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At least 919 records · Page 51

Aragonite saturation horizon variability along North Pacific seamounts and implications for deep-sea coral reefs

The 2014 discovery of living deep-sea coral reefs along the Northwest Hawaiian Islands (NWHI) and lower Emperor Seamount Chain (ESC), despite the North Pacific’s shallow aragonite saturation horizon (ASH) and high CaCO3 dissolution rates, underscores the need to understand the local seawater chemistry that allows these reefs to persist. We investigated seawater carbonate chemistry using discrete samples along the NWHI and ESC from two cruises ~1 year apart (08/26/21 – 09/26/21, 09/09/22 – 10/24/22). Across the two cruises, ASH depth difference ranged from 15 to 77 m. Since the Pacific ASH shoals by 1–2 m yr?¹, this long-term trend cannot explain the magnitude of ASH change observed between cruises. Temperature-salinity plots similarly indicate no major shifts in intermediate water masses that could account for these changes. Instead, ASH depth variability was primarily governed by localized biogeochemical processes, namely changes in intermediate water respiration and CaCO3 dissolution. Indicators for dissolution (TA*) and respiration (AOU) suggest changes in ASH depth were driven by changes in dissolution at the northern- and southern-most sites, whereas respiration exerted stronger control at central sites. Combining 2021 and 2022 data with data from 2014 – 2019 (excluding 2018) revealed high interannual ASH variability, by as much as >200 m at one site. Deep-sea coral reefs across the NWHI and ESC currently reside close to the ASH depth and likely experience seasonal and interannual shifts between under- and supersaturation. As ocean acidification progresses however, persistent exposure to undersaturated seawater could further threaten these critical deep-sea ecosystems.

coral reefs↗

In-situ monitoring of seeded and unseeded stage III corrosion using Raman spectroscopy

Abstract Stage III glass dissolution, the occasionally observed tendency for accelerated aqueous corrosion after extensive time spent at low reaction rates, is a major area of technical uncertainty in long-term glass performance modeling for vitreous nuclear waste forms. Stage III dissolution behavior is thought to be caused by the precipitation of zeolite phases that lower the activity of the rate-controlling orthosilicic acid ion and cause the acceleration of glass dissolution. The uncertainty lies mainly in a poor understanding of the growth kinetics of these key crystalline phases. It is particularly important to understand the impact of temperature and pH conditions on Stage III behavior. Accurate analysis of this phenomenon is complicated by the typically very long (e.g., years), and variable length of the induction period preceding the onset of Stage III behavior. In this study of a high-sodium aluminoborosilicate glass, we demonstrate the ability to initiate the onset of Stage III behavior in a controllable fashion so as to both reduce the time delay of the incubation period, and to also be able to initiate Stage III dissolution in controlled conditions. In this case, we demonstrate that Stage III glass corrosion behavior is possible at 70 °C, a lower temperature than previously observed (90 °C), even in an unseeded experiment. We confirm, through a comparison study, that seeded and unseeded Stage III corrosion rates are equivalent. This enables wide-scale testing of Stage III corrosion rates for many glass compositions in relatively short times through this technique. We also report further development of the use of in situ Raman spectroscopy monitoring of boron concentration and pH through simple and chemometric analysis methods.

36 MATERIALS SCIENCE↗

Mechanistic Understanding of Interphase-driven Aging in Silicon Anodes

Conventional solid electrolyte interphases (SEIs) strongly adhere to micro-silicon (µ-Si) and crack under volume changes, causing poor cycling performance. Nano-silicon improves cycling performance but remains costly with limited calendar life. Here potentiostatic ageing tests demonstrate that both calendar and cycle ageing are governed by SEI cracking and dissolution with different relative contributions. When the system is not dominated by SEI dissolution, the relative calendar life of Si anodes could correlates positively with their cycle life. LiF-rich SEI that enables long cycle life in µ-Si is therefore expected to enhance calendar life as well. Using this framework, we screened electrolytes, SEIs and electrodes and validated them with full-cell storage. LiF-rich SEI minimizes cracking and dissolution, enabling μ-Si to achieve excellent calendar life, whereas nano-silicon suffers from SEI dissolution and needs reduced electrolyte–electrode contact for better calendar life. This work clarifies calendar-ageing behaviour and accelerates electrolytes and SEI development for long-life Si anodes.

Johnson, Christopher S.↗

Importance of interlayer H bonding structure to the stability of layered minerals

Layered (oxy) hydroxide minerals often possess out-of-plane hydrogen atoms that form hydrogen bonding networks which stabilize the layered structure. However, less is known about how the ordering of these bonds affects the structural stability and solubility of these minerals. Here, we report a new strategy that uses the focused electron beam to probe the effect of differences in hydrogen bonding networks on mineral solubility. In this regard, the dissolution behavior of boehmite (γ-AlOOH) and gibbsite (γ-Al(OH)3) were compared and contrasted in real time via liquid cell electron microscopy. Under identical such conditions, 2D-nanosheets of boehmite (γ-AlOOH) exfoliated from the bulk and then rapidly dissolved, whereas gibbsite was stable. Further, substitution of only 1% Fe(III) for Al(III) in the structure of boehmite inhibited delamination and dissolution. Factors such as pH, radiolytic species, and knock on damage were systematically studied and eliminated as proximal causes for boehmite dissolution. Instead, the creation of electron/hole pairs was considered to be the mechanism that drove dissolution. The widely disparate behaviors of boehmite, gibbsite, and Fe-doped boehmite are discussed in the context of differences in the OH bond strengths, hydrogen bonding networks, and the presence or absence of electron/hole recombination centers.

58 GEOSCIENCES↗

Observing the colloidal stability of iron oxide nanoparticles in situ

Colloidal processes such as nucleation, growth, ripening, and dissolution are fundamental to the synthesis and application of engineered nanoparticles, as well as numerous natural systems. In nanocolloids consisting of a dispersion of nanoparticles in solution, colloidal stability is in?uenced by factors including the particle surface facet and capping layer, and local temperature, chemistry, and acidity. In this paper, we investigate colloidal stability through the real-time manipulation of nanoparticles using in situ liquid cell Scanning Transmission Electron Microscopy (STEM). In a distribution of uniform iron oxide nanoparticles, we use the electron beam to precisely control the local chemistry of the solution and observe the critical role that surface chemistry plays in nanoparticle stability. By functionalizing the nanoparticle surfaces with charged amino acids and peptides, stability can be tuned to promote dissolution, growth, or agglomeration, either permanently or reversibly. STEM imaging is used to quantify kinetics of individual nanoparticles subject to local variations in chemistry. These measurements of dissolution and growth rates of iron oxide nanoparticles provide insights into nanoparticle stability relevant to synthesis and functionalization for biomedical applications.

Hufschmid, Ryan D.↗

Concentration Dependent Interfacial Chemistry of the NaOH(aq):Gibbsite Interface

Caustic conditions are often employed for dissolution of a wide variety of minerals, where ion sorption, surface diffusion, and interfacial organization impact surface reactivity. In the case of gibbsite, gamma-Al(OH)3, the chemistry at the NaOH(aq) interface is deeply intertwined with industrial processing of aluminum, including metal production and the disposition of Al-containing wastes. To date, little is known about the structure, speciation, and dynamic behavior of gibbsite interfaces (and that of many other minerals) with NaOH(aq)—particularly as a function of ionic strength. Yet concentration-dependent interfacial organization and dynamics are a critical starting point to develop a fundamental understanding of the factors that influence dissolution. This work reports equilibrium molecular dynamics simulations of the gamma-Al(OH)3:NaOH(aq) interface, revealing the sorption behavior and speciation of ions from 0.5–10 M [NaOH]. As inner-sphere complexes, Na+ primarily coordinates to the side of the gibbsite hexagonal cavities, while OH accepts hydrogen-bonding from the surface-OH groups. The mobility of inner-sphere Na+ and OH ions is significantly reduced due to a strong surface affinity in comparison to previous reports of NaCl, CaCl2, or BaCl2 electrolytes. At high [NaOH], contact ion pairing that is observed in the bulk solution is partially disrupted upon sorption to the gibbsite surface by the individual ion–surface interactions. The molecular-scale changes to surface speciation and competition between ion–surface vs. ion–ion interactions influence surface characterization of gibbsite and potential dissolution processes, providing a valuable baseline for starting conditions needed within future reactive molecular simulations.

alkaline solutions, IDREAM, gibbsite, molecular dy↗

Emerging investigator series: kinetics of diopside reactivity for carbon mineralization in mafic–ultramafic rocks

The ongoing use of fossil fuels to supply modern energy demands has necessitated research on combating carbon dioxide (CO 2 ) emissions and climate change. Carbon storage via mineral trapping in basalt and related rocks is a promising strategy. However, mineralization rates depend on the variable minerology that makes up these rock formations. Diopside (CaMgSi 2 O 6 ) is a common pyroxene mineral in ultramafic and mafic rocks including basalt, but relatively little work has been done to understand its carbon mineralization kinetics using hydrated supercritical CO 2 , which induces the formation of reactive nanoscale interfacial water films. Here, in situ XRD experiments at 50–110 °C and 90 bar indicate that diopside transforms into a myriad of Mg/Ca carbonates, including huntite [Mg 3 Ca(CO 3 ) 4 ] and very high magnesium calcite (VHMC, i.e., protodolomite). Through ex situ characterization, we were able to constrain reaction pathways for the dissolution–precipitation transformation process including metastable intermediate precipitates. Experiments performed at variable temperatures enabled Avrami-derived rate constants and an apparent activation energy of 97 ± 16 kJ mol –1 , implying the dissolution of diopside is the rate-limiting step. Density functional theory (DFT) calculations, used to gain molecular insight into the surface stability of the diopside during dissolution, suggest that exposed calcium cations are susceptible to dissolution when put in contact with water given their coordination environment. The collective results point to the high CO 2 mineralization potential of diopside in basalts, which could help guide parameterization of reactive transport models needed to design and permit commercial-scale subsurface carbon storage operations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Semi-Dynamic Leach Testing of Densified Silicon-based Iodine Waste Forms

Iodine waste forms (IWF) require a conceptual corrosion release model (CCRM) to provide iodine (I) release rates for performance modeling nuclear waste disposal repositories. To develop a CCRM, an understanding of the corrosion mechanisms of the IWF are required along with data from consistent test methods to parameterize the model. The present study has advanced both areas by providing and assessing the corrosion resistance of IWF types based on their processing history in minor variations of semi-dynamic leach tests. The test included a series of semi-dynamic leach tests using monolithic IWFs in deionized water (leachant). Several experiments were conducted under alternate test conditions with changes to temperature, leachant replacement, leachant pH, leachant volume, masking, and surface finish to elucidate if varying these conditions impacted IWF corrosion behavior. Tests were conducted on two classes of IWFs: (1) I-bearing silver-mordenite (AgZ) materials processed by hot isostatic pressing (HIP) at different temperatures, pressures, sizes, and times; and (2) I-bearing silver-functionalized silica aerogels (SFA) processed by either HIP or spark plasma sintering (SPS). The corrosion susceptibility of AgZ samples was influenced by HIP temperature and pressure. The SPS SFAs retained I far better than HIP SFAs. Additional findings in this study include: (1) The iodine dissolution rate decreased with decreasing temperature, (2) a common ion effect may occur and slow dissolution of the host phase if the leachant is not regularly replaced, (3) pH controls the dissolution rate, and (4) the iodine dissolution rate slows with extended test time (up to 224 days). Based on this work, these parameters should thus be represented when developing a CCRM.

corrosion↗

Solubility and Diffusivity: Important Metrics in the Search for the Root Cause of Light- and Elevated Temperature-Induced Degradation

Light- and elevated temperature-induced degradation (LeTID) is a detrimental effect observed under operating conditions in p-type multicrystalline silicon (mc-Si) solar cells. In this paper, we employ synchrotron-based techniques to study the dissolution of precipitates due to different firing processes at grain boundaries in LeTID-affected mc-Si. The synchrotron measurements show clear dissolution of collocated metal precipitates during firing. We compare our observations with degradation behavior in the same wafers. The experimental results are complemented with process simulations to provide insight into the change in bulk point defect concentration due to firing. Several studies have proposed that LeTID is caused by metal-rich precipitate dissolution during contact firing, and we find that the solubility and diffusivity are promising screening metrics to identify metals that are compatible with this hypothesis. While slower and less soluble elements (e.g., Fe and Cr) are not compatible according to our simulations, the point defect concentrations of faster and more soluble elements (e.g., Cu and Ni) increase after a high-temperature firing process, primarily due to emitter segregation rather than precipitate dissolution. Finally, these results are a useful complement to lifetime spectroscopy techniques, and can be used to evaluate additional candidates in the search for the root cause of LeTID.

14 SOLAR ENERGY↗

A method for preparation and cleaning of uniformly sized arsenopyrite particles

The oxidative dissolution of sulfide minerals, such as arsenopyrite (FeAsS), is of critical importance in many geochemical systems. A comprehensive understanding of their dissolution rates entails careful preparation of the mineral surface. Measurements of dissolution rates of arsenic from arsenopyrite are dependent on the size and degree of oxidation of its particles, among other factors. In this work, a method was developed for preparation and cleaning of arsenopyrite particles with size range of 150–250 μm. Four different cleaning methods were evaluated for effectiveness based on the removal of oxidized species of iron (Fe), arsenic (As) and sulfur (S) from the surface. The percentage oxidation of the surface was determined using X-ray photoelectron spectroscopy (XPS), and surface stoichiometry was measured using scanning electron microscopy – energy dispersive X-ray spectroscopy (SEM-EDS). Results indicate that sonicating the arsenopyrite particles and then cleaning them with 12N HCl followed by 50% ethanol, and drying in nitrogen was the most effective method. This method was successful in greatly reducing the oxide species of Fe while completely removing oxides of As and S from the arsenopyrite surface. Although sonication and acid cleaning have been widely used for mineral preparation, the method described in this study can significantly reduce grain size heterogeneity as well as surface oxidation, which enables greater control in surface and dissolution experiments.

58 GEOSCIENCES↗

Novel Geochemistry Determined from High Pressure, High Temperature Simulation Experiments of Hydraulic Fracture Test Site 2

A standard method in unconventional oil and gas production is the process of hydraulic fracturing followed by a shut-in period, during which the fracture fluid remains pressurized in the reservoir for up to three weeks before production begins. Despite this widely used process, very little is known about what occurs in the reservoir during this shut-in process. In order to properly delineate potential reservoir reactions that may occur during shut-in that would lead to corrosion and scaling events, experiments were conducted in high pressure, high temperature reactors to simulate conditions of the Wolfcamp Formation in the Delaware Basin. Experimental design allowed the assessment of the effect of proppant, microbiology, and time on the mineralogy and fluid chemistry in the reservoir. Results suggest the biggest impact on fluid chemistry and shale mineralogy during shut-in is time. Analyses demonstrate dissolution of the shale material, with maximum dissolved ions occurring after 7 days of the shut-in period. After 21 days, results suggest precipitation occurs. The Delaware Basin is demonstrated to be high in sulfate content, which further increases in the fluid due to dissolution reactions during shut-in. The pressure vessel experiments suggest there was no significant contribution to reactions from microbiology during the shut-in period. Furthermore, early production samples demonstrate a significant selection of the microorganism Caminicella, a genus of which has previously been correlated to corrosion and sulfide production. Results suggest shut-in conditions may provide high sulfate concentrations that could later be utilized by a shifted microbial community to drive potential well infrastructure failure. This is the first study to incorporate microbiology, mineralogy, and fluid chemistry to investigate the fundamental geochemical reactions that occur during shut-in and early phase production of the Delaware Downloaded from http://onepetro.org/URTECONF/proceedings-pdf/21URTC/2-21URTC/D021S032R001/2477425/urtec-2021-5219-ms.pdf/1 by Carol Worster on 28 February 2022 Basin. Results from this study can complement observations from the Hydraulic Fracture Test Site 2 observations

58 GEOSCIENCES↗

Geochemical Impact of Acid Spearhead and Slickwater Stimulation on Wolfcamp Shale from the Hydraulic Fracturing Test Site

The Hydraulic Fracturing Test Site 1 (HFTS-1) was a field study performed in the Wolfcamp Formation in the West Texas Permian (Midland) Basin, USA, with a focus on improving the efficiency of hydraulic fracturing. Investigating site-specific rock-fluid geochemical interactions during hydraulic fracturing is an important step to understanding the impact on formation shale porosity, permeability, and long-term shale gas production. During field operations in this region, hydraulic fracturing fluid (HFF) injection usually starts with a concentrated acid spearhead for rapid rock dissolution, followed by the injection of near-neutral pH slickwater containing chemicals and proppants. A multistep sequential injection approach was used to investigate different stages of rock-fluid interactions. The carbonate content in the host rock is important when acid spearhead is considered, as carbonate mineral dissolution is rapid and can result in porosity and permeability changes in the shale matrix. Here, in this study, we designed flow-through experiments using fractured carbonate-rich and clay-rich Wolfcamp shale cores with (1) a short-time acid soaking step and (2) a long-term slickwater flow-through step to simulate the injection method used at HFTS-1. The fluid chemistry was analyzed. A thorough mineralogical progression [e.g., Calcium (Ca) dissolution and iron (Fe) redox progression] in the cores during HFF injection was also characterized and imaged by synchrotron microprobe. Reactive transport modeling was performed based on the experimental setup. The results showed that the acid spearhead is a crucial step in creating a reaction front by mineral dissolution, especially in carbonate-rich shales. A slight layer of ferrihydrite precipitated during the slickwater flow-through period. This study provides insights into potential geochemical impact due to hydraulic fracturing operations in the Permian Basin.

clastic rock↗

Geo-Chemo-Mechanical Studies for Permanent CO 2 Storage in Geologic Reservoirs

This two-pronged study investigated the rates and mechanisms of formation of Ca and Mg carbonate minerals via reaction of aqueous fluids with silicate minerals and rocks, and the geomechanical effects of such reactions. The kinetic studies focused on the separation of variables, following from previous studies demonstrating rapid formation of carbonates via reaction of the mineral olivine with aqueous fluids rich in NaHCO 3 (plus KHCO 3 and RbHCO 3 ) and NaCl at a high partial pressure of CO 2 . We wished to separate and quantify the effects of NaHCO 3 and NaCl, and to investigate whether bicarbonate-rich, aqueous fluids would also cause rapid formation of carbonates via reaction with other minerals and rocks. Further, we wished to improve upon previous work by adding precise characterization of grain size distributions and surface area, and their changes as a result of reaction. We confirmed previous reports of very rapid olivine carbonation. We found that at a given temperature and CO 2 partial pressure the previously observed rate enhancement in olivine carbonation is due mainly to NaHCO 3 , and not to dissolved NaCl. Further, though reaction of the mineral plagioclase, and two rock compositions, were all faster in the presence of NaHCO 3 -rich fluids, compared with saline and de-ionized water, they were all much slower than reaction of olivine. In the experiments showing the fastest reaction rate, average grain size tended to increase during experiments, presumably due to dissolution of small reactant grains plus growth of product phases on reactant surfaces. Porosity/surface area of grains tended to change with reaction progress, due to the formation of dissolution pits and irregular growth of product phases on reactant grain surfaces. Development of a passivating phase (e.g., a layer of silica) due to incongruent dissolution of solid reactants and/or precipitation of solid products was detected, but was relatively minor and did not have a discernable effect on reaction progress. Geomechanical experiments did not identify pressure-temperature-composition conditions under which porous olivine aggregates undergo reaction driven cracking. Little carbonate formed in these experiments. Though we fulfilled the milestones for this project, a variety of reasons for this remain to be investigated in the future. Reaction of porous olivine aggregates with brines rich in NaHCO 3 caused substantial weakening of samples in compression, due to formation of dissolution pits along olivine-olivine grain boundaries, reducing the solid-solid surface area. A preliminary modeling study funded in part by this grant emphasized potential rate enhancements due to reaction-driven cracking. In related research, not funded by this grant, several additional experimental and modeling studies of reaction-driven cracking are underway.

54 ENVIRONMENTAL SCIENCES↗

Chemical Composition and PCT Data for the Initial Set of Hanford Enhanced Waste Loading Glasses

In this report, the Savannah River National Laboratory provides chemical analyses and Product Consistency Test results for 20 simulated high level waste glasses fabricated by the Pacific Northwest National Laboratory. The results of these analyses will be used as part of efforts to revise or extend the validation ranges of the current Hanford Waste Treatment and Immobilization Plant glass property models to cover a broader span of waste compositions. The measured chemical composition data are reported and compared with the targeted values for each component for each glass. Two components of the study glasses, fluorine and silver, were not measured since each of these species would have required the use of an additional preparation method and their measured values were likely to be near or below analytical detection limits. Some of the glasses were difficult to prepare for chemical analysis. A sodium peroxide fusion dissolution method was successful in completely dissolving the glasses. Components present in the glasses in minor concentrations can be difficult to measure using this dissolution method due to dilution requirements. The use of a lithium metaborate preparation method for the minor components (planned for use since it is typically successful in digesting Defense Waste Processing Facility HLW glasses) resulted in an unacceptable amount of undissolved solids remaining in the sample solutions. An acid dissolution method was used instead, which provided more thorough dissolution of the glasses, although a small amount of undissolved material remained for some of the study glasses. The undissolved material was analyzed to determine those components of the glasses that did not fully dissolve. These components (e.g., calcium and chromium) were present in sufficient quantities to be reported from the measurements resulting from the sodium peroxide fusion preparation method, which did not leave undissolved material. Overall, the analyses resulted in sums of oxides that ranged from about 98 to 101.5 wt % for the study glasses, indicating excellent recovery of all the components in the chemical composition analyses. Comparisons of the targeted and measured chemical compositions indicated that, in general, the measured values for the glasses met the targeted concentrations. Exceptions were Cr 2 O 3 , MgO, and P 2 O 5 . The measured values for Cr 2 O 3 were somewhat low when compared to the targeted values for all of the study glasses targeting Cr 2 O 3 concentrations above 0.5 wt %. Many of the measured MgO and P 2 O 5 values were below the targeted values for those glasses that contained these components. Two of the study glasses exhibited differences from the targeted compositions that may indicate a batching error. Glasses EWG-HAI-Centroid-2 and EWG-OL-1672 had measured values for Al 2 O 3 and SiO 2 that were lower than the targeted values, and measured values for B 2 O 3 that were higher than the targeted values. Glass EWG-HAI-Centroid-2 also had a measured value for Fe 2 O 3 that was lower than the targeted value. A review of the PCT data, including standards and blanks, revealed no issues with the performance of the tests. The PCT results were normalized to both the targeted and measured compositions of the study glasses. Comparisons of the normalized PCT results for both the quenched and Canister Centerline Cooled versions of the study glasses are made with the Environmental Assessment benchmark glass for reference.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Reconstructing paleo-SMT positions on the Casadia margin using magnetic susceptibility

Magnetic susceptibility (κ) is a mixed signal in marine sediments, representing primary depositional and secondary diagenetic processes. Production of hydrogen sulfide via anaerobic oxidation of methane (AOM) at the sulfate-methane transition (SMT) and organoclastic sulfate reduction above the SMT can result in the dissolution of iron oxides, altering κ in sediments in methane gas and gas hydrate bearing regions. We investigated records of κ on the Cascadia margin (ODP Sites 1249 and 1252; IODP Site 1325) using a Zr/Rb heavy mineral proxy from XRF core scanning to identify intervals of primary detrital magnetic susceptibility and intervals and predict intervals affected by magnetite dissolutions. We also measured total sulfur content, grain size distributions, total organic carbon (TOC) content, and magnetic mineral assemblage. The upper 100 m of Site 1252 contains a short interval of κ driven by primary magnetite, with multiple intervals (> 90 m total) of decreased κ correlated with elevated sulfur content, consistent with dissolution of magnetite and re-precipitation of pyrite. In the upper 90 m of Site 1249, κ is almost entirely altered by diagenetic processes, with much of the low κ explained by a high degree of pyritization, and some intervals affected by the precipitation of magnetic iron sulfides. At Site 1325, κ between 0-20 and 51-73 mbsf represents primary mineralogy, and in the interval 24-51 mbsf, κ may be reduced due to pyritization. This integrated approach allows for a prediction of primary κ and the amount of κ loss at each site when compared to actual κ measurements. In the case of magnetite dissolution and full pyritization, these drawdowns in κ are supported by sulfur measurements, and the exposure times of magnetite to hydrogen sulfide can be modeled. The presence of methane and methane hydrates at these sites, as well as large variations in TOC content, suggest that the past migration rates of the SMT and variation in sulfate reduction rates may influence κ alteration along the Cascadia margin.

03 NATURAL GAS↗

Progress Report on FY15 Crystalline Experiments M4FT-15LL0807052

Colloid-facilitated plutonium transport is expected to be the dominant mechanism in its migration through the environment. The forms of Pu colloids (intrinsic versus pseudo-colloid) and their stabilities control temporal and spatial scales of Pu transport in the environment. In the present study, we examine the stability of Pu intrinsic colloids freshly prepared in alkaline solution relative to Pu-montmorillonite pseudo-colloids using a dialysis device and modeling approaches. Intrinsic colloids prepared under alkaline conditions were found to be unstable over a timescale of months. The kinetics of multiple processes, including hydrolysis/precipitation of Pu(IV), dissolution of intrinsic colloids in the absence and presence of the clay colloids, transport of dissolved Pu species across the dialysis membrane, and formation of pseudo-colloids were examined. The dissolution of intrinsic colloids was the rate-limiting process in most cases. The apparent intrinsic colloid dissolution rate constants range from 6×10 -7 to 1×10 - 6 mol·m -2 ·day -1 and 4×10 -6 to 8×10 -6 mol·m -2 ·day -1 at 25 and 80°C, respectively, while the apparent diffusion rate constants for Pu ions crossing the dialysis membrane are >200 times higher. Elevated temperatures enhance dissolution of Pu colloids and the activation energy for the process is estimated to be 28 kJ mol -1 . The sorption of Pu to montmorillonite appears to be endothermic as the affinity of Pu for the clay increases with increasing temperature. Our results provide an in-depth understanding of how intrinsic and pseudo-colloids interact with each other kinetically. Although the fact that intrinsic colloids tend to dissolve in the presence of montmorillonite and transform into pseudo-colloids may limit the migration of intrinsic colloids, the thermodynamically more stable pseudo-colloids may play an important role in Pu transport in the environment over significant temporal and spatial scales.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Dealloying, Microstructure and the Corrosion/Protection of Cast Magnesium Alloys

The purpose of this project was to develop a greater understanding of micro-galvanic corrosion effects in cast magnesium alloys using both experimental and computational methods. Experimental accomplishments have been made in the following areas of interest: characterization, aqueous free-corrosion, atmospheric corrosion, ionic liquid dissolution, rate kinetics of oxide dissolution, and coating investigation. Commercial alloys (AZ91D, AM60, and AZ31B), binary-phase alloys (αMg-2at.%Al, αMg-5at.%Al, and Mg-8at.%Al), and component phases (Mg, Al, β-Mg, β-1%Zn, MnAl3) were obtained and characterized using energy dispersive spectroscopy (EDS), X-ray diffraction (XRD), and scanning electron microscopy (SEM). Full immersion in aqueous chloride was used to characterize the corrosion behavior of alloys. Rotating disc electrodes (RDEs) were used to observe accelerated long-term corrosion behavior. Al surface redistribution for freely corroded samples was analyzed using SEM, EDS, and lithium underpotential deposition (Li UPD). Atmospheric corrosion was observed using contact angle evolution, overnight pH monitoring, and surface pH evolution studies. Ionic liquid corrosion characterization was performed using linear sweep voltammetry and potentiostatic dissolution in 150° choline chloride-urea (cc-urea). Two surface coatings were investigated: (1) Li-carbonate and (2) cc-urea. Li-carbonate coatings were characterized using X-ray photoelectron spectroscopy (XPS), SEM, and aqueous free corrosion potential monitoring. Hydrophobic cc-urea coatings were characterized using contact angle measurements and electrochemical impedance spectroscopy. Oxide dissolution rate kinetics were studied using inductively coupled plasma mass spectroscopy (ICP-MS). Computational accomplishments have been made through the development of Kinetic Monte Carlo (KMC) simulations which model time- and composition-dependent effects on the microstructure due to spatial redistribution of alloying elements during corrosion.

36 MATERIALS SCIENCE↗

FY2017 ILAW Glass Corrosion Testing with the Single-Pass Flow-Through Method

The inventory of immobilized low-activity waste (ILAW) produced at the Hanford Tank Waste Treatment and Immobilization Plant (WTP) will be disposed of at the near-surface, on-site Integrated Disposal Facility (IDF). When groundwater comes into contact with the waste form, the glass will corrode and radionuclides will be released into the near-field environment. Because the release of the radionuclides is dependent on the dissolution rate of the glass, it is important that the performance assessment (PA) model accounts for the dissolution rate of the glass as a function of various conditions. To accomplish this, an IDF PA glass dissolution model based on Transition State Theory (TST) can be employed. The model is able to account for changes in temperature, exposed surface area, and pH of the contacting solution as well as the effect of silicon solution concentrations, specifically the activity of orthosilicic acid (H4SiO4), whose concentration is directly linked to the glass dissolution rate. In addition, the IDF PA model accounts for the ion exchange process. The effect of temperature, pH, H4SiO4 activity, and the rate of ion exchange can be parameterized and implemented directly into the PA rate model. The rate model parameters are derived from laboratory tests with the single-pass flow-through (SPFT) method. The provided data can be used by glass researchers to further the understanding of ILAW glass behavior, by IDF PA modelers to use the rate model parameters in PA modeling efforts, and by Department of Energy (DOE) contractors and decision makers as they assess the IDF PA program.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗