Different lead sources in an abandoned uranium mine (Urgeirica - Central Portugal) and its environment impact - isotopic evidence

Different lead sources were identified in a large uranium tailings deposit (5Mton) in the Central Region of Portugal using lead isotopic ratios obtained by ICP-QMS. These ratios helped to clarify the different sources of Pb within the tailings deposit and the impact of the tailings on the surroundings. Ten depth profiles were used for isotopic characterization of the tailings deposit; the lead background signature was evaluated in seven regional rocks (granites) and was defined as being 28 +/- 1 mg kg(-1) for Pb bulk concentration and with isotopic ratios of 1.264(2) for Pb-206/Pb-207 and 1.962(7) for Pb-208/Pb-206. In order to understand Pb isotope distribution within the tailings deposit, simple mixing/mass balance models were used to fit experimental data, involving: (1) the background component; (2) uranium ores (pitchblende) characterized by the ratios Pb-206/Pb-207 of 1.914(3) and Pb-208/Pb-206 of 1.235(2); and (3) an unknown Pb source (named 'Fonte 5') characterized by the ratios Pb-206/Pb-207 of 3.079(7) and Pb-208/Pb-206 of 0.715(1). This unknown source showed high radiogenic ratios found in the water of some tailings depth profiles located in a very specific position in the dump. In terms of isotopic characterization, 69% of the deposit material resulted from the background source, 25% from uranium minerals and only 6% from other uranium mines in the region. Finally, the environment impact revealed that the pollution was focused only in the beginning of the stream and not in the surroundings, nor in the groundwater system. The lead in the water was found only in colloidal form with a clear pitchblende signature. Those data revealed possible remobilization phenomena along the bedside and margins of the watercourse.

Assessment of a UASB reactor for the removal of sulfate from acid mine water

A bench-scale Upflow Anaerobic Sludge Blanket (UASB) reactor was used to study the treatment of acid mine drainage through the biological reduction of sulfate. The reactor was fed with acid mine drainage collected at the Osamu Utsumi uranium mine (Caldas, MG, Brazil) and supplemented with ethanol as an external carbon source. Anaerobic granular sludge originating from a reactor treating poultry slaughterhouse wastewater was used as the inoculum. The reactor's performance was studied according to variations in the chemical oxygen demand (COD)/SO42- ratio, influent dilution and liquid-phase recirculation. The digestion of a dilution of the acid mine drainage resulted in a 46.3% removal of the sulfate and an increase in the effluent pH (COD/SO42- = 0.67). An increase in the COD/SO42- ratio to 1.0 resulted in an 85.6% sulfate reduction. The reduction of sulfate through complete oxidation of the ethanol was the predominant path in the reactor, although the removal of COD was not greater than 68% in any of the operational stages. The replenishment of the liquid phase with tap water positively affected the reactor, whereas the recirculation of treated effluent caused disequilibrium and decreased efficiency. (C) 2012 Elsevier Ltd. All rights reserved.

Water quality assessment in piracicamirim creek upstream and downstream a sugar and ethanol industry through toxicity tests with cladocerans

An environmental impact study was conducted to determine the Piracicamirim's creek water quality in order to assess the influence of effluents from a sugar industry in this water body. For this, toxicity tests were performed with a water sample upstream and downstream the industry using the microcrustaceans Daphnia magna, Ceriodaphnia dubia and Ceriodaphnia silvestrii as test organisms, as well as physical and chemical analysis of water. Results showed that physical and chemical parameters did not change during the sampling period, except for the dissolved oxygen. No toxicity was observed for D. magna and reproduction of C. dubia and C. silvestrii in both sampling points. Thus, the industry was not negatively impacting the quality of this water body.

Intracellular biosynthesis and removal of copper nanoparticles by dead biomass of yeast isolated from the wastewater of a mine in the brazilian Amazonia

In this study was developed a natural process using a biological system for the biosynthesis of nanoparticles (NPs) and possible removal of copper from wastewater by dead biomass of the yeast Rhodotorula mucilaginosa. Dead and live biomass of Rhodotorula mucilaginosa was used to analyze the equilibrium and kinetics of copper biosorption by the yeast in function of the initial metal concentration, contact time, pH, temperature, agitation and inoculum volume. Dead biomass exhibited the highest biosorption capacity of copper, 26.2 mg g(-1), which was achieved within 60 min of contact, at pH 5.0, temperature of 30°C, and agitation speed of 150 rpm. The equilibrium data were best described by the Langmuir isotherm and Kinetic analysis indicated a pseudo-second-order model. The average size, morphology and location of NPs biosynthesized by the yeast were determined by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS) and transmission electron microscopy (TEM). The shape of the intracellularly synthesized NPs was mainly spherical, with an average size of 10.5 nm. The X-ray photoelectron spectroscopy (XPS) analysis of the copper NPs confirmed the formation of metallic copper. The dead biomass of Rhodotorula mucilaginosa may be considered an efficiently bioprocess, being fast and low-cost to production of copper nanoparticles and also a probably nano-adsorbent of this metal ion in wastewater in bioremediation process

Biosynthesis and uptake of copper nanoparticles by dead biomass of Hypocrea lixii isolated from the metal mine in the Brazilian Amazon Region

A biological system for the biosynthesis of nanoparticles (NPs) and uptake of copper from wastewater, using dead biomass of Hypocrea lixii was analyzed and described for the first time. The equilibrium and kinetics investigation of the biosorption of copper onto dead, dried and live biomass of fungus were performed as a function of initial metal concentration, pH, temperature, agitation and inoculum volume. The high biosorption capacity was observed for dead biomass, completed within 60 min of contact, at pH 5.0, temperature of 40 °C and agitation speed of 150 rpm with a maximum copper biosorption of 19.0 mg g(-1). The equilibrium data were better described using the Langmuir isotherm and kinetic analysis indicated that copper biosorption follows a pseudo-second-order model. The average size, morphology and location of NPs biosynthesized by the fungus were determined by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS) and transmission electron microscopy (TEM). NPs were mainly spherical, with an average size of 24.5 nm, and were synthesized extracellularly. The X-ray diffraction (XRD) analysis confirms the presence of metallic copper particles. Infrared spectroscopy (FTIR) study revealed that the amide groups interact with the particles, which was accountable for the stability of NPs. This method further confirmed the presence of proteins as stabilizing and capping agents surrounding the copper NPs. These studies demonstrate that dead biomass of Hypocrea lixii provides an economic and technically feasible option for bioremediation of wastewater and is a potential candidate for industrial-scale production of copper NPs.

Phytostabilisation : use of wetland plants to treat mine tailings

Mine tailings can be rich in sulphide minerals and may form acid mine drainage (AMD) through reaction with atmospheric oxygen and water. AMD contains elevated levels of metals and arsenic (As) that could be harmful to animals and plants. An oxygen-consuming layer of organic material and plants on top of water-covered tailings would probably reduce oxygen penetration into the tailings and thus reduce the formation of AMD. However, wetland plants have the ability to release oxygen through the roots and could thereby increase the solubility of metals and As. These elements are released into the drainage water, taken up and accumulated in the plant roots, or translocated to the shoots. The aim was to examine the effects of plant establishment on water-covered mine tailings by answering following questions: A) Is plant establishment on water-covered mine tailings possible? B) What are the metal and As uptake and translocation properties of these plants? C) How do plants affect metal and As release from mine tailings, and which are the mechanisms involved? Carex rostrata Stokes, Eriophorum angustifolium Honck., E. scheuchzeri Hoppe, Phragmites australis (Cav.) Steud., Salix phylicifolia L. and S. borealis Fr. were used as test plants. Influences of plants on the release of As, Cd, Cu, Pb, Zn and in some cases Fe in the drainage water, and plant element uptake were studied in greenhouse experiments and in the field. The results obtained demonstrate that plant establishment are possible on water-covered unweathered mine tailings, and a suitable amendment was found to be sewage sludge. On acidic, weathered tailings, a pH increasing substance such as ashes should be added to improve plant establishment. The metal and As concentrations of the plant tissue were found to be generally higher in roots than in shoots. The uptake was dependent on the metal and As concentrations of the tailings and the release of organic acids from plant roots may have influenced the uptake. The metal release from tailings into the drainage water caused by E. angustifolium was found to depend greatly on the age and chemical properties of the tailings. However, no effects of E. angustifolium on As release was found. Water from old sulphide-, metal- and As-rich tailings with low buffering capacity were positively affected by E. angustifolium by causing higher pH and lower metal concentrations. In tailings with relatively low sulphide, metal and As contents combined with a low buffering capacity, plants had the opposite impact, i.e. a reduction in pH and elevated metal levels of the drainage water. The total release of metal and As from the tailings, i.e. drainage water together with the contents in shoots and roots, was found to be similar for C. rostrata, E. angustifolium and P. australis, except for Fe and As, where the release was highest for P. australis. The differences in metal and As release from mine tailings were mainly found to be due to the release of O2 from the roots, which changes the redox potential. Release of organic acids from the roots slightly decreased the pH, although did not have any particular influence on the release of metal and As. In conclusion, as shown here, phytostabilisation may be a successful technique for remediation of mine tailings with high element and sulphide levels, and low buffering capacity.

Spatio-temporal variation of macrofaunal assemblages in the deep Blanes submarine canyon

The spatio-temporal variations in diversity and abundance of deep-sea macrofaunal assemblages (excluding meiofaunal taxa, as Nematoda, Copepoda and Ostracoda) from the Blanes Canyon (BC) and adjacent open slope are described. The Catalan Sea basin is characterized by the presence of numerous submarine canyons, which are globally acknowledged as biodiversity hot-spots, due to their disturbance regime and incremented conveying of organic matter. This area is subjected to local deep-sea fisheries activities, and to recurrent cold water cascading events from the shelf. The upper canyon (~900 m), middle slope (~1200 m) and lower slope (~1500 m) habitats were investigated during three different months (October 2008, May 2009 and September 2009). A total of 624 specimens belonging to 16 different taxa were found into 67 analyzed samples, which had been collected from the two study areas. Of these, Polychaeta, Mollusca and Crustacea were always the most abundant groups. As expected, the patterns of species diversity and evenness were different in time and space. Both in BC and open slope, taxa diversity and abundance are higher in the shallowest depth and lowest at -1500 m depth. This is probably due to different trophic regimes at these depths. The abundance of filter-feeders is higher inside BC than in the adjacent open slope, which is also related with an increment of predator polychaetes. Surface deposit-feeders are more abundant in the open slope than in BC, along with a decrement of filter-feeders and their predators. Probably these differences are due to higher quantities of suspended organic matter reaching the canyon. The multivariate analyses conducted on major taxa point out major differences effective taxa richness between depths and stations. In September 2009 the analyzed communities double their abundances, with a corresponding increase in richness of taxa. This could be related to a mobilizing event, like the release of accumulated food-supply in a nepheloid layer associated to the arrival of autumn. The highest abundance in BC is detected in the shallowest depth and in late summer (September), probably due to higher food availability caused by stronger flood events coming from Tordera River. The effects of such events seemed to involve adjacent open slope too. The nMDS conducted on major taxa abundance shows a slight temporal difference between the three campaigns samples, with a clear clustering between samples of Sept 09. All depth and all months were dominated by Polychaeta, which have been identified to family level and submitted to further analysis. Family richness have clearly minimum at the -1200 m depth of BC, highlighting the presence of a general impact affecting the populations in the middle slope. Three different matrices have been created, each with a different taxonomic level (All Taxa “AT”, Phylum Level “PL” and Polychaeta Families “PF”). Multivariate analysis (MDS, SIMPER) conducted on PL matrix showed a clear spatial differences between stations (BC and open slope) and depths. MDSs conducted on other two matrices (AT and PF) showed similar patterns, but different from PL analysis. A 2 nd stage analysis have been conducted to understand differences between different taxonomic levels, and PL level has been chosen as the most representative of variation. The faunal differences observed were explained by depth, station and season. All work has been accomplished in the Centre d’estudis avançats de Blanes (CEAB-CSIC), within the framework of Spanish PROMETEO project "Estudio Integrado de Cañones y Taludes PROfundos del MEdiTErráneo Occidental: un hábitat esencial", Ref. CTM2007-66316-C02- 01/MAR.

Laboratory study of grouted macadams impregnated with mine waste geopolymeric binder

A new type of pavement has been gaining popularity over the last few years in Europe. It comprises a surface course with a semi-flexible material that provides significant advantages in comparison to both concrete and conventional asphalt, having both rut resistance and a degree of flexibility. It also provides good protection against the ingress of water to the foundation, since it has an impermeable surface. The semi-flexible material, generally known as grouted macadam, comprises an open-graded asphalt skeleton with 25% to 35% voids into which a cementitious slurry is grouted. This hybrid mixture provides good rut resistance and a surface highly resistant to fuel and oil spillage. Such properties allow it to be used in industrial areas, airports and harbours, where those situations are frequently associated with heavy and slow traffic. Grouted Macadams constitute a poorly understood branch of pavement technology and have generally been relegated to a role in certain specialist pavements whose performance is predicted on purely empirical evidence. Therefore, the main objectives of this project were related to better understanding the properties of this type of material, in order to predict its performance more realistically and to design pavements incorporating grouted macadam more accurately. Based on a standard mix design, several variables were studied during this project in order to characterise the behaviour of Grouted Macadams in general, and the influence of those variables on the fundamental properties of the final mixture. In this research project, one approach was used to the design of pavements incorporating Grouted Macadams: a traditional design method, based on laboratory determined of the stiffness modulus and the compressive strength.

The release of zinc and lead from mine tailings

Mining and processing of metal ores are important causes of soil and groundwater contamination in many regions worldwide. Metal contaminations are a serious risk for the environment and human health. The assessment of metal contaminations in the soil is therefore an important task. A common approach to assess the environmental risk emanating from inorganic contaminations to soil and groundwater is the use of batch or column leaching tests. In this regard, the suitability of leaching tests is a controversial issue. In the first part of this work the applicability and comparability of common leaching tests in the scope of groundwater risk assessment of inorganic contamination is reviewed and critically discussed. Soil water sampling methods (the suction cup method and centrifugation) are addressed as an alternative to leaching tests. Reasons for limitations of the comparability of leaching test results are exposed and recommendations are given for the expedient application of leaching tests for groundwater risk assessment. Leaching tests are usually carried out in open contact with the atmosphere disregarding possible changes of redox conditions. This can affect the original metal speciation and distribution, particularly when anoxic samples are investigated. The influence of sample storage on leaching test results of sulfide bearing anoxic material from a former flotation dump is investigated in a long-term study. Since the oxidation of the sulfide-bearing samples leads to a significant overestimation of metal release, a feasible modification for the conduction of common leaching tests for anoxic material is proposed, where oxidation is prevented efficiently. A comparison of leaching test results to soil water analyzes have shown that the modified saturation soil extraction (SSE) is found to be the only of the tested leaching procedures, which can be recommended for the assessment of current soil water concentrations at anoxic sites if direct investigation of the soil water is impossible due to technical reasons. The vertical distribution and speciation of Zn and Pb in the flotation residues as well as metal concentrations in soil water and plants were investigated to evaluate the environmental risk arising from this site due to the release of metals. The variations in pH and inorganic C content show an acidification of the topsoil with pH values down to 5.5 in the soil and a soil water pH of 6 in 1 m depth. This is due to the oxidation of sulfides and depletion in carbonates. In the anoxic subsoil pH conditions are still neutral and soil water collected with suction cups is in equilibrium with carbonate minerals. Results from extended x-ray absorption fine-structure (EXAFS) spectroscopy confirm that Zn is mainly bound in sphalerite in the subsoil and weathering reactions lead to a redistribution of Zn in the topsoil. A loss of 35% Zn and S from the topsoil compared to the parent material with 10 g/kg Zn has been observed. 13% of total Zn in the topsoil can be regarded as mobile or easily mobilizable according to sequential chemical extractions (SCE). Zn concentrations of 10 mg/L were found in the soil water, where pH is acidic. Electron supply and the buffer capacity of the soil were identified as main factors controlling Zn mobility and release to the groundwater. Variable Pb concentrations up to 30 µg/L were observed in the soil water. In contrast to Zn, Pb is enriched in the mobile fraction of the oxidized topsoil by a factor of 2 compared to the subsoil with 2 g/kg Pb. 80% of the cation exchange capacity in the topsoil is occupied by Pb. Therefore, plant uptake and bioavailability are of major concern. If the site is not prevented from proceeding acidification in the future, a significant release of Zn, S, and Pb to the groundwater has to be expected. Results from this study show that the assessment of metal release especially from sulfide bearing anoxic material requires an extensive comprehension of leaching mechanisms on the one hand and on weathering processes, which influence the speciation and the mobility of metals, on the other hand. Processes, which may change redox and pH conditions in the future, have to be addressed to enable sound decisions for soil and groundwater protection and remediation.

Effects of Resources Exploitation on Water Quality: case studies in Salt Water Intrusion and Acid Mine Drainage

Throughout the world, pressures on water resources are increasing, mainly as a result of human activity. Because of their accessibility, groundwater and surface water are the most used reservoirs. The evaluation of the water quality requires the identification of the interconnections among the water reservoirs, natural landscape features, human activities and aquatic health. This study focuses on the estimation of the water pollution linked to two different environmental issues: salt water intrusion and acid mine drainage related to the exploitation of natural resources. Effects of salt water intrusion occurring in the shallow aquifer north of Ravenna (Italy) was analysed through the study of ion- exchange occurring in the area and its variance throughout the year, applying a depth-specific sampling method. In the study area were identified ion exchange, calcite and dolomite precipitation, and gypsum dissolution and sulphate reduction as the main processes controlling the groundwater composition. High concentrations of arsenic detected only at specific depth indicate its connexion with the organic matter. Acid mine drainage effects related to the tin extraction in the Bolivian Altiplano was studied, on water and sediment matrix. Water contamination results strictly dependent on the seasonal variation, on pH and redox conditions. During the dry season the strong evaporation and scarce water flow lead to low pH values, high concentrations of heavy metals in surface waters and precipitation of secondary minerals along the river, which could be released in oxidizing conditions as demonstrated through the sequential extraction analysis. The increase of the water flow during the wet season lead to an increase of pH values and a decrease in heavy metal concentrations, due to dilution effect and, as e.g. for the iron, to precipitation.

Geomorfologia della piattaforma continentale nella Baia di Milazzo (NE Sicilia) e relazioni tra l'assetto morfo-tettonico ed idrografico e le testate dei canyon sottomarini attuali

In questo studio vengono misurati e descritti nel dettaglio i canali sottomarini che si sviluppano sulle testate dei canyon presenti nella Baia di Milazzo (NE Sicilia) attraverso sezioni sismiche a riflessione e dati batimetrici di tipo Multibeam. In base alla creazione della carta geomorfologica della piattaforma continentale che copre l'intera area di studio (31 km2) ed alla correlazione dei profili sismici è stato possibile formulare ipotesi sulle dinamiche in atto nell'evoluzione geomorfologica delle testate dei canyon dell'area. L'evoluzione e la posizione attuale delle testate dei canyon sono condizionate dall'intensa attività tettonica della Sicilia nord-orientale caratterizzata da un forte uplift. Sono anche state descritte le relazioni tra l'assetto tettonico e le dinamiche fluviali poiché queste contribuiscono ai fenomeni osservati in ambiente sottomarino. Si è visto infine che le testate dei canyon sono in arretramento e che ciò produce un forte disequilibrio nel bilancio sedimentario delle spiagge dell'area causandone l'erosione.