Impact of IrRu oxygen evolution reaction catalysts on Pt nanostructured thin films under start-up/shutdown cycling
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Cullen, David A.↗
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Electrochemical study of Aluminum-Fly Ash composites obtained by powder metallurgy
In this paper, two different ASTM C 618 Class C fly ashes (FA) were used for the production of aluminum metal matrix composites (MMCs) using powder metallurgy (PM) technology. Calcareous FAs were sampled from the electrostatic precipitators of two different lignite-fired power stations: from Megalopolis, Southern Greece (MFA) and from Kardia, Northen Greece (KFA), under maximum electricity load. FAs were milled in order to reduce the mean particle diameter and Aluminum-FA composites containing 10% and 20% of FA were then prepared and compacted. The green products were sintered for 2 h at 600 Degree-Sign C. Sintered Al-FA MMCs showed increased hardness and wear resistance suggesting their possible use in industrial applications for example in covers, casings, brake rotors or engine blocks. As most possible industrial applications of MMCs not only require wear resistance, but also corrosion resistance in different mild aggressive medias, this paper aims to study the electrochemical behavior of FA MMCs in order to evaluate their corrosion resistance. The morphology and chemical composition of the phases in the Aluminum-FA composite samples were investigated using Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectroscopy (EDXS). Moreover, topographic and Volta potential maps were acquired by Scanning Kelvin Probe Force Microscopy (SKP-FM). Volta potential maps provide information about the electrochemical behavior of the different phases in absence of electrolyte. The electrochemical behavior was investigated by Open Circuit Potential measurements and potentiodynamic polarization, while the corrosion mechanisms were studied by SEM observations after different times of immersion in a mild corrosive medium. In all cases it could be stated that the addition of the FA particles into the Al matrix might cause an increase of the hardness and mechanical properties of the pure aluminum but deteriorates the corrosion resistance. The degradation phenomena occurring on the FA containing samples might be related to the following mechanisms: 1) Partial detachment or dissolution of the FA soluble phases, in particular based on Si, Fe and Ca; 2) dissolution of the Al matrix surrounding the FA particles due to crevice corrosion; 3) Al localized dissolution due to galvanic coupling between the Fe-rich intermetallics and the matrix. - Highlights: Black-Right-Pointing-Pointer Aluminum metal matrix composites containing two types of fly ashes have been characterized. Black-Right-Pointing-Pointer The microstructure and the electrochemical behavior have been studied using different techniques. Black-Right-Pointing-Pointer The addition of FA deteriorates the corrosion resistance of the aluminum. Black-Right-Pointing-Pointer Degradation mechanisms: galvanic coupling, crevice corrosion, detachment of FA particles.
36 MATERIALS SCIENCE↗
Internal friction sensitivity to precipitation in Al-12 wt% Mg alloy
Highlights: • Internal friction is sensible to semi coherent and non-coherent phases (β′ and β). • Internal friction is not enough sensible to coherent GP zones formation in Al-12 wt% Mg. • Appearance of two IF peaks is due to β′ and β phases formation and dissolution. - Abstract: In order to improve the understanding of the sensibility of the internal friction phenomena to different stages of precipitation in Al-Mg alloys, the ageing effect of a supersaturated solid solution on the Temperature Dependent Internal Friction (TDIF) spectra has been studied. The research showed that the dissolution of the β phase and the transfer of Mg atoms to a solid solution and the formation of β′ metastable phase have an effect on internal friction. Thus, it was proved that the precipitation or the dissolution of β phase plays an important role in the anelasticity of Al-Mg alloys. A detailed TDIF analysis revealed the sensibility of the internal friction technique to the formation of semi-coherent and non-coherent phases (β′ and β) but it is not sensitive enough to the formation of coherent phases (GP zones). Several observations on the nature and the shape of the precipitates are also discussed.
36 MATERIALS SCIENCE↗
Synthesis and electrochemical properties of NiO nanospindles
Graphical abstract: NiO nanospindles with a different electrochemical activity as compared to those previous reports were synthesized via an agglomeration–dissolution–recrystallization growth process without the addition of any surfactant. - Highlights: • NiO nanospindles were synthesized without the addition of any surfactant. • The agglomeration–dissolution–recrystallization growth process was used to explain the precursors’ formation process of the spindle-like NiO. • As-obtained spindle-like NiO showed a different electrochemical activity as compared to those previous reports. - Abstract: NiO nanospindles were successfully synthesized via a hydrothermal and post-treatment method. The as-synthesized nanospindles were about several hundred nanometers in width and about one micrometer in length. X-ray diffraction (XRD) analysis revealed that the spindle-like structure was cubic NiO phase crystalline. Scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM) analysis indicated that these NiO nanospindles were of single crystal nature. On the basis of time-dependent experiments, a possible agglomeration–dissolution–recrystallization growth process was proposed to explain the formation process of the spindle-like precursors. The cyclic voltammetry (CV) measurement showed that the as-prepared spindle-like NiO exhibited a pseudo-capacitance behavior.
36 MATERIALS SCIENCE↗
An international initiative on long-term behavior of high-level nuclear waste glass
Nations using borosilicate glass as an immobilization material for radioactive waste have reinforced the importance of scientific collaboration to obtain a consensus on the mechanisms controlling the long-term dissolution rate of glass. This goal is deemed to be crucial for the development of reliable performance assessment models for geological disposal. The collaborating laboratories all conduct fundamental and/or applied research using modern materials science techniques. This paper briefly reviews the radioactive waste vitrification programs of the six participant nations and summarizes the current state of glass corrosion science, emphasizing the common scientific needs and justifications for on-going initiatives.
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
Striking stability of a mixed-valence thallium(III)-thallium(I) complex in some solvents
At the dissolution of solid anhydrous thallium(III) trifluoromethanesulfonate, Tl(CF 3 SO 3 ) 3 , or thallium(III) trifluoroacetate, Tl(CF 3 COO) 3 , in dimethylsulfoxide (dmso) or N,N,N’,N’-tetramethylurea (tmu), intensely red-colored complexes are formed. This red thallium complex is stable for years in dmso, while it is reduced fairly rapidly to thallium(I) in tmu with a half-life time of an hour. At the dissolution of Tl(CF 3 SO 3 ) 3 in N,N-dimethylpropyleneurea (dmpu) an immediate reduction to thallium(I) takes place. A stable colorless aqueous thallium(III) solution is obtained at the dissolution in acidic water. Stable dmso solutions and solid dmso solvates of thallium(III) perchlorate, nitrate and trifluormethanesulfonate can be prepared by adding dmso to concentrated acidic aqueous thallium(III) solutions. These experimental observations conclude that the pure solids Tl(CF 3 SO 3 ) 3 and Tl(CF 3 COO) 3 play an essential role in the formation of the red-colored thallium complexes. 205 Tl NMR data show that the red thallium complex contains equal amounts of thallium(III) and thallium(I). The structure of the red thallium complex in dmso, as determined by EXAFS, has Tl–O bond distances of 2.216(3) and 2.80(2) Å, which are in very close agreement with the bond distances obtained in the pure dmso solvates of the thallium(III) and thallium(I) ions, respectively, and a Tl···Tl distance of 3.49(1) Å bridged by oxygen atoms. From the EXAFS data it is impossible to distinguish if dmso molecules and/or trifluoromethanesulfonate ions act as bridges. DFT calculations could eliminate some structures due to the irrelevant structural parameters or the energetics of the proposed reactions.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Mechanical behavior of post-processed Inconel 718 manufactured through the electron beam melting process
Here, the electron beam melting (EBM) process was used to fabricate Inconel 718. The microstructure and tensile properties were characterized in both the as-fabricated and post-processed state transverse (T-orientation) and longitudinal (L-orientation) to the build direction. Post-processing involved both a hot isostatic pressing (HIP) and solution treatment and aging (STA) to homogenize the microstructure. In the as-fabricated state, EBM Inconel 718 exhibits a spatially dependent microstructure that is a function of build height. Spanning the last few layers is a cored dendritic structure comprised of the products (carbides and Laves phase) predicted under equilibrium solidification conditions. With increasing distance from the build's top surface, the cored dendritic structure becomes increasingly homogeneous with complete dissolution of the secondary dendrite arms. Further, temporal phase kinetics are observed to lead to the dissolution of the strengthening γ"γ" and precipitation of networks of fine δ needles that span the grains. Microstructurally, post-processing resulted in dissolution of the δ networks and homogeneous precipitation of γ'"γ'" throughout the height of the build. In the as-fabricated state, the monotonic tensile behavior exhibits a height sensitivity within the T-orientation at both 20 and 650 °C. Along the L-orientation, the tensile behavior exhibits strength values comparable to the reference wrought material in the fully heat-treated state. After post-processing, the yield strength, ultimate strength, and elongation at failure for the EBM Inconel 718 were observed to have beneficially increased compared to the as-fabricated material. Further, as a result of post-processing the spatial variance of the ultimate yield strength and elongation at failure within the transverse direction decreased by 4 and 3× respectively.
36 MATERIALS SCIENCE↗
Sensitivity analysis for characterizing the impact of HNGD model on the prediction of hydrogen redistribution in Zircaloy cladding using BISON code
Hydrogen in zirconium cladding is able to precipitate into zirconium hydrides which impacts cladding integrity. The Hydride Nucleation-Growth-Dissolution (HNGD) model in the BISON code accounts for the precipitation and dissolution kinetics of hydride in Zircaloy material. This paper presents global sensitivity analyses of the HNGD model aiming to enhance our understanding of the hydride precipitation phenomena by quantifying the variance that key parameters have on the prediction of hydrogen behavior under various environmental conditions. Here, model predictions are compared to experimental data obtained under two different conditions: 1) with uniformly precharged specimens subjected to a linear thermal gradient, and 2) specimens precharged with a cathodically applied hydride rim at one end of the sample and subjected to an asymmetric thermal gradient. The Sobol sensitivity analysis identifies the key parameters in the HNGD model for both types of specimens. For linear temperature cases, the heat of transport dominates the accuracy of predictions when no precipitation occurs at the cold end, while Terminal Solid Solubility for Dissolution (TSSD) is the most important parameter when precipitation occurs. A large variation in the predicted hydrogen concentration profiles is found in the range of high TSSD due to the occurrence of precipitation. For asymmetric temperature cases, the solubility coefficient gives the largest impact on the predicted hydrogen distribution, as it determines the amount of solute hydrogen dissolved from the initially applied hydride rim. A large discrepancy in hydrogen distribution between simulations and experiments exists with the asymmetric specimens because BISON simulations fail to predict the precipitation of hydride at the cooler end. Comparative studies using former and updated models verifies the significant impact of the hydride growth mechanism on predicted hydrogen concentration profiles. In particular, when hydride initially exists, changes in TSSD generate a large variation in the predicted amount of precipitation by hydride growth, giving large uncertainty in predicting the hydrogen distribution over the sample length. The outputs characterize the significant impact of the hydride growth mechanism in the HNGD model on predicting hydrogen behavior, and improve the understanding of the precipitation of hydride in Zircaloy cladding within a range of expected environmental conditions. The analyses indicate work is still needed to improve the hydride solvus models in the BISON code to accurately predict experimentally observed hydride concentrations and distributions.
36 MATERIALS SCIENCE↗
Impact of Brine/CO 2 exposure on the transport and mechanical properties of the Mt Simon sandstone
When sandstone rocks are exposed to CO 2 -saturated brine, their transport and mechanical properties can change due to brine/CO 2 -induced chemical reactions. The present study investigates the change in the flow-through characteristics, porosity, and the mechanical behavior of Mt. Simon Sandstone samples caused by exposure to brine/CO 2 . The cores, extracted from a depth interval of 2110.4–2111.4 m (6924–6927 ft) in the Mt. Simon formation, were first characterized for their mechanical and transport properties, and then aged in CO 2 -saturated brine at pressures of 17.24 MPa (2500 psi) and temperature of 50°C for one to two weeks. Following that, the changes in the transport and mechanical properties of the samples were analyzed using He pycnometry, flow perporometry and triaxial testing. Our experiments show that the porosity of the Mt. Simon samples slightly increases after exposure to CO 2 /brine, while the permeability increases more substantially depending on the stress state. Measurements of the flow-through pore size distribution (PSD) are indicative of the changes occurring and are consistent with the observed increases in permeability. Nitrogen adsorption tests (BET), before and after incubation, show a significant loss of pore volume in the mesoporous range that is indicative of clay dissolution. Weakening of the materials was observed based on the mechanical properties studied, a result that is consistent with the observed dissolution of clays that play a central role in the cementation of the quartz grains. Finally, the analysis of the brine compositions reveals an increase in concentration of most cations after incubation with the Mt. Simon cores. This is also consistent with mineral/clay dissolution, confirmed by the porosity, transport, and mechanical property measurements as well as electron microscopy analysis of the same samples.
58 GEOSCIENCES↗
Eco-friendly copper recovery process from waste printed circuit boards using Fe{sup 3+}/Fe{sup 2+} redox system
Highlights: • We developed an ecofriendly mediated electrochemical process for copper recovery. • The recovery of copper was achieved without mechanical pretreatment of the samples. • We identified the optimal flow rate for the leaching and electrowinning of copper. • The copper content of the obtained cathodic deposits was over 99.9%. - Abstract: The present study aimed at developing an original and environmentally friendly process for the recovery of copper from waste printed circuit boards (WPCBs) by chemical dissolution with Fe{sup 3+} combined with the simultaneous electrowinning of copper and oxidant regeneration. The recovery of copper was achieved in an original set-up consisting of a three chamber electrochemical reactor (ER) connected in series with a chemical reactor (CR) equipped with a perforated rotating drum. Several experiments were performed in order to identify the optimal flow rate for the dissolution of copper in the CR and to ensure the lowest energy consumption for copper electrodeposition in the ER. The optimal hydrodynamic conditions were provided at 400 mL/min, leading to the 75% dissolution of metals and to a low specific energy consumption of 1.59 kW h/kg Cu for the electrodeposition process. In most experiments, the copper content of the obtained cathodic deposits was over 99.9%.
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
Selective sulfur removal from semi-dry flue gas desulfurization coal fly ash for concrete and carbon dioxide capture applications
High-sulfur mixed fly ash residues from semi-dry flue gas desulfurization units in coal-fired power plants are unsuitable for use as supplementary cementitious material (SCM) for concrete production or carbon dioxide utilization. In this work, we explore the potential for upcycling a representative spray dry absorber ash (10.44 wt% SO 3 ) into concrete-SCM by selective sulfur removal via weak acid dissolution while simultaneously exploring the possibility for CO 2 capture. Towards this effort, parametric studies varying liquid-to-solid ratio, acidity, and CO 2 pressure were conducted in a batch reactor to establish the sulfur removal characteristics in de-ionized water, nitric acid, and carbonic acid, respectively. The dissolution studies show that the leaching of sulfur from calcium sulfite hemihydrate, which is the predominant S phase, is rapid and achieves a concentration plateau within 5 min, and subsequently, appears to be controlled by the primary mineral solubility. Here, preferential S removal was sufficient to meet SCM standards (e.g., 5.0 wt% as per ASTM C618) using all three washing solutions with 0.62–0.72 selectivity (S^), defined as the molar ratio of S to Ca in the leachate, for a raw fly ash with bulk S^ = 0.3. Acid dissolution with 1.43 meq/g of ash or under 5 atm CO 2 retained > 18 wt% CaO and other Si-, Al-rich phases in the fly ash. Based on the experimental findings, two sulfur removal schemes were suggested for either integration with CO 2 capture and utilization processes using flue gas or to produce fly ash for use as a SCM.
01 COAL, LIGNITE, AND PEAT↗
Experimental Investigation of Barium Sources and Fluid–Rock Interaction in Unconventional Marcellus Shale Wells Using Ba Isotopes
Produced waters from unconventional Marcellus Shale gas wells have anomalously high barium (Ba) concentrations and yield some of the isotopically heaviest Ba measured to date. Experiments were conducted to constrain the source of Ba in these fluids and the controls on barite (BaSO 4 ) precipitation and dissolution in oil and gas wells. Experiments simulating the acidizing stage evaluated the solubility of pure barite and drilling mud in 2 M HCl at 80 °C for periods of 2, 6, and 48 h and resulted in <0.01% barite dissolution with no appreciable change in δ 138 Ba ( 138 Ba/ 134 Ba normalized to NIST standard 3104a). Static autoclave experiments conducted at 66 °C and 20.7 MPa with combinations of ground Marcellus Shale solids and/or barite-bearing drilling mud with synthetic low-Ba fracturing fluid resulted in decreased Ba concentrations in the fluid, with the largest decrease in the shale-only run. Fluid δ 138 Ba values increased by about 0.5‰ as Ba concentrations decreased, consistent with closed-system Rayleigh fractionation. Flow-through experiments in Marcellus Shale core conducted for 28 days resulted in effluent Ba concentrations an order of magnitude lower than the influent, while sulfate concentrations increased over time. Effluent δ 138 Ba values increased over the first 12 days and plateaued at about 1‰ higher than the influent. Modeling suggests a combination of the release of labile shale Ba and barite precipitation. This work indicates that the processes of Ba release from fluid–shale interactions and barite precipitation in fractures and the well bore, while capable of producing high δ 138 Ba fluids, are unlikely to generate fluids with high-Ba concentrations and δ 138 Ba values like those in Marcellus-produced waters. As a result, we find that the release of sulfate from shale pyrite oxidation rapidly catalyzes barite precipitation and that dissolution of drilling mud barite or natural barite in the shale is unlikely to be the major source of Ba in Marcellus-produced waters.
54 ENVIRONMENTAL SCIENCES↗
Fe Oxidation and Species Distribution at the Rock–Fluid Interface of Marcellus Shale Reacted with Hydraulic Fracturing Fluid
Hydraulic fracturing of shale reservoirs resulted in significant opportunity for increased oil and gas production in the United States. Rock-fluid interactions can cause mineral dissolution and precipitation reactions that lead to permeability changes in the shale matrix, which ultimately may affect transport pathways and hydrocarbon production. Understanding the distribution of secondary precipitates, such as barite and Fe(III) (hydro)oxides, and cation leaching at the rock-fluid interface is an important step to further investigate how these geochemical processes can change permeability and transport pathways. In this study, thin sections of the fracture-matrix interface were made from reacted Marcellus shale cores. The thin sections were characterized using synchrotron X-ray fluorescence imaging and synchrotron X-ray absorption spectroscopy. Fe species with different oxidation states were identified in the maps, together with barite and Ca distribution. The results show that ferrihydrite, as newly formed Fe(III)-bearing precipitates, aligned well with the border of the Ca (e.g., calcite) leaching region in the reaction front. Some Fe-containing clay also dissolved, but the dissolution region for the clay was not as deep as the calcite. Further, the reaction front is about three times deeper in the direction parallel to the shale bedding than that perpendicular to the bedding. The Ca leaching region can be an index for reaction front detection for Marcellus shale. Reactive transport modeling was conducted and the predicted Ca leaching boarder align well with ferrihydrite precipitation, consistent with the experimental observation. The carbonate mineral dissolution can be crucial to promote fluid access into the shale matrix. Together with our previous study on the shale reactive surface, this follow-up study showed similar Ca leaching region and Fe(III) precipitates distribution in the reaction front regardless of barite precipitation on the surface, indicating that the barite coatings on the surface may not pose a significant impact on reactive transport at the shale-fluid interface.
04 OIL SHALES AND TAR SANDS↗
Thicknesses of Chemically Altered Zones in Shale Matrices Resulting from Interactions with Hydraulic Fracturing Fluid
Hydraulic fracturing of unconventional shale reservoirs increases the fracture network surface area to access hydrocarbons from the low permeability rock matrix. Porosity and permeability of the matrix, through which hydrocarbons migrate to fractures, are important for determining production efficiency and can be altered by chemical interactions between shale and hydraulic fracturing fluids (HFFs). Here, we present results from an experimental study that characterizes the thickness of the alteration zone in the shale matrix after shale–HFF interactions. Experiments were conducted with whole cores submerged in HFF both with and without added barium and sulfate to promote barite scale formation. After 3 weeks of reaction at 77 bar and 80°C, the cores were characterized using X-ray microtomography, synchrotron X-ray fluorescence microprobe imaging, and synchrotron X-ray absorption spectroscopy. Our results show that the thickness of the altered zone depends on shale mineralogical composition and varies for different chemical reactions. Reactions between the low-carbonate Marcellus shale and HFF, pyrite (FeS 2 ) oxidation manifests as both a thick zone of sulfur oxidation (>0.5 cm) and a thinner zone of iron oxidation (100–150 $μ$m). Carbonate dissolution extended 100–200 μm into the matrix, with the resulting observable secondary porosity localized at the shale–fluid interface where mineral grains were removed by either dissolution or mechanical erosion. In solutions oversaturated with respect to barite, barite precipitates were observed in the reaction fluid and at the shal–HFF interface. In contrast, the carbonate dissolution zone in the high-carbonate Eagle Ford was only 30–40 μm thick, within which a uniform texture of increased porosity was observed. Pyrite oxidation in the Eagle Ford was evident from an iron oxidation zone (150–200 μm thick), while sulfur oxidation was minor and hard to observe. Barite precipitation extended 1–2 mm into the matrix when the initial HFF was oversaturated with respect to barite, filling shale microcracks down to the submicrometer length scale. Our findings provide a scientific basis to predict the extent of chemical alteration in shale reservoirs during hydraulic fracturing and its impacts on hydrocarbon production.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Seasonal Fluctuations in Iron Cycling in Thawing Permafrost Peatlands
In permafrost peatlands, up to 20% of total organic carbon (OC) is bound to reactive iron (Fe) minerals in the active layer overlying intact permafrost, potentially protecting OC from microbial degradation and transformation into greenhouse gases (GHG) such as CO 2 and CH 4 . During the summer, shifts in runoff and soil moisture influence redox conditions and therefore the balance of Fe oxidation and reduction. Whether reactive iron minerals could act as a stable sink for carbon or whether they are continuously dissolved and reprecipitated during redox shifts remains unknown. We deployed bags of synthetic ferrihydrite (FH)-coated sand in the active layer along a permafrost thaw gradient in Stordalen mire (Abisko, Sweden) over the summer (June to September) to capture changes in redox conditions and quantify the formation and dissolution of reactive Fe(III) (oxyhydr)oxides. We found that the bags accumulated Fe(III) under constant oxic conditions in areas overlying intact permafrost over the full summer season. In contrast, in fully thawed areas, conditions were continuously anoxic, and by late summer, 50.4 ± 12.8% of the original Fe(III) (oxyhydr)oxides were lost via dissolution. Periodic redox shifts (from 0 to +300 mV) were observed over the summer season in the partially thawed areas. This resulted in the dissolution and loss of 47.2 ± 20.3% of initial Fe(III) (oxyhydr)oxides when conditions are wetter and more reduced, and new formation of Fe(III) minerals (33.7 ± 8.6% gain in comparison to initial Fe) in the late summer under more dry and oxic conditions, which also led to the sequestration of Fe-bound organic carbon. Our data suggest that there is seasonal turnover of iron minerals in partially thawed permafrost peatlands, but that a fraction of the Fe pool remains stable even under continuously anoxic conditions.
54 ENVIRONMENTAL SCIENCES↗
Effects of C/Mn Ratios on the Sorption and Oxidative Degradation of Small Organic Molecules on Mn-Oxides
We report manganese (Mn) oxides have a high surface area and redox potential that facilitate sorption and/or oxidation of organic carbon (OC), but their role in regulating soil C storage is relatively unexplored. Small OC compounds with distinct structures were reacted with Mn(III/IV)-oxides to investigate the effects of OC/Mn molar ratios on Mn–OC interaction mechanisms. Dissolved and solid-phase OC and Mn were measured to quantify the OC sorption to and/or the redox reaction with Mn-oxides. Mineral transformation was evaluated using X-ray diffraction and X-ray absorption spectroscopy. Higher OC/Mn ratios resulted in higher sorption and/or redox transformation; however, interaction mechanisms differed at low or high OC/Mn ratios for some OC. Citrate, pyruvate, ascorbate, and catechol induced Mn-oxide dissolution. The average oxidation state of Mn in the solid phase did not change during the reaction with citrate, suggesting ligand-promoted mineral dissolution, but decreased significantly during reactions with the other compounds, suggesting reductive dissolution mechanisms. Phthalate primarily sorbed on Mn-oxides with no detectable formation of redox products. Mn–OC interactions led primarily to C loss through OC oxidation into inorganic C, except phthalate, which was predominantly immobilized in the solid phase. Together, these results provided detailed fundamental insights into reactions happening at organo–mineral interfaces in soils.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Alteration and Erosion of Rock Matrix Bordering a Carbonate-Rich Shale Fracture
A novel reactive transport model has been developed to examine the processes that affect fracture evolution in a carbonate-rich shale. An in situ synchrotron X-ray microtomography experiment, flowing CO 2 saturated water through a single fracture mini-core of Niobrara Shale provided the experimental observations for the development and testing of the model. The phenomena observed included the development of a porous altered layer, flow channeling, and increasingly limited calcite dissolution. The experimental observations cannot be explained by models that consider only mineral dissolution and development of an altered layer. The difference between the fracture volume change recorded by the microtomography images and what would be expected from mineral dissolution alone suggest that there is erosion of the altered layer as it develops. The numerical model includes this additional mechanism, with the erosion rate based on the thickness of the altered layer, and successfully captures the evolution of the geochemical reactions and morphology of the fracture. The findings imply that the abundance (with a threshold of approximately 35%) and reactivity of the rapidly reacting mineral control the development and erodibility of the altered layer on the fracture surfaces, and therefore fracture opening.
58 GEOSCIENCES↗
The Effects of Phosphonate-Based Scale Inhibitor on Brine–Biotite Interactions under Subsurface Conditions
According to the article, To explore the effects of scale inhibitors on subsurface water–mineral interactions, here batch experiments on biotite dissolution (0–96 h) were conducted in solutions containing 0–1.0 mM diethylenetriaminepenta(methylene)phosphonate (DTPMP, a model scale inhibitor), at conditions simulating subsurface environments (95 °C and 102 atm CO2). The phosphonate groups in DTPMP enhanced biotite dissolution through both aqueous and surface complexations with Fe, with more significant effects at a higher DTPMP concentration. Surface complexation made cracked biotite layers bend, and these layers detached at a later stage (≥44 h). The presence of DTPMP also promoted secondary precipitation of Fe- and Al-bearing minerals both in the solution and on the reacted biotite surfaces. With 1.0 mM DTPMP after 44 h, significant coverage of biotite surfaces by precipitates and less detachment of cracked layers blocked reactive sites and inhibited further biotite dissolution. Furthermore, adsorption of DTPMP made the reacted biotite basal surfaces more hydrophilic, which may affect the transport of reactive fluids. This study provides new information on the impacts of phosphonates in brine–mineral interactions, benefiting safer and more environmentally sustainable design and operation of engineered subsurface processes.
bio-inspired, mechanical behavior, carbon sequestr↗