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At least 523 records · Page 29

Remediation of Technetium in Vadose Zone Sediments Using Ammonia and Hydrogen Sulfide Gases

The feasibility of applying a combination of H 2 S and NH 3 gases for Tc-99 remediation in vadose zone sediments evaluated in laboratory experiments showed a significant mobility decrease from 75 to 95% leachable Tc-99 in untreated sediments to 15 to 48% leachable Tc-99 after gas treatment. Individual H 2 S or NH 3 gas treatment of sediments had little lasting effect. For the combined gas treatment, the H 2 S gas created reducing conditions at the pore water/mineral interface that pertechnetate was temporarily reduced/precipitated. The NH 3 gas created alkaline pore water, which induces some mineral dissolution and subsequent aluminosilicate precipitation as the pH neutralizes, which may coat Tc-99 surface phases and render them less mobile. Surface phase analysis showed Tc-99 associated with weathered basalt clasts and sulfur, possibly from the precipitation of TcS x . Treatment performance was nearly the same at different Tc-99 concentration (34 to 6500 pCi/g), water content (1 to 8%), and gas injection rate, but was sensitive to gas concentrations. Low gas concentrations (< 3%) had insufficient reductant or slower mineral dissolution. High gas concentrations (>30%) formed NH 4 SH precipitate. The 15 - 23% mobile Tc-99 remaining after gas treatment may be caused by limited time for aluminosilicates to precipitate in experiments. Nitrogen species concentrations showed no nitrate or nitrite production and a significant decrease in the sediment microbial population over three months, suggesting nitrification of added ammonia was inhibited. Overall, this study showed that combined H 2 S and NH 3 gas treatment of low water content sediments was a robust technology to significantly decrease Tc-99 mobility.

54 ENVIRONMENTAL SCIENCES↗

Study on hydrogen isotopes permeation in fluidized state of liquid lithium-lead

Lithium-lead (Li-Pb) is one of the most promising candidate materials for the liquid blanket of fusion reactors. Hydrogen transfer under a fluidized condition of Li-Pb is investigated experimentally to design a Li-Pb blanket system. Li-Pb eutectic alloy flows inside a Ni tube in the experimental system, where H{sub 2} permeates into and out of the forced Li-Pb flow. The overall H{sub 2} permeation rate is analyzed using a mass balance model. Hydrogen atoms diffuse in Ni and Li-Pb. The steady-state H{sub 2} permeation rate obtained by this experiment is smaller than the result of the calculation model. A resistance factor is introduced to the present analysis in order to evaluate the influence of other H{sub 2} transfer mechanisms, such as diffusion in Li-Pb and dissolution reaction between Ni and Li-Pb. The contribution of the resistance to the overall H{sub 2} permeation rate becomes large when the flow rate of Li-Pb is low. This is because the boundary layer thickness between Ni and Li-Pb affects the overall H{sub 2} permeation rate. When the flow velocity of Li-Pb increases, the thickness of the boundary layer becomes thin, and the driving force of H{sub 2} permeation through the Ni wall becomes bigger. (authors)

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fundamental benchmarking of the discharge properties of negative electrodes in lead acid batteries

The unprecedented scale of energy storage deployment needed to allow high penetration of intermittent renewable energy sources into the electrical grid places significant economic cost and performance targets on battery technologies. Lead batteries, owing to their highly abundant and inexpensive raw materials, can be considered an important solution to grid storage as long as they achieve high material utilization, fast recharge rates, and long cycle life. To address the limitations in material utilization, we need to revisit the electrochemical processes during the discharge step and answer the following question: what are the fundamental limits of the discharge reaction? In this work we discuss how well-defined lead metal surfaces with nanometer scale roughness allow us to resolve the accessible discharge capacity for both faradaic and non-faradaic processes as a function of electrolyte concentration and in the presence of traditional additives. The direct connection between PbSO 4 layer morphology and discharge rates gives us important insights on the mechanism of discharge as related to the dissolution and passivation events. In conclusion, this work sets the stage for reimagining the design of lead batteries with implications to grid storage applications.

25 ENERGY STORAGE↗

Building Materials from Colloidal Nanocrystal Assemblies: Molecular Control of Solid/Solid Interfaces in Nanostructured Tetragonal ZrO 2

We describe in this paper a bottom-up approach to control the composition of solid/solid interfaces in nanostructured materials, and we test its effectiveness on tetragonal ZrO 2 , an inorganic phase of great technological significance. Colloidal nanocrystals capped with trioctylphosphine oxide (TOPO) or oleic acid (OA) are deposited, and the organic fraction of the ligands is selectively etched with O 2 plasma. The interfaces in the resulting all-inorganic colloidal nanocrystal assemblies are either nearly bare (for OA-capped nanocrystals) or terminated with phosphate groups (for TOPO-capped nanocrystals) resulting from the reaction of phosphine oxide groups with plasma species. The chemical modification of the interfaces has extensive effects on the thermodynamics and kinetics of the material. Different growth kinetics indicate different rate limiting processes of growth (surface diffusion for the phosphate-terminated surfaces and dissolution for the “bare” surfaces). Phosphate termination led to a higher activation energy of growth, and a 3-fold reduction in interfacial energy, and facilitated significantly the conversion of the tetragonal phase into the monoclinic phase. Finally, films devoid of residual ligands persisted in the tetragonal phase at temperatures as high as 900 °C for 24 h.

36 MATERIALS SCIENCE↗

Directly monitoring the shift in corrosion mechanisms of a model FeCrNi alloy driven by electric potential

Abstract Stainless steels are used in a myriad of engineering applications, including construction, automobiles, and nuclear reactors. Developing accurate, predictive mechanistic models for corrosion and electrochemical corrosion kinetics of stainless steels has been a topic of research studies over many decades. Herein, we quantified the aqueous corrosion kinetics of a model austenitic Fe–18Cr–14Ni (wt%) alloy in the presence and absence of applied potential using systematic in situ electrochemical atomic force microscopy (EC-AFM) and transmission electron microscopy (TEM). Without an applied bias, vertical dissolution of corrosion pits is controlled by the surface kinetics/diffusion hybrid mechanism, whereas lateral dissolution is diffusion controlled. When an electric bias is applied, the increase in corrosion rate is dominated by the nucleation of new pits. These insights gained by the in situ EC-AFM will allow applications of this method for a quantitative understanding of corrosion of a wider class of materials.

36 MATERIALS SCIENCE↗

Development of a kinetic-thermodynamic model for lime-stabilization of Na-bentonite

This study presents the first kinetic model to predict the solid and pore solution composition of Na-bentonite clay reacting with slaked lime over a period of 720 days. The model successfully accounts for most experimental data using a single kinetic rate constant. The following sequence of reactions was predicted by the model: initial rapid dissolution of portlandite within the first 7 days, leading to a decrease in pH and dissolved calcium, and concurrent formation of calcium silicate hydrates (C-S-H: jennite), calcium aluminate hydrate (C-A-H: C₄AH₁₃), calcium aluminosilicate hydrates (stratlingite) and hydrotalcite. After 7 days, jennite and stratlingite are predicted to transform into tobermorite-II, contributing to strength development up to 28 days. From 28 to 90 days, continued montmorillonite dissolution is predicted, along with minor formation of ettringite, partial tobermorite-II dissolution, and precipitation of secondary phases such as albite and talc. Experimentally, portlandite dissolution was confirmed by TGA and XRD and found to be complete within 7 days, in agreement with model predictions. However, other predicted solid-phase transformations (e.g., tobermorite-II formation and dissolution, ettringite, albite, and talc formation) could not be conclusively verified through experimental techniques. Aqueous phase measurements confirmed that the pH and Ca trends in solution, and that equilibrium was reached by 90 days.

Chemical kinetics↗

Code Comparison Study Fosters Confidence in the Numerical Simulation of Enhanced Geothermal Systems

Numerical simulation has become a standard analytical tool for scientists and engineers to evaluate the potential and performance of enhanced geothermal systems. A variety of numerical simulators developed by industry, universities, and national laboratories are currently available and being applied to better understand enhanced geothermal systems at the field scale. To yield credible predictions and be of value to site operators, numerical simulators must be able to accurately represent the complex coupled processes induced by producing geothermal systems, such as fracture aperture changes due to thermal stimulation, fracture shear displacement with fluid injection, rate of thermal depletion of reservoir rocks, and permeability alteration with mineral precipitation or dissolution. A suite of numerical simulators was exercised on a series of test problems that considered coupled thermal, hydraulic, geomechanical, and geochemical (THMC) processes. Problems were selected and designed to isolate selected coupled processes, to be executed on workstation class computers, and have simple but illustrative metrics for result comparisons. This paper summarizes the initial suite of seven benchmark problems, describes the code comparison activities, provides example results for problems and documents the capabilities of currently available numerical simulation codes to represent coupled processes that occur during the production of geothermal resources. Code comparisons described in this paper use the ISO (International Organization for Standardization) standard ISO-13538 for proficiency testing of numerical simulators. This approach was adopted for a recent code comparison study within the radiation transfer-modeling field of atmospheric sciences, which was focused on canopy reflectance models. This standard specifies statistical methods for analyzing laboratory data from proficiency testing schemes to demonstrate that the measurement results do not exhibit evidence of an unacceptable level of bias.

benchmark problems↗

Characterization of the Triassic Newark Basin of New York and New Jersey for geologic storage of carbon dioxide

The Newark Basin is a Triassic-aged rift basin underlying densely populated, industrialized sections of New York, New Jersey and Pennsylvania. The Basin is an elongate half-graben encompassing an area of more than 7,510 square-kilometers (2,900 square-miles), and could represent a key storage component for commercial scale management of carbon dioxide emissions via geologic sequestration. The project team first acquired published reports, surface and subsurface maps, and seismic data, which formed the basis for a three-dimensional model framework for the northern end of the Basin incorporating stratigraphic, hydrologic, and water quality data. Field investigations included drilling, coring, and logging of two stratigraphic test borings in Clarkstown, NY (Exit 14 Tandem Lot Well No. 1), drilled to a depth of 2,099 meters (6,885 feet); and Palisades, NY (Lamont-Doherty Earth Observatory Test Well No. 4) drilled to a depth of 549 meters (1,802 feet). Two two-dimensional seismic reflection data lines arrayed perpendicularly were acquired by Schlumberger/WesternGeco to help characterize the structure and stratigraphy and as part of pre-drilling field screening activities for the deep stratigraphic borehole. A total of 47 meters (155 feet) of continuous whole core was recovered from the Tandem Lot boring from depths of 1,393 meters (4,570 feet) to 1,486 meters (4,877 feet). Twenty-five horizontal rotary cores were collected in mudstones and sandstones in the surface casing hole and fifty-two cores were taken in various lithologies in the deep borehole. Rotary core plugs were analyzed by Weatherford Laboratories for routine and advanced testing. Rotary core plug trim end thin sections were evaluated by the New York State Museum for mineralogical analysis and porosity estimation. Using core samples, Lawrence Berkley National Laboratory designed and completed laboratory experiments and numerical modeling analyses to characterize the dissolution and reaction of carbon dioxide with formation brine and minerals, and resulting effects on injection rate, pressure, effective storage volume, and carbon dioxide migration within a prospective sandstone reservoir. $$Three potential porous and permeable sandstone units were identified in the Passaic Formation at the New York State Thruway Exit 14 location. Potential Flow Unit 1, at a depth of 643 meters (2,110 feet) to 751 meters (2,465 feet); Potential Flow Unit 2 at a depth of 853 meters (2,798 feet) to 1,000 meters (3,280 feet); and Potential Flow Unit 3, at a depth of 1,114 meters (3,655 feet) to 1,294 meters (4,250 feet). Reactive transport simulations of interactions between carbon dioxide, brine and formation minerals were carried out to evaluate changes in formation water chemistry, mineral precipitation and dissolution reactions, and any potential resulting effects on formation permeability. The experimental and modeling analyses suggest that mineral precipitation and dissolution reactions (within the target formation) are not expected to lead to significant changes to the underground hydrologic system over time frames (~30 years) typically relevant for carbon dioxide injection operations. Key findings of this basin characterization study include an estimate of carbon dioxide storage capacity in the Newark Basin. Assuming an average porosity of twelve percent and an aquifer volume of 6.1E+12 meters3, calculated ranges of likely storage capacity range from 1.9 – 20.2 gigatonnes under high temperature (low carbon dioxide density) conditions; and 2.9 – 30.2 gigatonnes under low temperature (low carbon dioxide density) conditions. Intra-basin faulting, geometry of the Palisades Sill, and the presence of altered meta-sediments above and below the Sill, increase potential compartmentalization within the basin. A structural/stratigraphic trap type may occur where porous/permeable sediments are cross-cut by the Palisades Sill. Potential injection intervals are present within the Stockton Formation of the Newark Basin. Additional porous/permeable intervals may be present within sandstones of the Passaic Formation, increasing projected storage capacity. Deeper wedges of strata are likely present in the deeper portions of the basin in southern New York and into northern New Jersey. Abundant mudstones are present in the Passaic, Lockatong, and Stockton Formations. These intervals have the requisite petrophysical properties to form effective primary and secondary containment intervals to industrial-scale sequestration of carbon dioxide in the Newark Basin. Hydro-thermally altered meta-sediments in the region immediately surrounding the top and base of the Palisades Sill is devoid of porosity/permeability and forms an additional effective lateral/vertical sealing cap rock.

58 GEOSCIENCES↗

Effect of AC Current Density on the Stress Corrosion Cracking Behavior and Mechanism of E690 High-Strength Steel in Simulated Seawater

In this work, we studied the impact of alternating current (AC) density on the stress corrosion cracking (SCC) behavior and mechanism of E690 high-strength steel in simulated seawater with electrochemical measurements, U-bend immersion tests and slow strain rate tensile tests. Results demonstrate that AC enhances both anodic and cathodic processes, especially localized anodic dissolution and hydrogen evolution, which manifests as the increase in i{sub corr} with AC current density rising. Therefore, AC leads to higher SCC susceptibility. Accordingly, SCC is dominated by anodic dissolution (AD) at low AC current density while in a mixed control of AD and hydrogen embrittlement (HE) at high AC current density as a result of increasing hydrogen concentration. Besides, 50 A/m{sup 2} corresponds to the threshold hydrogen concentration of the “hydrogen-induced plasticity to HE” transformation, which is due to the different interactions of dislocation and hydrogen.

36 MATERIALS SCIENCE↗

Morphological Evolution and Dealloying During Corrosion of Ni20Cr (wt.%) in Molten FLiNaK Salts

The dealloying corrosion behavior of the FCC Ni20Cr (wt%) in molten LiF-NaF-KF (FLiNaK) salts at 600 °C under varying applied potentials was investigated. Using in-operando electrochemical techniques and a multi-modal suite of characterization methods, we connect electrochemical potential, thermodynamic stability, and electro-dissolution kinetics to the corrosion morphologies. Notably, under certain potential regimes, a micron-scale bicontinuous structure, characterized by a network of interconnected pores and ligaments riched with the composition of the more noble (MN) element, becomes prominent. At other potentials both MN and less noble (LN) elements dealloy but at different rates. The dealloying process consists of lattice and grain boundary diffusion of Cr to the metal/salt interface, interphase Cr oxidation, accompanied by surface diffusion of Ni to form interconnected ligaments. At higher potentials, the bicontinuous porous structure undergoes further surface coarsening. Concurrently, Cr(II), Cr(III), and Ni(II) begin to dissolve, with the dissolution of Ni occurring at a significantly slower rate. When solid-state transport of Cr is exceeded by the interfacial rates, dealloying depths are limited.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Assessing the Role of Iron Sulfides in the Long Term Sequestration of Uranium by Sulfate-Reducing Bacteria

This overarching aim of this project was to identify the role of biogenic and synthetic iron-sulfide minerals in the long-term sequestration of reduced U(IV) formed under sulfate-reducing conditions when subjected to re-oxidizing conditions. The work reported herein was achieved through the collaborative research effort conducted at Arizona State University (ASU) and the University of Michigan (UM). Research at ASU, focused on the biogenesis aspects, examined the biogeochemical bases for iron-sulfide production by Desulfovibrio vulgaris, a Gram-negative bacterium that is one of the most-studied strains of sulfate-reducing bacteria. A series of experimental studies were performed to investigate comprehensively important metabolic and environmental factors that affect the rates of sulfate reduction and iron-sulfide precipitation, the mineralogical characteristics of the iron sulfides, and how uranium is reduced or co-reduced by D. vulagaris. FeS production studies revealed that controlling the pH affected the growth of D. vulgaris and strongly influenced the formation and growth of FeS solids. In particular, lower pH produced larger-sized mackinawite (Fe 1+x S). Greater accumulation of free sulfide, from more sulfate reduction by D. vulgaris, also led to larger-sized mackinawite and stimulated mackinawite transformation to greigite (Fe 3 S 4 ) when the free sulfide concentration was 29.3 mM. On the other hand, using solid Fe(III) (hydr)oxides as the iron source led to less productivity of FeS due to their slow and incomplete dissolution and scavenging of sulfide. Furthermore, sufficient free Fe 2+ , particularly during Fe(III) (hydr)oxide reductions, led to the additional formation of vivianite [Fe 3 (PO 4 ) 2 •8(H 2 O)]. The U(VI) reduction studies revealed that D. vulgaris reduced U(VI) fastest when accumulating sulfide from concomitant sulfate reduction, since direct enzymatic and sulfide-based reductions of U(VI) occurred in parallel. The UO 2 produced in presence of ferrous iron was poorly crystalline. At UM, laboratory-scale reactor studies were performed to assess the potential for the predominant abiotic reductants formed under sulfate reducing conditions (SRCs) to: (1) reduce U(VI) in contaminated groundwater sediments), and (2) inhibit the re-oxidation of U(IV) species, and in particular, uraninite (UO 2 (s)). Under SRCs, mackinawite and aqueous sulfide are the key reductants expected to form. To assess their potential for abiotic reduction of U(VI) species, a series of experiments were performed in which either FeS or S(-II) was added to solutions of U(VI), with the rates of conversion to U(IV) solids monitored as a function of pH, and carbonate and calcium concentration. In the presence of FeS and absence of oxygen or carbonate, U(IV) was completely reduced uraninite. S(-II) was also found to be an effective reductant of aqueous phase U(VI) species and produced uraninite, with the kinetics and extent of reduction depending on geochemical conditions. U(VI) reduction to uraninite was faster under higher S(-II) concentrations but was slowed by an increase in the dissolved Ca or carbonate concentration. Rapid reduction of U(VI) occurred at circumneutral pH but virtually no reduction occurred at pH 10.7. In general, dissolved Ca and carbonate slowed abiotic U(VI) reduction by forming stable Ca-U(VI)-carbonate soluble complexes that are resistant to reaction with aqueous sulfide. To investigate the stability of U(IV) against re-oxidation in the presence of iron sulfides by oxidants in simulated groundwater environments, and to develop a mechanistic understanding the controlling redox processes, continuously-mixed batch reactor (CMBR) and flow-through reactor (CMFR) studies were performed at UM. In these studies a series of experiments were conducted under various oxic groundwater conditions to examine the effectiveness of FeS as an oxygen scavenger to retard UO 2 dissolution. The results indicate that FeS is an effective oxygen scavenger, and can lower the rate of oxidative dissolution of UO 2 by over an order of magnitude compared to the absence of FeS, depending on pH, FeS content, and DO concentrations. Column reactor studies were performed at UM to assess the impact of mackinawite on uraninite oxidation under hydrodynamic flow conditions more representative of packed porous media at contaminated groundwater sites. In these studies, Rifle sediments were packed in the two columns which were subjected to different bioreduction steps and then run in parallel. The first column was bioreduced under SRCs (i.e., with sulfate in the influent) to generate mackinawite, mixed with uraninite, gamma-sterilized to inhibit subsequent microbiological activity, and then subjected to groundwater influent containing first nitrite and then oxygen. The second column was bioreduced (but in absence of sulfate in the influent) so that no iron sulfides would form, and then subjected to identical steps and influent as the first column. When nitrite was introduced in the influent of both columns, no significant release of U(VI) relative to the anoxic flow prior to nitrite addition occurred. However, when oxygen was introduced, the column which had undergone sulfate reduction (and had produced mackinawite as later verified by XAS) significantly lowered the peak U(VI) effluent concentrations, and in general, slowed U(VI) release considerably compared to the column with no FeS. Overall, these studies demonstrated that the presence of mackinawite can be a significant scavenger of oxygen and inhibit the oxidation of uraninite by oxygen, whereas nitrite had little impact on uraninite oxidation either in the presence or absence of FeS.

54 ENVIRONMENTAL SCIENCES↗

In situ reductive dissolution to remove Iodine-129 from aquifer sediments

The use of an aqueous reductant (Na-dithionite) with pH buffer (K-carbonate, pH 12) was evaluated in this laboratory study as a potential remedial approach for removing Fe oxide associated iodine and enhancing pump-and-treat extraction from iodine-contaminated sediments in the unconfined aquifer in the 200 West Area of the Hanford site. X-ray fluorescence data of untreated sediment indicated that iodine was largely associated with Fe (i.e., incorporated into Fe oxides), however, XANES data was inconclusive as to valence state. During groundwater leaching, aqueous and adsorbed iodine was quickly released, then additional iodine was slowly released potentially from dissolution of one or more surface phases. The Na-dithionite treatment removed greater iodine mass (2.9x) at a faster rate (1 to 4 orders of magnitude) compared to leaching with groundwater alone. Iron extractions for untreated and treated sediments showed a decrease in Fe(III)-oxides, which likely released iodine to aqueous solution. Solid phase inorganic carbon and aqueous Ca and Mg analysis further confirmed that significant calcite dissolution did not occur in these experiments meaning these phases did not release significant iodine. Although it was expected that, after treatment, 127 I concentrations would eventually be lower than untreated sediments, leaching experiments showed continued, elevated iodine concentrations for treated samples over 750 hours. Stop flow events during 1-D column leaching suggested that some iodide precipitated within the first few pore volumes. In the survey of metals during leaching, some silver was detected which could have been solubilized by the elevated pH of initial Na-dithionite injection. Then, silver (or other metals) could have subsequently precipitated with iodide during the initial stop flow event forming a slowly dissolving source. Although significantly greater iodine is removed with treatment, the long-term leaching needs to be investigated further as it may limit dithionite treatment at the field scale.

54 ENVIRONMENTAL SCIENCES↗

Iron addition to soil specifically stabilized lignin

The importance of lignin as a recalcitrant constituent of soil organic matter (SOM) remains contested. Associations with iron (Fe) oxides have been proposed to specifically protect lignin from decomposition, but impacts of Fe-lignin interactions on mineralization rates remain unclear. Oxygen (O 2 ) fluctuations characteristic of humid tropical soils drive reductive Fe dissolution and precipitation, facilitating multiple types of Fe-lignin interactions that could variably decompose or protect lignin. Here, we tested impacts of Fe addition on 13 C methoxyl-labeled lignin mineralization in soils that were exposed to static or fluctuating O 2 . Iron addition suppressed lignin mineralization to 21% of controls, regardless of O 2 availability. However, Fe addition had no effect on soil CO 2 production, implying that Fe oxides specifically protected lignin methoxyls but not bulk SOM. Iron oxide-lignin interactions represent a specific mechanism for lignin stabilization, linking SOM biochemical composition to turnover via geochemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Micromodel Investigation of Transport Effect on the Kinetics of Reductive Dissolution of Hematite

Reductive dissolution of hematite in porous media was investigated using a micromodel with realistic pore network structures that include distinctive advection domain, macro-pores and micro-pores created in silicon substrate. The micromodel pore surface was sputter deposited with a thin layer (230 nm) of hematite. The hematite in the micromodel was reduced by injecting pH-varying solutions containing a reduced form of flavin mononucleotide (FMNH2), a biogenic soluble electron transfer mediator produced by Shewanella species. The reduction kinetics was determined by measuring effluent Fe(II) concentration and by spectroscopically monitoring the hematite dissolution front in the micromodel. Batch experiment was also performed to estimate the hematite reduction rate under the well-mixed condition. The results showed a significant spatial variation in local redox reaction rate that was controlled by the coupled diffusion and reaction. The overall rate of the redox reaction in the micromodel required a three-domain numerical model to effectively describe with distinctive rate parameters in different pore domains. Results from this study demonstrated the important scaling effect when extrapolating geochemical or biogeochemical reaction rate from batch reactor to porous media and indicated a significant control of physical transport mechanisms on the reaction rate scaling.

Reactive transport, porous media, hematite↗

Timescales and Processes of Methane Hydrate Formation and Breakdown, With Application to Geologic Systems

Abstract Gas hydrate is an ice‐like form of water and low molecular weight gas stable at temperatures of roughly −10°C to 25°C and pressures of ~3 to 30 MPa in geologic systems. Natural gas hydrates sequester an estimated one sixth of Earth's methane and are found primarily in deepwater marine sediments on continental margins, but also in permafrost areas and under continental ice sheets. When gas hydrate is removed from its stability field, its breakdown has implications for the global carbon cycle, ocean chemistry, marine geohazards, and interactions between the geosphere and the ocean‐atmosphere system. Gas hydrate breakdown can also be artificially driven as a component of studies assessing the resource potential of these deposits. Furthermore, geologic processes and perturbations to the ocean‐atmosphere system (e.g., warming temperatures) can cause not only dissociation, but also more widespread dissolution of hydrate or even formation of new hydrate in reservoirs. Linkages between gas hydrate and disparate aspects of Earth's near‐surface physical, chemical, and biological systems render an assessment of the rates and processes affecting the persistence of gas hydrate an appropriate Centennial Grand Challenge. This paper reviews the thermodynamic controls on methane hydrate stability and then describes the relative importance of kinetic, mass transfer, and heat transfer processes in the formation and breakdown (dissociation and dissolution) of gas hydrate. Results from numerical modeling, laboratory, and some field studies are used to summarize the rates of hydrate formation and breakdown, followed by an extensive treatment of hydrate dynamics in marine and cryospheric gas hydrate systems.

58 GEOSCIENCES↗

Optimization of Saltcake Removal Flowsheet at SRS through Incorporation of Testing and In-Tank Waste Experience

Saltcake removal at SRS may be performed for several reasons: to provide space for evaporator operation (i.e., to precipitate more salt in the drop tank), to provide feed for salt processing (i.e. immobilize the waste), or to remove the salt for tank closure. Many different salt dissolution techniques have been employed in the 40 years that SRS has been performing salt removal, from a basic “Add, Sit, Remove” method (water is added on top of the saltcake and time is allowed for diffusion), to performing interstitial liquid removal, or using mixing devices to promote contact with the liquid. Lessons learned from previous saltcake removal campaigns, in addition to testing and modeling, have led to opportunities for improvements to the overall saltcake removal process. This includes better understanding of salt properties and behavior during dissolution; the primary concerns for salt dissolution are the release of radiolytic hydrogen and criticality prevention (post-dissolution). Recent developments in salt dissolution include the reuse of dilute supernate and a semi-continuous dissolution (SCD) process, where low volume mixing eductors are used to deliver water near the surface of the saltcake at the same rate as the salt solution is removed and transferred to a receipt tank.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Laboratory Evaluation to Increase Effectiveness of Field-Scale Soil Flushing in the Hanford 100 Areas

This laboratory study was initiated to develop an improved technical understanding of the key controlling geochemical and physical processes of mobilizing residual Cr(VI) in Hanford sediments to provide increased effectiveness in soil flushing activities planned for Hanford 100 Areas. This was accomplished by (1) quantifying Cr mass, release rate, and surface phase changes as Cr is leached from different Hanford sediments; (2) maximizing Cr leaching during soil flushing by evaluating different leach solutions and leach strategies; and (3) minimizing leaching of remaining residual Cr after soil flushing ends. To quantify geochemical controls on Cr leaching from sediments, sequential liquid extractions were used to identify aqueous, adsorbed, and solid Cr surface phases (precipitates or Cr incorporated into other phases) before and after water-saturated and unsaturated leach experiments with pH 8 artificial groundwater and with other amendment solutions. Changes in the Cr release rate from sediments were also correlated to changes in Cr surface phases. During unsaturated infiltration, water advection occurs primarily through larger pores, with less movement through smaller grain layers leading to a slower release of Cr trapped in smaller pores next to smaller grains. To quantify these physical controls on Cr leaching from sediments, 10 ft high 1-D infiltration experiments were conducted at differing leach solution application rates, and Cr leaching during application and subsequent residual water flow was quantified. Qualitative 2-D experiments were also conducted to evaluate surfactant addition to increase flow in low-permeability zones. Cr-contaminated Hanford sediments from the 100-H, 100-K, 100-D, and 200 East Areas exhibited a wide variety of leach behavior from rapid release of a small amount of Cr to fast (i.e., minutes) and slow (i.e., hours or more) release of high Cr. Sediments with low labile Cr (< 0.2 µg/g) exhibited fast Cr release but less overall release, and most (>95%) leached from the sediments within a few pore volumes in water-saturated columns. With nearly no sorption of chromate, aqueous and sorbed Cr (as chromate) were released quickly from sediment within the first few pore volumes, resulting in high leach concentrations, fast initial Cr release rates, and changes in pre- and post-leach extractions. In contrast, sediments with high labile Cr (0.2 to 20 µg/g) exhibited a combination of fast and slow Cr release due to multiple Cr surface phases contributing to Cr release from the sediment at different rates with greater overall release. This resulted in elevated Cr effluent concentrations even after dozens of pore volumes were leached. In addition, the Cr release rate decreased with increasing time during leaching. A decrease in labile Cr (aqueous Cr, adsorbed Cr, pH 5 acetate dissolved precipitates) in post-leach extractions compared to pre-leach extractions showed initial aqueous and adsorbed Cr release, followed by dissolution of high-solubility precipitates such as CaCrO 4 (if present), then slow dissolution of calcite that may contain some chromate and possibly BaCrO 4 . The labile Cr in all sediments correlated well with the Cr release rate (r 2 = 0.81). Labile Cr also correlated well with the leached mass in water-saturated columns (r 2 = 0.98), and therefore can be used for prediction of potential removal with flushing applications.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Dissolution flowsheet for high flux isotope reactor fuel

As part of the Spent Nuclear Fuel (SNF) processing campaign, H-Canyon is planning to begin dissolving High Flux Isotope Reactor (HFIR) fuel in late FY17 or early FY18. Each HFIR fuel core contains inner and outer fuel elements which were fabricated from uranium oxide (U 3 O 8 ) dispersed in a continuous Al phase using traditional powder metallurgy techniques. Fuels fabricated in this manner, like other SNF’s processed in H-Canyon, dissolve by the same general mechanisms with similar gas generation rates and the production of H 2 . The HFIR fuel cores will be dissolved and the recovered U will be down-blended into low-enriched U. HFIR fuel was previously processed in H-Canyon using a unique insert in both the 6.1D and 6.4D dissolvers. Multiple cores will be charged to the same dissolver solution maximizing the concentration of dissolved Al. The objective of this study was to identify flowsheet conditions through literature review and laboratory experimentation to safely and efficiently dissolve the HFIR fuel in H-Canyon. Laboratory-scale experiments were performed to evaluate the dissolution of HFIR fuel using both Al 1100 and Al 6061 T6 alloy coupons. The Al 1100 alloy was considered a representative surrogate which provided an upper bound on the generation of flammable (i.e., H 2 ) gas during the dissolution process. The dissolution of the Al 6061 T6 alloy proceeded at a slower rate than the Al 1100 alloy and was used to verify that the target Al concentration in solution could be achieved for the selected Hg concentration. Mass spectrometry and Raman spectroscopy were used to provide continuous monitoring of the concentration of H 2 and other permanent gases in the dissolution offgas allowing the development of H 2 generation rate profiles. The H 2 generation rates were subsequently used to evaluate if a full HFIR core could be dissolved in an H-Canyon dissolver without exceeding 60% of the calculated lower flammability limit (LFL) for H 2 at a given Hg concentration.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗