents’ distribution and associated potential hazards to environment and human health. The median value of total Hg for soil surface layer (0–10 cm) was 0.20 mg/kg (data ranging from 0.050 to 4.5 mg/kg) and for subsurface layer (10–20 cm) 0.18 mg/kg (data ranging from 0.046 to 3.0 mg/kg). The agricultural area showed higher Hg concentrations (ranging from 0.86 to 4.5 mg/kg) than urban area (ranging from 0.05 to 0.61 mg/kg), with some results exceeding target values set by the Dutch guidelines. Mercury concentrations observed in the studied area are more likely to be associated with the influence of the chlor-alkali plant and with the use of historically contaminated sludges and water from a nearby lagoon in agriculture, than to the impacts of urban development. The statistical correlations between Hg concentrations and soil properties suggest that anthropogenic metal sources should influence the spatial distribution more than the geological properties. Although the Hg emissions were drastically reduced 10 years ago, the area under influence of the chlor-alkali plant is still facing potential health and environmental threats arising from soil contamination.     

Using helicopter electromagnetic data to predict groundwater quality in fractured crystalline bedrock in a semi-arid region, Northeast Brazil

Geostatistical modeling, using airborne and borehole electromagnetic data, was used to estimate electrical conductivity in groundwater within fractured paragneisses and migmatites in a semi-arid climate in northeastern Brazil. Despite the geologic heterogeneity of crystalline aquifers, the use of high resolution helicopter electromagnetic (HEM) data enabled the characterization of groundwater electrical conductivity where data from drilled wells were insufficient. The tacit assumption is that HEM measurements can be used to relate rock electrical conductivity to groundwater electrical conductivity. In this study, the HEM data were used as an external drift variable in non-stationary estimation and stochastic simulation to identify the variability of groundwater electrical conductivity. Validation tests, comparing predicted values for groundwater conductivity with measurements in new wells, confirmed the success of these models in locating fresh groundwater sources in crystalline bedrock.     

Transcurrent continental tectonics model for the Ossa-Morena Zone Neoproterozoic–Paleozoic evolution,SW Iberian Massif,Portugal

The Ossa-Morena Zone (SW Iberian Massif) was affected by continuous orogen-parallel transcurrent continental tectonics from the Neoproterozoic to the Carboniferous times, involving transtension (TT) and transpression (TP) processes that co-existed together, occurred separately in neighbouring regions by the means of strain partitioning or even worked diachronically. A first stage of transpression TP1 took place during the Late Neoproterozoic–Lower Cambrian as a result of Cadomian arc-continent collisional processes. Structures generated by transtension TT1 from Cambrian to Lower Devonian were related to strong lithosphere stretching responsible for the development of basins controlled by major detachments, tilting, rifting and important tectono–thermal diachronic processes. Denudation phenomena and inhibition of sedimentation related with thermal uplift (asthenosphere upwelling) and consequent subsidence caused by isostatic equilibrium, involving generalized transgressions, were processes responsible for major unconformities. The Variscan TP2-TT2 episodes that followed diachronically TP1-TT1, by maintaining the orogen-parallel transport direction, were concomitant with syntectonic deposition of continental basins in the OMZ and foreland basins in the SPZ. TT2 local transtension and tectonic exhumation of deep crustal rocks along major shear zones, favoured the opening of tectonic troughs filled up by sediments and volcanism. TP2 shortening have generated fold axes parallel to the orogen-strike and composite dissymmetric flower structures.     

Stochastic micromechanical model of the deterioration of asphalt mixtures subject to moisture diffusion processes

The deleterious effect of moisture in the microstructure of asphalt mixtures, usually referred to as moisture damage, has been recognized as a main cause of early deterioration of asphalt pavements. The initiation and evolution of moisture‐related deterioration is strongly influenced by the internal air void structure of asphalt mixtures. Despite its importance, the majority of works conducted on the micromechanical modeling of asphalt mixtures overlook the role of the air void structure, mainly because of its high complexity and variability. This paper explores the influence of air void variability on the performance of asphalt mixtures subjected to moisture diffusion processes. A stochastic modeling technique based on random field theory was used to generate internal distributions of physical and mechanical properties of the asphalt matrix of the mixture that depend on probable air voids distributions. The analysis was conducted by means of a coupled numerical micromechanical model of moisture damage. The results showed that the variability and distribution of air voids are decisive in determining the moisture‐dependent performance of asphalt mixtures. Furthermore, it was also shown that a stochastic characterization of the diverse air void configurations is a feasible and useful approach to better represent and understand mechanically related deterioration processes in asphalt mixtures. Copyright © 2010 John Wiley & Sons, Ltd.     

Particulate matter geochemistry of a highly industrialized region in the Caribbean:Basis for future toxicological studies

Air pollution has become an important issue,especially in Caribbean urban areas,and,particulate matter(PM)emitted by different natural and anthropogenic sources causes environmental and health issues.In this work,we studied the concentrations of PM₁₀ and PM_2.5 sources in an industrial and port urban area in the Caribbean region of Colombia.PM samples were collected within 48-h periods between April and October 2018 by using a Partisol 2000 i-D sampler.Elemental geochemical characterization was performed by X-ray fluorescence(XRF)analysis.Further,ionic species and black carbon(BC)were quantified by ion chromatography and reflectance spectroscopy,respectively.Using the Positive Matrix Factorization(PMF)receptor model,the contributions of PM sources were quantified.The average concentration of PM₁₀ was 46.6±16.2μg/m³,with high concentrations of Cl and Ca.For PM_2.5,the average concentration was 12.0±3.2μg/m³,and the most abundant components were BC,S,and Cl.The receptor model identified five sources for PM₁₀ and PM_2.5.For both fractions,the contributions of marine sea spray,re-suspended soil,and vehicular traffic were observed.In addition,PM_2.5 included two mixed sources were found to be fuel oil combustion with fertilizer industry emissions,and secondary aerosol sources with building construction emissions.Further,PM₁₀ was found to also include building construction emissions with re-suspended soil,and metallurgical industry emissions.These obtained geochemical atmospheric results are important for the implementation of strategies for the continuous improvement of the air quality of the Caribbean region.     

An analytical study of the effect of penetration rate on piezocone tests in clay

Finite element cavity expansion analysis investigating the effect of penetration rate on piezocone tests in clay is presented. A coupled analysis was performed, in which the rate of cavity expansion was linked to the penetration rate of the cone and the cone angle, using the assumption that the deformation was wholly radial, and took place only between the cone tip and the cone shoulder. The soil was modelled using modified cam clay with two sets of parameters and varying values of overconsolidation ratio (OCR). The influence of penetration rate on the stress and pore pressure distributions was examined. For slower penetration rates, the excess pore pressure at the cone shoulder is lower since consolidation is permitted coincident with penetration. The radial profiles of post‐penetration voids ratio demonstrate that partially drained penetration is permitted by volume change in the near field, in addition to radial movement in the far field. The radial distribution of excess pore pressure after slow penetration differs from the undrained case, with a relatively low radial gradient existing at the cone face. As a result, the dissipation curves after slow penetration lag behind those following fast penetration. The cone velocity is made dimensionless by normalizing with the coefficient of consolidation and the cone diameter. ‘Backbone’ curves of normalized velocity against normalized tip resistance and excess pore pressure capturing the transition from undrained to drained penetration are derived. The normalized pore pressure backbone curve is unique, whilst the normalized tip resistance shows a small dependency on OCR. These backbone penetration curves are compared with centrifuge model piezocone tests conducted at varying rates, and subsequent dissipation tests. The numerical and experimental results suggest that the value of consolidation coefficient operative during the dissipation phase is 2–4 times higher than the virgin compression value due to changes in the operative soil stiffness, as demonstrated from the stress paths of individual soil elements. The use of multi‐rate penetration tests to deduce values of consolidation coefficient is discussed, in light of these differences. Copyright © 2005 John Wiley & Sons, Ltd.     

Treatment of Acid Mine Drainage (AMD) in South Brazil: Comparative active processes and water reuse

This work describes AMD techniques of neutralization, with lime, flocculation of the precipitates and comparative flocs/liquid separation by flotation with microbubbles or by lamellar settling (LS). The AMD treated water was characterized by its quality for recycling in terms of inorganic or organic elements, suspended or dissolved solids, among others. Two types of flocs were formed, “aerated” or not, in a special flocculation reactor, patented by this research group (RGF^®). Aerated flocs formed (within seconds) entered into contact with microbubbles under high shearing and raised-up at rates > 120 mh^− 1 allowing a rapid solid–liquid separation by flotation (HR-high rate), at about 13–15 m³m^− 2 h^− 1 loading capacity. Conversely, the non-aerated flocs settled at about 5–6 m h^− 1 in a lamella settler. Both AMD treatment techniques showed similar efficiencies (removal of ions > 90%) but the separation by lamella settling presented advantages, namely less reagents (no flotation collector required), lower power requirements and easier to operate. The operating costs (approximate values) of the AMD treatment by LS at pH 9 reaches about 0.3 US$ m^− 3 against 0.6 US$ m^− 3 for the HR-flotation process. Results found were proved to be similar to those found in recent ADM treatment installations in South Brazil. The quality of the treated water is fairly good, nearly free of heavy metals ion, low BOD (biological oxygen demand) and TOC (total organic content), low solids content and may be readily reused for irrigation, industrial processes and as wash water (among others, streets, vehicles, dust control). However, there is a need to extend the use of this treated water resource, but this, at least in Brazil, has not been legislated properly. It is concluded that this research will contribute in the discussion of this old and complex problem in acid mining effluents worldwide.     

Development of a Field Preconcentration/Elution Unit for Routine Determination of Dissolved Metal Concentrations by ICP-OES in Marine Waters: Application for Monitoring of the New Caledonia Lagoon

An iminodiacetate chelating resin was optimised for the rapid determination of Co, Cu, Fe, Mn and Ni in seawater. Using inexpensive, high-capacity, reusable cartridges allowed high flow rates of up to 25 ml min⁻¹. High preconcentration factors, of up to 500, were obtained in order to analyse samples using an ICP-OES. The requirement for a buffer was eliminated due to the high tolerance of the ICP-OES to interfering matrix elements, thereby further reducing the potential for contamination. Quantification limits in seawater were: Co = 6 ng l⁻¹, Cu = 8 ng l⁻¹, Fe = 6 ng l⁻¹, Mn = 5 ng l⁻¹ and Ni = 6 ng l⁻¹. The method was verified by the analysis of near shore seawater (CASS-4) and open ocean seawater (NASS-5) reference materials. In order to satisfy the high sampling demands using the iminodiacetate cartridges, a portable off-line preconcentration unit was developed for routine analysis. The multi-channel preconcentration unit, was capable of treating up to eight samples simultaneously with concentrating times as little as 30 minutes. The technique was also used to determine dissolved metals in fresh and interstitial waters. The technique has been successfully used in a number of environmental studies and impact assessments to evaluate the effects of mining on the New Caledonian lagoon.     

A New Interlaboratory Characterisation of Silicon,Rare Earth Elements and Twenty‐Two Other Trace Element Concentrations in the Natural River Water Certified Reference Material SLRS‐6 (NRC‐CNRC)

The natural river water reference material SLRS‐6 (NRC‐CNRC) is the newest batch of a quality control material routinely used in many international environmental laboratories. This work presents a nine‐laboratory compilation of measurements of major and trace element concentrations and their related uncertainties, unavailable in the NRC‐CNRC certificate (B, Cs, Li, Ga, Ge, Hf, Nb, P, Rb, Rh, Re, S, Sc, Se, Si, Sn, Th, Ti, Tl, W, Y, Y, Zr and REEs). Measurements were mostly made using inductively coupled plasma‐mass spectrometry. The results are compared with equivalent data for the last batch of the material, SLRS‐5, measured simultaneously with SLRS‐6 in this study. In general, very low concentrations, close to the quantification limits, were found in the new batch. The Sr isotopic ratio is also reported.     

3-D electromagnetic imaging of a Palaeozoic plate-tectonic boundary segment in SW Iberian Variscides (S Alentejo, Portugal)

In SW Iberian Variscides, the boundary between the South Portuguese Zone (SPZ) and the Ossa Morena Zone (OMZ) corresponds to a major tectonic suture that includes the Beja Acebuches Ophiolite Complex (BAOC) and the Pulo do Lobo Antiform Terrane (PLAT). Three sub-parallel and approximately equidistant MT profiles were performed, covering a critical area of this Palaeozoic plate-tectonic boundary in Portugal; the profiles, running roughly along an NE–SW direction, are sub-perpendicular to the main Variscan tectonic features. Results of the three-dimensional (3-D) modelling of MT data allow to generate, for the first time, a 3-D electromagnetic imaging of the OMZ–SPZ boundary, which reveals different conductive and resistive domains that display morphological variations in depth and are intersected by two major sub-vertical corridors; these corridors coincide roughly with the NE–SW, Messejana strike–slip fault zone and with the WNW–ESE, Ferreira–Ficalho thrust fault zone. The distribution of the shallow resistive domains is consistent with the lithological and structural features observed and mapped, integrating the expected electrical features produced by igneous intrusions and metamorphic sequences of variable nature and age. The development in depth of these resistive domains suggests that: (1) a significant vertical displacement along an early tectonic structure, subsequently re-taken by the Messejana fault-zone in Late-Variscan times, has to be considered to explain differences in deepness of the base of the Precambrian–Cambrian metamorphic pile; (2) hidden, syn- to late-collision igneous bodies intrude the meta-sedimentary sequences of PLAT; (3) the roots of BAOC are inferred from 12 km depth onwards, forming a moderate resistive band located between two middle-crust conductive layers extended to the north (in OMZ) and to the south (in SPZ). These conductive layers overlap the Iberian Reflective Body (evidenced by the available seismic reflection data) and are interpreted as part of an important middle-crust décollement developed immediately above or coinciding with the top of a graphite-bearing granulitic basement.