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At least 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Comparison of temperature adaptive calibration methods for laser induced fluorescence based fuel-in-oil instrument

Fuel dilution of engine oil (or fuel-in-oil, FiO) is an important issue as multiple and late-cycle fuel injection, integral to many combustion efficiency and emissions improvements (e.g., downsized boosted gasoline engines and catalyst thermal management) increases FiO rate. In addition to causing general wear and corrosion in engine due to decreased oil viscosity and pH buffering, FiO is also believed to cause destructive low speed pre-ignition (or super knock) in boosted SI engines. To understand the effects of engine operating conditions on the FiO rate, an optical diagnostic capable of measuring transient FiO on minute timescales was recently developed and demonstrated on a modified GM Ecotech engine system (Neupane et al., Applied Spectroscopy 2021). The measurement is based on adding a dye to the fuel and monitoring for its presence in oil via laser-induced fluorescence (LIF). The measured LIF signal is related to FiO concentration via pre-determined calibration factors using a multivariate classical least square (CLS) method.Since fluorescence quantum yield is a function of temperature, measured LIF intensity not only depends on FiO concentration but also oil temperature. To expand the applicability of the FiO diagnostic to transient oil-temperature conditions (e.g., cold start in practical engines), this study develops a method to account for oil-temperature variations. The effect of oil temperature (20°C - 95°C) on the LIF spectra of eight FiO samples ranging from ~0.8-15% was investigated. LIF intensities of the FiO samples decreased linearly with increasing temperature; the reductions being more significant at dye peaks. We develop a new calibration model (T-adaptive CLS) incorporating the temperature (T) effects on LIF intensity that enables simultaneous calculation of FiO and oil temperature. The improved FiO diagnostic with T-adaptive calibration is more robust, and applicable to varying oil-temperature conditions. For example, when strategies such as multiple/late fuel injections are applied to overcome cold-start instability due to use of low vaporization bio-based fuels such as ethanol, FiO rate is expected to be very high; the improved T-adaptive FiO diagnostic is hence relevant for engine- and fuel-system calibration and optimization. The diagnostic could also provide validation data for flow-field and spray interaction CFD models, further broadening the diagnostic’s utility for advancing engine technology and efficiency.

Neupane, Sneha↗
DOE OSTI2023

Structural Characterization of Toxicologically Relevant Cd 2+ -L-Cysteine Complexes

The exposure of humans to Cd exerts adverse human health effects at low chronic exposure doses, but the underlying biomolecular mechanisms are incompletely understood. To gain insight into the toxicologically relevant chemistry of Cd 2+ in the bloodstream, we employed an anion-exchange HPLC coupled to a flame atomic absorption spectrometer (FAAS) using a mobile phase of 100 mM NaCl with 5 mM Tris-buffer (pH 7.4) to resemble protein-free blood plasma. The injection of Cd 2+ onto this HPLC-FAAS system was associated with the elution of a Cd peak that corresponded to [CdCl 3 ] - /[CdCl 4 ] 2- complexes. The addition of 0.1–10 mM L-cysteine (Cys) to the mobile phase significantly affected the retention behavior of Cd 2+ , which was rationalized by the on-column formation of mixed CdCysxCly complexes. From a toxicological point of view, the results obtained with 0.1 and 0.2 mM Cys were the most relevant because they resembled plasma concentrations. The corresponding Cd-containing (~30 μM) fractions were analyzed by X-ray absorption spectroscopy and revealed an increased sulfur coordination to Cd 2+ when the Cys concentration was increased from 0.1 to 0.2 mM. The putative formation of these toxicologically relevant Cd species in blood plasma was implicated in the Cd uptake into target organs and underscores the notion that a better understanding of the metabolism of Cd in the bloodstream is critical to causally link human exposure with organ-based toxicological effects.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Simulation of the supercritical CO 2 recompression Brayton power cycle with a high-temperature regenerator

The supercritical carbon dioxide (sCO 2 ) recompression Brayton cycle promises higher efficiency and lower capital cost than traditional steam Rankine power cycles. However, achieving high efficiency requires large, highly effective recuperators. Regenerators may be a low-cost alternative to printed circuit and micro-tube heat exchangers for recuperation in sCO 2 power cycles. Regenerators are a periodic heat exchanger in which thermal energy is extracted from the hot stream, stored in solid media, and then released to the cold stream at a later time. Fixed bed regenerators with valves to direct fluid are the preferred method for implementing regenerators in power cycles, but the inherently transient nature of these systems has not been characterized for this application. This study presents the simulation of a high-temperature regenerator within a 10 MWe sCO 2 recompression Brayton cycle. A transient, one-dimensional regenerator model presented in a previous study is used to simulate the regenerator. Dynamic heat exchanger models are also developed for the precooler, low-temperature recuperator, and primary heat exchanger, and the compressors and the turbine are modeled with off-design performance maps. We assess two regenerator-valve design options; one for fast switching, and one for reduced flow rate fluctuations. System simulation finds that both designs see significant fluctuations in turbomachinery flow rate, turbomachinery and system power, and regenerator discharge process outlet temperature. While designing the regenerator-valve subsystem for lower fluctuations is possible, the regenerator cold discharge temperature and net power still fluctuate by ±77.6°C and 6%, respectively. Increasing buffer volume is not effective at sufficiently reducing these fluctuations, but adding a packed bed in between the regenerator and the primary heat exchanger can reduce regenerator discharge process outlet temperature fluctuations to 6.4°C. Further reductions could be possible by increasing the size of this packed bed.

42 ENGINEERING↗
DOE OSTI2022

Effects of Borate and Organics on U(VI) Solubility in WIPP Brine

The solubility of uranium (VI) in Waste Isolation Pilot Plant (WIPP)-relevant brine was determined to support ongoing WIPP recertification activities. This research was performed by the Los Alamos National Laboratory Carlsbad Operations (LANL-CO) Actinide Chemistry and Repository Science Program (ACRSP). The WIPP Actinide Source Term Program (ASTP) did not develop a model for the solubility of actinides in the VI oxidation state. The solubility of UO 2 2+ , in the absence of WIPP specific data, is presently set to be equal to a conservatively high 1 mM within the WIPP Performance Assessment (PA) for all expected WIPP conditions (SOTERM, 2019) as selected at the recommendation of the Environment Protection Agency (EPA) (EPA, 2005). According to the current WIPP chemistry model assumptions and conditions, the expected pC H+ is about 9.5 and controlled by MgO buffering CO 3 2- . The goal of this study is to perform screening experiments that account for the contributions of organics and borate on uranium solubility. In this report, the solubility of U(VI) was determined at pC H+ 9 WIPP brine in the absence or presence of borate and organics at under-saturation approach. Experiments were equilibrated for about 135 days. Organic compounds present in WIPP waste can form strong complexes with actinides and can affect the oxidation states of actinides. The organic compounds addressed in WIPP performance assessment include EDTA (Ethylenediaminetetraacetic Acid), oxalate, citrate, and acetate (SOTERM, 2019). These data quantify the effects of WIPP-relevant concentrations of borate and organics effects on the solubility of U(VI) to challenge the predictions of the WIPP actinide model and inform decisions and recommendations made in the upcoming recertification of the WIPP (CRA-2024). The experiments performed were done according to the U.S. Department of Energy (DOE) approved Test Plan entitled “Experimental Strategy to Challenge Actinide Solubility Predictions” and designated LCO-ACP-26. All data reported were obtained under the LANL-CO Quality Assurance Program, which is compliant with the DOE Carlsbad Field Office, Quality Assurance Program Document (CBFO/QAPD) (QAPD, 2017).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Lignin molecular weights of Populus trichocarpa residues after CELF pretreatment

Here we present a dataset of molecular weights of lignin from a woody energy crop (Populus trichocarpa) residues after a series of co-solvent enhanced lignocellulosic fractionation (CELF) pretreatment. The natural poplar variant GW-9947 from the Center for Bioenergy Innovation (CBI) was used. The poplar was knife milled and passed through a 1 mm sieve and CELF pretreatment was performed in a Parr autoclave reactor with 7.5 wt % solids loading, 0.5 wt% H2SO4 as catalyst at 150°C with various time. Tetrahydrofuran was added in a 1:1 mass ratio with water as the pretreatment solvent. Lignin was isolated from the pretreated samples after ball-milling in a porcelain jar with ceramic balls via Retsch PM 200 at 580 rpm for 2.5 h followed by enzymatic hydrolysis in acetate buffer (pH 4.8, 50 °C) for 48 h. The solid residue was isolated by centrifugation and hydrolyzed again with freshly added buffer and enzymes for another 48 h. After filtration, the solid residue was extracted twice with 96% (v/v) 1,4-dioxane/water mixture at room temperature overnight. The extracts were combined, rotary evaporated, and freeze-dried to recover lignin. The lignin samples were then derivatized in an acetic anhydride/pyridine (1:1, v/v) mixture and stirred at room temperature for 24 h. Ethanol was added to the reaction mixture, left for 30 min and then removed with a rotary evaporator. The addition and removal of ethanol was repeated at least 3 times until all traces of acetic acid were removed. Acetylated lignin samples were then dissolved in tetrahydrofuran (THF) at a concentration of 1.0 mg/mL. The molecular weight of acetylated lignin was measured by a gel permeation chromatography (GPC) on a PSS-Polymer Standards Service (Warwick, RI, USA) GPC SECurity 1200 system featuring Agilent HPLC 1200 components equipped with four Waters Styragel columns (HR1, HR2, HR4 and HR6) and an UV detector (270 nm). Tetrahydrofuran was used as the mobile phase and flow rate was 0.3 mL/min. The Polymer Standards Service WinGPC Unity software (Build 6807) was used for data processing for all the samples. The data provides information about the effects of CELF pretreatment time at 150 ºC on lignin molecular weights.

09 BIOMASS FUELS↗
DOE OSTI2020

Reduction of Hg(II) by Fe(II)-Bearing Smectite Clay Minerals

Aluminosilicate clay minerals are often a major component of soils and sediments and many of these clays contain structural Fe (e.g., smectites and illites). Structural Fe(III) in smectite clays is redox active and can be reduced to Fe(II) by biotic and abiotic processes. Fe(II)-bearing minerals such as magnetite and green rust can reduce Hg(II) to Hg(0); however, the ability of other environmentally relevant Fe(II) phases, such as structural Fe(II) in smectite clays, to reduce Hg(II) is largely undetermined. We conducted experiments examining the potential for reduction of Hg(II) by smectite clay minerals containing 0–25 wt% Fe. Fe(III) in the clays (SYn-1 synthetic mica-montmorillonite, SWy-2 montmorillonite, NAu-1 and NAu-2 nontronite, and a nontronite from Cheney, Washington (CWN)) was reduced to Fe(II) using the citrate-bicarbonate-dithionite method. Experiments were initiated by adding 500 µM Hg(II) to reduced clay suspensions (4 g clay L−1) buffered at pH 7.2 in 20 mM 3-morpholinopropane-1-sulfonic acid (MOPS). The potential for Hg(II) reduction in the presence of chloride (0–10 mM) and at pH 5–9 was examined in the presence of reduced NAu-1. Analysis of the samples by Hg LIII-edge X-ray absorption fine structure (XAFS) spectroscopy indicated little to no reduction of Hg(II) by SYn-1 (0% Fe), while reduction of Hg(II) to Hg(0) was observed in the presence of reduced SWy-2, NAu-1, NAu-2, and CWN (2.8–24.8% Fe). Hg(II) was reduced to Hg(0) by NAu-1 at all pH and chloride concentrations examined. These results suggest that Fe(II)-bearing smectite clays may contribute to Hg(II) reduction in suboxic/anoxic soils and sediments.

58 GEOSCIENCES↗
DOE OSTI2025

Selectivity of tris complexation for Ni(II), Co(II), and Fe(II) and its effect on carbonate precipitation under alkaline conditions

Simultaneous critical element recovery and ex-situ carbon mineralization of low-grade ultramafic deposits have garnered increasing interest. Understanding the selectivity of metal complexing organic ligands for various divalent metals present in ultramafic rocks during carbonate mineralization is required to optimize this process. Here we evaluate 2-amino-2-(hydroxymethyl)-1,3-propanediol (i.e., Tris) as a model for bidentate ligands that bind divalent metals with both amine and alcohol groups in alkaline conditions (pH 8–10.5) at 25 °C and 80 °C in carbonate-buffered solutions. Protonated Tris forms a stronger complex with metal ions and is selective for trace metals with Ni(II) > Co(II) > Fe(II) during carbonate precipitation, with the rates decreasing but selectivity increasing at lower temperature and lower pH. At 25 °C, metastable amorphous hydrated carbonates form, regardless of the amount of Tris present or pH values. At 80 °C and pH 8, the Co and Fe carbonates that form are a mixture of rosasite-group minerals (Co 2 CO 3 (OH) 2 (H 2 O) and Fe 2 CO 3 (OH) 2 ) and pure carbonates (sphaerocobaltite: CoCO 3 and siderite: FeCO 3 ), with the latter more stabilized with increasing Tris concentration. In mixed metal solutions without Tris at 25 °C where Fe:Ni or Fe:Co is 2:1, Fe increases the rates of Ni or Co carbonate precipitation. However, with increasing Tris concentration the presence of Ni or Co inhibits Fe carbonate precipitation. At 80 °C without Tris, Ni or Co substitute into the iron chukanovite (Fe 2 CO 3 (OH) 2 ) lattice, increasing Ni or Co carbonate precipitation rates. Increasing Tris concentration only slightly inhibits Fe and Co precipitation, but slows Ni precipitation up to 10 times, with Fe progressively partitioning into more pure carbonate phases with distinct crystalline morphologies. These findings suggest bidentate amine-bearing ligands may be effective at Ni and Co recovery during carbon mineralization of Fe-bearing ultramafic deposits at relatively low temperatures and slightly alkaline pH.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

A self-healing plastic ceramic electrolyte by an aprotic dynamic polymer network for lithium metal batteries

Abstract Oxide ceramic electrolytes (OCEs) have great potential for solid-state lithium metal (Li 0 ) battery applications because, in theory, their high elastic modulus provides better resistance to Li 0 dendrite growth. However, in practice, OCEs can hardly survive critical current densities higher than 1 mA/cm 2 . Key issues that contribute to the breakdown of OCEs include Li 0 penetration promoted by grain boundaries (GBs), uncontrolled side reactions at electrode-OCE interfaces, and, equally importantly, defects evolution (e.g., void growth and crack propagation) that leads to local current concentration and mechanical failure inside and on OCEs. Here, taking advantage of a dynamically crosslinked aprotic polymer with non-covalent –CH 3 ⋯CF 3 bonds, we developed a plastic ceramic electrolyte (PCE) by hybridizing the polymer framework with ionically conductive ceramics. Using in-situ synchrotron X-ray technique and Cryogenic transmission electron microscopy (Cryo-TEM), we uncover that the PCE exhibits self-healing/repairing capability through a two-step dynamic defects removal mechanism. This significantly suppresses the generation of hotspots for Li 0 penetration and chemomechanical degradations, resulting in durability beyond 2000 hours in Li 0 -Li 0 cells at 1 mA/cm 2 . Furthermore, by introducing a polyacrylate buffer layer between PCE and Li 0 -anode, long cycle life >3600 cycles was achieved when paired with a 4.2 V zero-strain cathode, all under near-zero stack pressure.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Electrochemical aptamer-based sensors: leveraging the sensing platform for minimally-invasive microneedle measurements and fundamental exploration of sensor biofouling dynamics

The ability to track the concentrations of specific molecules in the body in real time would significantly improve our ability to study, monitor, and respond to diseases. To achieve this, we require sensors that can withstand the complex environment inside the body. Electrochemical aptamer-based sensors are particularly promising for in vivo sensing, as they are among the only generalizable sensing technologies that can achieve real-time molecular monitoring directly in blood and the living body. In this project, we first focused on extending the application space of aptamer sensors to support minimally-invasive wearable measurements. To achieve this, we developed individually-addressable sensors with commercial off-the-shelf microneedles. We demonstrated sensor function in buffer, blood, and porcine skin (a common proxy for human skin). In addition to the applied sensing project, we also worked to improve fundamental understanding of the aptamer sensing platform and how it responds to biomolecular interferents. Specifically, we explored the interfacial dynamics of biofouling – a process impacting sensors placed in complex fluids, such as blood.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Pilot scale testing of an advanced solvent in a 0.7 MWe post-combustion CO 2 capture unit

An advanced Amine Promoted Buffer Solution (APBS), APBS-CDRMax® (CDRMax), developed by Carbon Clean Solutions Limited (CCSL), was tested at the 0.7 MWe CO 2 capture facility at Kentucky Utilities E.W. Brown Generation Station using a heat-integrated two-staged stripping CO 2 capture process. The performance of the solvent was evaluated to determine operating conditions that maximized the cyclic capacity of the solvent and results in energy savings. The regeneration energy ranged from 2.9 to 3.3 GJ/ton CO 2 with 14 vol % (dry) CO 2 inlet and approximately 90 % capture. The difference in the reboiler specific heat duty at stripper pressures of 1.7 and 2.1 bar was minimal as similar amounts of water vapor were observed in the CO 2 product stream at stripper outlet. Recycling of product CO 2 increased the inlet CO 2 concentration to the absorber from 14 to 16 vol% which enhanced mass transfer from the gas to the solvent resulting in about 5 % reduction in the energy of regeneration at the lower stripper pressure. The solvent circulation rate was reduced by about 30 % relative to previous 30 wt% MEA campaign for the CO 2 target capture of 90 %. Finally, the reduced solvent make-up rate of CDRMax shows promise for capital and operating cost savings for post-combustion CO 2 capture.

42 ENGINEERING↗
DOE OSTI2023

Origins of quench in buffered chemical polished and low temperature baked SRF cavities

Electropolishing (EP) and buffered chemical polishing (BCP) are conventional surface preparation techniques for superconducting radiofrequency (SRF) cavities that remove damaged material from the cavity surface. One main issue with EP and BCP treated SRF cavities is high field Q-slope (HFQS), a drop in quality factor at high gradients that limits quench field. High gradient performance in EP cavities can be improved by applying a low temperature bake (LTB), but LTB does not consistently remove HFQS in BCP cavities. There is no consensus as to the why LTB is not effective on BCP prepared cavities, and the cause of HFQS in BCP cavities is not well understood. We examine the origins of quench in EP, BCP, EP+LTB, and BCP+LTB treated SRF cavities. We also show the effect of these treatments on the onset of HFQS, heating within the cavity up to quench, concentration of free hydrogen, and surface roughness.

43 PARTICLE ACCELERATORS↗
DOE OSTI2023

Comparing the Effectiveness of Low Temperature Bake in EP and BCP Cavities

Electropolishing (EP) and buffered chemical polishing (BCP) are conventional surface preparation techniques for superconducting radiofrequency (SRF) cavities. Both EP and BCP treated SRF cavities display high field Q-slope (HFQS) which degrades performance at high gradients. While high gradient performance in EP cavities can be improved by introducing oxygen via a low temperature bake (LTB) of 120^{°}C by 48 hours, LTB does not consistently remove HFQS in BCP cavities. There is no consensus as to why LTB is not effective on BCP prepared cavities. We examine quench in EP, BCP, EP+LTB, and BCP+LTB treated 1.3 GHz single-cell Nb cavities by studying the heating behavior with field using a temperature mapping system. Cavity performance is correlated to characterizations of surface impurity profile obtained via time of flight secondary ion mass spectrometry studies. We observe a difference in near surface hydrogen concentration following BCP compared to EP that may suggest that the causes of quench in EP and BCP cavities are different.

43 PARTICLE ACCELERATORS↗
DOE OSTI2022

Impacts of Crystalline Host Rock on Repository Barrier Materials at 250 °C: Hydrothermal Co-Alteration of Wyoming Bentonite and Steel in the Presence of Grimsel Granodiorite

Direct disposal of dual-purpose canisters (DPC) has been proposed to streamline the disposal of spent nuclear fuel. However, there are scenarios where direct disposal of DPCs may result in temperatures in excess of the specified upper temperature limits for some engineered barrier system (EBS) materials, which may cause alteration within EBS materials dependent on local conditions such as host rock composition, chemistry of the saturating groundwaters, and interactions between barrier materials themselves. Here we report the results of hydrothermal experiments reacting EBS materials—bentonite buffer and steel—with an analogue crystalline host rock and groundwater at 250 °C. Experiment series explored the effect of reaction time on the final products and the effects of the mineral and fluid reactants on different steel types. Post-mortem X-ray diffraction, electron microprobe, and scanning electron microscopy analyses showed characteristic alteration of both bentonite and steel, including the formation of secondary zeolite and calcium silicate hydrate minerals within the bentonite matrix and the formation of iron-bearing clays and metal oxides at the steel surfaces. Swelling clays in the bentonite matrix were not quantitatively altered to non-swelling clay species by the hydrothermal conditions. The combined results of the solution chemistry over time and post-mortem mineralogy suggest that EBS alteration is more sensitive to initial groundwater chemistry than the presence of host rock, where limited potassium concentration in the solution prohibits conversion of the smectite minerals in the bentonite matrix to non-swelling clay species.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Yield stress and flow behavior of enzyme liquefied slurries from corn cobs and corn stover pellets

With the increase in population, the world will depend on renewable sources to meet the increasing energy needs. The use of lignocellulosic biomass as a renewable source has been proven efficient for conversion to cellulosic ethanol and capable of contributing to thresholds for energy demand while reducing greenhouse gases by 90% when compared with fossil fuels. However, limitations in feeding and flow within biorefineries is encountered when system plugging occurs due to biomass compaction and a high yield stress for slurries formed during its processing, thereby preventing transport of biomass materials between plant unit operations. In some cases, this leads to unexpected plant shutdowns increasing industrial operational costs. As an alternative, enzyme-assisted liquefaction for slurry creation from corn stover at solids loadings up to 30% is reported in this work. Two different kinds of biomass (pelleted corn stover and cobs) were liquefied in a fed-batch process using commercial enzymes Celluclast 1.5L or Ctec-2 at 1FPU or 3 FPU per gram of dry solids in 10 mM sodium citrate buffer solution (pH 4.8). Pellets were fed into a 1 L stirred bioreactor according to a pre-defined fed-batch protocol over the first 5 hours until reaching 30% of solids loading. After 6, 24 and 96 hours, samples were taken and characterized with respect to their sugar composition, rheology and water absorption. Successful slurry creation with dramatically reduced yield stress was achieved for corn stover for both assessed enzymes. Yield stresses of 178±7 Pa (3 FPU, Celluclast 1.5L) and 79±6 Pa (3 FPU, Ctec-2) were measured for corn stover at 24 hours, compared to 6,000 Pa for samples without enzyme. Yield stress was 155± 29 Pa (3FPU, Ctec-2) and 257 ± 72 Pa (1 FPU,Celluclast 1.5L) for corn cobs at 24 hours. Yield stress decreased when residence time increased with an enhanced fluidity noted for higher enzyme concentrations. A profile for 6, 24 and 96h of yield stress measurements is presented.

Guitierrez, Diana↗
DOE OSTI2023

Prediction of Long-Term Geochemical Change in Bentonite Based on the Interpretative THMC Model of the FEBEX In Situ Test

Since nuclear energy is crucial in the decarbonization of the energy supply, one hurdle to remove is the handling of high-level radioactive waste (HLW). Disposal of HLW in a deep geological repository has long been deemed a viable permanent option. In the design of a deep geological repository, compacted bentonite is the most commonly proposed buffer material. Predicting the long-term chemical evolution in bentonite, which is important for the safety assessment of a repository, has been challenging because of the complex coupled processes. Models for large-scale tests and predictions based on such models have been some of the best practices for such purposes. An 18-year-long in situ test with two dismantling events provided a unique set of chemical data that allowed for studying chemical changes in bentonite. In this paper, we first developed coupled thermal, hydrological, mechanical, and chemical (THMC) models to interpret the geochemical data collected in the in situ test and then extended the THMC model to 200 years to make long-term prediction of the geochemical evolution of bentonite. The interpretive coupled THMC model shows that the geochemical profiles were strongly affected by THM processes such as evaporation/condensation, porosity change caused by swelling, permeability change, and the shape of concentration profiles for major cations were largely controlled by transport processes, but concentration levels were regulated by chemical reactions, and the profiles of some species such as pH, bicarbonate, and sulfate were dominated by these reactions. The long-term THMC model showed that heating prolongs the time that bentonite becomes fully saturated in the area close to the heater/canister; however, once the bentonite becomes fully saturated, high concentrations of ions in bentonite near the heater, which was observed in the field test, will disappear; illitization continues for 50 years but will not proceed further.

Zheng, Liange↗
DOE OSTI2022

Impacts of sulfonic acids on fungal manganese oxide production

Microbial manganese (Mn) oxidation plays a critical role in Mn(III/IV) oxide formation in modern day environmental systems. These oxidation processes and resulting biominerals are sensitive to aqueous conditions, such as pH and dissolved constituent concentrations. With Mn and sulfur (S) biogeochemical cycling closely linked in many environmental systems, and dissolved organic sulfur comprising a substantial pool of total sulfur in several environments, the impact of dissolved organic sulfur compounds on Mn redox processes is important to consider. Sulfonic acids, environmentally ubiquitous organosulfur compounds, play substantial roles in S cycling in many natural and contaminated systems. Research to assess the effects of these abundant sulfonic acids on Mn biogeochemical cycling, microbial Mn oxidation processes, and Mn biominerals is needed for understanding and predicting the impact of coupled S and Mn biogeochemical cycles, particularly in environments with dynamic redox gradients or in anthropogenically contaminated systems. Further, with research on microbial and abiotic Mn oxidation processes often using aminosulfonic acids to control pH, understanding the impact of such sulfonic acids on microbial Mn oxidation processes is critical. Several recent studies found that commonly used zwitterionic N substituted aminosulfonic acids, known as Good’s buffers, such as HEPES and MES, can alter abiotic birnessite sheet structures. Here we investigate the impact of two sulfonic acids with broad applications to natural and contaminated sites as well as laboratory settings (HEPES and MES) on fungal Mn oxidation relative to a carbonate buffer and a buffer-free control by three Ascomycete fungi known to oxidize Mn(II): Stagonospora sp. SRC1lsM3a, Paraphaeosphaeria sporulosa AP3s5–JAC2a, and Plectosphaerella cucumerina DS2psM2a2. Structural analyses of the products show that sulfonic acids promote Mn oxidation by P. cucumerina, producing hexagonally symmetric phyllomanganates analogous to hexagonal birnessite or c–disordered H + birnessite [(Ca,Na,K)(Mn 4+ ,Mn 3+ ,$\square$)O 2 nH 2 O], with solid–associated Mn(II) bound to vacancy sites and biomass, while in their absence almost all Mn remains as either aqueous Mn(II) or solid–associated Mn(II) bound to biomass. In contrast, sulfonic acids exert the opposite effect on Mn oxidation by P. sporulosa, with their presence suppressing Mn(II) oxidation to Mn(IV), likely leading to the formation of mycogenic bixbyite (Mn 3+ 2 O 3 ) while the buffer–free control forms a poorly crystalline phyllo- or tectomanganate. Meanwhile, all treatments exert a minimal effect on Mn(II) uptake from solution and Mn oxidation with Stagonospora sp., with all experimental systems and controls forming poorly crystalline, hexagonally symmetric phyllomanganates. The fact that the sulfonic acids here studied exert similar effects on Mn oxidation, but substantially different effects for each fungus, suggests they affect Mn oxidation via mechanistically similar pathways that are likely dependent on interactions with fungal exudates (which vary from species to species) or specific fungal Mn oxidation processes. Interestingly, for all fungi, MES increases Mn(III) in the resulting biominerals, while the carbonate buffer consistently decreases Mn(III). Further, these results clearly demonstrate that sulfonic acids not only alter Mn oxide structures, as has been previously noted in abiotic studies, but can interfere with Mn oxidation reactions themselves, highlighting the incredible sensitivity of both Mn oxide structures and the Mn oxidation process to the aqueous environment.

58 GEOSCIENCES↗
DOE OSTI2023

Molybdenum in basalt-hosted seafloor hydrothermal systems: Experimental, theoretical, and field sampling approaches

Here, seafloor hydrothermal vents represent potential sources of Mo and other biologically relevant transition metals to the global ocean, complementing continental runoff. Here, we use a combination of experimental, theoretical, and field-sampling approaches to investigate the behavior of Mo in basalt-hosted seafloor hydrothermal systems to provide insight into the processes controlling Mo concentrations in hydrothermal fluids and to derive estimates of vent fluid Mo concentrations and fluxes. Results of this study demonstrate that reaction fluids generated from 350°C, 500 bar hydrothermal basalt alteration experiments contain 775–801 nmol/kg Mo and are thus comparable to a recently collected time series of natural seafloor vent fluids that contained 200–220 nmol/kg Mo at 302°C and 29–30 nmol/kg at 281–282°C (Evans et al., 2023). Synchrotron-based analyses of experimentally altered basalt produced in this study and additional natural samples of altered oceanic crust originally collected from Pito Deep Rift reveal the presence of Mo-rich particles consistent with trace molybdenite. Comparisons of Mo:Cu ratios in natural vent fluids and near-vent sediment trap samples from Main Endeavour Field indicate that vent fluid Mo is readily incorporated into buoyant plume particles and advected out of the near-vent field, analogous to previous mass balance studies of Cu in this region. Thermodynamic calculations of molybdenite solubility in the context of mineral-buffered hydrothermal fluids and comparisons with natural and experimental hydrothermal fluids suggest that high-temperature vent fluids contain 30–1500 nmol/kg Mo. While a minor component of the modern Mo budget, hydrothermal Mo fluxes are estimated to have constituted 0.3–200× the contemporaneous continental weathering fluxes prior to the ~2.4 Ga ago “Great Oxidation Event” and widespread oxidative continental weathering. Overall, identification of hydrothermal vents as a source of Mo-rich plume particles with potential for dispersal into the wider marine environment has significant implications for hypotheses regarding the co-evolution of Life and Earth’s environments, specifically the form and availability of Mo in anoxic Archean-Eon oceans, where Mo-dependent enzymatic pathways are thought to have emerged and subsequently evolved.

58 GEOSCIENCES↗
DOE OSTI2021

Fission product distribution in irradiated safety-tested and as-irradiated AGR-2 TRISO particles

In this work, two tristructural isotropic (TRISO)-coated nuclear fuel particles were examined by electron probe microanalysis (EPMA) as part of the Advanced Gas Reactor program. The compacts’ average irradiation temperatures ranged from approximately 1260 to 1290 °C. One particle was examined in the as-irradiated condition, while the other was subject to 1600 °C post-irradiation safety testing. This study was undertaken to test a newly-developed EPMA technique to determine fission product masses in TRISO particles on a layer-by-layer basis, and to compare fission product distributions between an as-irradiated and safety-tested particle. Fission product concentration profiles were collected along two radii in each particle, with measured concentrations used to compute the fission product mass in each TRISO particle layer. These measured masses were then compared to those predicted from ORIGEN modeling calculations. Data collected from these measurements show that for these two particles, masses determined via EPMA were within ± 20% of the calculated masses for the rare-earth elements, Mo, Zr, Cs, I, and Pd. Elements that tend to be less homogeneously distributed include Sr, Te, Eu, Ag, and possibly Ba. Measured Ag masses differed by more than 40% from the calculated mass. Lanthanides other than Eu remain primarily within the fuel kernel in the as-irradiated particle but in the safety-tested particle these element masses were divided approximately equally between the kernel and kernel periphery. In both particles, the majority of Sr and Eu accumulated in the carbon-rich kernel periphery, although in the safety-tested particle, Sr and Eu accumulated farther from the fuel kernel than occurred with irradiation alone. A greater mass fraction of mobile elements, such as Cs and I accumulated in the buffer and IPyC in the safety-tested particle as compared to the as-irradiated particle. When fully developed and tested, this mass balance approach to TRISO particle analysis has the potential to provide insight into fuel behavior.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗