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Sulfate reduction and its associated contaminant immobilization in marsh soils supporting a phosphogypsum stack was examined by pore-water and solid analysis, selective extractions, microscopy and sulfur K-edge X-ray absorption near-edge structure (XANES) spectroscopy. The negative impact of this stack on estuarine environments is a concerning problem. In the weathering profile, total concentrations of most pollutants increase with depth; instead, dissolved contents in pore-waters increase to middle of the saturated zone but then decrease drastically down to reach the marsh due to sulfide precipitation. Excess of acid-volatile sulfide plus pyritic sulfur over metals bound to the oxidizable fraction indicates that sulfide precipitation is the main mechanism responsible for metal removal in the marsh. Thus, abundant pyrite occurred as framboidal grains, in addition to other minor sulfides of As, Zn and Cu as isolated particles. Moreover, high contents of elemental sulfur were found, which suggest partial sulfide oxidation, but marsh may have capacity to buffer potential release of contaminants. The importance of sulfur species was quantitatively confirmed by XANES, which also supports the accuracy of selective extraction schemes. Accordingly, managing pore-water quality through organic carbon-rich amendments over phosphogypsum stacks could lead to a decrease in contaminant loading of leakages resulting from weathering., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Lanthanide series have been used as a record of the water-rock interaction and work as a tool for identifying impacts of acid mine drainage (lixiviate residue derived from sulphide oxidation). The application of North-American Shale Composite-normalized rare earth elements patterns to these minority elements allows determining the origin of the contamination. In the current study, geochemical patterns were applied to rare earth elements bioaccumulated in the soft tissue of the freshwater clam Corbicula fluminea after exposure to different acid mine drainage contaminated environments. Results show significant bioaccumulation of rare earth elements in soft tissue of the clam after 14 days of exposure to acid mine drainage contaminated sediment (ΣREE=1.3-8μg/gdw). Furthermore, it was possible to biomonitor different degrees of contamination based on rare earth elements in tissue. The pattern of this type of contamination describes a particular curve characterized by an enrichment in the middle rare earth elements; a homologous pattern (E MREE =0.90) has also been observed when applied NASC normalization in clam tissues. Results of lanthanides found in clams were contrasted with the paucity of toxicity studies, determining risk caused by light rare earth elements in the Odiel River close to the Estuary. The current study purposes the use of clam as an innovative "bio-tool" for the biogeochemical monitoring of pollution inputs that determines the acid mine drainage networks affection., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Phosphogypsum is the main waste generated by the phosphate fertilizer industry. Despite the high level of pollutants found in phosphogypsum and the proximity of stacks to cities, there are no specific regulations for the management of this waste. This study addresses this issue by applying to phosphogypsum, from a fertilizer plant in Huelva (SW Spain), the leaching tests proposed by the current European and US environmental regulations for wastes management and classification. Two main conclusions were obtained: 1) the anomalous metal and metalloid concentrations (e.g. As, Fe, Pb, Sb, Mn, V and Cu) and higher mobility observed in the Huelva phosphogypsum compared to other stacks worldwide, and 2) the discrepancies observed between EU and US regulations dealing with hazardousness classification of these materials. This latter finding suggests the need to use complementary assessment protocols to obtain a better characterization and classification of these wastes. An evaluation of the potential risk to the aquatic life according to the US EPA regulation is proposed in this study. The results warn about the acute and chronic effects on the aquatic life of this waste and suggest the adoption of more strict measures for a safe disposal of phosphogypsum stacks., (Copyright © 2017 Elsevier B.V. All rights reserved.)

As acid mine drainage (AMD) remediation is increasingly faced by governments and mining industries worldwide, the generation of metal-rich solid residues from the treatments plants is concomitantly raising. A proper environmental management of these metal-rich wastes requires a detailed characterization of the metal mobility as well as an assessment of this new residues stability. The European standard leaching test EN 12457-2, the US EPA TCLP test and the BCR sequential extraction procedure were selected to address the environmental assessment of dispersed alkaline substrate (DAS) residues generated in AMD passive treatment systems. Significant discrepancies were observed in the hazardousness classification of the residues according to the TCLP or EN 12457-2 test. Furthermore, the absence of some important metals (like Fe or Al) in the regulatory limits employed in both leaching tests severely restricts their applicability for metal-rich wastes. The results obtained in the BCR sequential extraction suggest an important influence of the landfill environmental conditions on the metals released from the wastes. To ensure a complete stability of the pollutants in the studied DAS-wastes the contact with water or any other leaching solutions must be avoided and a dry environment needs to be provided in the landfill disposal selected., (Copyright © 2012 Elsevier B.V. All rights reserved.)

In this study, experiments were conducted to investigate the applicability of low-cost alkaline paper mill wastes as acidity neutralizing agents for treatment of acid mine drainage (AMD). Paper wastes include a calcium mud by-product from kraft pulping, and a calcite powder from a previous study focused on sequestering CO(2) by carbonation of calcium mud. The neutralization process consisted of increase of pH by alkaline additive dissolution, decrease of metals solubility and precipitation of gypsum and poorly crystallized Fe-Al oxy-hydroxides/oxy-hydroxysulphates, which acted as a sink for trace elements to that extent that solutions reached the pre-potability requirements of water for human consumption. This improvement was supported by geochemical modelling of solutions using PHREEQC software, and observations by scanning electron microscope and X-ray diffraction of reaction products. According to PHREEQC simulations, the annual amount of alkaline additive is able to treat AMD (pH 3.63, sulphate 3800 mg L(-1), iron 348 mg L(-1)) with an average discharge of about 114 and 40 Ls(-1) for calcium mud and calcite powder, respectively. Likewise, given the high potential of calcium mud to sequester CO(2) and of resulting calcite powder to neutralize AMD, paper wastes could be a promising solution for facing this double environmental problem., (Copyright (c) 2009 Elsevier B.V. All rights reserved.)

The increasing CO(2) concentration in the Earth's atmosphere, mainly caused by fossil fuel combustion, has led to concerns about global warming. A technology that could possibly contribute to reducing carbon dioxide emissions is the in-situ mineral sequestration (long term geological storage) or the ex-situ mineral sequestration (controlled industrial reactors) of CO(2). In the present study, we propose to use coal combustion fly-ash, an industrial waste that contains about 4.1 wt.% of lime (CaO), to sequester carbon dioxide by aqueous carbonation. The carbonation reaction was carried out in two successive chemical reactions, first, the irreversible hydration of lime. second, the spontaneous carbonation of calcium hydroxide suspension. A significant CaO-CaCO(3) chemical transformation (approximately 82% of carbonation efficiency) was estimated by pressure-mass balance after 2h of reaction at 30 degrees C. In addition, the qualitative comparison of X-ray diffraction spectra for reactants and products revealed a complete CaO-CaCO(3) conversion. The carbonation efficiency of CaO was independent on the initial pressure of CO(2) (10, 20, 30 and 40 bar) and it was not significantly affected by reaction temperature (room temperature "20-25", 30 and 60 degrees C) and by fly-ash dose (50, 100, 150 g). The kinetic data demonstrated that the initial rate of CO(2) transfer was enhanced by carbonation process for our experiments. The precipitate calcium carbonate was characterized by isolated micrometric particles and micrometric agglomerates of calcite (SEM observations). Finally, the geochemical modelling using PHREEQC software indicated that the final solutions (i.e. after reaction) are supersaturated with respect to calcium carbonate (0.7 < or = saturation index < or = 1.1). This experimental study demonstrates that 1 ton of fly-ash could sequester up to 26 kg of CO(2), i.e. 38.18 ton of fly-ash per ton of CO(2) sequestered. This confirms the possibility to use this alkaline residue for CO(2) mitigation.

Presently, about 3 million tonnes of phosphogypsum are being generated annually in Spain as by-product from phosphoric acid in a fertilizer factory located in Huelva (southwestern Iberian Peninsula). Phosphate rock from Morocco is used as raw material in this process. Phosphogypsum wastes are stored in a stack containing 100Mt (approximately 1200ha of surface) over salt marshes of an estuary formed by the confluence of the Tinto and Odiel rivers, less than 1km away from the city centre. A very low proportion of this waste is used to improve fertility of agricultural soils in the area of the Guadalquivir river valley (Seville, SW Spain). The chemical speciation of potentially toxic elements (Ba, Cd, Cu, Ni, Sr, U and Zn) in phosphogypsum and phosphate rock was performed using the modified BCR-sequential extraction procedure, as described by the European Community Bureau of Reference (1999). This study has been done with the main of: (1) evaluate changes in the mobility of metals during the production of phosphoric acid; (2) estimate the amount of mobile metals that can affect the environmental surrounding; and (3) verify the environmentally safe use of phosphogypsum as an amendment to agricultural soils. The main environmental concern associated to phosphoric acid production is that Uranium, a radiotoxic element, is transferred from the non-mobile fraction in the phosphate rock to the bioavailable fraction in phosphogypsum in a rate of 23%. Around 21% of Ba, 6% of Cu and Sr, 5% of Cd and Ni, and 2% of Zn are also contained in the water-soluble phase of the final waste. Considering the total mass of phosphogypsum, the amount of metals easily soluble in water is approximately 6178, 3089, 1931, 579, 232, 193 and 77t for Sr, U, Ba, Zn, Ni, Cu and Cd, respectively. This gives an idea of the pollution potential of this waste.