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Understanding and Controlling Cesium Loading on Crystalline Silicotitanate - 19601

Savannah River Remediation (SRR) contracted with Westinghouse Electric Corporation (WEC), Columbia Energy and Environmental Services (CEES), to build and deliver a modular ion exchange process that will be used to remove radioactive cesium from dissolved salt solution contained in Tank 10 at the Savannah River Site (SRS). The resulting decontaminated salt solution will be sent to Tank 11 and then to Tank 50 for final disposition in grout at the Saltstone facility. At the end of processing, the loaded ion exchange (IX) columns are drained, rinsed, and dried. The IX columns are removed from the modular unit and stored at Interim Safe Storage (ISS). This ion exchange process is called the Tank Closure Cesium Removal (TCCR) system. The TCCR system consists of several unit operations and process monitoring capability housed within three modular units. The first modular unit contains the process control computer, the second modular unit contains the main process equipment (two prefilters, four IX columns, and resin trap (post filtration)), and the third modular unit is the ventilation system. The main unit operations of the TCCR system are filtration, ion exchange, and ventilation. The ion exchange media utilized is a form of inorganic Crystalline Silicotitanate (CST), IONSIV{sup TM} R9120-B supplied by UOP Honeywell. CST has a high selectivity for cesium (Cs) and has some affinity for other Group IA alkali metals on the periodic chart (hydrogen, lithium, sodium, potassium, rubidium, and francium). CST has also been shown to have affinity for strontium and actinides. Cesium loading on the CST is dependent on many factors including chemical composition (cations and anions), temperature, and pH of the salt solution. The actual amount of Cs loaded onto an IX column is dependent on the factors above along with the salt solution volume fed to the IX column. Because of CST's high selectivity for Cs, the Cs-137 equilibrium loading can contribute enough decay heat to result in an ion exchange column boiling event under no flow conditions in the IX column. The boiling event under no flow is a safety concern that must be prevented from occurring. To prevent boiling of the column under no flow conditions, the Cs-137 equilibrium loading must be determined and understood. Several methodologies were evaluated for performing the Cs-137 equilibrium loading determination for CST. After review of available research and development (R and D), batch equilibrium contact test data, and Zheng Anthony Miller (ZAM) model predictions for the salt solution chemistry in Tank 10, a methodology for determining the Cs-137 equilibrium loading on CST was selected. The methodology selected involves an in-tank batch equilibrium contact test performed in duplicate that considers additional corrections to account for anticipated operational evolutions. The in-tank batch equilibrium contact test utilizes ∼0.1 grams of CST secured in a slotted sample vial. The slotted sample vial design allows for salt solution to be in contact with the CST. The slotted sample vials containing the CST are submerged in Tank 10 and exposed to the salt solution for ten days. After ten days, the samples are retrieved and sent to the Savannah River National Laboratory (SRNL) for analysis of the Cs-137 equilibrium loading. Additional corrections are then made to the Cs-137 results to account for anticipated operational evolutions. Anticipated operational evolutions include external additions (water/caustic) to Tank 10 that result in a change to its chemical composition, tank temperature effects, departures from the laboratory testing (mixed vs. stagnant tank conditions), and IX column flushes. A description of the methodologies considered, feasibility of methodology deployment, and the down select process (benefits vs. risks) is discussed in this paper. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Internal Active Thermal Control System (IATCS) Sodium Bicarbonate/Carbonate Buffer in an Open Aqueous Carbon Dioxide System and Corollary Electrochemical/Chemical Reactions Relative to System pH Changes

The International Space Station (ISS) Internal Active Thermal Control System (IATCS) experienced a number of chemical changes driven by system absorption of CO2 which altered the coolant’s pH. The natural effects of the decrease in pH from approximately 9.2 to less than 8.4 had immediate consequences on system corrosion rates and corrosion product interactions with specified coolant constituents. The alkalinity of the system was increased through the development and implementation of a carbonate/bicarbonate buffer that would increase coolant pH to 9.0 – 10.0 and maintain pH above 9.0 in the presence of ISS cabin concentrations of CO2 up to twenty times higher than ground concentrations. This paper defines how a carbonate/bicarbonate buffer works in an open carbon dioxide system and summarizes the analyses performed on the buffer for safe and effective application in the on-orbit system. The importance of the relationship between the cabin environment and the IATCS is demonstrated as the dominant factor in understanding the system chemistry and pH trends before and after addition of the carbonate/bicarbonate buffer. The paper also documents the corollary electrochemical and chemical reactions the system has experienced and the rationale for remediation of these effects with the addition of the carbonate/bicarbonate buffer.

Stegman, Thomas W.↗

Development of high-speed balancing technology

An investigation into laser material removal showed that laser burns act in a manner typical of mechanical stress raisers causing a reduction in fatigue strength; the fatigue strength is lowered relative to the smooth specimen fatigue strength. Laser-burn zones were studied for four materials: Alloy Steel 4340, Stainless Steel 17-4 PH, Inconel 718, and Aluminum Alloy 6061-T6. Calculations were made of stress concentration factors K, for laser-burn grooves of each material type. A comparison was then made to experimentally determine the fatigue strength reduction factor. These calculations and comparisons indicated that, except for the 17-4 PH material, good agreement (a ratio of close to 1.0) existed between Kt and Kf. The performance of the 17-4 PH material has been attributed to early crack initiation due to the lower fatigue resistance of the soft, unaged laser-affected zone. Also covered in this report is the development, implementation, and testing of an influence coefficient approach to balancing a long, slender shaft under applied-torque conditions. Excellent correlation existed between the analytically predicted results and those data obtained from testing.

Demuth, R.↗

Prognostic analysis of high-flow nasal cannula therapy and non-invasive ventilation in mild to moderate hypoxemia patients and construction of a machine learning model for 48-h intubation prediction—a retrospective analysis of the MIMIC database

Background This study aims to investigate the clinical outcome between high-flow nasal cannula (HFNC) and non-invasive ventilation (NIV) therapy in mild to moderate hypoxemic patients on the first ICU day and to develop a predictive model of 48-h intubation. Methods The study included adult patients from the MIMIC III and IV databases who first initiated HFNC or NIV therapy due to mild to moderate hypoxemia (100 < PaO2/FiO2 ≤ 300). The 48-h and 30-day intubation rates were compared using cross-sectional and survival analysis. Nine machine learning and six ensemble algorithms were deployed to construct the 48-h intubation predictive models, of which the optimal model was determined by its prediction accuracy. The top 10 risk and protective factors were identified using the Shapley interpretation algorithm. Result A total of 123,042 patients were screened, of which, 673 were from the MIMIC IV database for ventilation therapy comparison (HFNC n = 363, NIV n = 310) and 48-h intubation predictive model construction (training dataset n = 471, internal validation set n = 202) and 408 were from the MIMIC III database for external validation. The NIV group had a lower intubation rate (23.1% vs. 16.1%, p = 0.001), ICU 28-day mortality (18.5% vs. 11.6%, p = 0.014), and in-hospital mortality (19.6% vs. 11.9%, p = 0.007) compared to the HFNC group. Survival analysis showed that the total and 48-h intubation rates were not significantly different. The ensemble AdaBoost decision tree model (internal and external validation set AUROC 0.878, 0.726) had the best predictive accuracy performance. The model Shapley algorithm showed Sequential Organ Failure Assessment (SOFA), acute physiology scores (APSIII), the minimum and maximum lactate value as risk factors for early failure and age, the maximum PaCO 2 and PH value, Glasgow Coma Scale (GCS), the minimum PaO 2 /FiO 2 ratio, and PaO 2 value as protective factors. Conclusion NIV was associated with lower intubation rate and ICU 28-day and in-hospital mortality. Further survival analysis reinforced that the effect of NIV on the intubation rate might partly be attributed to the other impact factors. The ensemble AdaBoost decision tree model may assist clinicians in making clinical decisions, and early organ function support to improve patients’ SOFA, APSIII, GCS, PaCO 2 , PaO 2 , PH, PaO 2 /FiO 2 ratio, and lactate values can reduce the early failure rate and improve patient prognosis.

Fu, Wei↗

Spider silk MASP1 and MASP2 proteins as carbon fiber precursors

The objective of this project is to develop an unconventional non-petroleum based carbon fiber precursor which has the potential to be produced in high yield and quantities. Methods will be developed to produce pilot-scale quantities of fibers from spider silk proteins with mechanical properties at least 75% that of the natural dragline silk fibers in tensile strength and elongations of less than 5%. The precursor fibers will be converted to carbon fibers, with a goal of >250Ksi strength and 1-2% elongation. Cost analysis will be performed and the process optimized. Task 1: Subtask 1. Protein production: We exceeded the go/ no go milestone of 1.0g/L of one of the spider silk protein (MSp2) purified last FY and have now increased from 5L to 500L fermentations. We have made a series of changes to the purification protocol from the initial report last FY. These led to a reduction in the time needed for the purification and reduced the purification costs by nearly 90%. Subtask 2. Fiber spinning: The major focus has been to produce more material to send 24 fiber thread to ONRL. We are still developing the methodology to successfully spin 24 fiber yarns. This involves both the spinning dope solutions as well as the methods to keep the fibers from fusing during the post spin stretch. The second area of focus has been to standardize the spin dopes for making the fibers. We now know that the conductivity (indicative of salt remaining with the protein after purification) is an important factor in successful spinning as is the pH. We now know that we need to be below 600 uS conductivity and that the most effective pH is protein dependent. Subtask 3. Silkworm silk: We have found the transgenic silkworms made using gene replacement at the fibroin light chain instead of heavy chain as we did previously have a higher tensile strength. See figures below showing the curve for the top end of the cocoon fibers. This tensile strength is the same as the average for spider dragline silk. Task 2. Carbonization: The major accomplishment in the latter part of the work is that the ONRL group has successfully heated the spider silk protein fibers all the way up to 1700°C and produced a very competitive carbon fiber based on mechanical properties. Several important factors were discovered during these initial trials: 1) the ramp speed for increasing the temperature is critical; 2) maintaining tension on the fiber during the heating process because as it is heated it tends to expand; and 3) narrow temperature window in which stretching the fiber during heating leads to much better final materials. Task 3. Techno-Economic Methods: The techno-economic analysis was expanded to determine the relative cost of production with the bacterial production system compared to the transgenic alfalfa and goat production systems. The comparisons show two important things. For all systems the key factor in the final price is the amount of spider silk protein produced for whatever measure of volume or weight is used. Second alfalfa can be the cheapest but is subject to the possible regulatory control unless the US develops a more comprehensive approach to GMOs. The silkworm analysis was not completed due to a variety of confounding factors. The primary one was that if the production were shifted overseas then the cost would likely be nearly equivalent to current silk prices of $5-15/kg. However if concerns about the location of production is important then it would need to be done in the US and initial costs would be much higher but if the later scenario is utilized then the cost would be lowered but it was not possible to calculate exact costs.

36 MATERIALS SCIENCE↗

pH-Dependent Vibrational Dynamics Drives Excited-State Quenching in the Phycobiliprotein Complex PC645

Phycocyanin 645 (PC645) is a closed-form lightharvesting complex found in the lumen of the photosynthetic membrane of cryptophyte algae. These peripheral antenna complexes contain bilin chromophores that absorb sunlight and transfer excitation energy to the core antenna complexes embedded in the thylakoid membrane. The location of cryptophyte antenna complex on the luminal side of the membrane is unusual. During photosynthetic activity, the pH of the lumen drops, by up to two pH units. There is little known about how this pH-change affects the light-harvesting complexes. In this study, we report multiscale simulations using a computationally efficient density functional tight-binding framework to investigate the spectroscopy and excitation energy transfer in the PC645 complex. Complementary experiments were conducted using both steady-state and time-resolved spectroscopic measurements at low, neutral, and high pH values. Our study shows that (de)protonation of specific bilin pigments, namely, the mesobiliverdins (MBVs), modulates the excitation energies, excitonic couplings, and spectral densities. These changes cause excitation transfer rates to increase by up to a factor of two to three, leading to pH-dependent energy transfer pathways in the complex. Using this model, we calculated the pH-dependent fluorescence quantum yield of the system, obtaining quantitative agreement with the experimental results. These computational simulations, supported by experiments, identify MBVs as a more prominent excitation sink than previously realized, and that this role is tuned by pH.

Maity, Sayan [Constructor Univ., Bremen (Germany);↗

Fabrication of core-shell Fe{sub 3}O{sub 4}@MIL-100(Fe) magnetic microspheres for the removal of Cr(VI) in aqueous solution

Facile regeneration of an adsorbent is very important for commercial feasibility. One typical highly porous metal-organic framework (MOF) materials based on MIL-100(Fe) and magnetic iron oxide particles (denoted as MMCs) with diameter about of 350 nm were successfully synthesized. The growth of MIL-100(Fe) shell on the surface of Fe{sub 3}O{sub 4} was utilized precursor as crystal seed via in-situ step hydrothermal reaction. It is a simple way to obtain well organized core-shell MOF composites, compared to the step-by-step method. MMCs were firstly used to uptake of Cr(VI) anions in aqueous solution. Adsorption experiments were carried out in batch sorption mode investigating with the factors of contact time (0–1000 min), pH (from 2 to 12), dose of adsorbent (4–25 mg), and initial Cr(VI) concentration (range from 10 to 100 ppm). - Graphical abstract: One typical highly porous metal-organic framework (MOF) materials based on MIL-100(Fe) and magnetic iron oxide particles (denoted as MMCs) were successfully synthesized. Utilizing Fe{sub 3}O{sub 4} precursor as crystal seed to grow MIL-100(Fe) shell by in-situ step hydrothermal reaction. It is a simple way to obtain core-shell MOF composites. MMCs could effectively uptake of Cr(VI) anions in aqueous solution. - Highlights: • Fe{sub 3}O{sub 4}@MIL-100(Fe) composites with core-shell structure were successfully prepared through a simple method. • The influence factors on Cr(VI) adsorption by Fe{sub 3}O{sub 4}@MIL-100(Fe) were investigated. • Cr(VI) can efficiently adsorbed by Fe{sub 3}O{sub 4}@MIL-100(Fe) composites from aqueous solution.

36 MATERIALS SCIENCE↗

Electron Donor Utilization and Secondary Mineral Formation during the Bioreduction of Lepidocrocite by Shewanella putrefaciens CN32

The bioreduction of Fe(III) oxides by dissimilatory iron reducing bacteria (DIRB) may result in the production of a suite of Fe(II)-bearing secondary minerals, including magnetite, siderite, vivianite, green rusts, and chukanovite; the formation of specific phases controlled by the interaction of various physiological and geochemical factors. In an effort to better understand the effects of individual electron donors on the formation of specific Fe(II)-bearing secondary minerals, we examined the effects of a series of potential electron donors on the bioreduction of lepidocrocite ($γ$-FeOOH) by Shewanella putrefaciens CN32. Biomineralization products were identified by X-ray diffraction, Mössbauer spectroscopy, and scanning electron microscopy. Acetate, citrate, ethanol, glucose, glutamate, glycerol, malate, and succinate were not effectively utilized for the bioreduction of lepidocrocite by S. putrefaciens CN32; however, substantial Fe(II) production was observed when formate, lactate, H 2 , pyruvate, serine, or N acetylglucosamine (NAG) was provided as an electron donor. Carbonate or sulfate green rust was the dominant Fe(II)-bearing secondary mineral when formate, H 2 , lactate, or NAG was provided, however, siderite formed with pyruvate or serine. Geochemical modeling indicated that pH and carbonate concentration are the key factors determining the prevalence of carbonate green rust verses siderite.

58 GEOSCIENCES↗

Photochemical Kinetic Modeling of Degradation of Aqueous Polyvinyl Alcohol in a UV/H{sub 2}O{sub 2} Photoreactor

This study presents a photochemical kinetics model to describe the degradation of water-soluble PVA (Polyvinyl Alcohol) polymer in a UV/H{sub 2}O{sub 2} batch reactor. Under the effect of UV light, the photolysis of hydrogen peroxide into hydroxyl radicals can generate a series of polymer scission reactions. For a better understanding and analysis of the UV/H{sub 2}O{sub 2} process in the cracking of the PVA macromolecules, a chemical reaction mechanism of the degradation process and a relevant photochemical kinetics model are developed to describe the disintegration of the polymer chains. Taking into account the probabilistic fragmentation of the polymer, the statistical moment approach is used to model the molar population balance of live and dead polymer chains. The model predicts the PVA molecular weight reduction, the acidity of the solution, and hydrogen peroxide residual. In addition to previously published data collected in this laboratory, a new set of experiments were conducted using a 500 mg/L PVA aqueous for different hydrogen peroxide/PVA ratios for model validation. Measurements of average molecular weights of the polymer, hydrogen peroxide concentrations and pH of the PVA solution were determinant factors in constructing a reliable photochemical model of the UV/H{sub 2}O{sub 2} process. Experimental data showed a decrease in the PVA molecular weight and a buildup of the solution acidity. The experimental data also served to determine the kinetics rate constants of the PVA photochemical degradation and validate the model whose predictions are in good agreement with data. The model can provide a comprehensive understanding of the impact of the design and operational variables.

36 MATERIALS SCIENCE↗

A Study on the Corrosion Behavior of Carbon Steel Exposed to a H{sub 2}S-Containing NH{sub 4}Cl Medium

NH{sub 4}Cl corrosion failure often occurs in the overhead systems of hydrotreaters, and this failure is always accompanied by the appearance of H{sub 2}S. A combination of electrochemical and surface spectroscopic (SEM/EDS, AFM, XRD) techniques was used to investigate the effect of different factors, including the surface roughness, temperature, dissolved oxygen, pH and H{sub 2}S concentration, on the corrosion behavior of carbon steel in an NH{sub 4}Cl environment with the presence of H{sub 2}S. The effect of H{sub 2}S concentrations (at the ppm level) on the corrosion behavior of carbon steel was systematically revealed. The experimental results clearly indicated that the corrosion rate reached a minimum value at 10 ppm H{sub 2}S. The steel surface was covered by a uniform corrosion product film in a 10 ppm H{sub 2}S environment, and the corrosion product film was tight and protective. The ammonia from NH{sub 4}Cl helped maintaining the protectiveness of the corrosion films in this environment. Dissolved oxygen mainly accelerated the cathodic reaction. The cathodic limiting current density increased with increasing temperature, and the anodic branch polarization curves were similar at different temperatures. The anodic current density decreased as the pH decreased, and the cathodic current density increased as the pH decreased. The absolute surface roughness (R{sub a}) of carbon steel increased from 132.856 nm at 72 h to 153.973 nm at 144 h, and the rougher surface resulted in a higher corrosion rate. The critical innovation in this research was that multiple influential factors were revealed in the NH{sub 4}Cl environment with the presence of H{sub 2}S.

36 MATERIALS SCIENCE↗

Synthesis of nano-sized ZnO particles by co-precipitation method with variation of heating time

Zinc oxide powders have been synthesized by a co-precipitation method at low temperature (85 °C), using zinc acetate dihydrate, ammonia, hydrochloric acid solutions as the reactants. A number of process parameters such as reaction temperature, solution basicity or pH and heating time are the main factors affecting the morphology and physical properties of the ZnO nanostructures. In this work the effect of heating time on the morphology and particles size were studied. The as-synthesized ZnO powders were characterized using transmission electron microscopy (TEM) and X-ray diffraction (XRD) techniques. The samples were also analyzed using Fourier transform infrared (FTIR). Rietveld refinement of XRD data confirms that ZnO crystallizes in the hexagonal wurtzite structure with high degree of purity and the (101) plane predominant. The XRD results show that the average crystallite sizes were about 66, 27 and 12 nm for 3, 4 and 5 h of heating times, respectively. The XRD analysis indicated that a fraction of nano-sized ZnO powders were in the form of aggregates, which was also verified by TEM image. The TEM photograph demonstrated that the nano-sized ZnO particles were a pseudo-spherical shape.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Seasonal variations in urinary risk factors among patients with nephrolithiasis

Twenty-four hour urine specimens from 5,677 stone-forming patients throughout the United States were analyzed for seasonal variations in urinary risk factors for nephrolithiasis. Determinations were performed for urine volume, pH, calcium, oxalate, phosphorus, sodium, magnesium, citrate, sulfate, uric acid, and the relative supersaturation (RS) of calcium oxalate, brushite, monosodium urate, and uric acid. Criteria for significant seasonal variation included a significant difference in monthly means of risk factors, seasonal grouping of the data by the Student-Newman-Keuls multiple range test, consistent year-to-year trends and a physiologically significant range. Minimum urine volume of 1.54 +/- 0.70 SD L/day occurred in October while a maximum urine volume of 1.76 +/- 0.78 SD L/day was observed during February. Minimum urine pH of 5.94 +/- 0.64 SD was observed during July and August while a maximum pH of 6.18 +/- 0.61 SD was observed during February. Daily urinary excretion of sodium was lowest during August, 158 +/- 74 SD mEq/day and highest during February 177 +/- 70 SD mEq/day. The RS of brushite and uric acid were found to display significant pH-dependent seasonal variation with a maximum RS of uric acid 2.26 +/- 1.98 SD in June and a low of 1.48 +/- 1.30 SD in February. Maximum RS of brushite 2.75 +/- 2.58 was observed during February. Minimum RS of brushite 1.93 +/- 1.70 SD was observed in June. Phosphorus excretion displayed seasonal variation about a spring-fall axis with a maximum value 1042 +/- 373 SD mg/day in April and a minimum value of 895 +/- 289 SD mg/day. Urine volume, sodium, and pH were significantly lower during the summer (June, July, August) than in the winter (December, January, February). The RS of uric acid was higher, but that of brushite and monosodium urate was lower in the summer than in the winter. The seasonal changes observed in urine volume, pH, sodium, and the RS of brushite and uric acid are consistent with summertime sweating and increased physical activity. Seasonal variations in phosphorus excretion are probably dietary in origin. The summertime was characterized by an increased propensity for the crystallization of uric acid but not of calcium oxalate or calcium phosphate.

NASA Discipline Regulatory Physiology↗

Efficient Removal of Fluoride Using Polypyrrole-Modified Biochar Derived from Slow Pyrolysis of Pomelo Peel: Sorption Capacity and Mechanism

In this study, a novel adsorbent was developed by loading polypyrrole (PPy) onto biochar (BC) prepared by slow pyrolysis of pomelo peel. This PPy-grafted BC mainly exhibited anion-exchange behavior, which dramatically increased fluoride adsorption capacity. The effects of various factors (adsorbent dosage, pyrrole concentration, initial solution pH, co-existing anions and temperature) on the fluoride adsorption were investigated. The adsorbent was characterized by scanning electronic microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and automatic titration methods. Results showed that the optimized adsorbent (BP-0.1) performed excellently at pH 2.8–10.0, and possessed positive charge at pH < 8.6. The adsorption isotherm data were fitted well by the Langmuir model and the maximum adsorption capacity was 18.52 mg/g at 25 ± 2 °C. The adsorption kinetics followed the pseudo-second-order model and adsorption equilibrium was achieved at 24 h. Although both HCO{sub 3}{sup −} and CO{sub 3}{sup 2−} had great influence on F{sup −} adsorption, there was no significant impact in the presence of Cl{sup −}, NO{sub 3}{sup −} and SO{sub 4}{sup 2−}. Real groundwater study showed that 2.5 g/L of BP-0.1 could effectively reduce F{sup −} from 10.0 to 1.4 mg/L at pH 5.0. Thermodynamic parameters confirmed the spontaneous and endothermic nature of the adsorption process. Effect of pH, XPS analysis and the change of amount between Cl{sup −} and F{sup −} in the adsorption process revealed that ion exchange and electrostatic attraction were involved in the adsorption process and ion exchange was the main adsorption mechanism.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Greenhouse gas emissions and crop yield in no-tillage systems: A meta-analysis

We report that no-tillage (NT) has been touted as one of several climate-smart agriculture (CSA) management practices that improve food security and enhance agroecosystem resilience to climate change. However, the sustainable effectiveness of NT greatly depends on trade-offs between NT-induced changes in crop yield and greenhouse gas (GHG, i.e. CH 4 , CO 2 , and N 2 O) emissions. Such trade-offs are regulated by climate fluctuations and heterogeneous soil conditions and have not been well addressed. Supporting CSA management decisions requires advancing our understanding of how NT affects crop yield and GHG emissions in different agroecological regions. In this study, a meta-analysis was conducted using 740 paired measurements from 90 peer-reviewed articles to assess the effects of NT on crop yield, GHG emissions, and the global warming potential (GWP) of major cereal cropping systems. Compared to conventional tillage (CT), NT reduced in GHG emissions and increased crop yield in dry, but not humid, climates, and reduced in the GWP at sites with acidic soils. Across different cropping systems, NT enhanced barley yield by 49%, particularly in dry climates, and it decreased the GWP of rice fields through a 22% reduction in both CO 2 and CH 4 emissions. Our synthesis suggests that NT is an effective CSA management practice because of its potential for climate change mitigation and crop yield improvement. However, the net effect of NT (relative to CT) was influenced by several environmental and agronomic factors (climatic conditions, tillage duration, soil texture, pH, crop species). Therefore, agroecological setting must be taken into consideration when conducting a comparative evaluation of different tillage practices.

54 ENVIRONMENTAL SCIENCES↗

A Theoretical Study of the Qualitative Reaction Mechanism for the Homogeneous Disproportionation of Pentavalent Uranyl Ions

There is significant interest in understanding the oxidation and reduction of aqueous uranium ions. In the literature, there is considerable variation in the results of attempts to reduce uranium depending on very small differences in reducing species, pH, spectator ions, mineral substrates, and other factors. Of particular curiosity is the fact that U(V) can be stabilized in the lab but is almost never found in the environment. In order to better understand these two phenomena, a direct computational study of homogenous, aqueous U(V) disproportionation was undertaken. Using a combination of Marcus Theory with Hartree– Fock and MP2 calculations, the rate constant of the electron-transfer reaction was calculated. Under the conditions studied, the electron-transfer reaction is slow (k observed ~10 -1 M-1 s-1). This reduced rate is a result of a variety of factors: the +1 charge of the reactants, the large encounter complex distance, and the electronic reorganization energies associated with the proton transfers. Excluding the energy from the coupled proton transfers, all of the remaining factors could be eliminated by small alterations of the uranium’s environment.

Environmental Molecular Sciences Laboratory↗

NitroNet: Smart System to Quantify Nitrous Oxide Emissions

Agricultural croplands are the largest anthropogenic source of nitrous oxide (N 2 O), the third most important greenhouse gas. Emissions are characterized by “hot spots” and “hot moments”, meaning emissions are highly heterogeneous in space and time. Emissions are driven by nitrification and denitrification processes which depend upon complex factors such as soil characteristics (type, compaction, pH, moisture, topography), management practices (fertilizer type and application, tillage, crop type, field history, irrigation), biogeochemistry (organic carbon, microbial composition), and meteorology (precipitation, temperature, and wind). For these reasons, quantifying cropland emissions by either measurements or modeling is extremely challenging with large uncertainties.

09 BIOMASS FUELS↗

CRUD Source Term Assessment and Development for VERA

In pressurized water reactors, corrosion of primary loop materials is an ongoing process, as primary loop components (steam generator, hot leg, cold leg, and core) are constantly exposed to the coolant. As a result of this corrosion, primary loop materials are released into the coolant in the form of aqueous metal ions and particulate oxides. These corrosion products are the source of materials that form crud deposits on fuel rod clad surfaces. The mass of corrosion products available to create crud will limit the rate and extent of crud buildup that occurs. This is commonly referred to as the crud “source term”. The major contribution to the source term mass comes from the steam generator, due to the large surface area exposed to the coolant. Steam generators are not identical; the wetted area exposed to the coolant and the alloy used in the steam generator tubes vary. Different alloys corrode at different rates; Inconel 690 corrodes at approximately one-third of the rate of corrosion of Inconel 600. The mass of corrosion products released from the steam generator also varies by the area exposed to the coolant. The release of these corrosion products depends on the local environmental factors within the primary loop, including temperature, pH, local fluid conditions, electrochemical potential, and thermodynamic solubilities of the species present within this system. As such, each PWR will have a different crud source term based on these plant-specific parameters. In order to accurately model and predict crud growth and issues that arise from the presence of crud (CIPS, CILC), the source of these corrosion product materials must be accurately modeled in a system mass balance. These models should be mechanistic, representative of the underlying physics phenomena, and account for the effects of the plant-specific design and operating parameters, including the alloys used, local temperatures, and fluid flow conditions.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

A Study Of Geological Disposal Facility (GDF) Ageing Phenomena In Bentonite - 17605

Since the 1950's, the UK's nuclear activity in energy, defence and medicine has led to the accumulation of a large amount of higher activity radioactive waste (HAW). Most of nuclear waste arises in a wide variety of physical and chemical forms with different radioisotopes and loadings. Due to complexity in HAW, it is imperative that there be a rigorous management system that ensures population and environmental safety over extended periods. The concept of Deep Geological Disposal of waste in a stable geological formation is, nowadays, an internationally accepted solution as the surest and the most viable long term method for management. Any future Geological Disposal Facility (GDF) will comprise, among other artificial and natural engineered barriers, a barrier immediately around the waste containers compounded by a sealing material. The long-term stability of a GDF will be determined by the design and construction of the engineered barriers, and the mechanical, hydraulic and geochemical interactions that may happen between the different engineered components as a result of combined processes such as the heat produced by radioactive decay and the ion water composition of the surrounding host rock. Bentonite clay has been selected as the most promising buffer and backfill material in many disposal programmes because of its swelling capacity, low permeability, plasticity and cation exchange capacity. In the nuclear scope, bentonite testing at different scale-lengths (laboratory and field scale) has been performed and implemented in order to examine the thermo-hydro-mechanical (THM) and thermo-hydro-geochemical (THG) processes that may happen in the engineered barriers and geological settings associated with a GDF. Two major European field scale tests have been performed to better understand bentonite performance and behaviour immediately after HAW emplacements. The Full-Scale Engineered Barriers Experiment (FEBEX) at the Grimsel Test Sit (Switzerland) and the Alternative Buffer Material (ABM) Project at the Aespoe Hard Rock Laboratory (Sweden). The Febex Experiment was a pilot project designed for 'field research' of HAW repository hosted in crystalline rock where surrogate HAW canisters were placed horizontally in drifts, surrounded by compacted blocks of bentonite, sealed by a concrete plug and maintaining a constant canister surface temperature of 100 deg. C. After five years of operation, a partial dismantling was carried out in 2002. Heater processes occurring in the surrounding bentonite. The dismantling of the heater no. 2 (after 18 years of operation) started in late 2014 and is planned to be finished at the end of 2016 (termed FEBEX-DP). The FEBEX Project utilised bentonite from the Cortijo de Archidona deposit (Almeria, Spain). This 'Febex' bentonite is sourced from calcium-magnesium montmorillonite with good properties in relation to swelling capacity, permeability, adsorption capacity, and thermal conductivity. The ABM Project is a large-scale programme that has been running since 2006. The programme is designed to study a suite of possible buffer materials and correlate the physical and chemical properties of eleven different types of bentonites to their fundamental mineralogical properties. The ABM test consists in three 'packages' containing a central heater tube surrounded by different pre-compacted bentonite blocks and instrumentation. Each 'package' was installed in separate boreholes. The target temperature for the surface of the heated tubes in contact with the bentonite was 130 deg. C. Both FEBEX and ABM test the bentonite was saturated with water percolating from surrounding host rock (FEBEX and ABM) and also via artificial supply systems (ABM), being the water itself acting as a long term corrosion agent. For both experiments and emerging interest is in the interaction of bentonite with metallic components, under geological disposal conditions are not considered to be thermodynamically stable and hence arising corrosion products could interact with the buffer. These interactions depend on various factors such as the redox potential, temperature, pH, solute concentration and buffer material characteristics. During the operational phases of the FEBEX and ABM and after its 'closure' a significant volume of air was found to be retained in the bentonite. Under these conditions a period of initial aerobic corrosion by the air in the bentonite barrier would have occurred followed by establishment of anaerobic corrosion would be the dominant process ongoing. The anaerobic corrosion began when the bentonite became water saturated. Under these conditions, the water acted as the major oxidant. The present project focuses on the characterization of samples arising from the FEBEX and ABM Projects as well as performing additional independent experiments designed to complement these prior studies. Characterization will focus mainly on corrosion related alteration combined with thermal effects. Through detailed sample characterization, the intention is to achieve a greater knowledge regarding the changes to the bentonite under the experimental conditions to which it was exposed, and plausible alterations in its THM and THG properties occurring during the experiment due to blended effects of temperature,water content, engineering structural components and solutes are also to be measured. The fulfilment of a large-scale 'in-situ' test is intricate, time-consuming and with an abundance of external variables that are not always well controlled. For this reason, the University of Bristol is performing a series of well constrained time-resolved laboratory tests which bentonite is being subjected to different possible scenarios that may happen whilst in a HAW repository. In virtue of this experiment, the UoB aims to understand the illitisation and cementation process and their effects on bentonite safety properties. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗