scholarly journals Processes of metastable-mineral formation in oxidation zones and mine waste

2020 ◽  
Vol 84 (3) ◽  
pp. 367-375 ◽  
Author(s):  
Juraj Majzlan

AbstractOxidation zones and mine wastes are metal-rich, near-surface environments, natural and man-made critical zones of ore deposits, respectively. They contain a number of minerals which, despite their metastability, occur consistently and in abundance. Field studies, presented as examples in this work, show that metastable minerals form not only directly from aqueous solutions, but also from more complex precursors, such as nanoparticles, gels, X-ray amorphous solids, or clusters. Initial precipitation of metastable phases and their conversion to stable phases is described by the Ostwald's step rule. Thermodynamic data show that there is a tendency, but no rule, that structurally more complex phases are also thermodynamically more stable. The Ostwald's step rule could then state that the initial metastable phases are structurally simple and easily assembled from aqueous solutions, nanoparticles, gels, disordered solids, or clusters. The structural similarity of the precursor and the forming phase is a kinetic factor favouring the crystallisation of the new phase. Calculation of saturation indices for mine drainage solutions show that they are mostly supersaturated with respect to the stable phases and the aqueous concentrations are sufficient to precipitate metastable minerals. In our fieldwork, we often encounter gelatinous substances with copper, manganese or tungsten that slowly convert to metastable oxysalt minerals. Another possibility is the crystallisation of various metastable minerals from solid, homogeneous ‘resins’ that are X-ray amorphous. Minerals typical for near-surface environments may be stabilised by their surface energy at high specific surface areas. For example, ferrihydrite is often described as a metastable phase but can be shown to be stable with respect to nanosised hematite.

2021 ◽  
Author(s):  
Jillian Helser ◽  
Valérie Cappuyns

<p>Proper management and storage of mine waste (e.g., tailings and waste rock) is one of the main issues that mining industries face. Additionally, there is already an uncountable amount of existent historical mine waste, which may, even centuries later, still be leaching contaminants into the environment. One solution to minimize the risks associated with the waste, with also potential economic benefits, is through the valorization of the waste. This can be done by first recovering valuable metals and removing hazardous contaminants. Then, the remaining residue can be valorized into green construction materials, such as geopolymers, ceramics or cement.  For some mine waste materials, such as those with only trace levels of metals, that are not economically viable to extract, the “waste” can be reused directly without this additional cleaning step. In the present study, mine waste originating from 3 different sites, both operational and historical mines, was characterized and assessed in comparison with the cleaned mine waste (i.e., cleaned by bioleaching or ion flotation methods) and with different types of green construction materials containing (cleaned and uncleaned) mine waste. Particular emphasis was given to the study of the mobilization of metal(loid)s from the mine waste and green construction materials (i.e., ceramics, geopolymers and cement) under different conditions, through a series of leaching tests (i.e., EN 12457-2, US EPA’s Toxicity Characteristic Leaching Procedure, and a pH-dependent leaching test). The standardized leaching tests were applied to either mimic neutral conditions in nature, conditions in a landfill (end of life), or a worst-case scenario (i.e., in extremely acidic or alkaline pH).</p><p>Mineralogical (X-ray diffraction) and chemical (X-ray fluorescence) characterizations of the original mine waste samples revealed high levels of Pb, Zn, and As in most samples. Additionally, the samples consisted mostly of quartz, micas, clay minerals and/or feldspars. Some samples also contained pyrite (FeS<sub>2</sub>), a key mineral that generates acid mine drainage. Based on the leaching studies, some geopolymers, ceramics, and cement efficiently immobilized certain metals (such as Pb and Zn). Also, longer curing durations of the geopolymers in most cases improved the immobilization of metal(loid)s. Overall, the leaching studies revealed that the concentrations of mine waste incorporated in the construction materials, as well as the pH of those materials, were the main factors influencing the mobility of metal(loid)s. Additionally, for ceramics, the temperature at which the test pieces were fired, also played a major role. Through this detailed characterization, the environmental impacts were assessed from the mine waste to the downstream products, determining which valorization methods are the most viable to close the circular economy loop.</p>


2010 ◽  
Vol 654-656 ◽  
pp. 930-933 ◽  
Author(s):  
Kenji Matsuda ◽  
Junya Nakamura ◽  
Keisuke Yamamoto ◽  
Tokimasa Kawabata ◽  
Yasuhiro Uetani ◽  
...  

The purpose of study is to investigate aging behavior, crystal structures of metastable phase and relative frequency of metastable phases in aged Al-Mg-Ge and Al-Mg-Ge-Si alloys using high resolution transmission electron microscope (HRTEM), energy dispersive X-ray spectroscopy (EDS) and electron energy-loss spectroscopy (EELS). Every alloy included rod-shaped precipitate which is the same as the typical metastable pahse, ’, in Al-Mg-Si alloy. Except to Mg-rich alloys, the Type-A precipitate, which is a typical metastable phase in the excess Si type Al-Mg-Si alloys and popular at over aged condition, was confirmed as a large rod-shaped precipitates in those alloys. This behavior is probably depends on the ratio of Mg/Ge. Also, Mg, Si and Ge were detected from the ’-phase in Al-Mg-Ge-Si alloy by EELS. This means that the ’-phase in Al-Mg-Ge-Si alloy consists of these 3 elements including Si, not just Ge to form metastable Mg2Ge.


2019 ◽  
Author(s):  
Claudia Dawson ◽  
◽  
Samara Ord ◽  
Daniel M. Sturmer ◽  
J. Caleb Chappell ◽  
...  

Author(s):  
A. Leineweber ◽  
M. Löffler ◽  
S. Martin

Abstract Cu6Sn5 intermetallic occurs in the form of differently ordered phases η, η′ and η′′. In solder joints, this intermetallic can undergo changes in composition and the state of order without or while interacting with excess Cu and excess Sn in the system, potentially giving rise to detrimental changes in the mechanical properties of the solder. In order to study such processes in fundamental detail and to get more detailed information about the metastable and stable phase equilibria, model alloys consisting of Cu3Sn + Cu6Sn5 as well as Cu6Sn5 + Sn-rich melt were heat treated. Powder x-ray diffraction and scanning electron microscopy supplemented by electron backscatter diffraction were used to investigate the structural and microstructural changes. It was shown that Sn-poor η can increase its Sn content by Cu3Sn precipitation at grain boundaries or by uptake of Sn from the Sn-rich melt. From the kinetics of the former process at 513 K and the grain size of the η phase, we obtained an interdiffusion coefficient in η of (3 ± 1) × 10−16 m2 s−1. Comparison of this value with literature data implies that this value reflects pure volume (inter)diffusion, while Cu6Sn5 growth at low temperature is typically strongly influenced by grain-boundary diffusion. These investigations also confirm that η′′ forming below a composition-dependent transus temperature gradually enriches in Sn content, confirming that Sn-poor η′′ is metastable against decomposition into Cu3Sn and more Sn-rich η or (at lower temperatures) η′. Graphic Abstract


Processes ◽  
2021 ◽  
Vol 9 (2) ◽  
pp. 217
Author(s):  
Marin Ugrina ◽  
Martin Gaberšek ◽  
Aleksandra Daković ◽  
Ivona Nuić

Sulfur-impregnated zeolite has been obtained from the natural zeolite clinoptilolite by chemical modification with Na2S at 150 °C. The purpose of zeolite impregnation was to enhance the sorption of Hg(II) from aqueous solutions. Chemical analysis, acid and basic properties determined by Bohem’s method, chemical behavior at different pHo values, zeta potential, cation-exchange capacity (CEC), specific surface area, X-ray powder diffraction (XRPD), scanning electron microscopy with energy-dispersive X-ray analysis (SEM-EDS), Fourier transform infrared spectroscopy (FTIR), as well as thermogravimetry with derivative thermogravimetry (TG-DTG) were used for detailed comparative mineralogical and physico-chemical characterization of natural and sulfur-impregnated zeolites. Results revealed that the surface of the natural zeolite was successfully impregnated with sulfur species in the form of FeS and CaS. Chemical modification caused an increase in basicity and the net negative surface charge due to an increase in oxygen-containing functional groups as well as a decrease in specific surface area and crystallinity due to the formation of sulfur-containing clusters at the zeolite surface. The sorption of Hg(II) species onto the sulfur-impregnated zeolite was affected by the pH, solid/liquid ratio, initial Hg(II) concentration, and contact time. The optimal sorption conditions were determined as pH 2, a solid/liquid ratio of 10 g/L, and a contact time of 800 min. The maximum obtained sorption capacity of the sulfur-impregnated zeolite toward Hg(II) was 1.02 mmol/g. The sorption mechanism of Hg(II) onto the sulfur-impregnated zeolite involves electrostatic attraction, ion exchange, and surface complexation, accompanied by co-precipitation of Hg(II) in the form of HgS. It was found that sulfur-impregnation enhanced the sorption of Hg(II) by 3.6 times compared to the natural zeolite. The leaching test indicated the retention of Hg(II) in the zeolite structure over a wide pH range, making this sulfur-impregnated sorbent a promising material for the remediation of a mercury-polluted environment.


2021 ◽  
Vol 7 (1) ◽  
Author(s):  
Lars Banko ◽  
Phillip M. Maffettone ◽  
Dennis Naujoks ◽  
Daniel Olds ◽  
Alfred Ludwig

AbstractWe apply variational autoencoders (VAE) to X-ray diffraction (XRD) data analysis on both simulated and experimental thin-film data. We show that crystal structure representations learned by a VAE reveal latent information, such as the structural similarity of textured diffraction patterns. While other artificial intelligence (AI) agents are effective at classifying XRD data into known phases, a similarly conditioned VAE is uniquely effective at knowing what it doesn’t know: it can rapidly identify data outside the distribution it was trained on, such as novel phases and mixtures. These capabilities demonstrate that a VAE is a valuable AI agent for aiding materials discovery and understanding XRD measurements both ‘on-the-fly’ and during post hoc analysis.


Metals ◽  
2021 ◽  
Vol 11 (2) ◽  
pp. 295
Author(s):  
Bong-Ju Kim ◽  
Yong-Kwon Koh ◽  
Jang-Soon Kwon

The microbially mediated recovery of valuable metals contained in mining waste presents an economical alternative to conventional hydrometallurgical processes. In order to investigate the effect of bacterial adaptation and biological oxidation on bioleaching, the microbially mediated bioleaching of a pyrrhotite sample from mine waste, with indigenous bacteria existing in acid mine drainage, was studied. The indigenous bacteria were sub-cultured repeatedly for iron adaptation, and Acidithiobacillus ferrooxidans was identified as the dominant member of the microbial consortium. The point of zero charge (PZC) of pyrrhotite sampled from mine waste was determined as 3.0. The performance of bioleaching by contact and non-contact biological oxidation was compared by conducting bioleaching under different initial pH (pHini) conditions (2.8 and 3.2). Negatively charged bacteria could be attached onto the pyrrhotite, which has a positive surface charge at lower pHini (2.8) than the PZC (3.0). Bacteria attachment and corrosion pits on the surface of the pyrrhotite residues were observed at pHini of 2.8. Under bacteria-adapted conditions, the leaching concentration of Fe (44.2 mg/L) at pHini of 2.8 was 2.1 times greater than that (21.3 mg/L) at pHini of 3.2. Under non-adapted bacteria conditions, the extent of Fe leaching was not significantly different between the pHini of 2.8 and 3.2. This could be attributed to the fact that the adapted bacteria could more easily attach onto the pyrrhotite surfaces at pHini 2.8, allowing contact biological oxidation during the bioleaching experiments. We demonstrate here that the bioleaching of pyrrhotite could increase Fe recovery through bacterial adaptation and contact biological oxidation.


Author(s):  
Teemu Karlsson ◽  
Lena Alakangas ◽  
Päivi Kauppila ◽  
Marja Liisa Räisänen

AbstractThe mobility of contaminants from mine waste can be assessed using different extraction methods. Aqua regia (AR) extraction is the most commonly used method in Finland. Another method is the analysis of leachate from net acid generation (NAG) tests, which is primarily designed for acid production potential assessment. We investigated the performance of single-addition NAG test leachate analysis and AR extraction in drainage quality prediction, using waste rock and drainage water samples from several Finnish waste rock sites. Our objective was to improve interpretation of the AR and single-addition NAG test leachate analysis results in drainage quality prediction. The AR extraction effectively reflected elements that occurred in elevated concentrations in drainage water, though it over-predicted Al, As, Cd, Co, Cu, and Ni in some circumneutral drainages, and Cr in general. The single-addition NAG test leachate analysis also performed well in assessing the mobility of contaminants including Al and Cr at acid mine drainage sites. As the contaminants tend to precipitate in neutral NAG test solution, the usability of the method in neutral mine drainage cases should be further investigated. Furthermore, the conclusions presented in this study are limited to waste rock samples collected from the surface of piles; future work will examine waste rock history, dump cores, drainage quality changes, etc. in more detail.


Nanomaterials ◽  
2021 ◽  
Vol 11 (5) ◽  
pp. 1068
Author(s):  
Xinyue Zhang ◽  
Yani Guo ◽  
Wenjun Li ◽  
Jinyuan Zhang ◽  
Hailiang Wu ◽  
...  

The treatment of wastewater containing heavy metals and the utilization of wool waste are very important for the sustainable development of textile mills. In this study, the wool keratin modified magnetite (Fe3O4) powders were fabricated by using wool waste via a co-precipitation technique for removal of Cu2+ ions from aqueous solutions. The morphology, chemical compositions, crystal structure, microstructure, magnetism properties, organic content, and specific surface area of as-fabricated powders were systematically characterized by various techniques including field emission scanning electron microscopy (FESEM), energy dispersive spectroscopy (EDS), X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), vibrating sample magnetometer (VSM), thermogravimetric (TG) analysis, and Brunauer–Emmett–Teller (BET) surface area analyzer. The effects of experimental parameters such as the volume of wool keratin hydrolysate, the dosage of powder, the initial Cu2+ ion concentration, and the pH value of solution on the adsorption capacity of Cu2+ ions by the powders were examined. The experimental results indicated that the Cu2+ ion adsorption performance of the wool keratin modified Fe3O4 powders exhibited much better than that of the chitosan modified ones with a maximum Cu2+ adsorption capacity of 27.4 mg/g under favorable conditions (0.05 g powders; 50 mL of 40 mg/L CuSO4; pH 5; temperature 293 K). The high adsorption capacity towards Cu2+ ions on the wool keratin modified Fe3O4 powders was primarily because of the strong surface complexation of –COOH and –NH2 functional groups of wool keratins with Cu2+ ions. The Cu2+ ion adsorption process on the wool keratin modified Fe3O4 powders followed the Temkin adsorption isotherm model and the intraparticle diffusion and pseudo-second-order adsorption kinetic models. After Cu2+ ion removal, the wool keratin modified Fe3O4 powders were easily separated using a magnet from aqueous solution and efficiently regenerated using 0.5 M ethylene diamine tetraacetic acid (EDTA)-H2SO4 eluting. The wool keratin modified Fe3O4 powders possessed good regenerative performance after five cycles. This study provided a feasible way to utilize waste wool textiles for preparing magnetic biomass-based adsorbents for the removal of heavy metal ions from aqueous solutions.


2003 ◽  
Vol 107 (46) ◽  
pp. 12562-12565 ◽  
Author(s):  
Shuji Matsuo ◽  
Ponnusamy Nachimuthu ◽  
Dennis W. Lindle ◽  
Hisanobu Wakita ◽  
Rupert C. C. Perera

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