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At least 703 records · Page 39

Arsenic mobilization in shallow aquifers due to CO 2 intrusion from storage reservoirs

We developed an integrated framework of combined batch experiments and reactive transport simulations to quantify water-rock-CO 2 interactions and arsenic (As) mobilization responses to CO 2 and/or saline water leakage into USDWs. Experimental and simulation results suggest that when CO 2 is introduced, pH drops immediately that initiates release of As from clay minerals. Calcite dissolution can increase pH slightly and cause As re-adsorption. Thus, the mineralogy of the USDW is ultimately a determining factor of arsenic fate and transport. Salient results suggest that: (1) As desorption/adsorption from/onto clay minerals is the major reaction controlling its mobilization, and clay minerals could mitigate As mobilization with surface complexation reactions; (2) dissolution of available calcite plays a critical role in buffering pH; (3) high salinity in general hinders As release from minerals; and (4) the magnitude and quantitative uncertainty of As mobilization are predicated on the values of reaction rates and surface area of calcite, adsorption surface areas and equilibrium constants of clay minerals, and cation exchange capacity. Results of this study are intended to improve ability to quantify risks associated with potential leakage of reservoir fluids into shallow aquifers, in particular the possible environmental impacts of As mobilization at carbon sequestration sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Epitaxial heterointerfacial electron bridge synchronizes oxygen evolution activity and stability on a layered double hydroxide surface

Scalable green hydrogen production via electrocatalytic water splitting is largely restricted by the insufficient activity and stability of oxygen evolution reaction (OER) catalysts at the anode. As a class of the most active OER catalysts in alkaline electrolyzers, the application of layered double hydroxides (LDHs) remains a main challenge owing to the unstable lattice oxygen dissolution due to the dominant lattice oxygen-involving OER mechanism during long-term operation. Herein, we found that using an epitaxial hetero-interfacing nickel hydroxide (namely Ni(OH) 2 ) as an electron bridge between an active FeCo LDH and Ni foam support to form an LDH*/NFO catalyst, the electronic storage capacity around the Fermi level (-0.5 to +0.5 eV, e-D FE ) sharply increases from 0.93 per cell to 1.51 per cell. Subsequently, we demonstrate that this high e-D FE enables ceaseless and fast power injection into the kinetic process of intermediate species conversion and inhibits lattice oxygen dissolution in the active FeCo LDH. Consequently, it demonstrated a low OER overpotential of 246 mV at a current density of 100 mA cm -2 and ultrahigh stability for up to 3500 hours with an ultraslow overpotential increase rate of 9.4 × 10 -3 mV h -1 . Therefore, we developed an epitaxial hetero-interfacial electron bridging strategy to synchronize the activity and stability of available catalysts for scalable green hydrogen production via electrocatalytic water splitting.

25 ENERGY STORAGE↗

The effect of Ca-Fe-As coatings on microbial leaching of metals in arsenic bearing mine waste

Globally arsenic (As) is a ubiquitous trace element derived from the natural weathering of As-bearing rock. With the onset of reducing conditions, the prevalence of aqueous As(III) may be intensified through biotic and abiotic processes. Here we evaluate the stability of arsenic bearing Ca-Fe hydroxide phases collected from exposed tailings at Ketza River mine, Yukon, Canada, during the reductive dissolution of both acid treated and untreated samples by Shewanella putrefaciens 200R and Shewanella sp. ANA-3. Samples were acid treated in order to remove Ca-Fe oxide coatings and evaluate the influence of these coatings on the rates of microbial Fe(III) and As(V) reduction. Environmental scanning electron microscope (ESEM) micrographs of the solid phase show significant differences in the chemistry and physical morphology of the material by the bacteria over time and are especially evident in the acid treated samples. Moreover, while solution chemistry showed similar As(III) respiration rates of the inoculated acid treated samples for both ANA3 and 200R at {approx}1.1 x 10{sup -6} {micro}M {center_dot} s{sup -1} {center_dot} m{sup -2}, the Fe(II) respiration rates differed at 1.4 x 10{sup -7} and 9.5 x 10{sup -8} {micro}M {center_dot} s{sup -1} {center_dot} m{sup -2} respectively, thus suggesting strain specific metal reduction metabolic pathways Additionally, the enhanced metal reduction observed in the acid treated inoculated samples suggests that the presence of the Ca-Fe hydroxide phase in the untreated samples acted as a barrier, inhibiting the bacteria from accessing the metals. This has implications for increased mobilization of metals by metal reducing bacteria within areas of increased acidity, such as acid mine drainage sites and industrial tailings ponds that can come into contact with surface and ground water sources.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Relationships between CO 2 , thermodynamic limits on silicate weathering, and the strength of the silicate weathering feedback

Recent studies have suggested that thermodynamic limitations on chemical weathering rates exert a first-order control on riverine solute fluxes and by extension, global chemical weathering rates. As such, these limitations may play a prominent role in the regulation of carbon dioxide levels (pCO 2 ) over geologic timescales by constraining the maximum global weathering flux. In this study, we develop a theoretical scaling relationship between equilibrium solute concentrations and pCO 2 based on equilibrium constants and reaction stoichiometry relating primary mineral dissolution and secondary mineral precipitation. Here, we test this theoretical scaling relationship against reactive transport simulations of chemical weathering profiles under open-and closed-system conditions, representing partially and fully water-saturated regolith, respectively. Under open-system conditions, equilibrium bicarbonate concentrations vary as a power-law function of pCO 2 (y =kx n )where nis dependent on reaction stoichiometry and kis dependent on both reaction stoichiometry and the equilibrium constant. Under closed-system conditions, bicarbonate concentrations vary linearly with pCO 2 at low values and approach open-system scaling at high pCO 2 . To describe the potential role of thermodynamic limitations in the global silicate weathering feedback, we develop a new mathematical framework to assess weathering feedback strength in terms of both (1) steady-state atmospheric pCO 2 concentrations, and (2) susceptibility to secular changes in degassing rates and transient carbon cycle perturbations, which we term 1st and 2nd order feedback strength, respectively. Finally, we discuss the implications of these results for the effects of vascular land plant evolution on feedback strength, the potential role of vegetation in controlling modern solute fluxes, and the application of these frameworks to a more complete functional description of the silicate weathering feedback. Most notably, the dependence of equilibrium solute concentrations on pCO 2 may represent a direct weathering feedback largely independent of climate and modulated by belowground organic carbon respiration.

58 GEOSCIENCES↗

Ambient aging of rhenium filaments used in thermal ionization mass spectrometry: Growth of oxo-rhenium crystallites and anti-aging strategies

Degassing is a common preparation technique for rhenium filaments used for thermal ionization mass spectrometric analysis of actinides, including plutonium. Although optimization studies regarding degassing conditions have been reported, little work has been done to characterize filament aging after degassing. In this study, the effects of filament aging after degassing were explored to determine a “shelf-life” for degassed rhenium filaments, and methods to limit filament aging were investigated. Zone-refined rhenium filaments were degassed by resistance heating under high vacuum before exposure to ambient atmosphere for up to 2 months. After degassing the nucleation and preferential growth of oxo-rhenium crystallites on the surface of polycrystalline rhenium filaments was observed by atomic force microscopy and scanning electron microscopy (SEM). Compositional analysis of the crystallites was conducted using SEM-Raman spectroscopy and SEM energy dispersive X-ray spectroscopy, and grain orientation at the metal surface was investigated by electron back-scatter diffraction mapping. Spectra collected by SEM-Raman suggest crystallites are composed primarily of perrhenic acid. The relative extent of growth and crystallite morphology were found to be grain dependent and affected by the dissolution of carbon into filaments during annealing (often referred to as carbonization or carburization). Crystallites were observed to nucleate in region specific modes and grow over time through transfer of material from the surface. Factors most likely to affect the rates of crystallite growth include rhenium substrate properties such as grain size, orientation, levels of dissolved carbon, and relative abundance of defect sites; as well as environmental factors such as length of exposure to oxygen and relative humidity. Thin (~180 nm) hydrophobic films of poly(vinylbenzyl chloride) were found to slow the growth of oxo-rhenium crystallites on the filament surfaces and may serve as an alternative carbon source for filament carburization.

36 MATERIALS SCIENCE↗

Response relationship between loading condition and corrosion fatigue behavior of nickel-aluminum bronze alloy and its crack tip damage mechanism

Highlights: • The differences of corrosion fatigue behavior of NAB alloy in air and in 3.5% NaCl solution are carefully compared. • The corrosion environment significantly accelerates the crack growth of NAB alloy and decreases the fatigue threshold. • The corrosion fatigue crack growth rate increases with the decrease of loading frequency. • The acidification and the dealumination occur in process of corrosion fatigue, resulting in the deterioration of crack tip. - Abstract: Corrosion fatigue is one of the major forms for nickel‑aluminum bronze alloy used in marine propeller. It is greatly important to understand the corrosion fatigue behavior of nickel‑aluminum bronze alloy in seawater for the purpose of improving the service life of marine equipment. In this study, corrosion fatigue crack growth rate of nickel‑aluminum bronze alloy in 3.5% NaCl solution was tested under various stress intensity factors, stress ratios and loading frequencies to reveal its corrosion fatigue mechanism. The results show that corrosion environment significantly accelerates the crack growth and decreases the corrosion fatigue threshold, which is attributed to the corrosion reactions between the metals of crack tip and corrosive medium. Among the various factors, loading frequency has more predominant influence on the corrosion fatigue crack growth rate of nickel‑aluminum bronze alloy, which can be rationally explained by the hydrogen embrittlement mechanism. Additionally, in the process of corrosion fatigue crack growth, the acidification and the dealumination would occur at the crack tip, resulting in the corrosion dissolution of κ phases and the deterioration in mechanical properties of crack tip.

36 MATERIALS SCIENCE↗

Alcove formation in dissolving cliffs driven by density inversion instability

We demonstrate conditions that give rise to cave-like features commonly found in dissolving cliffsides with a minimal two-phase physical model. Alcoves that are wider at the top and tapered at the bottom, with sharp-edged ceilings and sloping floors, are shown to develop on vertical solid surfaces dissolving in aqueous solvents. As evident from descending plumes, sufficiently large indentations evolve into alcoves as a result of the faster dissolution of the ceiling due to a solutal Rayleigh–Bénard density inversion instability. In contrast, defects of size below the boundary layer thickness set by the critical Rayleigh number smooth out, leading to stable planar interfaces. Furthermore, the ceiling recession rate and the alcove opening area evolution are shown to be given to first-order by the critical Rayleigh number. By tracking passive tracers in the fluid phase, we show that the alcoves are shaped by the detachment of the boundary layer flow and the appearance of a pinned vortex at the leading edge of the indentations. The attached boundary layer past the developing alcove is then found to lead to rounding of the other sides and the gradual sloping of the floor.

58 GEOSCIENCES↗

Tantalum-stabilized ruthenium oxide electrocatalysts for industrial water electrolysis

The iridium oxide (IrO 2 ) catalyst for the oxygen evolution reaction used industrially (in proton exchange membrane water electrolyzers) is scarce and costly. Although ruthenium oxide (RuO 2 ) is a promising alternative, its poor stability has hindered practical application. Here, we used well-defined extended surface models to identify that RuO 2 undergoes structure-dependent corrosion that causes Ru dissolution. Tantalum (Ta) doping effectively stabilized RuO 2 against such corrosion and enhanced the intrinsic activity of RuO 2 . In an industrial demonstration, Ta-RuO 2 electrocatalyst exhibited stability near that of IrO 2 and had a performance decay rate of ~14 microvolts per hour in a 2800-hour test. At current densities of 1 ampere per square centimeter, it had an overpotential 330 millivolts less than that of IrO 2 .

Zhang, Jiahao [Sichuan Univ., Chengdu (China); Uni↗

Data for Catalyst and Reactor Design Considerations for Selective Production of Acids by Oxidative Cleavage of Alkenes with H2O2

Oxidative cleavage of alkenes and unsaturated fatty acids with hydrogen peroxide gives an efficient and sustainable process to obtain mono- and di-acids for polymers and lubricants with fewer safety risks and less environmental impact than processes that utilize ozone or other inorganic oxidizers (e.g., permanganate, dichromate, etc.). Guided by insight into the mechanisms for competing reaction pathways (i.e., epoxidation of alkene on W–(η2-O2) complexes vs. H2O2 decomposition) and the apparent kinetics derived from kinetic experiments, here, we postulate that W-based heterogeneous catalysts can provide high performance and stable operations at low H2O2 concentrations. Semi-batch reactors with continuous introduction of H2O2 solutions offer the means to maintain low H2O2 concentrations while providing sufficient quantities of H2O2 to satisfy the reaction stoichiometry. We derived simple kinetic model equations for the epoxidation, ring-opening, oxidative cleavage, and oxidation steps and fit theses equations to batch experimental data to obtain kinetic parameters. This kinetic model describes the concentration profiles of reactant, oxidant, and products well as shown by agreement with experimental data. Further predictions of the optimal H2O2 feed rate for semi-batch operation utilized by the proposed rate expressions and the reactor design equations suggest that low H2O2 feed rate increases selectivity towards oxidative cleavage products and selective use of H2O2 for oxidative cleavage pathway. Comparisons of oxidative cleavage of 4-octene in batch and semi-batch reactors show that semi-batch reactors with optimized molar feed rates of H2O2 increased oxidative cleavage product selectivities (76% to 99%; with an increase in butyric acid selectivity from 1% to 55%) and H2O2 selectivity (3% to 30%). In addition, semi-batch reaction conditions used avoid H2O2-mediated dissolution of W-atoms from the catalyst. Analysis of these findings suggest that solid oxide catalysts will be effective for continuous oxidative cleavage reactions if deployed within fixed-bed reactors that allow for distributed introduction of reactants and therefore low in situ concentrations of H2O2.

Catalysis↗

Understanding the Importance of Labile Fe(III) during Fe(II)-Catalyzed Transformation of Metastable Iron Oxyhydroxides

Transformation of metastable Fe(III) oxyhydroxides is a prominent process in natural environments and can be significantly accelerated by the coexisting aqueous Fe(II) (Fe(II) aq ). Recent evidence points to the solution mass transfer of labile Fe(III) (Fe(III) labile ) as the primary intermediate species of general importance. However, a mechanistic aspect that remains unclear is the dependence of phase outcomes on the identity of the metastable Fe(III) oxyhydroxide precursor. Here, we compared the coupled evolution of Fe(II) species, solid phases, and Fe(III) labile throughout the Fe(II)-catalyzed transformation of lepidocrocite (Lp) versus ferrihydrite (Fh) at equal Fe(III) mass loadings with 0.2–1.0 mM Fe(II) aq at pH = 7.0. Similar to Fh, the conversion of Lp to product phases occurs by a dissolution–reprecipitation mechanism mediated by Fe(III) labile that seeds the nucleation of products. Though for Fh we observed a transformation to goethite (Gt), accompanied by the transient emergence and decline of Lp, for initial Lp we observed magnetite (Mt) as the main product. Further, a linear correlation between the formation rate of Mt and the effective supersaturation in terms of Fe(III) labile concentration shows that Fe(II)-induced transformation of Lp into Mt is governed by the classical nucleation theory. When Lp is replaced by equimolar Gt, Mt formation is suppressed by opening a lower barrier pathway to Gt by heterogeneous nucleation and growth on the added Gt seeds. The collective findings add to the mechanistic understanding of factors governing phase selections that impact iron bioavailability, system redox potential, and the fate and transport of coupled elements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evaluation of Ammonia Discharge into PUREX Crib 216-A-37-1 and Nitrogen Species Fate in the Subsurface

Based on published data, this report identifies potential fate and transport mechanisms for the ammonium hydroxide condensate that was discharged to 216-A-37-1 Crib from Hanford fuel rod decladding before PUREX dissolution and separation operations. Crib 216-A-37-1 received 377 million liters of alkaline condensate discharged from March 1977 through April 1989. The following major processes were identified as controlling the ammonia (NH 3 ) fate and transport: 1. Liquid migration rates through the vadose zone 2. NH 3 microbial oxidation to nitrite and nitrate 3. Ammonia species [NH4 + , NH 3 (aq)] sorption to sediments 4. NH3 precipitation reactions after pH buffering occurs in sediments The travel time through the vadose zone was estimated to be 2.5 to 9 months during periods of high subsurface discharge rates. These travel times are based on tritium migration through the vadose zone, a co-contaminant also discharged to the 216-A-37-1 crib.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Sticky roots--implications of widespread, cryptic, viral infection of plants in natural and managed ecosystems for soil carbon processing in the rhizosphere

Plants strongly influence soil properties through rhizodeposition, in which exudates diffuse from roots, additional secretions are actively released, and root cells are sloughed into the soil. This contribution by plants of carbon compounds belowground is at the core of soil health, water holding capacity, and the soil carbon storage that pulls carbon dioxide out of the atmosphere. Once in soil, organic matter can bind with minerals such as iron hydroxides, where it can be protected from microbial attack for millenia, preserving very large terrestrial soil carbon pools. However, those same compounds contributed by roots to soil may also destabilize the long-term protective associations of SOM with minerals, making that soil organic matter (SOM) more vulnerable to microbial attack and decomposition. Plant roots thus influence both the buildup and breakdown of soil carbon pools. DOE’s E3SM Land Model (ELM) includes a representation of soil carbon storage on minerals, but the potential vulnerability of SOM–mineral associations to effects of rhizodeposition is not yet represented in ELM. To begin testing for this effect of rhizodeposition on soil carbon storage and decomposition, we worked to develop a novel approach during this TES Exploratory project DE-SC0019142 – we harnessed the power of plant viral infection. We examined whether plant virus infection can serve as a tool to intensify rhizodeposition at the root surface, and therefore possibly intensify mobilization of SOM from minerals making it visible to our analytical techniques. Viral infection is widespread in terrestrial ecosystems; 25-70% of plants have virus infection, yet the influence of such infection on root traits and terrestrial soil carbon dynamics remains largely unexplored. We used two plant hosts: the annual Avena sativa (oats) and the genetically tractable, model grass Brachypodium distachyon. These grasses were infected with the broad host range virus Barley Yellow Dwarf Virus (BYDV) via aphids (Rhopalosiphum padi). BYDV infects at least 150 grass species in agricultural and natural ecosystems, and in previous experiments, oats infected with BYDV had roots that were very sticky to the touch, strongly suggesting that infection altered rhizodeposition. We developed this new experimental approach mostly in a one virus (Barley Yellow Dwarf Virus)–one plant (Avena sativa) system. (Several effects of infection in a Brachypodium-BYDV system were similar in nature to effects on Avena sativa, but were more variable.) In the BYDV-Avena system, we developed protocols for consistently infecting target plants (and avoiding infection of control plants) using aphid caging on leaves. We measured that infected plants exhibited reduced photosynthesis, plant (including root) biomass, and root:shoot ratio, as well as simplified root system architecture. We established procedures for sampling the organic compounds carried specifically in phloem (vascular tissue) of leaves and roots, using aphid stylectomy. We used FTICR-MS, Orbitrap GC-MS, and LC-MS/MS to analyze organic compounds in phloem, liquid around roots of plants grown hydroponically, and pore water around roots in soil, and found differences in the compounds in solution bathing roots when infected and uninfected plants were grown hydroponically. Finally, we synthesized isotopically-labeled mineral–organic matter (MAOM) associations in the lab and developed assays using them in solution and in soil. Assays quantified the extent and rate of mineralization of labeled MAOM that was mobilized by functionally distinct rhizodeposits and then attacked by microbes. Two mechanisms for MAOM mobilization emerged, with distinct dynamics. During “direct” mobilization, rhizodeposits such as the strong ligand oxalic acid could drive rapid dissolution of minerals, mobilizing MAOM. During “indirect” mobilization, rhizodeposits such as the simple sugar glucose did not attack minerals directly but instead intensified microbial activity, which led to mobilization via changes in e.g. pH, Eh, and microbial metabolite production (Li et al. 2021). Mechanistic understanding derived from these data and our ongoing experiments using these techniques will inform future development of ELM. Plant roots not only contribute newly fixed organic compounds to soils, but also root activities can drive mineralization of the carbon and nutrients mobilized off minerals via “indirect” or “direct” mechanisms. Using viral infection as a new tool, ongoing combined experimentation and modeling will explore the strength and larger-scale significance of the cascade of processes from rhizodeposition to MAOM mobilization for soil carbon storage and nutrient cycling in terrestrial ecosystems. And if viral infection leads quite generally to “sticky roots”, our perception of the potential importance of prevalent virus infection in terrestrial landscapes will be transformed.

54 ENVIRONMENTAL SCIENCES↗

Modeling CO 2 -Brine-Rock Interaction Including Mercury and H 2 S Impurities in the Context of CO 2 Geologic Storage

This study uses modeling and simulation approaches to investigate the impacts on injectivity of trace amounts of mercury (Hg) in a carbon dioxide (CO 2 ) stream injected for geologic carbon sequestration in a sandstone reservoir at ~2.5 km depth. At the range of Hg concentrations expected (7-190 ppbV, or ~ 0.06-1.6 mg/std.m 3 CO 2 ), the total volumetric plugging that could occur due to complete condensation of Hg, or due to complete precipitation of Hg as cinnabar, results in a very small porosity change. In addition, Hg concentration much higher than the concentrations considered here would be required for Hg condensation to even occur. Concentration of aqueous Hg by water evaporation into CO 2 is also unlikely because the higher volatility of Hg relative to H 2 O at reservoir conditions prevents the Hg concentration from increasing in groundwater as dry CO 2 sweeps through, volatilizing both H 2 O and Hg. Using a model-derived aqueous solution to represent the formation water, batch reactive geochemical modeling show that the reaction of the formation water with the CO 2 -Hg mixture causes the pH to drop to about 4.7 and then become buffered near 5.2 upon reaction with the sediments, with a negligible net volume change from mineral dissolution and precipitation. Cinnabar (HgS(s)) is found to be thermodynamically stable as soon as the Hg-bearing CO 2 reacts with the formation water which contains small amounts of dissolved sulfide. Liquid mercury (Hg(l)) is not found to be thermodynamically stable at any point during the simulation. Two-dimensional radial reactive transport simulations of CO 2 injection at a rate of 14.8 kg/s into a 400 m-thick formation at isothermal conditions of 106°C and average pressure near 215 bar, with varying amounts of Hg and H 2 S trace gases, show generally that porosity changes only by about ±0.05% (absolute, i.e., new porosity = initial porosity ±0.0005) with Hg predicted to readily precipitate from the CO 2 as cinnabar in a zone mostly matching the single-phase CO 2 plume. The precipitation of minerals other than cinnabar, however, dominates the evolution of porosity. Main reactions include the replacement of primarily Fe-chlorite by siderite, of calcite by dolomite, and of K-feldspar by muscovite. Chalcedony is also predicted to precipitate from the dissolution of feldspars and quartz. Although the range of predicted porosity change is quite small, the amount of dissolution and precipitation predicted for these individual minerals is not negligible. These reactive transport simulations assume that Hg gas behaves ideally. To examine effects of non-ideality on these simulations, approximate calculations of the fugacity coefficient of Hg in CO 2 were made. Results suggest that Hg condensation could be significantly overestimated when assuming ideal gas behavior, making our simulation results conservative with respect to impacts on injectivity. The effect of pressure on Henry’s constant for Hg is estimated to yield Hg solubilities about 10% lower than when this effect is not considered, a change that is considered too small to affect the conclusions of this report. Although all results in this study are based on relatively mature data and modeling approaches, in the absence of experimental data and more detailed site-specific information, it is not possible to fully validate the results and conclusions.

54 ENVIRONMENTAL SCIENCES↗

Effect of HCO 3 - on electrochemical kinetics of carbon steel corrosion in CO 2 -saturated brines

The effect of HCO 3 – (aq) on CO 2 corrosion of carbon steel was investigated in deaerated 3.5 wt% NaCl solutions at 30 °C from pH 3.96 to 7.15. In the CO 2 -saturated solutions, the pH was adjusted with different HCO 3 – (aq) concentrations, c[HCO 3 – (aq)]. The corrosion rate decreased by a factor of 2 as the pH and c[HCO 3 – (aq)] increased. The cathodic current density during polarization increased at higher pH with higher c[HCO 3 – (aq)], indicating that HCO 3 – (aq) acted as an additional hydrogen source for the hydrogen evolution reaction. As the pH increased, the active dissolution regions displayed similar anodic Tafel slopes and suggested a modified Bockris mechanism for the Fe oxidation reaction. The exchange current densities for the half reactions were calculated to study kinetics of the anodic and cathodic half reactions independently. The anodic exchange current density ( j 0,a ) increased by one order of magnitude in the presence of CO 2 , indicating the involvement of CO 2 (aq) in the Fe oxidation reaction. As the pH and c[HCO 3 – (aq)] increased, the cathodic exchange current density ( j 0,c ) decreased by a factor of 50 because the increase in j 0,c [HCO 3 – (aq)] was not high enough to compensate the decline from the other hydrogen sources, especially j 0,c [H + (aq)]; and j 0,a decreased by a factor of 2.4 because HCO 3 – (aq) may have competed with CO 2 (aq) for the surface coverage and the increase in j 0,a [CO 2 (aq)] could not compensate the decrease in j 0,a [CO 2 (aq)]. It suggests that the reaction rate constant of HCO 3 – (aq) was smaller than CO 2 (aq) for the anodic half reaction and was smaller than H + (aq) for the cathodic half reaction. The XPS results verified that the corrosion products transitioned from iron carbonate to hydroxide as the pH increased while iron carbonate remained the major product. As the pH increased with HCO 3 – (aq), a second time constant was observed at lower frequencies of the electrochemical impedance spectroscopy (EIS) results.

36 MATERIALS SCIENCE↗

Efficient sulfur host based on NiCo{sub 2}O{sub 4} hollow microtubes for advanced Li-S batteries

High energy density and cost effectiveness make lithium-sulfur battery a promising candidate for next-generation electrochemical energy storage technology. Here, we have synthesized a highly efficient sulfur host namely NiCo{sub 2}O{sub 4} hollow microtubes/sulfur composite (NiCo{sub 2}O{sub 4}/S). The hollow interior cavity providing structural integrity while sufficient self-functionalized surfaces of NiCo{sub 2}O{sub 4} chemically bind polysulfides to prevent their dissolution in the organic electrolyte. When used in lithium-sulfur batteries, the synthesized NiCo{sub 2}O{sub 4}/S cathode delivers high specific capacity (1274 mAh g{sup −1} at 0.2 C), long cycling performance at 0.5 C, and good rate capability at high current rates. - Highlights: • Hollow NiCo{sub 2}O{sub 4}/S microtubes were evaluated as an efficient sulfur host. • The designed 1D hollow architecture resulted in better cycling performance. • NiCo{sub 2}O{sub 4}/S delivered high capacity, long cycle life and good rate capability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Analysis of Monolith Cores from an Engineering Scale Demonstration of a Prospective Cast Stone Process

The primary disposition path of Low Activity Waste (LAW) at the DOE Hanford Site is vitrification. A cementitious waste form is one of the alternatives being considered for the supplemental immobilization of the LAW that will not be treated by the primary vitrification facility. Washington River Protection Solutions (WRPS) has been directed to generate and collect data on cementitious or pozzolanic waste forms such as Cast Stone. This report documents the coring and leach testing of monolithic samples cored from an engineering-scale demonstration (ES Demo) with non-radioactive simulants. The ES Demo was performed at SRNL in October of 2013 using the Scaled Continuous Processing Facility (SCPF) to fill an 8.5 ft. diameter x 3.25 ft. high container with simulated Cast Stone grout. The Cast Stone formulation was chosen from the previous screening tests. Legacy salt solution from previous Hanford salt waste testing was adjusted to correspond to the average LAW composition generated from the Hanford Tank Waste Operation Simulator (HTWOS). The dry blend materials, ordinary portland cement (OPC), Class F fly ash, and ground granulated blast furnace slag (GGBFS or BFS), were obtained from Lafarge North America in Pasco, WA. In 2014 core samples originally obtained approximately six months after filling the ES Demo were tested along with bench scale molded samples that were collected during the original pour. A latter set of core samples were obtained in late March of 2015, eighteen months after completion of the original ES Demo. Core samples were obtained using a 2” diameter x 11” long coring bit. The ES Demo was sampled in three different regions consisting of an outer ring, a middle ring and an inner core zone. Cores from these three lateral zones were further segregated into upper, middle and lower vertical segments. Monolithic core samples were tested using the Environmental Protection Agency (EPA) Method 1315, which is designed to provide mass transfer rates (release rates) of inorganic analytes contained in monolithic material under diffusion controlled release conditions as a function of leaching time. Compressive strength measurements and drying tests were also performed on the 2015 samples. Leachability indices reported are based on analyte concentrations determined from dissolution of the dried samples.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Characterization of a fluvial aquifer at a range of depths and scales: the Triassic St Bees Sandstone Formation, Cumbria, UK

Fluvial sedimentary successions represent porous media that host groundwater and geothermal resources. Additionally, they overlie crystalline rocks hosting nuclear waste repositories in rift settings. The permeability characteristics of an arenaceous fluvial succession, the Triassic St Bees Sandstone Formation in England (UK), are described, from core-plug to well-test scale up to ~1 km depth. Within such lithified successions, dissolution associated with the circulation of meteoric water results in increased permeability (K~10{sup −1}–10{sup 0} m/day) to depths of at least 150 m below ground level (BGL) in aquifer systems that are subject to rapid groundwater circulation. Thus, contaminant transport is likely to occur at relatively high rates. In a deeper investigation (> 150 m depth), where the aquifer has not been subjected to rapid groundwater circulation, well-test-scale hydraulic conductivity is lower, decreasing from K~10{sup −2} m/day at 150–400 m BGL to 10{sup −3} m/day down-dip at ~1 km BGL, where the pore fluid is hypersaline. Here, pore-scale permeability becomes progressively dominant with increasing lithostatic load. Notably, this work investigates a sandstone aquifer of fluvial origin at investigation depths consistent with highly enthalpy geothermal reservoirs (~0.7–1.1 km). At such depths, intergranular flow dominates in unfaulted areas with only minor contribution by bedding plane fractures. However, extensional faults represent preferential flow pathways, due to presence of high connective open fractures. Therefore, such faults may (1) drive nuclear waste contaminants towards the highly permeable shallow (< 150 m BGL) zone of the aquifer, and (2) influence fluid recovery in geothermal fields.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Effects of citrate on hexavalent chromium reduction by structural Fe(II) in nontronite

Iron-bearing clay minerals and organic matter are two important components in natural environments that influence hexavalent chromium (Cr(VI)) reduction. Previous studies have shown that organic ligands could influence Cr(VI) reduction by aqueous Fe2+ and pyrite. However, the effects of organic ligands on Cr(VI) reduction by structural Fe(II) in clays are not well understood. In this study, the effects of citrate on Cr(VI) reduction by nontronite (NAu-2) were investigated under near neutral pH condition (pH=6). Our results showed that the presence of citrate decreased the rate but increased the amount of Cr(VI) reduction by structural Fe(II) in NAu-2. The decreased reaction rate was likely due to competitive sorption of citrate and polyanionic dichromate (Cr2O7- ), because sorption of dichromate appeared to be the first step for subsequent Cr(VI) reduction. The increased amount of Cr(VI) reduction in the presence of citrate was likely because citrate provided additional reducing power through ligand-metal electron transfer in the presence of soluble Fe 3+ derived from dissolution of reduced NAu-2. Soluble Cr(III)-citrate complex was the possible form of reduced chromium when citrate was present. In contrast, nanometer-sized Cr2O3 particles were the product of Cr(VI) reduction by reduced NAu-2 without citrate. Our study highlights the importance of organic ligands on Cr(VI) reduction and immobilization when iron-bearing clay minerals are applied to treat Cr(VI) contaminant in organic matter rich environments.

Environmental Molecular Sciences Laboratory↗