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At least 955 records · Page 53
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

TCCR Operational Summary and Optimization for Tank 9 Processing - 20314

Savannah River Remediation (SRR) manages and operates the liquid waste facilities at Savannah River Site (SRS) for the Department of Energy (DOE). Stored liquid waste is a complex mixture of insoluble solids (sludge) and soluble salts in an alkaline solution. SRR has deployed the Tank Closure Cesium Removal (TCCR) system, a tank-side ion exchange process, to remove radioactive cesium from salt waste and enable onsite disposal of the resulting decontaminated salt solution as low-level waste at the Saltstone facilities. The TCCR system consists of two prefilters, four ion exchange (IX) columns, one resin trap, and a ventilation system. The IX process uses a form of inorganic crystalline silicotitanate (CST), which has a high affinity for cesium and other alkali metals, strontium, and actinides. This process is currently deployed utilizing salt feed from Tank 10, with future plans to dissolve solid salt in Tank 9 and transfer the salt solution to Tank 10 for processing through TCCR. The feed for TCCR must be created from salt-cake in Tank 10 through a dissolution process. Once enough salt has been dissolved, a qualification process is entered. This process characterizes the feed and ensures the cesium loading on the columns will not cause boiling of waste within the columns during or after processing. Once the batch has been qualified, salt waste is fed to the TCCR system through a transfer pump in the center of the tank. The waste is filtered through a set of two shielded, dead-end prefilters that prevent solids buildup in the columns. The filtered salt solution then travels to the shielded IX columns, which can be operated individually or in series, where the cesium is sorbed on the CST media. The decontaminated salt solution (DSS) then travels through a resin trap and out of the module to Tank 11. TCCR has successfully processed approximately 795,000 L of Tank 10H radioactive salt waste over two batches to date. There has not yet been a system induced shutdown. The prefilters performed as expected with only minor degradation in recovery of differential pressure after a backflush sequence. The time between backflushes decreased as each batch reached the end of processing. The hydraulics in the IXCs mostly performed as expected at all flow rates, except for one IXC that will be further investigated during Batch 3 processing. The TCCR system has shown some opportunities for more efficient processing during the length of the demonstration so far. For future processing of material from Tank 9H through Tank 10H and the TCCR unit, TCCR 1A will implement changes to the prefilters and the IXCs. The prefilters will have an increased surface area and a new filter media in an effort to increase time between filter swaps and improve backwashing cleaning capability. The IXCs will have a reduced diameter to allow for increased heat transfer out of the column and increased loading of Cs-137. Additionally, a new form of CST with an increased kinetic performance is being investigated for use during TCCR 1A operation. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2019

The Microstructure, and Mechanical and Corrosion Properties of As-Cast and As-Extruded Mg-2%Zn-x%Cu Alloys After Solution and Aging Heat Treatments

The effects of different Cu concentrations and heat treatment on the microstructure, mechanical and corrosion properties of the as-cast and hot-extruded Mg-2%Zn alloys were studied. The results showed that T6 heat treatment led to the dissolution of intermetallics and breaking the continuous networks of intermetallics. Also, the grain size of the base alloy decreased with further Cu additions after solution and aging heat treatments. Microstructural characterization indicated that Mg(Zn,Cu) and Mg(Zn,Cu){sub 2} intermetallics were formed which their volume fractions increased with exceeding Cu additions. Moreover, the addition of 3 wt.% Cu and T6 heat treatment increased the Brinell hardness of both as-cast and hot-extruded specimens reached to 94 HBN and 116 HBN, respectively. The optimum amounts of the ultimate tensile strength and elongation values obtained from 0.1 wt.% Cu addition for both conditions after T6 treatment which were 253 MPa, 11.5% and 263 MPa, 14.7%, respectively. However, more Cu addition (> 0.5 wt.%) deteriorated the tensile properties of the alloy due to the high volume fraction of intermetallics. The yield tensile strength increased continuously with different Cu additions for the cast and extruded alloys after solution and aging heat treatments. After T6 heat treatment, extruded alloys showed better anti-corrosion properties than those of the cast alloys, while the extruded Mg-2%Zn-0.1%Cu alloy exhibited the best anti-corrosion property. Further Cu addition increased the volume fraction of intermetallics and enhanced the corrosion rate which was due to the galvanic couple effect.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Vertical Co 9 S 8 hollow nanowall arrays grown on a Celgard separator as a multifunctional polysulfide barrier for high-performance Li–S batteries

Lithium–sulfur (Li–S) batteries have been regarded as one of the most promising next-generation energy-storage devices, due to their low cost and high theoretical energy density (2600 W h kg -1 ). However, the severe dissolution of lithium polysulfides (LiPSs) and the fatal shuttle effect of the sulfur cathode seriously hinder the practical applications of Li–S batteries. To address such issues, we present here, for the first time, a novel metal organic framework (MOF)-derived Co 9 S 8 nanowall array with vertical hollow nanoarchitecture and high electrical conductivity, which is grown in situ on a Celgard separator (Co 9 S 8 –Celgard) via a feasible and scalable liquid-reaction approach, as an efficient barrier for LiPSs in Li–S batteries. Benefiting from the direct in situ growth of vertical Co 9 S 8 hollow nanowall arrays as a multifunctional polar barrier, the Co 9 S 8 –Celgard separator possesses large surface area, excellent mechanical stability, and particularly strong LiPS-trapping ability via chemical and physical interactions. With these advantages, even with a pure sulfur cathode with a high sulfur loading of 5.6 mg cm -2 , the Li–S cells with the Co 9 S 8 –Celgard separator exhibit outstanding electrochemical performance: the initial specific capacity is as high as 1385 mA h g -1 with a retention of 1190 mA h g -1 after 200 cycles. The cells deliver a high capacity of 530 mA h g -1 at a 1C rate (1675 mA g -1 ) even after an impressive number of 1000 cycles with an average capacity fade of only 0.039% per cycle, which is promising for long-term cycling application at high charge/discharge current densities, and pouch-type Li–S cells with the Co 9 S 8 –Celgard separator display excellent cycling performance. When the optimized cathode with the sulfur loading in well-designed yolk–shelled carbon@Fe 3 O 4 (YSC@Fe 3 O 4 ) nanoboxes is employed, the cell with Co 9 S 8 –Celgard delivers a high initial capacity of 986 mA h g -1 at a 1C rate with a capacity retention as high as 83.2% even after a remarkable number of 1500 cycles. In conclusion, this work presents a strategy to grow on the separator a multifunctional polar interlayer with unique nanoarchitecture and high conductivity to chemically and physically trap the LiPSs, thus significantly enhancing the performance of Li–S batteries.

25 ENERGY STORAGE↗
DOE OSTI2022

Characterization of Contaminants and Mobility in WMA A-AX Boreholes D0006 and D0008

This study was initiated to determine if subsurface contaminants in the A-AX vadose zone at the Hanford site (boreholes D0006 and D0008) caused corrosion of nearby stainless steel well casings (299-E-24-19, 299-E25-46, and 299-E25-236) and, based on the type and distribution of contaminants, determine if contaminants are from one or more sources including a) the A-104 and/or A-105 tanks, b) the 242A evaporator, and c) the 200-E-286 ditch. A tiered approach was used for characterizing contaminants in vadose zone sediments starting with mobile and total contaminant concentrations (Tier 1), characterizing contaminant speciation (Tier 2), and measuring contaminant leaching (Tier 3). Total and mobile contaminant measurements at seven depths showed elevated sulfate and nitrate in all samples (130 to 280 ft depth), elevated chloride in five depths, and no elevated radionuclides except I-129 in D0006 at 206 to 208 ft depth. If these contaminants were initially acidic, stainless-steel corrosion would occur. However, because sediments likely have a high acid neutralization capacity, an acidic spill would have been neutralized within tens of feet, so casing corrosion would likely occur in shallow sediments. GEL labs data also shows low (but above natural) chromate from shallow to 170 ft depth, then higher chromate to 280 ft, suggesting a surface Cr spill or casing corrosion. GEL labs data also showed evidence of more than one plume, with deep nitrate, sulfate, and chloride migration, but only shallow tritium migration. Tritium should migrate nearly unretarded in the subsurface like nitrate and chloride. Elevated aqueous cations and anions in the D0006 206 to 208' depth pore water (SO 4 2- , NO 3 - , Na + , K + , Ca 2+ , Mg 2+ , Si) could be the result of acid disposal and calcite dissolution at shallow depth, with deeper migration of SO 4 2- , NO 3 - from acids and Ca 2+ and Mg 2+ from calcite. Elevated Si (160 mg/L) indicates dissolution of clays or other silicates, which can also occur in acids. Acid extractable metals did show elevated Cr (but not Fe, Ni, Mo, and Mn) above natural levels, which may indicate stainless-steel well corrosion or transport of metals from a shallow spill. The elevated I-129 in D0006 at 206 to 208' depth was low with 0.34 μg/g in pore water and 1.5 μg/g total extractable I-129 in the sediment, which indicates significant fraction of I-129 was bound in one or more precipitates. Although total I-129 was below detection limits in most extractions due to high molybdate interference, I-127 analysis provided some insight into potential precipitate phases. Total I-127 was mainly extracted by acetate or acetic acid (67%), which may be iodine in calcite. Inorganic carbon measurement identified 1.65% calcite, and total organic carbon (TOC) was below detection limits, so iodine was not associated with organic matter. Nearly all the I-127 was present as iodide. In 1-D leach experiments, I-127 as iodide leached from the sediment within 2 pore volumes. Due to high and dynamic molybdate leaching from the sediment and interference with I-129 analysis, there were few quantifiable I-129 measurements. The calculated molybdate release rates from the sediment suggested Mo was being released from the same precipitate phase, such as molybdate incorporated into calcite. Overall, because there was little radioactive contamination measured in D0006 and D0008 boreholes, potential releases from A-104 and A-105 did not reach this location south of the A tank farm. Elevated cations and anions found in D0006 and D0008 at depth as the result of acidic disposal could cause shallow stainless steel casing corrosion. The nearby 242A evaporator generally contained alkaline waste and tritium, but the nearby 200-E-286 ditch generally contained high Cl - liquid effluent, so these are unlikely to be acidic sources.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2018

Dual in-aquifer and near surface processes drive arsenic mobilization in Cambodian groundwaters

Millions of people globally, and particularly in South and Southeast Asia, face chronic exposure to arsenic from reducing groundwaters in which. Arsenic release to is widely attributed largely to reductive dissolution of arsenic-bearing iron minerals, driven by metal reducing bacteria using bioavailable organic matter as an electron donor. However, the nature of the organic matter implicated in arsenic mobilization, and the location within the subsurface where these processes occur, remains debated. In a high resolution study of a largely pristine, shallow aquifer in Kandal Province, Cambodia, we have used a complementary suite of geochemical tracers (including 14 C, 3 H, 3 He, 4 He, Ne, δ 18 O, δD, CFCs and SF 6 ) to study the evolution in arsenic-prone shallow reducing groundwaters along dominant flow paths. The observation of widespread apparent 3 H- 3 He ages of <55years fundamentally challenges some previous models which concluded that groundwater residence times were on the order of hundreds of years. Surface-derived organic matter is transported to depths of >30m, and the relationships between age-related tracers and arsenic suggest that this surface-derived organic matter is likely to contribute to in-aquifer arsenic mobilization. A strong relationship between 3 H- 3 He age and depth suggests the dominance of a vertical hydrological control with an overall vertical flow velocity of ~0.4±0.1m·yr-1 across the field area. A calculated overall groundwater arsenic accumulation rate of ~0.08±0.03μM·yr -1 is broadly comparable to previous estimates from other researchers for similar reducing aquifers in Bangladesh. Although apparent arsenic groundwater accumulation rates varied significantly with site (e.g. between sand versus clay dominated sequences), rates are generally highest near the surface, perhaps reflecting the proximity to the redox cline and/or depth-dependent characteristics of the OM pool, and confounded by localized processes such as continued in-aquifer mobilization, sorption/desorption, and methanogenesis.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2019

Root-driven weathering impacts on mineral-organic associations in deep soils over pedogenic time scales

Plant roots are primary weathering agents in deep soils, yet the impact of resulting mineral transformations on the vast deep soil carbon (C) reservoir are largely unknown. Root-driven weathering of primary minerals causes the formation of reactive secondary minerals, which may protect mineral-organic associations (MOAs) for centuries or millennia. Conversely, root-driven weathering may also transform secondary minerals, potentially enhancing the bioavailability of C previously protected in MOAs. Here we examined the impact of root-driven weathering on MOAs and their capacity to store C over pedogenic time scales. To accomplish this, we compared soil that experienced root-driven weathering, resulting in the formation of discrete rhizosphere zones in deep soil horizons (100-160 cm) of the Santa Cruz Marine Terrace chronosequence (65ka-226ka), with adjacent soil that experienced no root growth. Using a combination of radiocarbon, mass spectrometry, Mössbauer spectroscopy, and X-ray spectromicroscopy approaches, we characterized transformations of mineral-organic associations in relation to changes in C content, turnover and chemistry across four soils ranging in age from 65 to 226 ka. We found that the onset of root-driven weathering (65-90ka) increased the amount of C associated with poorly crystalline iron (Fe) and aluminum (Al) phases, particularly highly-disordered np-goethite. This increase coincided with greater C concentrations, longer C residence times, and a greater abundance of microbially-derived C. Continued root-driven weathering (137-226ka) did not significantly change the amount of C associated with crystalline Fe and Al phases, but resulted in a decline in the amount of C associated with poorly crystalline metal phases. This decline coincided with a decrease in C concentrations and potential turnover rates, and a shift toward plant-derived C. In contrast, soil not affected by root-driven weathering showed comparatively low amounts of C bound in poorly crystalline Fe and Al phases regardless of soil age and, correspondingly, lower C concentrations and estimated residence times. Furthermore, our results demonstrate that root driven-formation and disruption of poorly crystalline Fe and Al phases is a direct control on both C accrual and loss in deep soil. This finding suggests that root impacts on soil C storage are dependent on soil weathering stage, a consideration that is critical for future predictions of the vulnerability of deep soil C to global change.

58 GEOSCIENCES↗
DOE OSTI2018

Integrated characterization of CO 2 storage reservoirs on the Rock Springs Uplift combining geomechanics, geochemistry, and flow modeling

This project improves understanding of the effects CO 2 injection and storage on geomechanical, petrophysical, and other properties on two potential reservoirs, the Madison Limestone and Weber Sandstone, at the Rock Springs Uplift, southwest Wyoming. Rock physics studies, laboratory experiments, and computer simulations were employed. Two groups of rock samples were prepared, one aged with formation brine and the second aged with CO 2 -saturated formation brine and subsequently used for geomechanical, geochemical, and petrophysical testing. Rock physics studies provided a facies classification to discriminate among different lithologies and to investigate the feasibility of predicting petrophysical properties using seismic inversion. By applying a zone-wise regression relation established in this facies analysis, a 3D reservoir model was developed. It was determined that time-lapse seismic data are not feasible for monitoring CO 2 displacement at the Rock Springs Uplift or to mitigate leakage-risks situations because pressure and fluid saturation have small effects on elastic velocities and synthetic seismograms. The small variations that do occur are due to the low porosity of the sandstone and the high stiffness of the dolomite. In the Madison Limestone, mineral dissolution due to reaction with CO 2 -saturated brine was observed in highly permeable pathways while mineral precipitation happened in intergranular or micropores. Changes in pore size were quantified via Time-Domain Nuclear Magnetic Resonance transverse relaxation time (T 2 ) and diffusion coefficient distributions. As opposed to continuous injection of CO 2 -saturated brine, a subtle increase in porosity after static ‘soaking’ with CO 2 -saturated brine increases permeability due to the heterogeneity of changes in pore and pore throat sizes. Porosity-permeability relationships are fitted using a power-law function that can be adopted to model time-evolved porosity and permeability in a transport-limited CO 2 injection process. The effect of CO 2 -saturated brine on the linear elastic properties of Weber Sandstone and Madison Limestone cannot be generally concluded. Considering horizontal and vertical orientations and different confining pressures, no consistent relationship between stress (or strain) data and reaction with CO 2 -saturated brine was observed in the nonlinear plastic and post-failure regime. The change of elastic constants due to reaction with CO 2 -saturated brine is more significant in Madison Limestone than in Weber Sandstone; however, no consistent trend was observed. Reservoir simulations suggest that injectivity for Weber Sandstone is adversely impacted by low permeability. Changes in confining pressure do not impact injection rate and can be ignored while the effect of changes to pore pressure cannot. The effect of confining pressure and pore pressure on the size of the CO 2 plume in the Madison Limestone is negligible because of higher permeability. Geomechanical and petrophysical properties induced by CO 2 -brine-rock reactions were time-dependent. Simulations considered these time-dependent properties and indicate that injectivity, porosity distribution, pressure distribution and CO 2 saturation were affected.

58 GEOSCIENCES↗
DOE OSTI2020

Investigation of Thermolytic Hydrogen Generation Rate in Tank 44 Dissolved Saltcake Samples

Saltcake core samples collected from Tank 44 in 2006 were dissolved to provide material for HGR measurements applicable to F-Area dissolved saltcake material. Additionally, characterization was performed on the Tank 44 saltcake material. The following are key results from the Tank 44 saltcake characterization. The Tank 44 Upper Saltcake Composite, corresponding to the 171 to 285 inch tank level, contained by mass approximately 69% sodium nitrate, 11% sodium carbonate, 8% sodium nitrite, smaller amounts of other salts and components, and 9% unquantified (which includes water, water of hydration, oxygen/hydrogen content of oxides and hydroxides, and uncertainty). The Tank 44 Lower Saltcake Composite, corresponding to the 76 to 114 inch tank level, contained by mass approximately 49% sodium carbonate, 18% sodium nitrate, smaller amounts of other salts, at least 8% sludge, and 9% unquantified (see above). The dissolved saltcake contained free hydroxide less than quantifiable (<0.01 M) due to the limited quantity of material that could be removed from the Shielded Cells based on the sample radioactivity. Measurement by pH paper provided an approximate pH of 12. The following are key results from the Tank 44 HGR testing. During boiling at 106.7 °C, HGR for Tank 44 dissolved saltcake without added glycolate was 7.2×10 -8 ft 3 h -1 ga l-1 . During boiling at 106.9 °C, HGR for Tank 44 dissolved saltcake with 1000 mg/L of added glycolate was 8.2×10 -8 ft 3 h -1 gal -1 . ∙ For the test without added glycolate, the first several HGR measurements at 70, 85, and 100 °C gave indication of the release of dissolved hydrogen and should not be used to represent the sustained thermolytic HGR for those temperatures. The measurements at boiling are the best representation of thermolysis in this testing. Carbon dioxide was observed at concentrations up to 6 vol% in the flow-system offgas for the test at boiling. ∙ Methane generation was observed at 100 °C and boiling. Methane concentration in the total gas generated during testing remained well below the lower flammability limit for methane in air. The addition of 1000 mg/L of glycolate did not have a significant impact on the hydrogen generation rates measured during this testing. The low hydroxide concentration in the Tank 44 dissolved saltcake likely influenced the relatively low thermolytic HGR and high carbon dioxide release observations in this testing. Based on the observation that methane was generated or released upon heating SRS radioactive Tank 44 waste samples to 100 °C and above, we recommend gaining a greater understanding of the cause and mechanism of its generation. First, the applicable literature should be reviewed to reveal the thermolytic methane generation mechanisms of possible methane generating species in the SRS CSTF. If warranted, a plan should be developed for simulant tests with methylated siloxanes and other applicable compounds in order to gain a better mechanistic understanding of methane generation in the SRS CSTF.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2021

Investigation of Thermolytic Hydrogen Generation Rate in Tank 44 Dissolved Saltcake Samples

Saltcake core samples collected from Tank 44 in 2006 were dissolved to provide material for HGR measurements applicable to F-Area dissolved saltcake material. Additionally, characterization was performed on the Tank 44 saltcake material. The following are key results from the Tank 44 saltcake characterization. The Tank 44 Upper Saltcake Composite, corresponding to the 171 to 285 inch tank level, contained by mass approximately 69% sodium nitrate, 11% sodium carbonate, 8% sodium nitrite, smaller amounts of other salts and components, and 9% unquantified (which includes water, water of hydration, oxygen/hydrogen content of oxides and hydroxides, and uncertainty). The Tank 44 Lower Saltcake Composite, corresponding to the 76 to 114 inch tank level, contained by mass approximately 49% sodium carbonate, 18% sodium nitrate, smaller amounts of other salts, at least 8% sludge, and 9% unquantified (see above). The dissolved saltcake contained free hydroxide less than quantifiable (<0.01 M) due to the limited quantity of material that could be removed from the Shielded Cells based on the sample radioactivity. Measurement by pH paper provided an approximate pH of 12. The following are key results from the Tank 44 HGR testing. During boiling at 106.7 °C, HGR for Tank 44 dissolved saltcake without added glycolate was 7.2×10 -8 ft 3 h -1 gal -1 . During boiling at 106.9 °C, HGR for Tank 44 dissolved saltcake with 1000 mg/L of added glycolate was 8.2×10 -8 ft 3 h -1 gal -1 . For the test without added glycolate, the first several HGR measurements at 70, 85, and 100 °C gave indication of the release of dissolved hydrogen and should not be used to represent the sustained thermolytic HGR for those temperatures. The measurements at boiling are the best representation of thermolysis in this testing. Carbon dioxide was observed at concentrations up to 6 vol% in the flow-system offgas for the test at boiling. Methane generation was observed at 100 °C and boiling. Methane concentration in the total gas generated during testing remained well below the lower flammability limit for methane in air. The addition of 1000 mg/L of glycolate did not have a significant impact on the hydrogen generation rates measured during this testing. The low hydroxide concentration in the Tank 44 dissolved saltcake likely influenced the relatively low thermolytic HGR and high carbon dioxide release observations in this testing. Based on the observation that methane was generated or released upon heating SRS radioactive Tank 44 waste samples to 100 °C and above, we recommend gaining a greater understanding of the cause and mechanism of its generation. First, the applicable literature should be reviewed to reveal the thermolytic methane generation mechanisms of possible methane generating species in the SRS CSTF. If warranted, a plan should be developed for simulant tests with methylated siloxanes and other applicable compounds in order to gain a better mechanistic understanding of methane generation in the SRS CSTF.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

Nanoscale observations of Fe(ii)-induced ferrihydrite transformation

Because of its sorption properties, transformation of the nanomineral ferrihydrite (Fh) into more stable lepidocrocite (Lp) or goethite (Gt) has important impacts on the fate of metals, nutrients, and contaminants in soils/sediments. Although it is well known that the transformation rate is greatly accelerated under suboxic conditions by aqueous Fe(II), the enabling mass transfer process remains an ongoing debate among various mechanisms including dissolution/reprecipitation, solid-state recrystallization, and particle-mediated growth. In this paper, using electron microscopy, we examine the mineralogical evolution of 2-line Fh to Lp/Gt catalyzed by Fe(II) under strict anoxic conditions, including evaluation of Cl–SO 4 –HCO 3 anion effects. Emergence of Lp/Gt crystallites at the nanoscale was observed at ~20 min of reaction, earlier than previously reported. Lp is the first phase to nucleate in Cl-rich solutions without HCO 3 – ; whereas Lp and Gt concomitantly nucleate in SO 4 2– -rich solutions, and also when co-solute HCO 3 – is added. Lp crystallites nucleate as quasi-2D nanosheets one-unit-cell thick that contour the Fh surface; in contrast, rod-shaped (in Cl/SO 4 ) or acicular needle-shaped (in HCO 3 ) Gt crystals nucleate and grow radially outward from the Fh aggregates. Stages of transformation monitored by in situ μ-XRD coupled with aqueous Fe(II) uptake/release measurements are correlated with a short initial sorption stage followed by the onset of Lp/Gt growth that then progresses to Lp loss in favor of Gt. Microscopy data overwhelmingly support dissolution/reprecipitation as the underlying mechanism, including direct evidence for classical ion-by-ion Lp/Gt growth and Lp dissolution. The collective findings imply that the iron mass transfer through solution to distal Lp/Gt growth fronts is a critical enabling process facilitating rapid transformation.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Produced Fluid Induced Mineralogy and Elemental Alterations of Caney Shale, Southern Oklahoma

ABSTRACT This study involves batch reactor experiments and subsequent analyses of samples from Caney Shale in the Ardmore Basin of South-Central Oklahoma. Samples include mainly rock cores and cuttings recovered from two wells respectively drilled vertically through and horizontally across the Caney Shale. Mineralogical compositions are obtained by X-Ray Diffraction (XRD) measurements whilst microstructure and elemental distribution are acquired by Scanning Electron Microscopy/Energy Dispersive Spectroscopy (SEM/EDS) respectively. Batch experiments are then conducted using selected rock samples and produced fluid from the Caney Formation. Deionized water is also reacted with some samples to serve as standard. Experiments are conducted at 95°C and ambient pressure for 7 and 30 days to assess the geochemical rock-fluid interactions. Results show rock mineralogical compositions are predominantly quartz, feldspar, carbonates, and clay with minor pyrite. Post-experimental mineralogical changes observed in samples include increased amorphous entities especially within the clay portions of XRD plots and dissolution of feldspar and carbonate minerals and formation of new mineral phases, mostly clays and salts. These are corroborated by EDS elemental analyses which show decreased elemental compositions. The implications of reactions mentioned above include but not limited to, scale formation, clay fines migration and shale softening all of which pose significant permeability impairment on formation over time. INTRODUCTION Shale reservoirs account for a large share of unconventional reservoirs in the world (Lyu et al., 2015). However, ultra-low permeability and high clay compositions pose significant challenges when producing from these reservoirs (Dawuda and Srinivasan, 2022, 2023). Producing from these reservoirs therefore requires horizontal drilling and hydraulic fracturing technologies which have proven their efficacy in generating substantial permeability in reservoirs to ensure production (Fujian et al., 2019; Liu et al., 2018). Even after expensive horizontal drilling and hydraulic fracturing, geochemical reactions between engineered fluids and formation leads to fracture constriction and adversely impact petrophysical properties (permeability and porosity) of the reservoir. These technologies are therefore under constant development and improvement in various aspects to ensure fine tuning for specific reservoirs. Under present conditions, much of the hydrocarbon reserves in unconventional shale reservoirs are left unproduced due to rapid decline in permeability following resumption to production after hydraulic fracturing. It is therefore essential to understand the range of geochemical reactions that cause rapid depletion of permeability after hydraulic fracturing and apply these to each shale reservoir to ensure substantial recovery rates.

Awejori, G. A.↗
DOE OSTI2015

Alkali-activated Class F Fly Ash-rich Portland Cement Blends as Alternative Thermal Shock Resistant Cements

This study focused on evaluating the resistance of 300°C-autocalved alkali-activing Class F fly ash (FAF)-rich Type II Ordinary Portland Cement (OPC) blends with 80/20 and 90/10 FAF/OPC ratios to five thermal-shock (TS) fatigue cycles (one cycle, 600°C heat – 25°C water quenching). The factors to be evaluated included the hydration behaviors, crystalline/ amorphous phaseidentifications, -compositions and -transformations, and microstructural-developments andalterations for blended cements assembled by three different alkaline activators, sodium metasilicate (SMS), soda ash (SA), and sodium sulfate (SS). All factors were related directory to the changes in compressive strength after TS testing. The setting time of cement slurries at 25° and 85°C depended on the alkaline activators; SMS and SA contributing to a strong alkalinity hastened setting, while SS with moderate alkalinity extended the setting time. A more prolonged setting time was observed from non-activated cement. In this case, there were two separated hydration reactions: The first reaction was the hydration of OPC; the second one was associated with the dissolution and pozzolanic activity of FAF. In contrast, all alkali- activated cements engendered the concomitant hydration of OPC and FAF, thereby conferring a higher compressive strength on them than that of the non-activator one. The principal contributor to the development of strength of both the non-activated and activated cements at 300°C was the amorphous NaO 2 - or CaO-Al 2 O 3 - SiO 2 -H 2 O (N,C-A-S-H) phase formed by the interactions between alkaline activator, OPC, and FAF. This phase played an important role in minimizing the loss in strength after TS. On the other hand, adding SMS and SA introduced the mixed crystalline FAF-OPC hydrates, such as garranite and wairakite, as the major phases, into the autoclaved cement bodies. Also, these activators induced the formation of two FAF-related crystalline hydrates, analcime as the major phase and riversidelite (0.9 nm tobermorite) as the minor one. However, these identified phases were sensitive to TS, so converting the major phases into minor phases or vanishment. In contrast, three crystalline phases including calcite and anhydrous sodium sulfate as the major ones and 1.1 nm tobermorite as the minor one, that formed in non-activated and activated cements remained unchanged after TS. Additionally, SAactivated cement revealed porous microstructure created by the incorporation of copious amount of carbonate reaction products into the cement, raising concerns that cements might enhance the rate of water transportation and reduce compressive strength. Nevertheless, TS-insensitive amorphous N,C-A-S-H phase as the major cementitions structure coexisting with TS-insensitive crystalline products were responsible for sustaining the integrity of alkali-activated FAF-rich OPC cement systems in such harsh heat-cooling fatigue environments.

15 GEOTHERMAL ENERGY↗
DOE OSTI2014

Manipulating surface reactions in lithium-sulphur batteries using hybrid anode structures

Lithium-sulphur batteries have high theoretical energy density and potentially low cost, but significant challenges such as severe capacity degradation prevent its widespread adoption. Here we report a new design of lithium-sulphur battery using electrically connected graphite and lithium metal as a hybrid anode to control undesirable surface reactions on lithium. Lithiated graphite placed in front of the lithium metal functions as an artificial, self-regulated solid electrolyte interface layer to actively control the electrochemical reactions and minimize the deleterious side reactions, leading to significant performance improvements. Lithium-sulphur cells incorporating this hybrid anodes deliver capacities of >800 mAhg(-1) for 400 cycles at a high rate of 1,737mAg(-1), with only 11% capacity fade and a Coulombic efficiency >99%. This simple hybrid concept may also provide scientific strategies for protecting metal anodes in other energy-storage devices.

Huang, C↗
DOE OSTI2015

Change of translational-rotational coupling in liquids revealed by field-cycling {sup 1}H NMR

Applying the field-cycling nuclear magnetic resonance technique, the frequency dependence of the {sup 1}H spin-lattice relaxation rate, R{sub 1}(ω)=T{sub 1}{sup −1}(ω), is measured for propylene glycol (PG) which is increasingly diluted with deuterated chloroform. A frequency range of 10 kHz–20 MHz and a broad temperature interval from 220 to about 100 K are covered. The results are compared to those of experiments, where glycerol and o-terphenyl are diluted with their deuterated counter-part. Reflecting intra- as well as intermolecular relaxation, the dispersion curves R{sub 1}(ω,x) (x denotes mole fraction PG) allow to extract the rotational time constant τ{sub rot}(T, x) and the self-diffusion coefficient D(T, x) in a single experiment. The Stokes-Einstein-Debye (SED) relation is tested in terms of the quantity D(T, x) τ{sub rot}(T, x) which provides a measure of an effective hydrodynamic radius or equivalently of the spectral separation of the translational and the rotational relaxation contribution. In contrast to o-terphenyl, glycerol and PG show a spectral separation much larger than suggested by the SED relation. In the case of PG/chloroform mixtures, not only an acceleration of the PG dynamics is observed with increasing dilution but also the spectral separation of rotational and translational relaxation contributions continuously decreases. Finally, following a behavior similar to that of o-terphenyl already at about x = 0.6; i.e., while D(T, x) τ{sub rot}(T, x) in the mixture is essentially temperature independent, it strongly increases with x signaling thus a change of translational-rotational coupling. This directly reflects the dissolution of the hydrogen-bond network and thus a change of solution structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Vitrification of Hanford Tank Waste 241-AP-105 in a Continuous Laboratory-Scale Melter

Low-activity waste (LAW) stored in underground tanks on the Hanford site in Washington State is planned to be filtered for solids removal and processed through ion exchange columns for cesium removal at the Low-Activity Waste Pretreatment System facility. These pretreatment steps will allow the waste to be transferred to the Hanford Tank Waste Treatment and Immobilization Plant LAW facility for immobilization into glass. The liquid waste will be combined with glass-forming chemicals (GFCs) to form a waste feed slurry that can be fed to electric melters for vitrification. The process of continuously converting the aqueous feed slurry into a melt is dynamic and includes multiple reactions, degassing, and dissolution processes that depend on heat from the melt below. In this conversion process, waste components are partitioned into one of two streams: glass and off-gas. Processing information and chemical information associated with these waste product streams has been requested by Washington River Protection Solutions for actual tank waste from tank 241-AP-105 (referred to as AP-105). To acquire this type of information, a small-scale melter system was desired that would not require high volumes of input waste or the large resource commitment of a full-scale melter system, while also providing dynamic information that would be difficult to determine from batch reactions in a crucible system. A continuous laboratory-scale melter (CLSM), has been designed to operate with a continuous feeding process, while periodically pouring glass product and collecting off-gas. The CLSM vessel has been sized to collect the relevant process and chemical information from obtainable volumes of AP-105 waste samples. Two CLSMs were constructed: one in a non-radioactive environment for processing waste simulants and another in a fume hood capable of handling radioactive material for processing actual Hanford tank waste. This dual-system setup allowed for comparison between simulated and real tank waste with essentially identical test equipment. AP-105 waste simulant was first tested in the non-radioactive CLSM to determine the processability and desired operating window for the actual tank waste. Rhenium (Re) was added to the simulant to act as a surrogate for technetium-99 ( 99 Tc), a key waste component found in the actual tank waste. The partitioning of Re into the glass and off-gas products during the continuous feeding of simulant was determined, which allowed the Re retention, the mass flow rate of Re out of the CLSM via the glass product with respect to the mass flow rate of Re into the CLSM via the feed slurry, to be calculated. Key processing results and the average Re retention, from the CLSM test run with AP-105 simulant feed slurry are shown in Table ES.1.

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DOE OSTI2019

Dissolution of Light Curium Oxide with a Catalyzed Electrolytic Process

The ability to produce transcurium elements and isotopes, such as 249 Bk and 252 Cf, requires the appropriate feed material and a high thermal neutron flux. Currently, at Oak Ridge National Laboratory (ORNL), the High Flux Isotope Reactor (HFIR) provides one of the world’s highest steady state thermal neutron fluxes. The feed material consists of recycled curium from the decades of production of 249 Bk, 252 Cf, 253 Es, and 255/257 Fm at the Radiochemical Engineering Development Center (REDC). Over time, the feed material has been depleted and needs to be replenished. The current feed material is called “heavy recycled curium” and consists of over 50 wt% of 246/248 Cm isotopes. In order to replenish this stock material, additional curium is needed. The only curium material that is currently available consists predominantly (greater than 80 wt%) of 244 Cm. This material also contains 240 Pu from the radioactive decay of the 244 Cm. Because of the amount of 244 Cm is greater than 50% of the total Cm, this material is termed “light curium.” Today, 249 Bk and 252 Cf are produced in only two places in the world: the United States and Russia. In the United States, the US Department of Energy and its predecessors have made these isotopes and others available to research agencies and commercial users since the late 1960s as part of the Department of Energy heavy-element production program located at ORNL. Currently these materials are provided through the DOE Office of Science Nuclear Physics-Isotope Development and Production for Research and Applications and the Basic Energy Science-Heavy Element Chemistry. Feedstock for the production of 252 Cf and other transcurium element by-product isotopes was originally prepared by means of irradiation of multi-kilograms of 239 Pu in the large production reactors at the Savannah River Site. Products of the Savannah River Site irradiation were predominantly 242 Pu, 243 Am, and 244 Cm. These materials were shipped to ORNL for production of multi-milligram amounts per year of 252 Cf and other transcurium element isotopes by means of irradiation in the HFIR, followed by separation and purification processing in the Radiochemical Engineering Development Center (REDC). The transcurium element isotopes produced were distributed to other US and collaborating foreign laboratories for research studies to determine the nuclear and chemical properties of these rare materials. The Cm feed material plays a key role in the efficient production of 252 Cf. The early targets irradiated in HFIR contained only the 242 Pu, 243 Am, and 244 Cm produced at Savannah River Site, and the rate of production of 252 Cf was less than 1 mg per 8 g of target material as shown in Figure 1. Also, shown in Figure 1 is the significant difference in 252 Cf production between the light and heavy curium; it differs by approximately 2 orders of magnitude.

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DOE OSTI2018

Technetium Stabilization in Low-Solubility Sulfide Phases: A Review

We report that technetium contamination remains a major environmental problem at nuclear reprocessing sites, e.g., the Hanford Site, Washington, USA. At these sites, Tc is present in liquid waste destined for immobilization in a waste form or has been released into the subsurface environment. The high environmental risk associated with Tc is due to its long half-life (214 000 years) and the mobility of the oxidized anionic species Tc(VII)O 4 - . Under reducing conditions, TcO 4 - is readily reduced to Tc(IV), which commonly exists as a relatively insoluble and therefore immobile, hydrous Tc-oxide (TcO 2 · n H 2 O). The stability of Tc(IV) sequestered as solid phases depends on the solubility of the solid and susceptibility to reoxidation to TcO 4 - , which in turn depend on the (biogeo)chemical conditions of the environment and/or nuclear waste streams. Unfortunately, the solubility of crystalline TcO 2 or amorphous TcO 2 ·H 2 O is still above the maximum contaminant level (MCL) established by the U.S. EPA (900 pCi/L), and the kinetics of TcO 2 oxidative dissolution can be on the order of days to years. In addition to oxygen, sulfur can form complexes that significantly affect the adsorption, solubility, and reoxidation potential of Tc, especially Tc(IV). The principal technetium sulfides are TcS 2 and Tc 2 S 7 , but much less is known about the mechanisms of formation, stabilization, and reoxidation of Tc-sulfides. A common assumption is that sulfides are less soluble than their oxyhydrous counterparts. Determination of the molecular structure of Tc 2 S 7 in particular has been hampered by the propensity of this phase to precipitate as an amorphous substance. Recent work indicates that the oxidation state of Tc in Tc 2 S 7 is Tc(IV), in apparent contradiction to its nominal stoichiometry. Technetium is relatively immobile in reduced sediments and soils, but in many cases the exact sink for Tc has not been identified. Experiments and modeling have demonstrated that both abiotic and biologic mechanisms can exert strong controls on Tc mobility and that Tc binding or uptake into sulfide phases can occur. These and similar investigations also show that extended exposure to oxidizing conditions results in transformation of sulfide-stabilized Tc(IV) to a Tc(IV)O 2 -like phase without formation of measurable dissolved TcO 4 - , suggesting a solid-state transformation in which Tc(IV)-associated sulfide is preferentially oxidized before the Tc(IV) cation. This transformation of Tc(IV)-sulfides to Tc(IV)-oxides may be the main process that limits remobilization of Tc as Tc(VII)O 4 - . The efficacy of the final waste form to retain Tc also strongly depends on the ability of oxidizing species to enter the waste and convert Tc(IV) to Tc(VII). Finally, many waste form designs are reducing (e.g., cementitious waste forms such as salt stone) and, therefore, attempt to restrict access of oxidizing species such that diffusion is the rate-limiting step in remobilization of Tc.

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