Academic literature on the topic 'Interface coupled dissolution-reprecipitation reactions'

Gold–(silver) telluride minerals constitute a major part of the gold endowment at a number of important deposits across the globe. A brief overview of the chemistry and structure of the main gold and silver telluride minerals is presented, focusing on the relationships between calaverite, krennerite, and sylvanite, which have overlapping compositions. These three minerals are replaced by gold–silver alloys when subjected to the actions of hydrothermal fluids under mild hydrothermal conditions (≤220 °C). An overview of the product textures, reaction mechanisms, and kinetics of the oxidative leaching of tellurium from gold–(silver) tellurides is presented. For calaverite and krennerite, the replacement reactions are relatively simple interface-coupled dissolution-reprecipitation reactions. In these reactions, the telluride minerals dissolve at the reaction interface and gold immediately precipitates and grows as gold filaments; the tellurium is oxidized to Te(IV) and is lost to the bulk solution. The replacement of sylvanite is more complex and involves two competing pathways leading to either a gold spongy alloy or a mixture of calaverite, hessite, and petzite. This work highlights the substantial progress that has been made in recent years towards understanding the mineralization processes of natural gold–(silver) telluride minerals and mustard gold under hydrothermal conditions. The results of these studies have potential implications for the industrial treatment of gold-bearing telluride minerals.

AbstractTo determine the mechanism of acid-leaching of ilmenite to ultimately forming rutile, we have carried out an experimental study of ilmenite alteration in autoclaves at 150ºC in HCl solutions. The resulting products were studied by X-ray diffraction, scanning electron microscopy, electron microprobe and Raman spectroscopy. In some experiments the solution was initially enriched in 18O and the distribution of the isotope in the alteration products mapped from the frequency shift of cation oxygen stretching bands in the Raman spectra. The alteration begins at the original ilmenite crystal surface and has also taken place along an intricate branching network of fractures in the ilmenite, generated by the reaction. Element-distribution maps and chemical analyses of the reaction product within the fractures show marked depletion in Fe and Mn and a relative enrichment of Ti. Chemical analyses however, do not correspond to any stoichiometric composition, and may represent mixtures of TiO2 and Fe2O3. The fracturing is possibly driven by volume changes associated with dissolution of ilmenite and simultaneous reprecipitation of the product phases (including rutile) from an interfacial solution along an inward moving dissolution-reprecipitation front. Raman spectroscopy shows that the 18O is incorporated in the rutile structure during the recrystallization. Throughout the alteration process, the original morphology of the ilmenite is preserved although the product is highly porous. The rutile inherits crystallographic information from the parent ilmenite, resulting in a triply-twinned rutile microstructure. The results indicate that the ilmenite is replaced directly by rutile without the formation of any intermediate reaction products. The reaction is described in terms of an interface-coupled dissolution-precipitation mechanism.

The increasing release of potentially toxic metals from industrial processes can lead to highly elevated concentrations of these metals in soil, and ground- and surface-waters. Today, metal pollution is one of the most serious environmental problems and thus, the development of effective remediation strategies is of paramount importance. In this context, it is critical to understand how dissolved metals interact with mineral surfaces in soil–water environments. Here, we assessed the processes that govern the interactions between six common metals (Zn, Cd, Co, Ni, Cu, and Pb) with natural brucite (Mg(OH)2) surfaces. Using atomic force microscopy and a flow-through cell, we followed the coupled process of brucite dissolution and subsequent nucleation and growth of various metal bearing precipitates at a nanometer scale. Scanning electron microscopy and Raman spectroscopy allowed for the identification of the precipitates as metal hydroxide phases. Our observations and thermodynamic calculations indicate that this coupled dissolution–precipitation process is governed by a fluid boundary layer at the brucite–water interface. Importantly, this layer differs in composition and pH from the bulk solution. These results contribute to an improved mechanistic understanding of sorption reactions at mineral surfaces that control the mobility and fate of toxic metals in the environment.

ABSTRACTNanoscale characterization (TEM on FIB-SEM-prepared foils) was undertaken on feldspars undergoing transformation from early post-magmatic (deuteric) to hydrothermal stages in granites hosting the Olympic Dam Cu-U-Au-Ag deposit, and from the Cu-Au skarn at Hillside within the same iron-oxide copper-gold (IOCG) province, South Australia. These include complex perthitic textures, anomalously Ba-, Fe-, or REE-rich compositions, and REE-flourocarbonate + molybdenite assemblages which pseudomorph pre-existing feldspars. Epitaxial orientations between cryptoperthite (magmatic), patch perthite (dueteric) and replacive albite (hydrothermal) within vein perthite support interface-mediated reactions between pre-existing alkali-feldspars and pervading fluid, irrespective of micro-scale crystal morphology. Such observations are consistent with a coupled dissolution-reprecipitation reaction mechanism, which assists in grain-scale element remobilization via the generation of transient interconnected microporosity. Micro-scale aggregates of hydrothermal hyalophane (Ba-rich K-feldspar), crystallizing within previously albitized areas of andesine, reveal a complex assemblage of calc-silicate, As-bearing fluorapatite and Fe oxides along reaction boundaries in the enclosing albite-sericite assemblage typical of deuteric alteration. Such inclusions are good REE repositories and their presence supports REE remobilization at the grain-scale during early hydrothermal alteration. Iron-metasomatism is recognized by nanoscale maghemite inclusions within ‘red-stained’ orthoclase, as well as by hematite in REE-fluorocarbonates, which reflect broader-scale zonation patterns typical for IOCG systems. Potassium-feldspar from the contact between alkali-granite and skarn at Hillside is characterized by 100–1000 ppm REE, attributable to pervasive nanoscale inclusions of calc-silicates, concentrated along microfractures, or pore-attached. Feldspar replacement by REE-fluorcarbonates at Olympic Dam and nanoscale calc-silicate inclusions in feldspar at Hillside are both strong evidence for the role of feldspars in concentrating REE during intense metasomatism. Differences in mineralogical expression are due to the availability of associated elements. Lattice-scale intergrowths of assemblages indicative of Fe-metasomatism, REE-enrichment and sulfide deposition at Olympic Dam are evidence for a spatial and temporal relationship between these processes.

AbstractDuring chemical weathering and natural hydrothermal reactions, apatite can form by replacing calcium carbonates. In hydrothermal experiments in which aragonite and calcite single crystals have been reacted with phosphate solutions, the carbonates are replaced by polycrystalline hydroxylapatite (HAP). In both cases the crystals have retained their overall morphology while their compositions have changed significantly. The HAP appears to have a crystallographic relationship to the parent carbonate crystals. The textural relationships are consistent with an interface-coupled dissolution-precipitation mechanism. Structural relationships and relative molar volumes and solubilities appear to be factors that greatly affect replacement reactions.

ABSTRACTThe interface with reactive transport models used in performance assessment calculations is described to identify aspects of the glass waste form degradation model important to long-term predictions. These are primarily the conditions that trigger the change from the residual rate to the Stage 3 rate and the values of those rates. Although the processes triggering the change and controlling the Stage 3 rate are not yet understood mechanistically, neither appears related to an intrinsic property of the glass. The sudden and usually significant increase in the glass dissolution rate suggests the processes that trigger the increase are different than the processes controlling glass dissolution prior to that change. Application of a simple expression that was derived for mineral transformation to represent the kinetics of coupled glass dissolution and secondary phase precipitation reactions is shown to be consistent with experimental observations of Stage 3 and useful for modeling long-term glass dissolution in a complex disposal environment.

Aluminum alloys are pickled and/or etched as a preliminary step prior to anodization or conversion coating. The chemistry of the etching/pickling process must be carefully engineered to avoid the enrichment of the alloying elements such metallic Cu which can interfere with subsequent treatments. Understanding and optimizing the etching process is therefore a major concern for the use of aluminum alloys, and especially, the Cu-rich high strength aluminum alloys. The etching reaction is a mixed potential process similar to other forms of aqueous corrosion. However, the dynamic nature of the interface makes it difficult to apply conventional electrochemistry to determine the rates and mechanisms of the different reactions and therefore, to predict how the etching process will vary with electrolyte composition. Among the many complicating factors, we can cite the very high dissolution rate of the alloy coupled with the formation of gas and the release of intermetallic particles. The dissolution of alloying elements such as Cu and Mg – the reactions of interest – occur at rates several orders of magnitude below that of Al dissolution. For example, Cu dissolution makes a negligible contribution to either electron exchange or mass loss. Finally, the rapid reaction rates and the short time scale of the process preclude the appearance of a true steady state, necessary for the interpretation of many electrochemical techniques. Therefore, to gain insight into the mechanism of the acid etching process, we have used an element-resolved electrochemical technique, atomic emission spectroelectrochemistry (AESEC) (Gharbi et al., 2016; Gharbi et al., 2017; Sultan et al., 2022). This permits the direct measurement of the elemental dissolution rates as a function of time, on an element-by-element basis. In this work, we illustrate the element-resolved electrochemical approach to surface treatment focusing on the acid etching of three alloys: a commercial high-strength AA7449 alloy (containing Zn, Cu, and Mg), and binary Al-Cu and Al-Mg alloys to represent the extremes of alloying element nobility. In sulfuric acid, the binary alloys also represent the extremes of selective versus congruent dissolution. The Al-Mg binary alloy undergoes a simultaneous, congruent dissolution mechanism with Mg dissolving simultaneously with Al. By contrast, the Al-Cu binary alloy exhibits a selective dissolution mechanism with Al dissolving to leave behind dealloyed metallic Cu on the surface of the material. This is ultimately followed by the release of Cu-rich particles due to anodic undermining. The electrolytes investigate in this work represent a range of oxidizing strengths from pure sulfuric acid to pure nitric acid and various mixtures of the two. The effect of Fe(III), an important component of many state-of-the-art etching solutions, was also investigated. Experimental elemental Evans diagrams were determined to clarify the electrochemical nature of the dissolution reactions, specifically how the elemental dissolution rates were related to one another and how they were coupled to the cathodic reactions. An example is shown in the Figure (right), based on the 2022 publication of Sultan et al. On the left, we show a cartoon representation of the dissolution process as determined for a high strength AA7449 alloy. On the right, we show the experimental element-resolved Evans diagram for the same alloy in sulfuric acid. It was found that Cu would not dissolve at the open circuit potential in sulfuric acid, but displayed active dissolution with a well-defined Tafel slope of 44 mV/decade at higher potential. The dissolution rate of Cu in the etching solutions was controlled by the redox potential of the electrolyte as determined by the addition of nitric acid and/or Fe(III). Based on our results, the Fe(III) additive in the presence of nitrate appears to serve a catalytic role, enhancing the rate of electron transfer between Cu and nitrate. The dissolution of Al and Mg were independent of potential suggesting simultaneous dissolution across an oxide film. The rates and mechanisms of Cu particle release will also be discussed. BBM Sultan, D Thierry, JM Torrescano-Alvarez, K Ogle, “Selective dissolution during acid pickling of aluminum alloys by element-resolved electrochemistry”, Electrochim. Acta, 404(2022)139737. O Gharbi, N Birbilis, K Ogle, “In-situ monitoring of alloy dissolution and residual film formation during the pretreatment of Al-alloy AA2024-T3”, J. Electrochem. Soc. 163 (2016)C240. O Gharbi, N Birbilis, K Ogle, “Li reactivity during the surface pretreatment of Al-Li alloy AA2050-T3”, Electrochim. Acta 243(2017)207-219. Figure 1

The hypothesis that interface coupled dissolution-reprecipitation reactions (ICDR) can play a key role in scavenging minor elements has been investigated via exploring the fate of U during the experimental sulfidation of hematite to chalcopyrite and the exsolution of chalcopyrite from bornite digenite solid solution (bdss) under hydrothermal conditions. The results of experiments with two kinds of Uranium (U) sources; either as solid UO₂₊ₓ(s) or as a soluble uranyl complex, differed from the U-free experiments. In the reactions from hematite to chalcopyrite under 220-300°C hydrothermal conditions, pyrite precipitated initially, before the onset of chalcopyrite precipitation. In addition, when UO₂₊ₓ(s) was included in the experiments, enhanced hematite dissolution led to increased porosity and precipitation of pyrite+magnetite within the hematite core. However, in uranyl nitrate bearing experiments, abundant pyrite formed initially, before being replaced by chalcopyrite. Uranium scavenging was mainly associated with the pyrite precipitation, as a result that a thin U-rich layer along the original hematite grain surface precipitated out. In the reactions of chalcopyrite exsolution from bdss during annealing under hydrothermal conditions in a solutions nominally containing Cu(I) and hydrosulfide in a pH₂₅°C [°C subscript] ~6 acetate buffer, a similar U-rich rim was observed along the original grain when uranyl nitrate as U-source was included in the reactions. The precipitation of uranium was related to the presences of HS- in buffer. Chemical mapping and X-ray absorption near edge structure (XANES) spectroscopy showed the UO₂₊ₓ(s) was the mainly restricted to the U-rich layer. The two sets of experiments demonstrate that the presence of minor components can affect the pathway of ICDR reactions. Reactions between U- and Cu-bearing fluids and hematite or chalcopyrite can explain the Cu-U association prominent in some iron oxide-copper-gold (IOCG) deposits. In this study, synchrotron-based X-ray fluorescence (SXRF) mapping was used to trace the distribution of uranium in natural samples from different geological contexts (sandstone-hosted U-deposit; IOCG) for investigating the deportment of uranium and its paragenesis in the context of thin-section scale textural complexity. It has been confirmed that the enrichment of U occurs via late dissolution-reprecipitation reactions in the bornite ores of the Moonta and Wallaroo IOCG deposits (South Australia), and that the U distribution in the ores of sandstone-hosted U-deposit is complex. Image analysis also revealed a number of new results for other minor elements, e.g. (i) the distribution of μm-sized Pt-rich grains and evidence for Ti-mobility during the formation of schistosity at the Fifield Pt prospect (New South Wales, Australia); (ii) the presence of Ge contained in organic matter and of Hg minerals associated within quartzite clasts in the Lake Frome U ores (South Australia); and (iii) confirmation of the two-stage Ge-enrichment in the Barrigão deposit, with demonstration of the presence of Ge in solid solution in the early chalcopyrite (Portuguese Iberian Pyrite Belt).
Thesis (Ph.D.) (Research by Publication) -- University of Adelaide,School of Chemical Engineering, 2016.

Abstract The wettability alteration is the most prominent mechanism for a favorable effect of low salinity water flooding in enhanced oil recovery. It has been accepted that the surface charge at crude oil/brine and rock/brine interfaces significantly influences the interaction of the crude oil with rock surface and thus wettability changes. In this study, the interface characteristics were coupled with a solute transport model to simulate low salinity waterflooding in carbonate and sandstone reservoirs. The ionic transport and two- phase flow of oil and water equations were solved and coupled with IPhreeqc for geochemical calculations. The dissolution and precipitation of minerals were considered thorough thermodynamic equilibrium reactions in IPhreeqc. In addition, a triple layer surface complexation model was employed in IPhreeqc to predict electrokinetic properties of crude oil/brine and rock/brine interfaces. The wettability alteration was calculated based the adsorbed polar components of crude oil on minerals’ surface, which changes the relative permeability. The coupled model able to predict the spatiotemporal variation of ionic profiles, surface and zeta potentials, dissolution and precipitation of minerals, total disjoining pressure, and wettability index in addition to oil recovery for the injection of brines. The validity of the coupled model results was tested against PHREEQC in a single-phase flow without the presence of oil. Moreover, the modelling results were compared with the published experimental data for a single-phase flow in carbonate cores. A very good agreement between experimental data and modelling results was obtained. Furthermore, the coupled model was applied to predict ionic concentration, pH profile, and oil recovery in both carbonate and sandstone cores and verified with experimental data. The modelling results reproduce well the experimental data, suggesting that model captures the geochemical and interface reactions. Finally, the coupled model can be used to optimize brine composition for improved oil recovery in carbonate and sandstone reservoirs.

Abstract Low Salinity Polymer (LSP) flooding is one of the emerging synergic techniques in enhance oil recovery (EOR). Previous experimental studies showed an exceptional improvement in displacement efficiency, polymer rheology, injectivity, and polymer viscoelasticity. Nevertheless, when it comes to modeling LSP flooding, it is still challenging to develop a mechanistic predictive model that captures polymer-rock-brine interactions. Therefore, this study employs a coupled geochemical-reservoir numerical model to investigate the effect of water chemistry on polymer-brine-rock geochemical interactions during LSP flooding through varying overall salinity as well as the concentrations of monovalent and divalent ions. In this study, the MATLAB Reservoir Simulation Toolbox (MRST) was coupled with a geochemical interface module i.e., pH-Redox-Equilibrium in C programming language (PHREEQC), termed as IPHREEQC. The coupled MRST-IPHREEQC simulator enables simulating the effects on different parameters on polymer viscosity including the Todd-Longstaff mixing model, inaccessible pore volume, permeability reduction, polymer adsorption, salinity, and shear rate. For describing the related geochemistry, the presence of polymer in the aqueous phase was considered by introducing novel solution specie to the Phreeqc database. Using this coupled simulator, several geochemical reactions and parameters can be assessed including rock and injected water compositions, injection schemes, and other polymer characteristics where the focus of this work is on water chemistry. Moreover, different injection schemes were analyzed including low-salinity water, low-salinity polymer injection (1×LSP), and 5-times spiked low-salinity polymer injection (5×LSP) with their related effects on polymer viscosity. The results showed that polymer viscosity during low-salinity polymer flooding is directly affected by calcium (Ca2+) and magnesium (Mg2+) ions and indirectly affected by sulfate ion (SO42−) as a result of polymer-rock-brine interactions on a dolomite rock-forming mineral. Furthermore, the findings showed that monovalent ions such as sodium (Na+) and potassium (K+) have less pronounced effects on the polymer viscosity. However, the release of calcium (Ca2+) and magnesium (Mg2+) ions due to the dissolution of dolomite led to the formation of polymer (acrylic acid, C3H4O2) complexes and consequently, a pronounced decrease in polymer viscosity. In addition, the increase of sulfate ion (SO42−) concentration in the injected LSP solution affects the interactions between the polymer and positively charged aqueous species and leads to less polymer viscosity loss. Additionally, as a de-risking measure for LSP flood designs, estimating the effect of each ion can be highly useful step. The effect of cations is also related to charge ratio (CR), which renders it the key objective to determine the optimum CR ratio at which viscosity loss of LSP flood is avoided or at least minimal. The coupled simulator works as an integrated tool, which is sound, precise, and adaptable with the ability to encapsulate the reactions required for LSP mechanistic modeling. This paper is among the very few, which describe mechanistic geochemical modeling of the low-salinity polymer flooding technique. The coupled simulator provided new insights into understanding the mechanisms controlling LSP flooding. Based on the findings of this work, several successful low salinity-polymer field pilots can be designed.