Minerals2014, 4(3), 716-745; doi:10.3390/min4030716 - published online 23 July 2014 Show/Hide Abstract
Abstract: Among the diverse research fields and wide range of studies encompassed by environmental magnetism, the present work elaborates on critical aspects of the geochemistry of trace metals that emerged through years of original research in a variety of environmental compartments. This review aims at sharing the insights gained on (a) tracing metal pollution sources; and (b) identifying processes and transport pathways from sources to depositional environments. Case studies on the Elefsis Gulf (Greece) and the Gulf of Lions (France) demonstrate the potential of combined magnetic measurements and chemical analysis to trace pollution signals resulting from land-based sources and atmospheric deposition. Case studies on estuarine environments, namely the Louros, Acheloos, and Asopos Estuaries (Greece), address modes of trace metal behavior under the influence of different hydrological regimes and elucidate in situ processes within the transitional estuarine zone, that define their ultimate fate. As sources, transport pathways, and processes of trace metals are fundamental in environmental management assessments, the involvement of magnetic measurements in the policy cycle could facilitate the development and implementation of appropriate regulatory measures for the integrated management of river basins, coastal, and marine areas.
Minerals2014, 4(3), 690-715; doi:10.3390/min4030690 - published online 14 July 2014 Show/Hide Abstract
Abstract: Incorporation reactions play an important role in dictating immobilization and release pathways for chemical species in low-temperature geologic environments. Quantum-mechanical investigations of incorporation seek to characterize the stability and geometry of incorporated structures, as well as the thermodynamics and kinetics of the reactions themselves. For a thermodynamic treatment of incorporation reactions, a source of the incorporated ion and a sink for the released ion is necessary. These sources/sinks in a real geochemical system can be solids, but more commonly, they are charged aqueous species. In this contribution, we review the current methods for ab initio calculations of incorporation reactions, many of which do not consider incorporation from aqueous species. We detail a recently-developed approach for the calculation of incorporation reactions and expand on the part that is modeling the interaction of periodic solids with aqueous source and sink phases and present new research using this approach. To model these interactions, a systematic series of calculations must be done to transform periodic solid source and sink phases to aqueous-phase clusters. Examples of this process are provided for three case studies: (1) neptunyl incorporation into studtite and boltwoodite: for the layered boltwoodite, the incorporation energies are smaller (more favorable) for reactions using environmentally relevant source and sink phases (i.e., ΔErxn(oxides) > ΔErxn(silicates) > ΔErxn(aqueous)). Estimates of the solid-solution behavior of Np5+/P5+- and U6+/Si4+-boltwoodite and Np5+/Ca2+- and U6+/K+-boltwoodite solid solutions are used to predict the limit of Np-incorporation into boltwoodite (172 and 768 ppm at 300 °C, respectively); (2) uranyl and neptunyl incorporation into carbonates and sulfates: for both carbonates and sulfates, it was found that actinyl incorporation into a defect site is more favorable than incorporation into defect-free periodic structures. In addition, actinyl incorporation into carbonates with aragonite structure is more favorable than into carbonates with calcite structure; and (3) uranium incorporation into magnetite: within the configurations tested that preserve charge neutrality (U6+ → 2Fe3+oct/tet or U4+ → Fe2+oct), uranium incorporation into magnetite is most favorable when U6+ replaces octahedral Fe3+ with charge balancing accomplished by an octahedral Fe3+ iron vacancy. At the end of this article, the limitations of this method and important sources of error inherent in these calculations (e.g., hydration energies) are discussed. Overall, this method and examples may serve as a guide for future studies of incorporation in a variety of contexts.
Minerals2014, 4(3), 667-689; doi:10.3390/min4030667 - published online 10 July 2014 Show/Hide Abstract
Abstract: The diagenetic evolution of the magnetic minerals during burial in sedimentary basins has been recently proposed. In this study, we provide new data from the Grès d’Annot basin, SE France. We analyze fine-grained clastic rocks that suffered a burial temperature from ~60 to >250 °C, i.e., covering oil and gas windows. Low temperature magnetic measurements (10–300 K), coupled with vitrinite reflectance data, aim at defining the magnetic mineral evolution through the burial history. Magnetite is documented throughout the entire studied transect. Goethite, probably occurring as nanoparticles, is found for a burial temperature <80 °C. Micron-sized pyrrhotite is highlighted for a burial temperature >200 °C below the Alpine nappes and the Penninic Front. A model of the evolution of the magnetic assemblage from 60 to >250 °C is proposed for clastic rocks, containing iron sulfides (pyrite) and organic matter. This work provides the grounds for a better understanding of the magnetic properties of petroleum plays.
Minerals2014, 4(3), 642-666; doi:10.3390/min4030642 - published online 8 July 2014 Show/Hide Abstract
Abstract: The mining industry is a fundamental industry involved in the development of modern society, but is also the world’s largest waste producer. This role will be enhanced in the future, because ore grades are generally decreasing, thus leading to increases in the waste/metal production ratio. Mine wastes deposited on-land in so-called tailings dams, impoundments or waste-dumps have several associated environmental issues that need to be addressed (e.g., acid mine drainage formation due to sulphide oxidation, geotechnical stability, among others), and social concerns due to land use during mining. The mining industry recognizes these concerns and is searching for waste management alternatives for the future. One option used in the past was the marine shore or shallow submarine deposition of this waste material in some parts of the world. After the occurrence of some severe environmental pollution, today the deposition in the deep sea (under constant reducing conditions) is seen as a new, more secure option, due to the general thought that sulphide minerals are geochemically stable under the reduced conditions prevailing in the deep marine environment. This review highlights the mineralogical and geochemical issues (e.g., solubility of sulphides in seawater; reductive dissolution of oxide minerals under reducing conditions), which have to be considered when evaluating whether submarine tailings disposal is a suitable alternative for mine waste.
Minerals2014, 4(3), 621-641; doi:10.3390/min4030621 - published online 8 July 2014 Show/Hide Abstract
Abstract: Sulphidic mine tailings are among the largest mining wastes on Earth and are prone to produce acid mine drainage (AMD). The formation of AMD is a sequence of complex biogeochemical and mineral dissolution processes. It can be classified in three main steps occurring from the operational phase of a tailings impoundment until the final appearance of AMD after operations ceased: (1) During the operational phase of a tailings impoundment the pH-Eh regime is normally alkaline to neutral and reducing (water-saturated). Associated environmental problems include the presence of high sulphate concentrations due to dissolution of gypsum-anhydrite, and/or effluents enriched in elements such as Mo and As, which desorbed from primary ferric hydroxides during the alkaline flotation process. (2) Once mining-related operations of the tailings impoundment has ceased, sulphide oxidation starts, resulting in the formation of an acidic oxidation zone and a ferrous iron-rich plume below the oxidation front, that re-oxidises once it surfaces, producing the first visible sign of AMD, i.e., the precipitation of ferrihydrite and concomitant acidification. (3) Consumption of the (reactive) neutralization potential of the gangue minerals and subsequent outflow of acidic, heavy metal-rich leachates from the tailings is the final step in the evolution of an AMD system. The formation of multi-colour efflorescent salts can be a visible sign of this stage.
Minerals2014, 4(3), 603-620; doi:10.3390/min4030603 - published online 8 July 2014 Show/Hide Abstract
Abstract: Sea level rise is able to change the geochemical conditions in coastal systems. In these environments, transport of contaminants can be controlled by the stability and adsorption capacity of iron oxides. The behavior of adsorbed and co-precipitated arsenic in jarosite, schwertmannite, ferrihydrite, and goethite in sea water (common secondary minerals in coastal tailings) was investigated. The aim of the investigation was to establish As retention and transport under a marine flood scenario, which may occur due to climate change. Natural and synthetic minerals with co-precipitated and adsorbed As were contacted with seawater for 25 days. During this period As, Fe, Cl, SO4, and pH levels were constantly measured. The larger retention capability of samples with co-precipitated As, in relation with adsorbed As samples, reflects the different kinetics between diffusion, dissolution, and surface exchange processes. Ferrihydrite and schwertmannite showed good results in retaining arsenic, although schwertmannite holding capacity was enhanced due its buffering capacity, which prevented reductive dissolution throughout the experiment. Arsenic desorption from goethite could be understood in terms of ion exchange between oxides and electrolytes, due to the charge difference generated by a low point-of-zero-charge and the change in stability of surface complexes between synthesis conditions and natural media.