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Purpose: Dredging of sediments, a requirement for harbor maintenance, removes millions of tons of mineral wastes, contaminated at varying degrees with trace metals, from the water. In previous investigations, Cu and Zn have been identified as highly concentrated trace metals associated to sulfides, mineral phases sensitive to oxidation. In order to ensure their sustainable management, the solidification/stabilization (S/S) and/or the valorization of contaminated sediments as secondary raw materials is a way to be promoted. Indeed, their reuse as a substitute of sand in cemented mortar formulation would allow combining both treatment and valorization of such wastes., Methods: In the present study, the environmental assessment of mortars formulated with raw and weathered marine sediments (in particular contaminated with Cu, Pb and Zn), compared to sand reference mortars, was conducted through two kinetic leaching tests: weathering cell tests (WCTs), in which mortars were crushed and leached twice a week, and a tank monolith leaching test (MLT), in which leaching was performed on monolithic mortars with increasing leachate renewal time., Results: In both leaching tests, calcium and sulfur were released continuously from sediment mortars, showing the oxidation-neutralization processes of sulfides and carbonates. In the MLT, Cu was released by sediment mortars through diffusion, particularly by weathered mortars, at low concentrations during 60 days of the test duration. With the more aggressive WCT, Cu concentrations were higher at the beginning but became negligible after 7 days of testing. Pb was released through diffusion mechanisms until depletion in both tests, whereas Zn was particularly well immobilized in the cemented matrices., Conclusions: The S/S process applied using hydraulic binders proved to be efficient in the stabilization of Cu, Pb, and Zn highly presents in studied sediments, and further valorization in civilian engineering applications could be considered.

In some developing countries, base-metal residues that were abandoned in tailing ponds or impoundments are increasingly used as construction material without any control, engineering basis, or environmental concern. This uncontrolled reuse of mine tailings may constitute a new form of pollution risks for humans and ecosystems through metal leaching. Therefore, the aim of the current study is to assess mine drainage, metal mobility, and geochemical behavior of two abandoned mine tailings commonly used in the upper-Moulouya region (eastern Morocco) as fine aggregates for mortar preparation. Their detailed physical, chemical, and mineralogical properties were subsequently evaluated in the context of developing appropriate alternative reuses to replace their conventional disposal and limit their weathering exposure. The obtained results showed that both tailings contain relatively high quantities of residual metals and metalloids with lead (ranging between 3610 and 5940 mg/kg) being the major pollutant. However, the mineralogical investigations revealed the presence of abundant neutralizing minerals and low sulfide content which influence mine drainage geochemistry and subsequently lower metals mobility. In fact, leachate analyses from weathering cell kinetic tests showed neutral conditions and low sulfide oxidation rates. According to these results, the tailings used as construction material in the upper-Moulouya region have very low generating potential of contaminated effluents and their reuse as aggregates may constitute a sustainable alternative method for efficient tailing management.

Contaminated dredged sediments are often considered hazardous wastes, so they have to be adequately managed to avoid leaching of pollutants. The mobility of inorganic contaminants is a major concern. Metal sulfides (mainly framboïdal pyrite, copper, and zinc sulfides) have been investigated in this study as an important reactive metal-bearing phase sensitive to atmospheric oxygen action. An oxygen consumption test (OC-Test) has been adapted to assess the reactivity of dredged sediments when exposed to atmospheric oxygen. An experimental column set-up has been developed allowing the coupling between leaching and oxygen consumption test to investigate the reactivity of the sediment. This reactivity, which consisted of sulfide oxidation, was found to occur for saturation degree between 60 and 90 % and until the 20th testing week, through significant sulfates releases. These latter were assumed to come from sulfide oxidation in the first step of the test, then probably from gypsum dissolution. Confrontation results of OC-Test and leachate quality shows that Cu was well correlated to sulfates releases, which in turn, leads to Ca and Mg dissolution (buffer effect). Cu, and mostly Zn, was associated to organic matter, phyllosilicates, and other minerals through organo-clay complexes. This research confirmed that the OC-Test, originally developed for mine tailings, could be a useful tool in the dredged sediment field which can allow for intrinsic characterization of reactivity of a material suspected to readily reacting with oxygen and for better understanding of geochemical processes that affect pollutants behavior, conversion, and transfer in the environment.

The tools developed for acid mine drainage (AMD) prediction were proven unsuccessful to predict the geochemical behavior of mine waste rocks having a significant chemical sorption capacity, which delays the onset of contaminated neutral drainage (CND). The present work was performed in order to test a new approach of water quality prediction, by using a chelating agent solution (0.03 M EDTA, or ethylenediaminetetraacetic acid) in kinetic testing used for the prediction of the geochemical behavior of geologic material. The hypothesis underlying the proposed approach is that the EDTA solution should chelate the metals as soon as they are released by sulfide oxidation, inhibiting their sorption or secondary precipitation, and therefore reproduce a worst-case scenario where very low metal attenuation mechanisms are present in the drainage waters. Fresh and weathered waste rocks from the Lac Tio mine (Rio tinto, Iron and Titanium), which are known to generate Ni-CND at the field scale, were submitted to small-scale humidity cells in control tests (using deionized water) and using an EDTA solution. Results show that EDTA effectively prevents the metals to be sorbed or to precipitate as secondary minerals, therefore enabling to bypass the delay associated with metal sorption in the prediction of water quality from these materials. This work shows that the use of a chelating agent solution is a promising novel approach of water quality prediction and provides general guidelines to be used in further studies, which will help both practitioners and regulators to plan more efficient management and disposal strategies of mine wastes.

The underground extraction of Pb-Zn mineralization in the Touiref area stopped in 1958. A large volume of flotation tailings (more than 500 Mt) containing sulfides were deposited in a tailings impoundment. The goals of this study are to evaluate the neutralization capacity of the unoxidized and oxidized tailings, to assess the speciation of metals between the different components of the tailings material, and to assess the mobility of metals and the secondary minerals' precipitation in pore waters using geochemical modeling. To accomplish these objectives, representative samples from both fresh and oxidized zones were collected along a vertical profile through the tailings pile. Physical, chemical (ICP-MS), and mineralogical characterization (X-ray diffraction (XRD), reflected light microscopy, scanning electron microscope (SEM)) of these samples was performed. Grain size analysis shows that the tailings are dominated by silt- to sand-sized fractions. The microscopic observation highlights the presence of pyrite, marcasite, galena, and sphalerite as primary minerals in a carbonated matrix. The study reveals also the presence of secondary minerals represented by cerussite, smithsonite, anglesite, and Fe oxi-hydroxides as important scavengers for trace elements. The static tests show that the presence of calcite in the tailing samples ensures acid-neutralizing capacity (ANC), which is significantly greater than the acidity potential (PA). The geochemical characterization of the unoxidized samples shows higher Cd, Pb, and Zn concentrations than the oxidized samples containing the highest values for Fe and SO4. Sequential extraction tests show that significant percentages of metals are distributed between the acid-soluble fractions (Cd, Pb, and Zn) and the reducible one (Zn). Pore water analysis indicates that Ca is the dominant cation (8,170 and 6,200 mg L(-1), respectively), whereas sulfate is the principal anion (6,900 and 5,100 mg L(-1), respectively). Saturation index (SI) calculations of minerals in pore water extracted from both the oxidized and unoxidized samples are indicative of gypsum (SI >0) and Fe(III) oxides (SI ≫0) precipitation. The latter controls the Fe concentration in solution.

The environmental assessment of potential effects of contaminated harbor sediments stabilized with hydraulic binders and the determination of remediation endpoints require the determination of pollutants leaching potentials. Moreover, little information about the speciation and mobility of inorganic contaminants in these specific solid matrices is available in the literature. The objective of this paper is to investigate the relationship between mineralogy and leachability of contaminants (copper, lead, and zinc) present in a French harbor sediment stabilized with quicklime and Portland cement. Batch equilibrium leaching tests at various pH, chemical analysis of leachates, and mineralogical studies (X-ray diffraction, scanning electron microscopy-energy dispersive spectroscopy, and diffuse reflectance infrared Fourier transform) have been combined in the present investigation. The acid neutralization capacity of the stabilized matrix studied is first controlled by the dissolution of portlandite (pH ~12), followed by the dissolution of C-S-H (pH ~11) and the dissolution of ettringite (pH ~10). Finally, a very high buffering capacity of this stabilized sediment is observed for pH values around 6. This equilibrium is mainly controlled by the dissolution of iron sulfides and carbonate minerals. Consequently, the mobilization of inorganic contaminants as a function of pH remains very low (<0.1 wt%) for pH values above 6 and significantly increases for pH below these values. This research confirms the importance of a combined methodology for the intrinsic characterization of potential mobilization of contaminants in a stabilized sediment and for a better understanding of geochemical processes that affect contaminant fate, transformation, and transport in the subsurface environment.