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This data set reports stream temperature, specific conductance, pH, dissolved oxygen percent saturation, dissolved oxygen concentration, turbidity, and fluorescent dissolved organic matter for East Fork Poplar Creek at a location approximately 5.4 kilometers
Spatially resolved deep-UV Raman spectroscopy was applied to solutions of CO2 and H2O or D2O subject to a temperature gradient in a thermally regulated high-pressure concentric-tube Raman cell in an attempt to measure a Soret effect in the vicinity of the critical point of CO2. Although Raman spectra of solutions of CO2 dissolved in D2O, at 10 MPa and temperatures near the critical point of CO2, had adequate signal-to-noise and spatial resolution to observe a Soret effect with a Soret coefficient with magnitude |ST| > 0.03, no evidence for an effect of this size was obtained for applied temperature gradients up to 19 C. In contrast, the concentration of CO2 dissolved in H2O was shown to vary significantly across the temperature gradient when excess CO2 was present, but the results could be explained simply by the variation in CO2 solubility over the temperature range and not to kinetic factors. For mixtures of D2O dissolved in scCO2 at 10 MPa and temperatures close to the critical point of CO2, the Raman peaks for D2O were too weak to measure with confidence even at the limit of D2O solubility.
There is a growing understanding of the role that bedrock weathering can play as a source of nitrogen (N) to soils, groundwater and river systems. The significance is particularly apparent in mountainous environments where weathering fluxes can be large. However, our understanding of the relative contributions of rock-derived, or geogenic, N to the total N supply of mountainous watersheds remains poorly understood. In this study, we develop the High-Altitude Nitrogen Suite of Models (HAN-SoMo), a watershed-scale ensemble of process-based models to quantify the relative sources, transformations, and sinks of geogenic and atmospheric N through a mountain watershed. Our study is based in the East River Watershed (ERW) in the Upper Colorado River Basin. The East River is a near-pristine headwater watershed underlain primarily by an N-rich Mancos Shale bedrock, enabling the timing and magnitude of geogenic and atmospheric contributions to watershed scale dissolved N-exports to be quantified. Several calibration scenarios were developed to explore equifinality using >1600 N concentration measurements from streams, groundwater, and vadose zone samples collected over the course of four years across the watershed. When accounting for recycling of N through plant litter turnover, rock weathering accounts for approximately 12% of the annual dissolved N sources to the watershed in the most probable calibration scenario (0–31% in other scenarios), and 21% (0–44% in other scenarios) when considering only “new” N sources (i.e. geogenic and atmospheric). On an annual scale, instream dissolved N elimination, plant turnover (including cattle grazing) and atmospheric deposition are the most important controls on N cycling.
Denitrification is microbially-mediated through enzymes containing metal cofactors. Laboratory studies of pure cultures have highlighted that the availability of copper (Cu), required for the multicopper enzyme nitrous oxide reductase, can limit nitrous oxide (N2O) reduction. However, in natural aquatic systems, such as wetlands and hyporheic zones in stream beds, the role of Cu in controlling denitrification remains incompletely understood. In this study, we collected soils and sediments from three natural environments -- riparian wetlands, marsh wetlands, and a stream -- to investigate their nitrogen species transformation activity at background Cu levels and different supplemented Cu loadings. All of the systems contained solid-phase associated Cu below or around geological levels (40–280 nmol g-1) and exhibited low dissolved Cu (3–50 nM), which made them appropriate sites for evaluating the effect of limited Cu availability on denitrification.The dataset contains the variation in the nutrient (nitrate (NO3-), nitrite (NO2-), and ammonium (NH4+)) and N2O concentrations during the incubation experiments to evaluate the effect of Cu. We have also reported the variation in metal concentrations (Cu, iron(Fe) and manganese (Mn)) and dissolved organic carbon (DOC) concentrations during the incubations. The parameters obtained using a kinetic model to quantitatively report the effect of Cu on nitrogen species conversion in natural aquatic systems are also added in the dataset. The dataset also contains the labile concentration of Cu estimated using a speciation model in MINTEQ. All data are provided in text-based CSV format with header sections indicating the data contained in each file and the corresponding units.Our study suggests that high concentrations of N2O accumulated in all microcosms lacking Cu amendment except for one stream sediment sample. With Cu added to provide dissolved concentrations at trace levels (10–300 nM), the reduction rate of N2O to N2 in the wetland soils and stream sediments was enhanced. A kinetic model could account for the trends in nitrogen species by combining the reactions for microbial reduction of NO3- to NO2-/N2O/N2 and abiotic reduction of NO2 to nitrogen (N2_. The model revealed that the rate of N2O to N2 conversion increased significantly in the presence of Cu. For riparian wetland soils and stream sediments, the kinetic model also suggested that overall denitrification is driven by abiotic reduction of NO2- in the presence of inorganic electron donors. This study demonstrated that natural aquatic systems containing Cu at concentrations less than or equal to crustal abundances may display incomplete reduction of N2O to N2 that would cause N2O accumulation and release to the atmosphere.
This dataset contains data associated with the preprint “Fire removes preexisting pyrogenic organic matter from the ecosystem through the mechanisms of both direct combustion and increasing mineralizability” (Luo et al., 2025b), which is the complementary study to the published paper “Reburning pyrogenic organic matter: a laboratory method for dosing dynamic heat fluxes from above” (Luo et al., 2025a). We designed a full-factorial experiment with different burial depths of jack pine (Pinus banksiana Lamb) pyrogenic organic matter (PyOM) (Surface, 1 cm, and 5 cm) and different heat-flux profiles (High, Low, and Control) to examine how subsequent fires affect the properties of preexisting PyOM. We measured total carbon (C), pH, dissolved organic carbon (DOC), dissolved inorganic carbon (DIC), and mineralized C (as CO₂-C, from a 12-week incubation).We found that high heat flux and/or surface placement resulted in substantial direct C losses through combustion. Intermediate heat exposure produced both combustion losses and increases in DOC and mineralizability, which may have complex long-term implications: an increased dissolved fraction of PyOM may promote downward transport into mineral soils and potentially contribute to deeper, longer-term C storage, but it may also make PyOM more susceptible to microbial decomposition. Under the lowest heat flux and deepest burial, most PyOM was retained, and changes in DOC and C mineralization were minimal. Finally, PyOM pH, an important chemical property, decreased under low-temperature heating but increased under higher temperatures.We uploaded pH data for all samples (“pH_of_all_samples.csv”); pH and temperature-related data (peak temperature and degree hours) for samples in High and Low heat-flux treatments (“pH_vs_peakT_and_degree_hours_only_for_heated_samples.csv”); total C data (“CN_pct_C_stock_C_loss_in_samples.csv”); DOC and DIC data (“doc_dic.csv”); and mineralized C (CO₂-C) data (“CO2-C_all_original.csv”). Additional details can be found in the Methods & Sampling section.All datasets uploaded to ESS-DIVE are clearly labeled, cleaned, and include both raw and derived data, ready for reuse in other analyses. All analysis code and raw datasets are also available on GitHub: https://github.com/MengmengLuo/Fire-removes-preexisting-pyrogenic-organic-matter-from-the-ecosystem.
Geochemically-Driven Petrophysical Transformations in Caney Shale and Their Impact on Reservoir Productivity
The corrosion behavior of A516 carbon steel was evaluated to determine the effect of the dissolved chloride content in molten binary Solar Salt. Corrosion tests were conducted in a molten salt consisting of a 60-40 weight ratio of NaNO{sub 3} and KNO{sub 3} at 400{sup o}C and 450{sup o}C for up to 800 hours. Chloride concentrations of 0, 0.5 and 1.0 wt.% were investigated to determine the effect on corrosion of this impurity, which can be present in comparable amounts in commercial grades of the constituent salts. Corrosion rates were determined by descaled weight losses, corrosion morphology was examined by metallographic sectioning, and the types of corrosion products were determined by x-ray diffraction. Corrosion proceeded by uniform surface scaling and no pitting or intergranular corrosion was observed. Corrosion rates increased significantly as the concentration of dissolved chloride in the molten salt increased. The adherence of surface scales, and thus their protective properties, was degraded by dissolved chloride, fostering more rapid corrosion. Magnetite was the only corrosion product formed on the carbon steel specimens, regardless of chloride content or temperature.
Pacific Northwest National Laboratory (PNNL), operated by Battelle, has identified a reference process for the production of molybdenum-99 (99Mo) for use in a chromatographic generator to separate the daughter product, technetium-99m (99mTc). The reference process uses the neutron capture reaction of natural or enriched molybdenum oxide via the reaction 98Mo(n,γ)99Mo. The irradiated molybdenum is dissolved in an alkaline solution, whereby the molybdenum, dissolved as the molybdate anion, is loaded on a proprietary ion exchange material in the chromatographic generator. The approach of this investigation is to provide a systematic collection of technologies to make the neutron capture method for Mo-99 production economically viable. This approach would result in the development of a technetium Tc99m generator and a new type of target. The target is comprised of molybdenum, either natural or enriched, and is tailored to the design of currently operating U.S. research reactors. The systematic collection of technologies requires evaluation of new metallurgical methods to produce the target, evaluation of target geometries tailored to research reactors, and chemical methods to dissolve the irradiated target materials for use in a chromatographic generator. A Technical specification for testing the target and neutron capture method in a research reactor is also required. This report includes identification of research and demonstration activities needed to enable deployment of neutron capture production method, including irradiations of prototypic targets, chemical processing of irradiated targets, and loading and extraction tests of Mo99 and Tc99m on the sorbent material in a prototypic generator design. The prototypical generator design is based on the proprietary method and systems for isotope product generation. The proprietary methods and systems described in this report are clearly delineated with footnotes. Ultimately, the Tc-99m generator solution provided by the system has exactly the same chemical and radiochemical characteristics as the Tc-99m currently produced by standard generator systems. Analysis results indicate: • The production of Mo99 is a function of the neutron flux in the thermal and epithermal region, the target volume, and the target geometry. Calculations show that neutron self-absorption is not very important such that large (2 cm OD or more) cylinders of molybdenum can be irradiated without significant losses. • Efficient use of target volume design is function of simultaneously optimizing the amount of molybdenum that can be inserted into each irradiation capsule and the amount of interconnected porosity within the specimen body to enhance the rate of post-irradiation dissolution. • Neutron capture of natural molybdenum may effectively achieve up to 1 Ci/g Mo99 in a 144 hour irradiation period, when using the fuel annulus plus a beryllium reflector configuration.
The objective of this project is to identify single chemical agents that exhibit a desirable rheological property whereby if such a chemical is dissolved in salt water it increases the solution viscosity significantly with time. We term that behavior as 'self-thickening' and have nicknamed this as 'T85 technology'. As detailed in the original project proposal, such single chemical products can be applied to advantage as agents for selectively slowing or blocking high flow water channels in subsurface oil reservoirs. The net effect is a decrease in water and an increase in oil flow and production. The initial testing has focused on five different synthetic co-polymers that have two or more chemical groups. These chemicals were dissolved at a concentration of 2500 ppm into different salt solutions (sodium chloride, potassium chloride, and calcium chloride) that encompass a range of dissolved salt concentrations. For the sodium chloride and potassium chloride solutions the salt concentration ranged from 1-5 wt%. The calcium chloride dihydrate sample concentrations ranged from 0.1-1 wt%. One set of samples being aged at 25 C and a second set at 50 C. Viscosity measurements versus aging time show two of these agents may exhibit apparent self-thickening behavior under certain salinity and temperature conditions. Generally the effect is greater in lower salinity NaCl brines and at 25 C. Preliminary flow experiments confirm that the aged fluids exhibit increased effective viscosity while flowing through a porous medium (sand pack). These flow tests include the case of the chemical fluid being aged on the bench before injection into a sand pack, and also a second series of sand packs where fresh chemical fluid is injected and allowed to age in-situ. Thus, the results of the static ageing tests together with the flow tests are a technical validation of the T85 concept.
The Defense Waste Processing Facility has experienced significant issues with the stripping and recovery of mercury in the Chemical Processing Cell (CPC). The stripping rate has been inconsistent, often resulting in extended processing times to remove mercury to the required endpoint concentration. The recovery of mercury in the Mercury Water Wash Tank has never been high, and has decreased significantly since the Mercury Water Wash Tank was replaced after the seventh batch of Sludge Batch 5. Since this time, essentially no recovery of mercury has been seen. Pertinent literature was reviewed, previous lab-scale data on mercury stripping and recovery was examined, and new lab-scale CPC Sludge Receipt and Adjustment Tank (SRAT) runs were conducted. For previous lab-scale data, many of the runs with sufficient mercury recovery data were examined to determine what factors affect the stripping and recovery of mercury and to improve closure of the mercury material balance. Ten new lab-scale SRAT runs (HG runs) were performed to examine the effects of acid stoichiometry, sludge solids concentration, antifoam concentration, form of mercury added to simulant, presence of a SRAT heel, operation of the SRAT condenser at higher than prototypic temperature, varying noble metals from none to very high concentrations, and higher agitation rate. Data from simulant runs from SB6, SB7a, glycolic/formic, and the HG tests showed that a significant amount of Hg metal was found on the vessel bottom at the end of tests. Material balance closure improved from 12-71% to 48-93% when this segregated Hg was considered. The amount of Hg segregated as elemental Hg on the vessel bottom was 4-77% of the amount added. The highest recovery of mercury in the offgas system generally correlated with the highest retention of Hg in the slurry. Low retention in the slurry (high segregation on the vessel bottom) resulted in low recovery in the offgas system. High agitation rates appear to result in lower retention of mercury in the slurry. Both recovery of mercury in the offgas system and removal (segregation + recovery) from the slurry correlate with slurry consistency. Higher slurry consistency results in better retention of Hg in the slurry (less segregation) and better recovery in the offgas system, but the relationships of recovery and retention with consistency are sludge dependent. Some correlation with slurry yield stress and acid stoichiometry was also found. Better retention of mercury in the slurry results in better recovery in the offgas system because the mercury in the slurry is stripped more easily than the segregated mercury at the bottom of the vessel. Although better retention gives better recovery, the time to reach a particular slurry mercury content (wt%) is longer than if the retention is poorer because the segregation is faster. The segregation of mercury is generally a faster process than stripping. The stripping factor (mass of water evaporated per mass of mercury stripped) of mercury at the start of boiling were found to be less than 1000 compared to the assumed design basis value of 750 (the theoretical factor is 250). However, within two hours, this value increased to at least 2000 lb water per lb Hg. For runs with higher mercury recovery in the offgas system, the stripping factor remained around 2000, but runs with low recovery had stripping factors of 4000 to 40,000. DWPF data shows similar trends with the stripping factor value increasing during boiling. These high values correspond to high segregation and low retention of mercury in the sludge. The stripping factor for a pure Hg metal bead in water was found to be about 10,000 lb/lb. About 10-36% of the total Hg evaporated in a SRAT cycle was refluxed back to the SRAT during formic acid addition and boiling. Mercury is dissolved as a result of nitric acid formation from absorption of NO x . The actual solubility of dissolved mercury in the acidic condensate is about 100 times higher than the actual concentrations measured. Mercury metal present in the MWWT from previous batches could be dissolved by this acidic condensate. The test of the effect of higher SRAT condenser temperature on recovery of mercury in the MWWT and offgas system was inconclusive. The recovery at higher temperature was lower than several low temperature runs, but about the same as other runs. Factors other than temperature appear to affect the mercury recovery. The presence of chloride and iodide in simulants resulted in the formation of mercurous chloride and mercurous iodide, respectively, in the offgas system. Actual waste data shows that the chloride content is much less than the simulant concentrations. Future simulant tests should minimize the addition of chloride. Similarly, iodine addition should be eliminated unless actual waste analyses show it to be present; currently, total iodine is not measured on actual waste samples.
Spatially resolved deep-UV Raman spectroscopy was applied to solutions of CO 2 and H 2 O (or D 2 O), which were subject to a temperature gradient in a thermally regulated high-pressure concentric-tube Raman cell in an attempt to measure a Soret effect in the vicinity of the critical point of CO 2 . Although Raman spectra of solutions of CO 2 dissolved in D 2 O at 10 MPa and temperatures near the critical point of CO 2 had adequate signal-to-noise and spatial resolution to observe a Soret effect with a Soret coefficient with magnitude of |S T | > 0.03, no evidence for an effect of this size was obtained for applied temperature gradients up to 19⁰C. The presence of 1 M NaCl did not make a difference. In contrast, the concentration of CO 2 dissolved in H 2 O was shown to vary significantly across the temperature gradient when excess CO 2 was present, but the results could be explained simply by the variation in CO 2 solubility over the temperature range and not to kinetic factors. For mixtures of D 2 O dissolved in scCO 2 at 10 MPa and temperatures close to the critical point of CO 2 , the Raman peaks for H 2 O were too weak to measure with confidence even at the limit of D 2 O solubility.
During irradiation of nuclear fuel in a reactor, the five metals, Mo, Pd, Rh, Ru, and Tc, migrate to the fuel grain boundaries and form small metal particles of an alloy known as epsilon metal (ε-metal). When the fuel is dissolved in a reprocessing plant, these metal particles remain behind with a residue - the undissolved solids (UDS). Some of these same metals that comprise this alloy that have not formed the alloy are dissolved into the aqueous stream. These metals limit the waste loading for a borosilicate glass that is being developed for the reprocessing wastes. Epsilon metal is being developed as a waste form for the noble metals from a number of waste streams in the aqueous reprocessing of used nuclear fuel (UNF) - (1) the ε-metal from the UDS, (2) soluble Tc (ion-exchanged), and (3) soluble noble metals (TRUEX raffinate). Separate immobilization of these metals has benefits other than allowing an increase in the glass waste loading. These materials are quite resistant to dissolution (corrosion) as evidenced by the fact that they survive the chemically aggressive conditions in the fuel dissolver. Remnants of ε-metal particles have survived in the geologically natural reactors found in Gabon, Africa, indicating that they have sufficient durability to survive for ≈ 2.5 billion years in a reducing geologic environment. Additionally, the ε-metal can be made without additives and incorporate sufficient foreign material (oxides) that are also present in the UDS. Although ε-metal is found in fuel and Gabon as small particles (≈10 µm in diameter) and has survived intact, an ideal waste form is one in which the surface area is minimized. Therefore, the main effort in developing ε-metal as a waste form is to develop a process to consolidate the particles into a monolith. Individually, these metals have high melting points (2617°C for Mo to 1552°C for Pd) and the alloy is expected to have a high melting point as well, perhaps exceeding 1500°C. The purpose of the work reported here is to find a potential commercial process with which ε-metal plus other components of UDS can be consolidated into a solid with minimum surface area and high strength Here, we report the results from the preliminary evaluation of spark-plasma sintering (SPS), hot-isostatic pressing (HIP), and microwave sintering (MS). Since bulk ε-metal is not available and companies could not handle radioactive materials, we prepared mixtures of the five individual metal powders (Mo, Ru, Rh, Pd, and Re) and baddeleyite (ZrO 2 ) to send the vendors of SPS, HIP, and MS. The processed samples were then evaluated at the Pacific Northwest National Laboratory (PNNL) for bulk density and phase assemblage with X-ray diffraction (XRD) and phase composition with scanning electron microscopy (SEM). Physical strength was evaluated qualitatively. Results of these scoping tests showed that fully dense cermet (ceramic-metal composite) materials with up to 35 mass% of ZrO 2 were produced with SPS and HIP. Bulk density of the SPS samples ranged from 87 to 98% of theoretical density, while HIP samples ranged from 96 to 100% of theoretical density. Microwave sintered samples containing ZrO 2 had low densities of 55 to 60% of theoretical density. Structurally, the cermet samples showed that the individual metals alloyed in to ε-phase - hexagonal-close-packed (HCP) alloy (4-95 mass %), the α-phase - face-centered-cubic (FCC) alloy structure (3-86 mass %), while ZrO 2 remained in the monoclinic structure of baddeleyite. Elementally, the samples appeared to have nearly uniform composition, but with some areas rich in Mo and Re, the two components with the highest melting points. The homogeneity in distribution of the elements in the alloy is significantly improved in the presence of ZrO 2 . However, ZrO 2 does not appear to react with the alloy, nor was Zr found in the alloy.
The overall objective of the present work was to develop a new scale-prevention technology by continuously precipitating and removing dissolved mineral ions (such as calcium and magnesium) in cooling water while the COC could be doubled from the present standard value of 3.5. The hypothesis of the present study was that if we could successfully precipitate and remove the excess calcium ions in cooling water, we could prevent condenser-tube fouling and at the same time double the COC. The approach in the study was to utilize pulse spark discharges directly in water to precipitate dissolved mineral ions in recirculating cooling water into relatively large suspended particles, which could be removed by a self-cleaning filter. The present study began with a basic scientific research to better understand the mechanism of pulse spark discharges in water and conducted a series of validation experiments using hard water in a laboratory cooling tower. Task 1 of the present work was to demonstrate if the spark discharge could precipitate the mineral ions in water. Task 2 was to demonstrate if the self-cleaning filter could continuously remove these precipitated calcium particles such that the blowdown could be eliminated or significantly reduced. Task 3 was to demonstrate if the scale could be prevented or minimized at condenser tubes with a COC of 8 or (almost) zero blowdown. In Task 1, we successfully completed the validation study that confirmed the precipitation of dissolved calcium ions in cooling water with the supporting data of calcium hardness over time as measured by a calcium ion probe. In Task 2, we confirmed through experimental tests that the self-cleaning filter could continuously remove precipitated calcium particles in a simulated laboratory cooling tower such that the blowdown could be eliminated or significantly reduced. In addition, chemical water analysis data were obtained which were used to confirm the COC calculation. In Task 3, we conducted a series of heat transfer fouling tests using a condenser heat exchanger in the laboratory cooling tower, from which we confirmed that the plasma water treatment technology could prevent or significantly mitigate mineral foulings in condenser tubes when compared with the no-treatment case. With the completion of the present work, a cooling water treatment technology using pulse spark discharges is currently ready for field-validation tests. The plasma water treatment technology is a true mechanical water softener with almost no maintenance, which continuously converts hard water to soft water spending a relatively small amount of energy. Such a mechanical water softener could find wide-spread applications to solve hard water problems both in industry and at home.
A program of laboratory experiments, modeling and fieldwork was carried out at Yale University, University of Maryland, and University of Hawai‘i, under a DOE Award (DE-FE0004375) to study mineral carbonation as a practical method of geologic carbon sequestration. Mineral carbonation, also called carbon mineralization, is the conversion of (fluid) carbon dioxide into (solid) carbonate minerals in rocks, by way of naturally occurring chemical reactions. Mafic and ultramafic rocks, such as volcanic basalt, are natural candidates for carbonation, because the magnesium and iron silicate minerals in these rocks react with brines of dissolved carbon dioxide to form carbonate minerals. By trapping carbon dioxide (CO 2 ) underground as a constituent of solid rock, carbonation of natural basalt formations would be a secure method of sequestering CO 2 captured at power plants in efforts to mitigate climate change. Geochemical laboratory experiments at Yale, carried out in a batch reactor at 200°C and 150 bar (15 MPa), studied carbonation of the olivine mineral forsterite (Mg 2 SiO 4 ) reacting with CO 2 brines in the form of sodium bicarbonate (NaHCO 3 ) solutions. The main carbonation product in these reactions is the carbonate mineral magnesite (MgCO 3 ). A series of 32 runs varied the reaction time, the reactive surface area of olivine grains and powders, the concentration of the reacting fluid, and the starting ratio of fluid to olivine mass. These experiments were the first to study the rate of olivine carbonation under passive conditions approaching equilibrium. The results show that, in a simple batch reaction, olivine carbonation is fastest during the first 24 hours and then slows significantly and even reverses. A natural measure of the extent of carbonation is a quantity called the carbonation fraction, which compares the amount of carbon removed from solution, during a run, to the maximum amount that could have been removed if the olivine initially present had fully dissolved and the cations released had subsequently precipitated in carbonate minerals. The carbonation fractions observed in batch experiments with olivine grains and powders varied significantly, from less than 0.01 (1%) to more than 0.5 (50%). Over time, the carbonation fractions reached an upper limit after about 24 to 72 hours of reaction, then stayed constant or decreased. The peak Final Scientific/Technical Report DE-FE0004275 | Mineral Carbonation | 4 coincided with the appearance of secondary magnesium-bearing silicate minerals, whose formation competes for magnesium ions in solution and can even promote conditions that dissolve magnesite. The highest carbonation fractions resulted from experiments with low ratios of concentrated solution to olivine, during which amorphous silica spheres or meshes formed, instead of secondary silicate minerals. The highest carbonation fractions appear to result from competing effects. Precipitation of silica layers on olivine reduces the reactive surface area and, thus, the rate of olivine dissolution (which ultimately limits the carbonation rate), but these same silica layers can also inhibit the formation of secondary silicate minerals that consume magnesite formed in earlier stages of carbonation. Simulation of these experiments with simple geochemical models using the software program EQ3/6 reproduces the general trends observed—especially the results for the carbonation fraction in short-run experiments. Although further experimentation and better models are needed, this study nevertheless provides a framework for understanding the optimal conditions for sequestering carbon dioxide by reacting CO 2 -bearing fluids with rocks containing olivine minerals. A series of experiments at the Rock Physics Laboratory at the University of Maryland studied the carbonation process during deformation of thermally cracked olivine-rich rock samples (dunite) saturated with CO 2 brines of varying compositions. A goal of these geomechanical experiments was to see if flow and deformation processes, which accompany natural carbonation reactions in underground settings, work to enhance or inhibit the reactions. The experiments involved hydrostatic compaction, followed by deformation at a constant rate of strain. Sample permeability was monitored during the reactions. Comparison of the samples’ volume changes to their axial strains (shortening) during deformation indicates that samples reacted with CO 2 -saturated brines accommodate more axial compaction, before the onset of dilation (a swelling that precedes rock failure), than samples reacted with distilled water. Analyses of the reacted samples with scanning electron microscope (SEM) images indicate, first, that dissolution of olivine occurring in the initial stages of carbonation can provide pathways to fluid flow that sustain the reaction, and, second, that carbonate minerals precipitated along existing fractures in the rocks may serve as asperities, or roughness on a crack’s surface that restricts its closure. Final Scientific/Technical Report DE-FE0004275 | Mineral Carbonation | 5 In a related study undertaken by one of the principal investigators as a spin-off of the main project, a simple model of (magnesite) crystal growth in the pore space of basalts undergoing carbonation was developed. The model suggests that, under a carefully controlled program of CO 2 injection, carbonate mineral growth can harden the rock formation against earthquakes that might otherwise be induced by the injection of large fluid volumes (Yarushina and Bercovici, 2013). The overall conclusion of the research project is that mineral carbonation of underground mafic and ultramafic rock formations is a viable candidate for long-term sequestration of man-made carbon dioxide. No results obtained during the project indicate that the method is inherently intractable in its implementation; moreover, enormous volumes of basalt near Earth’s surface are candidate locations for large-scale injection programs. The geochemical experiments do indicate, however, that there will be significant engineering challenges in maintaining high rates of carbonation, by delaying the onset of chemical conditions that promote formation of secondary silicate minerals and, therefore, slow down, or even reverse, the carbonation process. It remains an open question as to whether carbonation processes can be sustained for many years in an engineered system operating on a large scale—a scale capable of accommodating millions of tons of CO 2 annually. The development of realistic theoretical models that can systematically describe the combined effects of reactive flow, precipitation and geomechanical deformation is a major barrier to further understanding of the practical viability of mineral carbonation as large-scale method of carbon sequestration.
DOE sites conduct traditional environmental monitoring programs that require collecting, processing, and analyzing water, sediment, and fish samples. However, recently developed passive sampling technologies, such as Diffusive Gradient in Thin films (DGT), may measure the chemical phases that are available and toxic to organisms (the bioavailable fraction), thereby producing more accurate and economical results than traditional methods. Our laboratory study showed that dissolved copper concentrations measured by DGT probes were strongly correlated with the uptake of copper by Lumbriculus variegatus, an aquatic worm, and with concentrations of copper measured by conventional methods. Dissolved copper concentrations in DGT probes increased with time of exposure, paralleling the increase in copper with time that ocurred in Lumbriculus. Additional studies with a combination of seven dissolved metals showed similar results. These findings support the use of DGT as a biomimetic monitoring tool and provide a basis for refinement of these methods for cost-effective environmental monitoring at DOE sites.
Plant-level modeling and simulation of a used nuclear fuel prototype dissolver is presented. Emphasis is given in developing a modeling and simulation approach to be explored by other processes involved in the recycle of used fuel. The commonality concepts presented in a previous communication were used to create a model and realize its software module. An initial model was established based on a theory of chemical thermomechanical network transport outlined previously. A software module prototype was developed with the required external behavior and internal mathematical structure. Results obtained demonstrate the generality of the design approach and establish an extensible mathematical model with its corresponding software module for a wide range of dissolvers. Scale up numerical tests were made varying the type of used fuel (breeder and light-water reactors) and the capacity of dissolution (0.5 t/d to 1.7 t/d). These tests were motivated by user requirements in the area of nuclear materials safeguards. A computer module written in high-level programing languages (MATLAB and Octave) was developed, tested, and provided as open-source code (MATLAB) for integration into the Separations and Safeguards Performance Model application in development at Sandia National Laboratories. The modeling approach presented here is intended to serve as a template for a rational modeling of all plant-level modules. This will facilitate the practical application of the commonality features underlying the unifying network transport theory proposed recently. In addition, by example, this model describes, explicitly, the needed data from sub-scale models, and logical extensions for future model development. For example, from thermodynamics, an off-line simulation of molecular dynamics could quantify partial molar volumes for the species in the liquid phase; this simulation is currently at reach for high-performance computing. From fluid mechanics, a hold-up capacity function is needed for the dissolver device; this simulation is currently at reach for computational fluid mechanics given the existing CAD geometry. From chemical transport phenomena, a simulation of the particle-scale dissolution front is needed to derive an improved solid dissolution kinetics law by predicting the local surface area change; an example was provided in this report. In addition, the associated reaction mechanisms for dissolution are presently largely untested and simplified, hence even a parallel experimental program in reaction kinetics is needed to support modeling and simulation efforts. Last but not least, a simple account of finite rates of solid feed and transfer can be readily introduced via a coupled delayed model. These are some of the theoretical benefits of a rational plant-level modeling approach which guides the development of smaller length and time scale modeling. Practical, and other theoretical benefits have been presented on a previous report.
The Savannah River National Laboratory (SRNL) was tasked with preparing and shipping samples for Hg speciation by Eurofins Frontier Global Sciences (FGS), Inc. in Bothell, WA on behalf of the Savannah River Remediation (SRR) Mercury Program Team. These samples were analyzed for seven species including: total mercury, dissolved mercury, inorganic mercury ((Hg(I) and Hg(II)), elemental mercury, methylmercury, ethylmercury, and dimethylmercury, with an eighth species, particulate mercury, calculated from the difference between total and dissolved mercury after subtracting the elemental mercury. The species fraction of total mercury measured has ranged broadly from a low of 32% to a high of 146%, though the vast majority of samples have been <100%. This can be expected since one is summing multiple values that each have at least a ± 20% measurement uncertainty. Two liquid waste tanks particularly important to understanding the distribution of mercury species in the Savannah River Site (SRS) Tank Farm were selected for a round robin analysis by Eurofins FGS and BrooksApplied Laboratories (BAL). The analyses conducted by BAL on the Tank 22 and 38 samples and their agreement with those obtained from Eurofins FGS for total mercury, dissolved mercury, methylmercury, ethylmercury, and dimethylmercury provide a strong degree of confidence in these species measurements
In the field of nuclear forensics, one of the biggest challenges is to dissolve postdetonation debris for analysis. Debris generated after a nuclear detonation is a glassy material that is difficult to dissolve with chemicals. Traditionally, concentrated nitric acid, hydrofluoric acid, or sulfuric acid are employed during the dissolution. These acids, due to their corrosive nature, are not suitable for in-field/on-site sample preparations. Uranium oxides are commonly present in nuclear fuel processing plants and nuclear research facilities. In uranium oxides, the level of uranium isotope enrichment is a sensitive indicator for nuclear nonproliferation and is monitored closely by the International Atomic Energy Agency (IAEA) to ensure there is no misuse of nuclear material or technology for nuclear weapons. During an IAEA on-site inspection at a facility, environmental surface swipe samples are collected and transported to the IAEA headquarters or network of analytical laboratories for further processing. Uranium oxide particles collected on the swipe medium are typically dissolved with inorganic acids and are then analyzed for uranium isotopic compositions. To improve the responsiveness of on-site inspections, in-field detection techniques have been recently explored. However, in-field analysis is bottlenecked by time-consuming and hazardous dissolution procedures, as corrosive inorganic acids must be used. Corrosive chemicals are difficult to use in the field due to personnel safety considerations, and the transportation of such chemicals is highly regulated. It was therefore necessary to develop fast uranium oxide dissolution methods using less hazardous chemicals in support of the rapid infield detection of anomalies in declared nuclear processes.