Thermal flux, fugitive gas emission and geotechnical instability in a complex tailings legacy site.

Several years after decommissioning, a magnesium dross and mixed waste heap at a former industrial facility is still reactive, as evidenced by the emission of heat, Volatile Organic Carbon (VOCs), acetylene (C2H2), cyanide (HCN) and ammonia (NH3) from deep, discordant, epigenetic fissures. To evaluate the longer-term stability of the waste heap material, four cores were collected to evaluate vertical variations in temperature, moisture, gas composition, geochemistry, and mineralogy. Temperature increased with depth and peaked at around 8 m, reaching in excess of 90 °C. The waste heap was a mixture of unreacted materials (mainly MgO and CaO) and a variety of hydrated secondary reaction products. Formation of the latter could account for the generation of heat and creation of the fissures via thermal and secondary mineral volumetric expansion. With a large inventory of unreacted CaO and MgO and substantial in situ water present, the waste heap will probably remain reactive in the foreseeable future. Importantly, the CaO/MgO ratio of solid materials in the waste heap provides a useful proxy for down hole temperature, pH, and fugitive gas concentrations. Fugitive gases emitted by the waste heap are related to the reaction of co-existing minerals in the heap based on an historical analysis of site waste disposal. These waste materials include calcium carbide (CaC2), magnesium nitride (Mg3N2) and calcium cyanamide (CaCN2). Capping to limit the ingress of additional meteoric water and targeted venting to facilitate cooling and the controlled release and dispersion of gases are recommended to manage the environmental risk.

Coupling SEM-EDS and confocal Raman-in-SEM imaging: A new method for identification and 3D morphology of asbestos-like fibers in a mineral matrix.

Asbestos consists in natural minerals crystallized in a specific habit and possessing in particular properties. In the case of Naturally Occurring Asbestos, usual methods applied to the identification of mineral fibers and the determination of their possible asbestiform nature seems not efficient, especially in the case of mineral fibers included in mineral matrix. We present a new in-situ method based on the use of confocal Raman-in-SEM imaging implemented in a Scanning Electron Microscope as an efficient method for in-situ mineralogy. The limitation of conventional methods is discussed. We applied 2D-Raman imaging to the identification of sub-micrometric fibers included in different mineral matrix. We were able to identify actinolite fibers down to 400 nm in diameter, included in feldspar, quartz and/or calcite matrix. Moreover, Confocal Raman allows the collection of 3D data that would provide access to critical information on the morphology of the amphibole fibers in the volume, such as aspect ratio, fibers distribution and amphibole volume fraction. We performed this method on various examples of rocks containing actinolite fibers of mean structural formula is: Na0,04-0,12 Mg2,79-3,73 Al0,29-0,58 K0,01 Ca1,79-1,98 Mn0,01-0,09 Fe2+0,99-1,91 Fe3+Si7,64-7,73 O22(OH)2. We demonstrated that coupling confocal Raman imaging and SEM is a new and efficient in-situ method for identification and morphological characterization of amphibole fibers.

Multiscale structure of nacre biomaterial: Thermomechanical behavior and wear processes.

Sheet nacre is a hybrid biocomposite with a multiscale structure, including nanograins of CaCO3 (97% wt% - 40 nm in size) and two organic matrices: (i) the interlamellar mainly composed of ß-chitin and proteins, and (ii) the intracrystalline composed by silk-fibroin-like proteins. This material is currently contemplated for the manufacture of small prostheses (e.g., rachis and dorsal vertebra prostheses) which are subjected to micro-slip or fretting motion. In this work, the tribological behavior of nacre is studied by varying the frictional dissipated power from few nW to several hundred mW, in order to assess the various responses of the different nacre's components, independently. Results reveal various dissipative mechanisms vs. dissipated frictional power: organic thin film lubrication, tablet's elastoplastic deformations, stick-slip phenomenon and/or multiscale wear processes, including various thermo-mechanical processes (i.e., mineral phase transformation, organics melting and friction-induced nanoshocks process on a large range). All these mechanisms are controlled by the multiscale and anisotropy of its structure - and especially by its both matrices and respective orientation vs. the sliding direction.

Raman-in-SEM, a multimodal and multiscale analytical tool: performance for materials and expertise.

The availability of Raman spectroscopy in a powerful analytical scanning electron microscope (SEM) allows morphological, elemental, chemical, physical and electronic analysis without moving the sample between instruments. This paper documents the metrological performance of the SEMSCA commercial Raman interface operated in a low vacuum SEM. It provides multiscale and multimodal analyses as Raman/EDS, Raman/cathodoluminescence or Raman/STEM (STEM: scanning transmission electron microscopy) as well as Raman spectroscopy on nanomaterials. Since Raman spectroscopy in a SEM can be influenced by several SEM-related phenomena, this paper firstly presents a comparison of this new tool with a conventional micro-Raman spectrometer. Then, some possible artefacts are documented, which are due to the impact of electron beam-induced contamination or cathodoluminescence contribution to the Raman spectra, especially with geological samples. These effects are easily overcome by changing or adapting the Raman spectrometer and the SEM settings and methodology. The deletion of the adverse effect of cathodoluminescence is solved by using a SEM beam shutter during Raman acquisition. In contrast, this interface provides the ability to record the cathodoluminescence (CL) spectrum of a phase. In a second part, this study highlights the interest and efficiency of the coupling in characterizing micrometric phases at the same point. This multimodal approach is illustrated with various issues encountered in geosciences.

Mobility and phytoavailability of Cu, Cr, Zn, and As in a contaminated soil at a wood preservation site after 4 years of aided phytostabilization.

The remediation of copper-contaminated soils by aided phytostabilisation in 16 field plots at a wood preservation site was investigated. The mobility and bioavailability of four potentially toxic trace elements (PTTE), i.e., Cu, Zn, Cr, and As, were investigated in these soils 4 years after the incorporation of compost (OM, 5 % w/w) and dolomite limestone (DL, 0.2 % w/w), singly and in combination (OMDL), and the transplantation of mycorrhizal poplar and willows. Topsoil samples were collected in all field plots and potted in the laboratory. Total PTTE concentrations were determined in soil pore water (SPW) collected by Rhizon soil moisture samplers. Soil exposure intensity was assessed by Chelex100-DGT (diffusive gradient in thin films) probes. The PTTE phytoavailability was characterized by growing dwarf beans on potted soils and analyzing their foliar PTTE concentrations. OM and DL, singly and in combination (OMDL), were effective to decrease foliar Cu, Cr, Zn, and As concentrations of beans, the lowest values being numerically for the OM plants. The soil treatments did not reduce the Cu and Zn mineral masses of the bean primary leaves, but those of Cr and As decreased for the OM and DL plants. The Cu concentration in SPW was increased in the OM soil and remained unchanged in the DL and OMDL soils. The available Cu measured by DGT used to assess the soil exposure intensity correlated with the foliar Cu concentration. The Zn concentrations in SPW were reduced in the DL soil. All amendments increased As in the SPW. Based on DGT data, Cu availability was reduced in both OM and OMDL soils, while DL was the most effective to decrease soil Zn availability.

The co-effect of organic matrix from carp otolith and microenvironment on calcium carbonate mineralization.

In vitro mineralization experiment is an effective way to study the effect of organic matrix on calcium carbonate crystallization, and to reveal the relationship between organic matrix and inorganic crystal in natural biominerals. In natural biominerals, organic matrix plays an important role in crystal formation and stability, together with microenvironment changes, they can affect crystal polymorph, morphology, density, size, orientation etc. In this work, we systematically studied the effects of different organic matrices in fish otoliths, the organic matrix concentration changes, as well as the co-effect of organic matrices with temperature, pH value and Mg ion changes in the in vitro CaCO3 mineralization experiments. The organic matrix and concentration change experiments prove that water soluble matrix (WSM) plays an important role in crystal form transition. It can induce CaCO3 crystals with same crystal polymorph as the otolith from which organic matrix was extracted. The temperature change experiment proves that CaCO3 has a tendency to form calcite, vaterite, and then aragonite in priority as temperature goes up. Under different temperature, WSM from lapillus/asteriscus still has the effect to mediate different CaCO3 crystals. The pH change experiment shows that, near the neutral environment, as pH value goes up, calcites have a tendency to form crystal aggregates with more faces exposed, the organic matrix still keeps crystal mediation effect. The Mg(2+) experiment shows that, Mg ion can promote aragonite formation, together with lapillus organic matrix, aragonites with different shapes are formed.

A novel growth process of calcium carbonate crystals in silk fibroin hydrogel system.

We report an interesting finding of calcium carbonate (CaCO3) crystal growth in the silk fibroin (SF) hydrogel with different concentrations by a simple ion diffusion method. The experimental results indicate that the CaCO3 crystals obtained from silk fibroin gels with low and high concentrations are all calcites with unusual morphologies. Time-dependent growth study was carried out to investigate the crystallization process. It is believed that silk fibroin hydrogel plays an important role in the process of crystallization. The possible formation mechanism of CaCO3 crystals is proposed. This study provides a better explanation of the influence of silk fibroin concentration and its structure on CaCO3 crystals growth.

Effects of additives and templates on calcium carbonate mineralization in vitro.

The review focuses on the effects of several important additives and templates controlling the calcium carbonate crystals formation and the complexity of the crystal morphologies in vitro. Additives include soluble matrices extracted from shells and pearls, amino-acids, magnesium ions and collagen among others. Templates include modified single crystal silicon, natural biominerals among others. Mechanisms proposed to explain the phenomena are not systematic, further studies are necessary to explain how organic matrices mediate calcium carbonate mineralization.

Dynamics of sheet nacre formation in bivalves.

Formation of nacre (mother-of-pearl) is a biomineralization process of fundamental scientific as well as industrial importance. However, the dynamics of the formation process is still not understood. Here, we use scanning electron microscopy and high spatial resolution ion microprobe depth-profiling to image the full three-dimensional distribution of organic materials around individual tablets in the top-most layer of forming nacre in bivalves. Nacre formation proceeds by lateral, symmetric growth of individual tablets mediated by a growth-ring rich in organics, in which aragonite crystallizes from amorphous precursors. The pivotal role in nacre formation played by the growth-ring structure documented in this study adds further complexity to a highly dynamical biomineralization process.

Forming nacreous layer of the shells of the bivalves Atrina rigida and Pinctada margaritifera: an environmental- and cryo-scanning electron microscopy study.

A key to understanding control over mineral formation in mollusk shells is the microenvironment inside the pre-formed 3-dimensional organic matrix framework where mineral forms. Much of what is known about nacre formation is from observations of the mature tissue. Although these studies have elucidated several important aspects of this process, the structure of the organic matrix and the microenvironment where the crystal nucleates and grows are very difficult to infer from observations of the mature nacre. Here, we use environmental- and cryo-scanning electron microscopy to investigate the organic matrix structure at the onset of mineralization in the nacre of two mollusk species: the bivalves Atrina rigida and Pinctada margaritifera. These two techniques allow the visualization of hydrated biological materials coupled with the preservation of the organic matrix close to physiological conditions. We identified a hydrated gel-like protein phase filling the space between two interlamellar sheets prior to mineral formation. The results are consistent with this phase being the silk-like proteins, and show that mineral formation does not occur in an aqueous solution, but in a hydrated gel-like medium. As the tablets grow, the silk-fibroin is pushed aside and becomes sandwiched between the mineral and the chitin layer.

Multiscale structure of sheet nacre.

This work was conducted on Pinctada maxima nacre (mother of pearl) in order to understand its multiscale ordering and the role of the organic matrix in its structure. Intermittent-contact atomic force microscopy with phase detection imaging reveals a nanostructure within the tablet. A continuous organic framework divides each tablet into nanograins. Their shape is supposed to be flat with a mean extension of 45nm. TEM performed in the darkfield mode evidences that at least part of the intracrystalline matrix is crystallized and responds like a 'single crystal'. The tablet is a 'hybrid composite'. The organic matrix is continuous. The mineral phase is thus finely divided still behaving as a single crystal. It is proposed that each tablet results from the coherent aggregation of nanograins keeping strictly the same crystallographic orientation thanks to a hetero-epitaxy mechanism. Finally, high-resolution TEM performed on bridges from one tablet to the next, in the overlying row, did not permit to evidence a mineral lattice but crystallized organic bridges. The same organic bridges were evidenced by SEM in the interlaminar sequence.

Sheet nacre growth mechanism: a Voronoi model.

Shell nacre (mother of pearl) of Pinctada margaritifera was analyzed by scanning electron microscopy. The originality of this work concerns the sampling performed to observe incipient nacre on the mantle side. The whole animal is embedded in methyl methacrylate followed by separation of the shell from the hardened mantle. It is revealed this way how each future nacre layer pre-exists as a film or compartment. Experimental observations also show for the first time, the progressive lateral crystallization inside this film, finishing under the form of a non-periodic pattern of polygonal tablets of bio-aragonite. It is evidenced that nuclei appear in the film in the vicinity of the zone where aragonite tablets of the underlying layer get in contact to each other. A possible explanation is given to show how nucleation is probably launched in time and space by a signal coming from the underlying layer. Finally, it is evidenced that tablets form a Voronoi tiling of the space: this suggests that their growth is controlled by an "aggregation-like" process of "crystallites" and not directly by the aragonite lattice growth.