Thermodynamic evidence of giant salt deposit formation by serpentinization: an alternative mechanism to solar evaporation.

The evaporation of seawater in arid climates is currently the main accepted driving mechanism for the formation of ancient and recent salt deposits in shallow basins. However, the deposition of huge amounts of marine salts, including the formation of tens of metres of highly soluble types (tachyhydrite and bischofite) during the Aptian in the South Atlantic and during the Messinian Salinity Crisis, are inconsistent with the wet and warm palaeoclimate conditions reconstructed for these periods. Recently, a debate has been developed that opposes the classic model of evaporite deposition and argues for the generation of salt by serpentinization. The products of the latter process can be called "dehydratites". The associated geochemical processes involve the consumption of massive amounts of pure water, leading to the production of concentrated brines. Here, we investigate thermodynamic calculations that account for high salinities and the production of soluble salts and MgCl2-rich brines through sub-seafloor serpentinization processes. Our results indicate that salt and brine formation occurs during serpentinization and that the brine composition and salt assemblages are dependent on the temperature and CO2 partial pressure. Our findings help explain the presence and sustainability of highly soluble salts that appear inconsistent with reconstructed climatic conditions and demonstrate that the presence of highly soluble salts probably has implications for global tectonics and palaeoclimate reconstructions.

A double layer model of the gas bubble/water interface.

Zeta potential is a physico-chemical parameter of particular importance to describe sorption of contaminants at the surface of gas bubbles. Nevertheless, the interpretation of electrophoretic mobilities of gas bubbles is complex. This is due to the specific behavior of the gas at interface and to the excess of electrical charge at interface, which is responsible for surface conductivity. We developed a surface complexation model based on the presence of negative surface sites because the balance of accepting and donating hydrogen bonds is broken at interface. By considering protons adsorbed on these sites followed by a diffuse layer, the electrical potential at the head-end of the diffuse layer is computed and considered to be equal to the zeta potential. The predicted zeta potential values are in very good agreement with the experimental data of H(2) bubbles for a broad range of pH and NaCl concentrations. This implies that the shear plane is located at the head-end of the diffuse layer, contradicting the assumption of the presence of a stagnant diffuse layer at the gas/water interface. Our model also successfully predicts the surface tension of air bubbles in a KCl solution.

Salt precipitation and trapped liquid cavitation in micrometric capillary tubes.

Laboratory evidence shows that the occurrence of solid salt in soil pores causes drastic changes in the topology of the porous spaces and possibly also in the properties of the occluded liquid. Observations were made on NaCl precipitation in micrometric cylindrical capillary tubes, filled with a 5.5 M NaCl aqueous solution and submitted to drying conditions. Solid plug-shaped NaCl (halite) commonly grows at the two liquid-air interfaces, isolating the inner liquid column. The initially homogeneous porosity of the capillary tube becomes heterogeneous because of these two NaCl plugs, apparently closing the micro-system on itself. After three months, we observed cavitation of a vapor bubble in the liquid behind the NaCl plugs. This event demonstrates that the occluded liquid underwent a metastable superheated state, controlled by the capillary state of thin capillary films persisting around the NaCl precipitates. These observations show, first, that salt precipitation can create a heterogeneous porous medium in an initially regular network, thus changing the transfer properties due to isolating significant micro-volumes of liquid. Second, our experiment illustrates that the secondary salt growth drastically modifies the thermo-chemical properties of the occluded liquid and thus its reactive behavior.

In-pore tensile stress by drying-induced capillary bridges inside porous materials.

We present here some evidences that capillary liquid bridges are able to deform micrometric cylindrical pores by tensile stress. Brine-soaked filter membranes are submitted to drying conditions leading to NaCl precipitation inside the 5-10 µm pores. A close examination demonstrated that two forms of NaCl crystallites are successively generated. First, primary cubic crystals grow, driven by the permanent evaporation. When this angular primary solid gets near the pore wall, while the evaporation makes the pore volume to be partly invaded by air, capillary liquid can bridge the now-small gap between the halite angles and the pore wall. In a second step, these small capillary bridges are frozen by a secondary precipitation event of concave-shaped NaCl. The proposed interpretation is that the liquid capillary bridges deform the host matrix of the membrane, and the situation is fossilized by the growth of solid capillary bridges. A quantitative interpretation is proposed and the consequences towards the natural media outlined.

Environmental impacts of unmanaged solid waste at a former base metal mining and ore processing site (Kirki, Greece).

The Kirki project aimed to identify, among the mining waste abandoned at a mine and processing plant, the most critical potential pollution sources, the exposed milieus and the main pathways for contamination of a littoral area. This was accompanied by the definition of a monitoring network and remedial options. For this purpose, field analytical methods were extensively used to allow a more precise identification of the source, to draw relevant conceptual models and outline a monitoring network. Data interpretation was based on temporal series and on a geographical model. A classification method for mining waste was established, based on data on pollutant contents and emissions, and their long-term pollution potential. Mining waste present at the Kirki mine and plant sites comprises (A) extraction waste, mainly metal sulfide-rich rocks; (B) processing waste, mainly tailings, with iron and sulfides, sulfates or other species, plus residues of processing reagents; and (C) other waste, comprising leftover processing reagents and Pb-Zn concentrates. Critical toxic species include cadmium and cyanide. The stormy rainfall regime and hilly topography favour the flush release of large amounts of pollutants. The potential impacts and remedial options vary greatly. Type C waste may generate immediate and severe chemical hazards, and should be dealt with urgently by careful removal, as it is localised in a few spots. Type B waste has significant acid mine drainage potential and contains significant amounts of bioavailable heavy metals and metalloids, but they may also be released in solid form into the surface water through dam failure. The most urgent action is thus dams consolidation. Type A waste is by far the most bulky, and it cannot be economically removed. Unfortunately, it is also the most prone to acid mine drainage (seepage pH 1 to 2). This requires neutralisation to prevent acid water accelerating heavy metals and metalloids transfer. All waste management options require the implementation of a monitoring network for the design of a remediation plan, efficiency control, and later, community alert in case of accidental failure of mitigation/remediation measures. A network design strategy based on field measurements, laboratory validation and conceptual models is proposed.

Reactivity of waste generated during lead recycling: an integrated study.

Lead consumption in Europe is 2.054 M tonnes/year, more than 70% of which is produced by recycling and, more specifically, the recycling of car batteries. This industry is jeopardised by the method employed so far, recycling by alkaline fusion, because the treatment produces 200,000 tonnes of toxic and unstable slag. The study presented here attempts to clarify the approach and the combined tools employed (mineralogy, chemistry, leaching, thermodynamics), to construct a coherent physicochemical model of slag behaviour. The model was then used to carry out sensitivity analyses with various landfill scenarios, and to propose adjustments to the process to recover the residual heavy metals and to upgrade as secondary raw products the co-products generated by the inerting of the slag.