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Low temperature dissolution flowsheet for plutonium metal

The H-Canyon flowsheet used to dissolve Pu metal for PuO 2 production utilizes boiling HNO 3 . SRNL was requested to develop a complementary dissolution flowsheet at two reduced temperature ranges. The dissolution and H 2 generation rates of Pu metal were investigated using a dissolving solution at ambient temperature (20-30 °C) and for an intermediate temperature of 50-60 °C. Additionally, the testing included an investigation of the dissolution rates and characterization of the off-gas generated from the ambient temperature dissolution of carbon steel cans and the nylon bags that contain the Pu metal when charged to the dissolver.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Progress on Plant-Level Modeling and Simulation of Used Nuclear Fuel Dissolution: Startup Condition with Quasi-Developed Flow and Varying Acid Concentration

An update to a previous report is presented here describing the startup condition of a continuous dissolver. The need for a careful implementation of a startup condition is twofold. First, by varing the used fuel composition and various other parameters of the model, it becomes difficult to solve the governing equations accurately or to obtain a converged solution for an arbitrary initial condition. This is evident when coupling the dissolver module with a third-party user simulator. The second impetus for improving the modeling of the startup process is that an improved realism is obtained and the model is more complete and useful for accounting material balances rigorously. The aforementioned previous report on this dissolver module is a required reading for the understanding of this update.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

The Influence of Microbial Priming Effects on the Hydro-bio-geochemistry of Large River Reservoirs

River-tributary confluences, where diverse organic matter (OM) sources mix, are considered aquatic critical zones for biogeochemical cycling. Here we evaluate dissolved OM composition and bioavailability in the mainstem of the Columbia River and three of its tributaries (Snake, Yakima, and Walla Walla rivers) along a hydrologic gradient in the Columbia River drainage basin using a variety of bulk and molecular level measurements. Field replicates and mixtures representing river-tributary confluences were incubated in the dark for 15 days to investigate the response of the microbial community to varying OM quantity/composition. The Columbia, Snake, and Yakima rivers did not differ in dissolved organic carbon (DOC), fluorescent dissolved OM (fDOM), or Chlorophyll-a (Chl-a) concentrations. However, the Walla Walla River had significantly greater DOC, fDOM, and Chl-a concentrations, indicative of greater contributions from algal DOM. FT-ICR-MS spectra for Walla Walla had significantly more peaks corresponding to amino sugars, carbohydrates and proteins while the Columbia River had more peaks for lignin, unsaturated hydrocarbons, and condensed aromatics. When incubated for 15 days in the dark, total DOC did not decrease for any of the river samples. DOC did decrease, however, in a mix representing the confluence of the Columbia and Walla Walla rivers, suggesting the microbial consortia of the Columbia River were primed by the Walla Walla River OM. OM composition was significantly different for several compound classes (e.g., lignin, protein, and tannin) following the incubations of unmixed river and tributary samples. However, the microbial community in the Walla Walla-Columbia mixture appeared to be indiscriminate of the molecular structure of the DOM as the compound class distribution did not change significantly. This provides preliminary evidence that the heterotrophs in river-tributary critical zones remineralize diverse OM structures.

54 ENVIRONMENTAL SCIENCES↗

Hydroelectric Power and Hydrogen Production Integration

Hydropower-based hydrogen production could introduce opportunities for new revenue streams for hydropower plants, including from energy storage and regeneration as well as from sale of the hydrogen product to external markets. Hydrogen-based energy storage and regeneration could also help support Idaho Power’s decarbonization goals by decreasing dependence on fossil-based peaking power plants. Additionally, integration of hydrogen production with hydropower generation could help address the issue of low dissolved oxygen river water conditions that commonly accompany hydropower plant operations by utilizing the oxygen byproduct from an electrolytic hydrogen production process as a resource for mitigation of low dissolved oxygen water conditions. Comprehensive techno-economic analysis of the hybrid hydroelectric and hydrogen energy storage system has revealed critical insights into the pathways and considerations for optimizing the economic value and environmental benefits of such systems. Among the three identified pathways of natural gas blending, regeneration, and direct sale of hydrogen, the direct sale of hydrogen emerges as the most profitable, particularly given the current pricing dynamics of hydrogen and electricity. However, as we anticipate a future grid characterized by higher renewable energy penetration, the landscape may evolve, featuring lower average electricity prices, heightened fluctuations, and more significant seasonal variations. Consequently, the attractiveness of electricity regeneration through hydrogen and the benefits of long-duration hydrogen storage are expected to increase substantially in such a dynamic energy scenario. The careful selection of component sizes within the hybrid system proves to be paramount for ensuring cost-effectiveness. Notably, the size of the hydrogen market has emerged as a critical determinant for the optimal size of the electrolyzer. Hydrogen storage should be sized to meet energy shifting requirements. The appropriate size of the fuel cell/microturbine generator hinges on the shape of electricity prices and the available revenue streams derived from participating in grid services. Striking the right balance among these components is essential for maximizing the overall efficiency and profitability of the hydrogen facility. Furthermore, the by-product of electrolysis, namely oxygen, introduces an additional dimension to the system's functionality. The oxygen generated can be effectively utilized for dissolved oxygen (DO) mitigation, particularly with larger electrolyzer sizes capable of satisfying the complete oxygen demand for this purpose. While the economic benefits derived from saved oxygen purchase costs may be relatively modest compared to other revenue streams, the environmental advantages of repurposing oxygen for DO mitigation could help Idaho Power meet their environmental obligations. In addition to the identified factors shaping the viability of hybrid hydrogen production and hydroelectric generation, it is noteworthy that the integration of hydrogen energy storage offers a unique advantage during unusually wet years. In such periods of increased water inflow, the hydrogen storage capacity serves as a valuable supplement to the reservoir. By utilizing hydrogen energy storage as a complementary reservoir, the system gains flexibility in reservoir management when dealing with fluctuations in water availability.

08 HYDROGEN↗

UT-GOM2-2 Preliminary Report: Terrebonne Basin Northern Gulf of Mexico, 30 July-28 September 2023

In the summer and fall of 2023, the Gulf of Mexico Deepwater Hydrate Coring Expedition (UT-GOM2-2) drilled, cored, made downhole measurements, and analyzed samples from the seafloor to the base of the gas hydrate stability zone in one location (Site H, WR313) in the Terrebonne basin, deepwater Gulf of Mexico. Analyses of data and samples from the expedition will inform biological, geochemical, and geomechanical models to constrain the role of gas hydrates in the carbon cycle and the potential for gas hydrates as an energy resource. Pressure and conventional cores were collected continuously to a depth of 155.1 meters below the seafloor (mbsf). At deeper depths, cores were taken periodically from hydrate-bearing sands and their bounding muds to a total depth of 861.3 mbsf. 162.6 m of conventional core and 54.8 m of pressure core were obtained. Twelve temperature measurements were made between 27.1 and 144.5 mbsf to determine the geothermal gradient. At the seafloor, more than 4 m of sandy silt of unknown origin was encountered. Beneath this sand, to a depth of ~200 mbsf, the section was composed of interbedded mud and biogenic carbonate ooze. The biogenic ooze correlated to low density and high porosity intervals observed in the previously acquired logging while drilling (LWD) data and as measured. Calcareous nannofossil biostratigraphy constrains the entire record to the Pleistocene (< 0.91 million years) with a pronounced increase in sedimentation rate with depth. Beneath 200 mbsf, the section was predominantly composed of mud with two thicker, hydrate-bearing coarse-grained intervals, which are commonly known as the Blue and Orange sands. The dissolved gas concentration was quantified from pressure cores. In the shallow section, dissolved methane concentration increased below the sulfate-methane transition zone (SMTZ) and reaches saturation (the limit of solubility for methane) at 147 mbsf. Gas expansion was very common in conventional and depressurized pressure (conventionalized) cores below the SMTZ. At deeper depths, the methane concentration within muds bounding the Blue and Orange reservoirs was generally found to be less than saturation. The dissolved and hydrate gas composition is consistent with a microbial source, containing greater than 99.99% methane and only trace concentrations of ethane, propane, and butane. The methane to ethane ratio (C 1 /C 2 ) and the methane to ethane plus propane (C 1 /(C 2 +C 3 )) decrease with depth down to at least 678 mbsf, mainly driven by the increase in ethane with depth. It is unclear if this trend continues through the Orange sand interval. The δ 13 C isotopic signature of methane ranges between -69.9 and -78.5 ‰ Vienna Pee Dee Belemnite (VPDB). Pressure core recovery of all sandy intervals was poor. However, pressure core logs of the Orange sand show intervals of low density and high velocity, which are indicative of high hydrate saturation. One core from within the Orange sand was composed of interbedded graded sandy silt and mud. The sandy silts from this core are composed of mainly quartz and feldspar with some lithics. Most of the recovered pressure core samples are maintained at near in-situ pressure and temperature (within the hydrate stability field) at the University of Texas Pressure Core Center awaiting analysis. In the shallow section, samples will be used to determine the flux of organic carbon through the basin system, find the rate at which that carbon was consumed, and understand the microbial population responsible for these processes. In the deeper section, samples from in and around the hydrate reservoirs will be used to determine the petrophysical properties of the reservoir and bounding seals in these systems.

03 NATURAL GAS↗

Modeling Functional Organic Chemistry in Arctic Rivers: An Idealized Siberian System

Rivers of the Arctic will become ever more important for the global climate, since they carry a majority of continental dissolved organic carbon flux into the rapidly changing polar ocean. Aqueous organics comprise a wide array of functional groups, several of which are likely to impact coastal and open water biophysical properties. Light attenuation, interfacial films, aerosol formation, gas release and momentum exchange can all be cited. We performed Lagrangian kinetic modeling for the evolution of riverine organic chemistry as the molecules in question make their way from the highlands to Arctic outlets. Classes as diverse as the proteins, sugars, lipids, re-condensates, humics, bio-tracers and small volatiles are all included. Our reduced framework constitutes an idealized northward flow driving a major hydrological discharge rate and primarily representing the Russian Lena. Mountainous, high solute and tundra sources are all simulated, and they meet up at several points between soil and delta process reactors. Turnover rates are parameterized beginning with extrapolated coastal values imposed along a limited tributary network, with connections between different terrestrial sub-ecologies. Temporal variation of our total dissolved matter most closely resembles the observations when we focus on the restricted removal and low initial carbon loads, suggesting relatively slow transformation along the water course. Thus, channel combinations and mixing must play a dominant role. Nevertheless, microbial and photochemical losses help determine the final concentrations for most species. Chemical evolution is distinct for the various functionalities, with special contributions from pre- and post-reactivity in soil and delta waters. Several functions are combined linearly to represent the collective chromophoric dissolved matter, characterized here by its absorption. Tributaries carry the signature of lignin phenols to segregate tundra versus taiga sources, and special attention is paid to the early then marine behaviors of low molecular weight volatiles. Heteropolycondensates comprise the largest percentage of reactive carbon in our simulations due to recombination/accumulation, and they tend to be preeminent at the mouth. Outlet concentrations of individual structures such as amino acids and absorbers lie above threshold values for biophysical influence, on the monolayer and light attenuation. The extent of coastal spreading is examined through targeted regional box modeling, relying on salinity and color for calibration. In some cases, plumes reach the scale of peripheral arctic seas, and amplification is expected during upcoming decades. Conclusions are mapped from the Lena to other boreal discharges, and future research questions are outlined regarding the bonding type versus mass release as permafrost degrades. Dynamic aqueous organic coupling is recommended for polar system models, from headwaters to coastal diluent.

54 ENVIRONMENTAL SCIENCES↗

Impacts of Hurricane Disturbance on Water Quality across the Aquatic Continuum of a Blackwater River to Estuary Complex

Hurricanes cause landscape-scale disturbances that affect biogeochemical cycling and water quality in coastal ecosystems. During Hurricane Irma’s passage through northern Florida, water movements driven by wind velocities up to 105 km h-1 caused a salinity peak in an estuary/blackwater river complex. Water quality was monitored across the 15 km site to detect the magnitude and duration of disturbance. Saline water intruded 15 km inland into a freshwater portion of the river that peaked at a salinity of 2 psu. Due to the volume of precipitation from the hurricane, significant runoff of freshwater and dissolved organic matter (DOM) caused a decrease in salinity, dissolved oxygen (DO), and Chlorophyll-a concentrations while increasing turbidity and fluorescent dissolved organic matter (fDOM). The disturbance caused rapid changes observed by in-situ water quality monitors over a 3-week period, but some effects persisted for longer periods as shown by 3-month weekly water sampling. This disturbance caused shifts in DOM loading, altered salinity dynamics, and reshaped landscapes due to wind and wave surge both in upland marsh and downstream estuary. Hurricane disturbance temporarily and abruptly alters the aquatic continuum, and observations of system response can help us understand the mechanisms associated with ecosystem resilience and recovery.

54 ENVIRONMENTAL SCIENCES↗

National Brackish Groundwater Assessment 2017

Brackish groundwater (BGW), defined for this assessment as having a dissolved-solids concentration between 1,000 and 10,000 milligrams per liter, is an unconventional source of water that may offer a partial solution to current (2016) and future water challenges. In support of the National Water Census, the U.S. Geological Survey has completed a BGW assessment to gain a better understanding of the occurrence and characteristics of BGW resources of the United States as an alternative source of water. Analyses completed as part of this assessment relied on previously collected data from multiple sources, and no new data were collected. One of the most important contributions of this assessment was the creation of a database containing chemical data and aquifer information for the known quantities of BGW in the United States. Data were compiled from single publications to large datasets and from local studies to national assessments, and includes chemical data on the concentrations of dissolved solids, major ions, trace elements, nutrients, radionuclides, and physical properties of the resource (pH, temperature, specific conductance). This database represents data from a compilation of water-quality samples from 100,000+ (major-ions data) to 300,000+ (dissolved-solids data) groundwater wells across the continental U.S., Alaska, Hawaii, Puerto Rico, the U.S. Virgin Islands, Guam, and American Samoa. The data are published here as an ESRI geodatabase with a point feature class and associated attribute table, and also as non-proprietary comma-separated value table. It was not possible to compile all data available for the Nation, and data selected for this investigation were mostly limited to larger datasets that were available in a digital format.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Silver Electrolysis for Disinfection of Spacecraft Potable Water: 2023 Update

Anodic dissolution of silver electrodes, or “silver electrolysis,” is being investigated as a means of introducing biocidal silver into potable water on exploration spacecraft. Last year’s paper reported a fault condition termed “electrode bridging,” in which silver deposits on interelectrode wetted materials, eventually bridging the electrode gap and providing an alternate conduction pathway that diminishes the silver output of the reactor. Since then, two strategies have been developed that prevent this fault from occurring: 1) increasing the frequency of polarity reversal and 2) separating the active surface of the electrode from the interelectrode wetted material. These strategies were tested independently, and in both cases, the reactor performed as expected with no occurrence of bridging for at least one crew-year equivalent of cumulative operation. Additional tests were conducted at varying levels of influent dissolved oxygen to better understand the nature of the cathode reaction and its impact on reactor performance. Results indicate that the primary cathode reaction is the reduction of dissolved oxygen, which could imply a dependence of reactor performance on dissolved oxygen concentration. However, it was found that at the typical oxygen concentrations anticipated for spacecraft processed water, the impact on silver electrolysis performance was negligible. Finally, multiphysics modelling of the reactor fluid mechanics and electrochemistry was undertaken to provide the capability to optimize the design of a future reactor prototype.

silver electrolysis↗

Silver Electrolysis for Disinfection of Spacecraft Potable Water: 2023 Update

Anodic dissolution of silver electrodes, or “silver electrolysis,” is being investigated as a means of introducing biocidal silver into potable water on exploration spacecraft. Last year’s paper reported a fault condition termed “electrode bridging,” in which silver deposits on interelectrode wetted materials, eventually bridging the electrode gap and providing an alternate conduction pathway that diminishes the silver output of the reactor. Since then, two strategies have been developed that prevent this fault from occurring: 1) increasing the frequency of polarity reversal and 2) separating the active surface of the electrode from the interelectrode wetted material. These strategies were tested independently, and in both cases, the reactor performed as expected with no occurrence of bridging for at least one crew-year equivalent of cumulative operation. Additional tests were conducted at varying levels of influent dissolved oxygen to better understand the nature of the cathode reaction and its impact on reactor performance. Results indicate that the primary cathode reaction is the reduction of dissolved oxygen, which could imply a dependence of reactor performance on dissolved oxygen concentration. However, it was found that at the typical oxygen concentrations anticipated for spacecraft processed water, the impact on silver electrolysis performance was negligible. Finally, multiphysics modelling of the reactor fluid mechanics and electrochemistry was undertaken to provide the capability to optimize the design of a future reactor prototype.

silver electrolysis↗

Safe Dissolution of High Flux Isotope Reactor Cores

The H-Canyon facility at the Savannah River Site is the U.S.A.’s only remaining full- scale chemical separations plant. H-Canyon maintains the capacity to safely and efficiently disposition a large inventory of excess nuclear material from across the Department of Energy (DOE) complex and used nuclear fuel from foreign and domestic research reactors. One such fuel that H-Canyon may dissolve is cores from the High Flux Isotope Reactor (HFIR). By employing realistic analysis, the need for administrative controls was eliminated. A new criticality modeling approach has eliminated the need for administrative controls for HFIR dissolution operations in H-Canyon. The primary upsets of concern are an over-mass event and an overconcentration event. Several initiating events were considered for each type of upset. Over-concentration events were deemed to be not credible by taking credit for the chemistry of acid consumption, i.e. there are not enough moles of acid to dissolve enough moles of uranium in order to reach a critical configuration. Over-mass events were deemed to be not credible by taking credit for the annular design of the fuel elements. By using realistic analysis, both types of upsets have been shown to be subcritical, and therefore administrative controls are not needed to prevent an inadvertent criticality. In this paper, the new methodology for performing criticality analyses for dissolving HFIR fuel elements will be presented, and the elimination of administrative controls will be discussed.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Advanced dismantling techniques applied in an industrial project for the dismantling of highly activated equipment - 15446

Commissioned in 1958 on the CEA nuclear site of Marcoule (France) and shut down in 1997, the former UP1 plant was dedicated to reprocess the spent fuel from G1, G2 and G3 GCR reactors. Since 1998, a wide program for cleaning-up and dismantling the plant has been developed in order to dismantle the process equipment, eliminate any radiological risk in all buildings concerned and remove all the resulting waste. Major technical challenges are related to the wide range of complex components and equipment in the facilities such as chemical dissolvers, extractor batteries, evaporators, tanks; and to a high risk of exposure, due to the presence of fission products. To address these challenges, CEA led R and D programs to develop advanced tools for complex dismantling projects: immersive virtual reality, laser cutting techniques, special remote-controlled arms combining dexterity and high resistance to irradiation The purpose of this paper is to provide an overview of a practical implementation and to show first results of these advanced techniques on a real case: the dismantling of dissolver's equipment from the dissolution workshop of UP1 plant. ONET Technologies has been chosen by CEA to design, build and operate the overall dismantling and waste treatment system for this project. ONET Technologies designed two main subsystems to meet all the requirements for this project: first, the 'Remotely-Operated Handling and Cutting Unit' and second the 'Waste Extraction and Conditioning Unit' and the combining innovative technologies. During the design phase, the 'Immersive Virtual Reality' has been used to qualify the kinematics in the final environment and the preliminary dismantling scenario. Following a first R and D program of CEA regarding the laser cutting technique applied to nuclear decommissioning, ONET Technologies and CEA realized elementary inactive tests based on a 6 kW Nd-Yag laser source to qualify the cutting performance according to material and thickness. Main objective was to meet the safety criteria and to check the physical characteristics of waste resulting from the laser cutting operation. The Remotely-Operated Handling and Cutting Unit was equipped with a MAESTRO manipulator, resulting from ten years of research and development cooperation between CEA and Cybernetix. This manipulator, a 6 axis hydraulic manipulator-arm specifically designed to work in harsh environment, entered in its industrial phase. ONET Technologies was responsible for the overall system integration, confinement and performance. A comprehensive qualification program in real conditions has been driven during 2014. The dismantling scenario was tested with a mockup at a full scale of dissolver equipment and confirmed at this stage the expected level of performance and safety. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Surface and Active Layer Pore Water Chemistry from Ice Wedge Polygons, Utqiagvik (Barrow), Alaska, 2013-2014

This data set reports the results of spatial surveys of aqueous geochemistry conducted at Intensive Site 1 of the Barrow Environmental Observatory in 2013 and 2014 (Herndon et al., 2015). Surface water and soil pore water samples were collected from multiple depths within the tundra active layer of different microtopographic features (troughs, ridges, center) of a low-centered polygon (Area A), high-centered polygon (Area B), flat-centered polygon (Area C), and transitional polygon (Area D). Reported analytes include dissolved organic and inorganic carbon, dissolved carbon dioxide and methane, major inorganic anions, and major and minor cations. This dataset contains one csv file and one pdf file.The Next-Generation Ecosystem Experiments: Arctic (NGEE Arctic), was a research effort to reduce uncertainty in Earth System Models by developing a predictive understanding of carbon-rich Arctic ecosystems and feedbacks to climate. NGEE Arctic was supported by the Department of Energy's Office of Biological and Environmental Research.The NGEE Arctic project had two field research sites: 1) located within the Arctic polygonal tundra coastal region on the Barrow Environmental Observatory (BEO) and the North Slope near Utqiagvik (Barrow), Alaska and 2) multiple areas on the discontinuous permafrost region of the Seward Peninsula north of Nome, Alaska.Through observations, experiments, and synthesis with existing datasets, NGEE Arctic provided an enhanced knowledge base for multi-scale modeling and contributed to improved process representation at global pan-Arctic scales within the Department of Energy's Earth system Model (the Energy Exascale Earth System Model, or E3SM), and specifically within the E3SM Land Model component (ELM).

54 ENVIRONMENTAL SCIENCES↗

Numerical modeling of cold magmatic CO 2 flux measurements for the exploration of hidden geothermal systems

The most accepted conceptual model to explain surface degassing of cold magmatic CO 2 in volcanic-geothermal systems involves the presence of a gas reservoir. Here, numerical simulations using the TOUGH2-ECO2N V2.0 package are performed to get quantitative insights into how cold CO 2 soil flux measurements are related to reservoir and fluid properties. While the modeling is based on flux data measured at a specific geothermal site, the Acoculco caldera (Mexico), some general insights have been gained. Both the CO 2 fluxes at the surface and the depth at which CO 2 exsolves are highly sensitive to the dissolved CO 2 content of the deep fluid. If CO 2 mainly exsolves above the reservoir within a fracture zone, the surface CO 2 fluxes are not sensitive to the reservoir size but depend on the CO 2 dissolved content and the rock permeability. For gas exsolution below the top of the reservoir, surface CO 2 fluxes also depend on the gas saturation of the deep fluid as well as the reservoir size. The absence of thermal anomalies at the surface is mainly a consequence of the low enthalpy of CO 2 . The heat carried by CO 2 is efficiently cooled down by heat conduction and to a certain extent by isoenthalpic volume expansion depending on the temperature gradient. Thermal anomalies occur at higher CO 2 fluxes (>37,000 g m -2 d -1 ) when the heat flux of the rising CO 2 is not balanced anymore. Lastly, specific results are obtained for the Acoculco area (reservoir depth, CO 2 dissolved content, and gas saturation state).

58 GEOSCIENCES↗

Sources of methane to an Arctic lake in Alaska: An isotopic investigation

Sources of dissolved methane (CH 4 ) at Toolik Lake, Alaska, include both diffusion from lake sediments and groundwater entering the lake from its perimeter. Here we use hydrogen and oxygen isotopes in water (H 2 O), carbon and hydrogen isotopes in CH 4 , and carbon isotopes in dissolved inorganic carbon (DIC) to calculate the relative importance of lake sediment and groundwater discharge as sources of dissolved CH 4 to Toolik Lake. We also resolve the relative importance of the source contribution spatially within the lake and determine the processes controlling CH 4 concentrations in groundwater surrounding the lake. Our findings, from a mixing model based on isotopes in CH 4 , suggest that groundwater is a more important source of CH 4 at the perimeter of the lake where the water-to-air flux is high. In addition, we find on the local scale that high groundwater methane concentrations may be better linked to areas around the lake where rain is the dominant source of water to the active layer, indicating that changes in precipitation and active layer thaw depth will impact methane concentrations in the active layer and, ultimately, the groundwater associated flux to Toolik Lake.

54 ENVIRONMENTAL SCIENCES↗

Accelerated Characterization of Electrode‐Electrolyte Equilibration

Operational durability is poorly characterized by traditional (photo)electrocatalyst discovery workflows, creating a barrier to scale-up and deployment. Corrosion is a prominent degradation mechanism whose thermodynamics depend on the concentration of corrosion products in electrolyte. We present an automated system for characterizing the equilibration of (photo)electrodes with dissolved metals in electrolyte for a given electrode, pH, and electrochemical potential. Automation of electrode selection, electrolyte preparation, and electrolyte aliquoting enables rapid identification of self-passivating electrodes and estimation of the equilibrium dissolved metals concentrations. The technique is demonstrated for metal oxide photoanodes in alkaline electrolyte, where BiVO 4 is found to continually corrode, in agreement the literature. An amorphous Ni−Sb−O photoanode is found to passivate with a Ni-rich coating on the order of 1 monolayer with less than 1 μM total dissolved metals in electrolyte, demonstrating its suitability for durable photoelectrochemical operation. The automation and throughput of the instrument are designed for incorporation in accelerated electrocatalyst discovery workflows so that durability can be considered on equal footing with activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Temporal variations of methane concentration and isotopic composition in groundwater of the St. Lawrence Lowlands, eastern Canada

Dissolved methane concentrations in shallow groundwater are known to vary both spatially and temporally. The extent of these variations is poorly documented although this knowledge is critical for distinguishing natural fluctuations from anthropogenic impacts stemming from oil and gas activities. This issue was addressed as part of a groundwater research project aiming to assess the risk of shale gas development for groundwater quality over a 500-km{sup 2} area in the St. Lawrence Lowlands (Quebec, Canada). A specific study was carried out to define the natural variability of methane concentrations and carbon and hydrogen isotope ratios in groundwater, as dissolved methane is naturally ubiquitous in aquifers of this area. Monitoring was carried out over a period of up to 2.5 years in seven monitoring wells. Results showed that for a given well, using the same sampling depth and technique, methane concentrations can vary over time from 2.5 to 6 times relative to the lowest recorded value. Methane isotopic composition, which is a useful tool to distinguish gas origin, was found to be stable for most wells, but varied significantly over time in the two wells where methane concentrations are the lowest. The use of concentration ratios, as well as isotopic composition of methane and dissolved inorganic carbon (DIC), helped unravel the processes responsible for these variations. This study indicates that both methane concentrations and isotopic composition, as well as DIC isotopes, should be regularly monitored over at least 1 year to establish their potential natural variations prior to hydrocarbon development.

54 ENVIRONMENTAL SCIENCES↗

Effect of ion exchange on the rate of aerobic microbial oxidation of ammonium in hyporheic zone sediments

Microbially mediated ammonium oxidation is a major process affecting nitrogen transformation and cycling in natural environments. The dissolved ammonium concentration is also affected by ion exchange in geologic media, such as in soils and groundwater systems. This study investigated whether ion exchange process can affect microbially mediated aerobic oxidation of ammonium. Sediments from the Columbia River hyporheic zone at US Department Energy's Hanford site Washington State were used as an example for this study. Experiments were conducted using the sediments in synthetic groundwater and river water with different ionic strength and chemical compositions. Results indicated that ammonium sorption through ion exchange decreased the rate of ammonium oxidation, apparently resulting from the influence of the ion exchange on dissolved ammonium concentration, thus decreasing the bioavailability of ammonium for microbial oxidation. However, with the decrease of dissolved ammonium concentration, the sorbed ammonium released back to aqueous phase, and became bioavailable so that all the ammonium in the suspensions were oxidized. Low ionic strength enhanced ammonium sorption, and thus decreased the rate of ammonium oxidation. Our results implied a dynamic change in ammonium oxidation kinetics in an environment such as at HZ where river water and groundwater exchanges frequently that can change ionic strength, and thus ammonium sorption and desorption.

Yan, Ailan↗